CN113878835B - Polytetrafluoroethylene/carbon fiber composite release film and preparation method and application thereof - Google Patents
Polytetrafluoroethylene/carbon fiber composite release film and preparation method and application thereof Download PDFInfo
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- CN113878835B CN113878835B CN202111488839.0A CN202111488839A CN113878835B CN 113878835 B CN113878835 B CN 113878835B CN 202111488839 A CN202111488839 A CN 202111488839A CN 113878835 B CN113878835 B CN 113878835B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
- B29C43/24—Calendering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
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Abstract
The invention provides a polytetrafluoroethylene/carbon fiber composite release film and a preparation method and application thereof. The preparation method comprises the following steps: step S1, performing surface treatment on the carbon fiber by adopting a heat treatment or acid treatment mode to obtain a surface modified carbon fiber; step S2, mixing polytetrafluoroethylene resin, surface modified carbon fiber and a lubricating additive, and curing to form a cured material; step S3, pressing and extruding the cured material to form a blank; step S4, rolling the blank into a film in a double-roller rolling mode to obtain a film material; and step S5, sequentially degreasing and shaping the membrane material to obtain the polytetrafluoroethylene/carbon fiber composite release membrane. The polytetrafluoroethylene/carbon fiber composite membrane prepared by the invention is very suitable for being used as a release membrane, and is particularly suitable for being used as the release membrane used in a coating process in the manufacturing process of a composite proton exchange membrane.
Description
Technical Field
The invention relates to the field of thin film materials, in particular to a polytetrafluoroethylene/carbon fiber composite release film and a preparation method and application thereof.
Background
Release films, also known as barrier films, release films, separation films, and the like, have been widely used in the fields of packaging, printing, screen printing, transfer printing, nameplates, membrane switches, flexible circuits, insulating products, circuit boards, laser anti-counterfeiting, bonding, electronics, films for sealing materials, reflective materials, waterproof materials, medicine (plaster paper), sanitary paper, adhesive products, die-cutting and stamping processes, and the like, and are closely related to our lives. At present, the most common release film product is a PET release film, and surface treatment is performed on a PET substrate, including coating a silicon release agent and a fluorine release agent or performing plasma treatment, so that the release film has extremely light and stable release force on different organic pressure-sensitive adhesives.
With the development of the hydrogen energy industry, the productivity of the composite proton exchange membrane is increased year by year. The release film used in the coating process applied to the manufacturing process of the composite proton exchange membrane needs to pass through a high-temperature oven (usually 150-200 ℃) under the condition of bearing great tension, and the flatness of the membrane surface needs to be ensured without deformation. The conventional PET release film cannot meet the process requirements, and the release agent on the surface of the film can pollute the coated slurry.
Polytetrafluoroethylene (PTFE) films have many excellent properties, such as chemical resistance, thermal stability. And because no branch chain exists on the main chain of the PTFE molecule, no cross chain is formed in the whole body, the molecular profile is smooth, and the PTFE monomer has perfect symmetry, so that the attraction force and the surface energy among the PTFE molecules are lower, therefore, the PTFE has extremely low surface friction coefficient, is an excellent release film material, has extremely low adhesiveness and excellent mold release performance, and is an excellent release film. The paper (Ebnesajjad S. Expanded PTFE Applications Handbook [ J ] 2017: 129-161.) details the paste extrusion molding theory for PTFE resins. Patents US3953566 and US4187390 of gore usa describe the preparation of expanded PTFE films. Patent CN 105666889 a discloses a preparation method of a high-strength PTFE membrane rolled film.
However, although the PTFE films prepared by these processes have a certain high temperature resistance, the mechanical properties are insufficient, and dimensional stability cannot be maintained. Practice proves that in a high-temperature oven, when the PTFE film is used as a release film and bears a larger tension, the film surface is easy to deform and uneven, and the coating process requirements cannot be met, so further research is needed.
Disclosure of Invention
The invention mainly aims to provide a polytetrafluoroethylene/carbon fiber composite release film and a preparation method and application thereof, and aims to solve the problem that a PTFE film in the prior art is easy to deform at high temperature and is not suitable for being used as a release film.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a polytetrafluoroethylene/carbon fiber composite release film, comprising the steps of: step S1, performing surface treatment on the carbon fiber by adopting a heat treatment or acid treatment mode to obtain a surface modified carbon fiber; step S2, mixing polytetrafluoroethylene resin, surface modified carbon fiber and a lubricating additive, and curing to form a cured material; step S3, pressing and extruding the cured material to form a blank; step S4, rolling the blank into a film in a double-roller rolling mode to obtain a film material; and step S5, sequentially degreasing and shaping the membrane material to obtain the polytetrafluoroethylene/carbon fiber composite release membrane.
Further, in step S1, the heat treatment process includes: treating the carbon fiber at 500-800 ℃ for 3-5 h to obtain surface modified carbon fiber; the acid treatment process comprises the following steps: putting the carbon fiber into a mixed acid solution at 70-90 ℃ for acid washing for 3-5 h, taking out and washing with water to obtain surface modified carbon fiber; wherein the mixed acid solution is a mixed solution of a nitric acid solution with the mass concentration of 60-70% and a sulfuric acid solution with the mass concentration of 95-98%.
Further, the volume ratio of the nitric acid solution to the sulfuric acid solution is (3-5): 1.
Further, step S2 includes: mixing polytetrafluoroethylene resin and surface modified carbon fiber to form a mixture; adding a lubricating assistant into the mixture in a spraying mode under the stirring state, and curing at the temperature of 40-50 ℃ for 10-12 h to obtain a cured material.
Further, the lubricating assistant is C10~C16More preferably Isopar M; the polytetrafluoroethylene resin is a dispersion resin with the crystallinity of more than 98 percent and the number average molecular weight of 600-1200 ten thousand.
Further, the polytetrafluoroethylene resin is one or more of Dajin F-106, Dajin F-107, Kemu 601X, and AGC CD 123E.
Furthermore, the addition amount of the surface modified carbon fiber is 10-30% of the weight of the polytetrafluoroethylene resin, and the addition amount of the lubricating additive is 15-25% of the weight of the polytetrafluoroethylene resin.
Further, step S3 includes: placing the cured material into a blank pressing machine at the temperature of 60-80 ℃, pressing the cured material into a column blank under the pressure of 3-5 MPa, and controlling the compression speed to be 20-50 mm/min during pressing; the column blank is placed into a material cavity of a pushing and pressing machine, heated to 100-120 ℃, extruded under the pressure of 5-8 MPa to form a blank, and the compression ratio is controlled to be 80-100 during extrusion.
Further, in step S4, the rolling temperature during the rolling film forming process is 60-80 ℃, the roller linear velocity is 5-15 m/min, and the rolling thickness is 0.05-0.3 mm.
Further, step S5 includes: degreasing the membrane material at 100-200 ℃, and then shaping at 350-400 ℃.
According to another aspect of the invention, a polytetrafluoroethylene/carbon fiber composite release film is provided, which is prepared by the preparation method.
According to another aspect of the invention, the application of the polytetrafluoroethylene/carbon fiber composite release film in a composite proton exchange membrane coating process is provided.
The preparation method provided by the invention is adopted to prepare the polytetrafluoroethylene/carbon fiber composite membrane by the steps of mixing, curing, pressing, extruding, calendaring, degreasing, shaping and the like of polytetrafluoroethylene resin (PTFE resin), surface modified carbon fiber and a lubricating additive. This complex film is because self polytetrafluoroethylene material reason possesses from the type function, need not spraying release agent, can not remain in the coating slurry because of the release agent in process of production, causes the pollution to the product. More importantly, the surface modified carbon fiber is compounded with the polytetrafluoroethylene, and a calendering process is combined, so that the carbon fiber can be in good contact and dispersion with the polytetrafluoroethylene base material, the strength of the membrane is effectively improved, the membrane can still keep the shape in a high-temperature environment, and the membrane is not easy to deform and has a smooth surface. Based on the reasons, the polytetrafluoroethylene/carbon fiber composite membrane prepared by the invention is very suitable for being used as a release film, and is particularly suitable for being used as the release film used in a coating process in the manufacturing process of a composite proton exchange membrane.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a cross-sectional scanning electron micrograph of a polytetrafluoroethylene resin/carbon fiber composite release film prepared according to example 1 of the present invention; and
fig. 2 shows a cross-sectional scanning electron micrograph of the teflon resin/carbon fiber composite release film prepared according to example 2 of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background, the PTFE films of the prior art are easily deformed under high temperature conditions and are not suitable as release films. In order to solve the problems, the invention provides a preparation method of a polytetrafluoroethylene/carbon fiber composite release film, which comprises the following steps: step S1, performing surface treatment on the carbon fiber by adopting a heat treatment or acid treatment mode to obtain a surface modified carbon fiber; step S2, mixing polytetrafluoroethylene resin, surface modified carbon fiber and a lubricating additive, and curing to form a cured material; step S3, pressing and extruding the cured material to form a blank; step S4, rolling the blank into a film in a double-roller rolling mode to obtain a film material; and step S5, sequentially degreasing and shaping the membrane material to obtain the polytetrafluoroethylene/carbon fiber composite release membrane.
The preparation method provided by the invention is adopted to prepare the polytetrafluoroethylene/carbon fiber composite membrane by the steps of mixing, curing, pressing, extruding, rolling, degreasing and shaping the polytetrafluoroethylene resin, the surface modified carbon fiber and the lubricating aid. This complex film is because self polytetrafluoroethylene material reason possesses from the type function, need not spraying release agent, can not remain in the coating slurry because of the release agent in process of production, causes the pollution to the product. More importantly, the surface modified carbon fiber is compounded with the polytetrafluoroethylene, and a calendering process is combined, so that the carbon fiber can be in good contact and dispersion with the polytetrafluoroethylene base material, the strength of the membrane is effectively improved, the membrane can still keep the shape in a high-temperature environment, and the membrane is not easy to deform and has a smooth surface. Based on the reasons, the polytetrafluoroethylene/carbon fiber composite membrane prepared by the invention is very suitable for being used as a release film, and is particularly suitable for being used as the release film used in a coating process in the manufacturing process of a composite proton exchange membrane.
Specifically, the carbon fiber is subjected to surface treatment in a heat treatment mode, so that part of the protective layer originally carried on the surface of the carbon fiber can be removed, a fine concave-convex structure is formed on the surface of the carbon fiber, and the surface roughness is increased. By the acid treatment, functional groups such as hydroxyl groups and carboxyl groups can be introduced to the surface of the carbon fibers. Therefore, the surface modified carbon fiber treated by the method can form better contact dispersion with polytetrafluoroethylene resin in the subsequent mixing, pressing, extruding and calendering film forming processes, the resin can fully wrap the carbon fiber, and the interface contact performance of the carbon fiber and the resin is good, so that the high strength of the composite release film is ensured.
In addition, due to good interface contact, during the rolling film formation process, the carbon fibers are spread in the planar direction of the film as the two-roll rolling proceeds, so that while good dispersion is formed in the matrix, orientation can also be formed in the planar direction. In the practical application process, greater tension is borne in the plane direction of the release film in a high-temperature environment, and the good dispersion and orientation of the carbon fibers on the plane enable the direction to have better mechanical property and temperature resistance, so that the tension is borne sufficiently, the stability of the release film structure is maintained, the deformation is inhibited, and the application effect is better.
The above heat treatment and acid treatment processes may be adjusted, and in order to further improve the surface modification effect on the carbon fiber, in a preferred embodiment, in step S1, the heat treatment process includes: treating the carbon fiber at 500-800 ℃ for 3-5 h to obtain surface modified carbon fiber; the acid treatment process comprises the following steps: putting the carbon fiber into a mixed acid solution at 70-90 ℃ for acid washing for 3-5 h, taking out and washing with water to obtain surface modified carbon fiber; wherein the mixed acid solution is a mixed solution of a nitric acid solution with a mass concentration of 60-70% (such as 60%, 65%, 70%) and a sulfuric acid solution with a mass concentration of 95-98% (such as 95%, 96%, 98%). In the specific treatment process, the carbon fibers can be placed into a mixed acid solution, and the acid washing treatment is carried out for 3-5 hours in a reflux state. And after the acid washing is finished, taking out the carbon fibers, and soaking and washing the carbon fibers by using pure water until the washing liquid is neutral.
In a preferred embodiment, the volume ratio of the nitric acid solution to the sulfuric acid solution is (3-5): 1. The ratio of the two is controlled in the range, so that the functional group can be introduced to the surface of the carbon fiber more favorably, and the modification effect is better.
In order to mix the components more uniformly, the step S2 includes: mixing polytetrafluoroethylene resin and surface modified carbon fiber to form a mixture; adding a lubricating assistant into the mixture in a spraying mode under the stirring state, and curing at the temperature of 40-50 ℃ for 10-12 h to obtain a cured material. The lubricating additive is added in a spraying mode under the stirring state, so that the lubricating additive can form better distribution on the surfaces of the polytetrafluoroethylene resin and the surface modified carbon fiber, the material distribution is better and uniform after subsequent curing, and the integral performance of the final release film is better promoted. Specifically, the polytetrafluoroethylene resin and the surface-modified carbon fibers can be uniformly mixed by using a roller mixer, then the lubricating additive is sprayed, the mixture is sprayed and mixed at the same time, and finally the mixture is placed into a curing box for curing.
The lubricating auxiliary agent is added, and the lubricating auxiliary agent can coat resin particles to form a lubricating layer, so that the resins are prevented from being rubbed with each other to form fine fibers in the stages of mixing, curing and prepressing on one hand, and the lubricating effect is achieved in the stage of extruding on the other hand. To more effectively exert the above effects, in a preferred embodiment, the lubricating aid is C10~C16More preferably Isopar M.
In order to further improve the processing performance, the high-temperature resistance and the mechanical property of the final release film, the polytetrafluoroethylene resin is preferably a dispersion resin with the crystallinity of more than 98 percent and the number average molecular weight of 600-1200 ten thousand, and more preferably one or more of Dajin F-106, Dajin F-107, Kemu 601X and AGC CD 123E.
In consideration of improvement of mechanical properties of the carbon fiber and consideration of processability and other properties, in a preferred embodiment, the surface-modified carbon fiber is added in an amount of 10 to 30% by weight of the polytetrafluoroethylene resin, and the lubricant additive is added in an amount of 15 to 25% by weight of the polytetrafluoroethylene resin.
In a preferred embodiment, the step S3 includes: placing the cured material into a blank pressing machine at the temperature of 60-80 ℃, pressing the cured material into a column blank under the pressure of 3-5 MPa, and controlling the compression speed to be 20-50 mm/min during pressing; the column blank is placed into a material cavity of a pushing and pressing machine, heated to 100-120 ℃, extruded under the pressure of 5-8 MPa to form a blank, and the compression ratio is controlled to be 80-100 during extrusion. The compression rate is the running speed of the compression rod during pressing, and the compression ratio is the area ratio between the column billet and the extruded strip billet. By pressing, a dense, tightly packed column blank, typically a cylindrical blank, of carbon fibers can be formed under compression. After the extrusion through the process, a strip-shaped blank suitable for subsequent calendering and film forming is formed. And the conditions of temperature, pressure and the like of each process are controlled in the range, so that blank forming is facilitated, the obtained strip-shaped blank is more stable in the subsequent calendering film forming process, and the film forming effect is good. In order to provide temperature conditions for the subsequent calendering film-forming process, in a preferred embodiment, after the extrusion is finished, the blank is subjected to heat preservation at the temperature of 50-80 ℃. The blank can be insulated in a water tank.
In order to provide more excellent performance after the release film is formed, in a preferred embodiment, in step S4, the calendering temperature during the calendering film forming process is 60 to 80 ℃, the roll linear velocity is 5 to 15m/min, and the calendering thickness is 0.05 to 0.3 mm. The carbon fiber is rolled into a film at the temperature and the speed, so that the carbon fiber can be better dispersed and oriented in the plane direction of the film, and the comprehensive performance of the final film is better.
In a preferred embodiment, step S5 includes: degreasing the membrane material at 100-200 ℃, and then shaping at 350-400 ℃. At the temperature, the auxiliary agent in the film material can be effectively removed, and meanwhile, the film layer can be better sintered and shaped, so that the release film with higher strength and better high-temperature resistance is prepared.
In view of the distribution of the carbon fibers in the film layer, the carbon fibers are preferably chopped carbon fiber powder materials, the diameter of which is 5-10 μm, and the length of which is 50-80 μm.
According to another aspect of the invention, the polytetrafluoroethylene/carbon fiber composite release film is also provided, and is prepared by the preparation method. Compared with the conventional PET release film, the composite release film prepared by the invention has high strength and good high-temperature resistance, and does not need to be sprayed with a release agent. The carbon fiber is subjected to surface treatment, so that the interface contact acting force of the carbon fiber and polytetrafluoroethylene resin can be increased, and compared with a common composite mode, the mechanical property enhancement effect is more obvious.
According to another aspect of the invention, the application of the polytetrafluoroethylene/carbon fiber composite release film in a composite proton exchange membrane coating process is also provided.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
This example uses a heat treatment process to surface-treat carbon fibers. Comprises the following preparation processes:
(1) carbon fiber surface modification treatment:
placing a carbon fiber powder material (Nanjing Yitai composite material Co., Ltd., diameter of 5-10 μm and length of 50-80 μm) in a box-type resistance furnace, setting the heating temperature to 700 ℃, keeping the temperature for 3h after the temperature reaches the set temperature, and taking out a sample after natural cooling.
(2) Mixing and curing raw materials:
the PTFE resin raw material is selected from DAJIN F-106 (with crystallinity of above 98% and number average molecular weight of 600 ten thousand), and is stored in a refrigerated cabinet at 5 deg.C, and taken out and placed in a drying chamber to room temperature when in use. 3kg of resin raw material is sieved out by a sieve with 10 meshes and added into a mixing barrel. Weighing 900g of the carbon fiber powder after heat treatment, adding the carbon fiber powder into a mixing barrel, and uniformly mixing. 600g of Isopar M additive is added into a mixing barrel in a spraying mode, and the mixture is sprayed and mixed at the same time. Putting the mixed materials into a curing box, and curing for 12 hours at 40 ℃.
(3) Casting and extruding:
placing the cured mixed material into a blank pressing machine at the temperature of 70 ℃ and pressing the mixed material into a cylindrical blank under the pressure of 5MPa, wherein the compression speed is 20 mm/min.
The cylindrical blank is placed into a material cavity of a pushing press, the heating temperature is 120 ℃, the bar blank is extruded under the pressure of 8MPa, and the compression ratio is 100. And (4) after the strip blank is formed, putting the strip blank into a water tank for heat preservation at the temperature of 80 ℃.
(4) Rolling:
rolling the strip blank into a film through a double-roller rolling machine, wherein the rolling temperature range is 80 ℃, the linear speed range of a roller is 5m/min, and the rolling thickness range is 0.10 mm. And rolling the rolled film through rolling equipment after the rolled film is formed.
(5) Degreasing and high-temperature shaping:
degreasing the film for 20min by using a blower at 150 ℃, and then sintering and shaping the film for 10min in an oven at 320 ℃ to prepare the high-strength and high-temperature-resistant PTFE/carbon fiber composite release film (fig. 1 is a scanning electron microscope photograph with the cross section magnification of 2000 times, and the good combination of the fiber and the resin interface can be seen).
The test shows that the sample has the thickness of 0.105mm, the tensile strength of 56.36MPa and the Vicat softening point of 218.6 ℃. The release film was used for coating experiments: placing a sample of 10 × 10cm into a baking oven at 200 deg.C, standing for 30min to make the membrane surface flat and not deformed; and (3) coating the perfluorinated sulfonic acid resin solution on the surface of the sample membrane by using a blade coater, drying in an oven, and testing that the peeling strength is less than 8.5N/m (180-degree peeling, the width is 25mm, and the peeling speed is 300 mm/min), so that the peeling effect is good.
Example 2
This example used an acid treatment process to surface treat carbon fibers. Comprises the following preparation processes:
(1) carbon fiber surface modification treatment:
mixing 98% concentrated sulfuric acid and 65% concentrated nitric acid according to a volume ratio of 3:1, adding 1000mL of mixed acid into a three-neck flask, adding 200g of carbon fiber powder (Nanjing Yitai composite material Co., Ltd., diameter of 5-10 μm and length of 50-80 μm), heating and stirring, setting the temperature to 90 ℃, keeping the temperature for 3h after the set temperature is reached, and naturally cooling to room temperature. And pouring the product into deionized water for dilution and washing, centrifuging to remove supernatant, repeating the dilution and centrifugation steps until the supernatant is neutral, performing suction filtration, and drying. And repeating the steps to prepare a plurality of groups of acid-treated carbon fiber powder.
(2) Mixing and curing raw materials:
the PTFE resin raw material is selected from DAJIN F-106, and is stored in a refrigerated cabinet at 5 deg.C, and is taken out and placed in a drying chamber to room temperature when in use. 3kg of resin raw material is sieved out by a sieve with 10 meshes and added into a mixing barrel. 900g of the carbon fiber powder after acid treatment is weighed and added into a mixing barrel to be uniformly mixed. 600g of Isopar M additive is added into a mixing barrel in a spraying mode, and the mixture is sprayed and mixed at the same time. Putting the mixed materials into a curing box, and curing for 12 hours at 40 ℃.
(3) Casting and extruding:
placing the cured mixed material into a blank pressing machine at the temperature of 70 ℃ and pressing the mixed material into a cylindrical blank under the pressure of 5MPa, wherein the compression speed is 20 mm/min.
The cylindrical blank is placed into a material cavity of a pushing press, the heating temperature is 120 ℃, the bar blank is extruded under the pressure of 8MPa, and the compression ratio is 100. And (4) after the strip blank is formed, putting the strip blank into a water tank for heat preservation at the temperature of 80 ℃.
(4) Rolling:
rolling the strip blank into a film through a double-roller rolling machine, wherein the rolling temperature range is 80 ℃, the linear speed range of a roller is 5m/min, and the rolling thickness range is 0.10 mm. And rolling the rolled film through rolling equipment after the rolled film is formed.
(5) Degreasing and high-temperature shaping:
degreasing the film for 15min by using a 200 ℃ blower, and then sintering and shaping the film for 10min in a 380 ℃ oven to obtain the high-strength and high-temperature-resistant PTFE/carbon fiber composite release film (FIG. 2 is a scanning electron microscope photograph with the cross section magnification of 2000 times, and the good combination of the fiber and the resin interface can be seen).
The test shows that the sample has the thickness of 0.107mm, the tensile strength of 58.96MPa and the Vicat softening point of 219.1 ℃. The release film was used for coating experiments: placing a sample of 10 × 10cm into a baking oven at 200 deg.C, standing for 30min to make the membrane surface flat and not deformed; and (3) coating the perfluorinated sulfonic acid resin solution on the surface of the sample membrane by using a blade coater, drying in an oven, and testing that the peeling strength is less than 8.5N/m (180-degree peeling, the width is 25mm, and the peeling speed is 300 mm/min), so that the peeling effect is good.
Example 3
This example uses a heat treatment process to surface-treat carbon fibers. Comprises the following preparation processes:
(1) carbon fiber surface modification treatment:
placing a carbon fiber powder material (Nanjing Yitai composite material Co., Ltd., diameter of 5-10 μm and length of 50-80 μm) in a box-type resistance furnace, setting the heating temperature to be 500 ℃, preserving the heat for 5h after the set temperature is reached, and taking out a sample after natural cooling.
(2) Mixing and curing raw materials:
the PTFE resin raw material is selected from DAJIN F-106, and is stored in a refrigerated cabinet at 5 deg.C, and is taken out and placed in a drying chamber to room temperature when in use. 3kg of resin raw material is sieved out by a sieve with 10 meshes and added into a mixing barrel. And weighing 600g of the heat-treated carbon fiber powder, adding into a mixing barrel, and uniformly mixing. 450g of Isopar M additive is added into a mixing barrel in a spraying mode, and the mixture is sprayed and mixed at the same time. Putting the mixed materials into a curing box, and curing for 12 hours at 40 ℃.
(3) Casting and extruding:
placing the cured mixed material into a blank pressing machine at the temperature of 80 ℃ and pressing the mixed material into a cylindrical blank under the pressure of 3MPa, wherein the compression speed is 20 mm/min.
The cylindrical blank is placed into a material cavity of a pushing press, the heating temperature is 80 ℃, the bar blank is extruded under the pressure of 8MPa, and the compression ratio is 100. And (4) after the strip blank is formed, putting the strip blank into a water tank for heat preservation at the temperature of 80 ℃.
(4) Rolling:
rolling the strip blank into a film through a double-roller rolling machine, wherein the rolling temperature range is 80 ℃, the linear speed range of a roller is 15m/min, and the rolling thickness range is 0.10 mm. And rolling the rolled film through rolling equipment after the rolled film is formed.
(5) Degreasing and high-temperature shaping:
and (3) passing the film through a high-temperature oven, removing the auxiliary agent, and sintering and shaping at high temperature, wherein the sintering temperature is 350 ℃, so as to prepare the high-strength and high-temperature-resistant PTFE/carbon fiber composite release film.
The test shows that the sample has the thickness of 0.103mm, the tensile strength of 54.23MPa and the Vicat softening point of 216.7 ℃. The release film was used for coating experiments: placing a sample of 10 × 10cm into a baking oven at 200 deg.C, standing for 30min to make the membrane surface flat and not deformed; and (3) coating the perfluorinated sulfonic acid resin solution on the surface of the sample membrane by using a blade coater, drying in an oven, and testing that the peeling strength is less than 8.5N/m (180-degree peeling, the width is 25mm, and the peeling speed is 300 mm/min), so that the peeling effect is good.
Example 4
This example uses a heat treatment process to surface-treat carbon fibers. Comprises the following preparation processes:
(1) carbon fiber surface modification treatment:
placing a carbon fiber powder material (Nanjing Yitai composite material Co., Ltd., diameter of 5-10 μm and length of 50-80 μm) in a box-type resistance furnace, setting the heating temperature to 800 ℃, keeping the temperature for 3h after reaching the set temperature, and taking out a sample after natural cooling.
(2) Mixing and curing raw materials:
the PTFE resin raw material is selected from DAJIN F-106, and is stored in a refrigerated cabinet at 5 deg.C, and is taken out and placed in a drying chamber to room temperature when in use. 3kg of resin raw material is sieved out by a sieve with 10 meshes and added into a mixing barrel. And weighing 300g of the carbon fiber powder subjected to heat treatment, adding the carbon fiber powder into a mixing barrel, and uniformly mixing. 750g of Isopar M additive is added into a mixing barrel in a spraying mode, and the mixture is sprayed and mixed at the same time. Putting the mixed materials into a curing box, and curing for 10 hours at 50 ℃.
(3) Casting and extruding:
placing the cured mixed material into a blank pressing machine at the temperature of 60 ℃ and pressing the mixed material into a cylindrical blank under the pressure of 5MPa, wherein the compression speed is 20 mm/min.
The cylindrical blank is placed into a material cavity of a pushing press, the heating temperature is 100 ℃, the bar blank is extruded under the pressure of 8MPa, and the compression ratio is 100. And (4) after the strip blank is formed, putting the strip blank into a water tank for heat preservation at the temperature of 100 ℃.
(4) Rolling:
rolling the strip blank into a film through a double-roller rolling machine, wherein the rolling temperature range is 60 ℃, the linear speed range of a roller is 10m/min, and the rolling thickness range is 0.10 mm. And rolling the rolled film through rolling equipment after the rolled film is formed.
(5) Degreasing and high-temperature shaping:
and (3) passing the film through a high-temperature oven, removing the auxiliary agent, sintering and shaping at high temperature, wherein the sintering temperature is 400 ℃, and thus obtaining the high-strength and high-temperature-resistant PTFE/carbon fiber composite release film.
The test shows that the sample has the thickness of 0.105mm, the tensile strength of 52.84MPa and the Vicat softening point of 214.3 ℃. The release film was used for coating experiments: placing a sample of 10 × 10cm into a baking oven at 200 deg.C, standing for 30min to make the membrane surface flat and not deformed; and (3) coating the perfluorinated sulfonic acid resin solution on the surface of the sample membrane by using a blade coater, drying in an oven, and testing that the peeling strength is less than 8.5N/m (180-degree peeling, the width is 25mm, and the peeling speed is 300 mm/min), so that the peeling effect is good.
Example 5
This example uses a heat treatment process to surface-treat carbon fibers. Comprises the following preparation processes:
(1) carbon fiber surface modification treatment:
placing a carbon fiber powder material (Nanjing Yitai composite material Co., Ltd., diameter of 5-10 μm and length of 50-80 μm) in a box-type resistance furnace, setting the heating temperature to be 500 ℃, preserving the heat for 5h after the set temperature is reached, and taking out a sample after natural cooling.
(2) Mixing and curing raw materials:
the PTFE resin raw material is selected from DAJIN F-106, and is stored in a refrigerated cabinet at 5 deg.C, and is taken out and placed in a drying chamber to room temperature when in use. 3kg of resin raw material is sieved out by a sieve with 10 meshes and added into a mixing barrel. And weighing 200g of the heat-treated carbon fiber powder, adding into a mixing barrel, and uniformly mixing. 430g of Isopar M additive is added into a mixing barrel in a spraying mode, and the mixture is mixed while spraying. Putting the mixed materials into a curing box, and curing for 12 hours at 40 ℃.
(3) Casting and extruding:
placing the cured mixed material into a blank pressing machine at the temperature of 80 ℃ and pressing the mixed material into a cylindrical blank under the pressure of 3MPa, wherein the compression speed is 20 mm/min.
The cylindrical blank is placed into a material cavity of a pushing press, the heating temperature is 80 ℃, the bar blank is extruded under the pressure of 8MPa, and the compression ratio is 100. And (4) after the strip blank is formed, putting the strip blank into a water tank for heat preservation at the temperature of 80 ℃.
(4) Rolling:
rolling the strip blank into a film through a double-roller rolling machine, wherein the rolling temperature range is 80 ℃, the linear speed range of a roller is 5m/min, and the rolling thickness range is 0.10 mm. And rolling the rolled film through rolling equipment after the rolled film is formed.
(5) Degreasing and high-temperature shaping:
and (3) passing the film through a high-temperature oven, removing the auxiliary agent, sintering and shaping at a high temperature of 330 ℃ to obtain the high-strength and high-temperature-resistant PTFE/carbon fiber composite release film.
The test shows that the sample has the thickness of 0.104mm, the tensile strength of 52.04MPa and the Vicat softening point of 213.8 ℃. The release film was used for coating experiments: placing a sample of 10 × 10cm into a baking oven at 200 deg.C, standing for 30min to make the membrane surface flat and not deformed; and (3) coating the perfluorinated sulfonic acid resin solution on the surface of the sample membrane by using a blade coater, drying in an oven, and testing that the peeling strength is less than 8.5N/m (180-degree peeling, the width is 25mm, and the peeling speed is 300 mm/min), so that the peeling effect is good.
Comparative example 1
The difference from example 1 is that no carbon fiber was added.
The test shows that the sample has the thickness of 0.105mm, the tensile strength of 50.69MPa and the Vicat softening point of 211.7 ℃. The release film was used for coating experiments: placing 10 × 10cm sample in 200 deg.C oven, standing for 30min to form deformed membrane surface; and (3) coating the perfluorinated sulfonic acid resin solution on the surface of the sample membrane by using a blade coater, drying in an oven, and testing that the peeling strength is less than 8.5N/m (180 DEG peeling, the width is 25mm, and the peeling speed is 300 mm/min), the glass performance is good, but the coating surface is not flat.
Comparative example 2
The difference from example 1 is that the carbon fiber is not surface-modified.
The test shows that the sample has the thickness of 0.104mm, the tensile strength of 50.98MPa and the Vicat softening point of 211.9 ℃. The release film was used for coating experiments: placing 10 × 10cm sample in 200 deg.C oven, standing for 30min to form deformed membrane surface; and (3) coating the perfluorinated sulfonic acid resin solution on the surface of the sample membrane by using a blade coater, drying in an oven, and testing that the peeling strength is less than 8.5N/m (180 DEG peeling, the width is 25mm, and the peeling speed is 300 mm/min), the glass performance is good, but the coating surface is not flat.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. The preparation method of the polytetrafluoroethylene/carbon fiber composite release film is characterized by comprising the following steps:
step S1, performing surface treatment on the carbon fiber by adopting a heat treatment or acid treatment mode to obtain a surface modified carbon fiber;
step S2, mixing polytetrafluoroethylene resin, the surface modified carbon fibers and a lubricating additive, and curing to form a cured material;
step S3, pressing and extruding the cured material to form a blank;
step S4, rolling the blank into a film in a double-roller rolling mode to obtain a film material;
step S5, sequentially degreasing and shaping the membrane material to obtain the polytetrafluoroethylene/carbon fiber composite release membrane;
wherein the heat treatment process comprises: treating the carbon fiber at 500-800 ℃ for 3-5 h to obtain the surface modified carbon fiber; the acid treatment process comprises the following steps: placing the carbon fiber into a mixed acid solution at 70-90 ℃ for acid washing for 3-5 h, taking out and washing with water to obtain the surface modified carbon fiber; the mixed acid solution is a mixed solution of a nitric acid solution with the mass concentration of 60-70% and a sulfuric acid solution with the mass concentration of 95-98%;
the step S2 includes: mixing the polytetrafluoroethylene resin and the surface modified carbon fiber to form a mixture; and adding the lubricating assistant into the mixture in a spraying mode under the stirring state, and curing at the temperature of 40-50 ℃ for 10-12 h to obtain the cured material.
2. The method according to claim 1, wherein the volume ratio of the nitric acid solution to the sulfuric acid solution is (3-5): 1.
3. The production method according to claim 1 or 2,
the lubricating assistant is C10~C16The isomeric alkane solvents of (a);
the polytetrafluoroethylene resin is a dispersion resin with the crystallinity of more than 98 percent and the number average molecular weight of 600-1200 ten thousand.
4. The method of claim 3, wherein the lubricating additive is Isopar M.
5. The method of claim 3, wherein the polytetrafluoroethylene resin is one or more of damascena F-106, damascena F-107, kemu 601X, AGC CD 123E.
6. The method according to claim 1 or 2, wherein the surface-modified carbon fiber is added in an amount of 10 to 30% by weight based on the polytetrafluoroethylene resin, and the lubricant additive is added in an amount of 15 to 25% by weight based on the polytetrafluoroethylene resin.
7. The production method according to claim 1 or 2, wherein the step S3 includes:
placing the cured material into a blank pressing machine at the temperature of 60-80 ℃, pressing the cured material into a column blank under the pressure of 3-5 MPa, and controlling the compression speed to be 20-50 mm/min during pressing;
and (3) putting the column blank into a material cavity of a pushing press, heating to 100-120 ℃, extruding under the pressure of 5-8 MPa to form the blank, and controlling the compression ratio to be 80-100 during extrusion.
8. The production method according to claim 1 or 2, wherein in the step S4, the rolling temperature in the rolling film forming process is 60 to 80 ℃, the roll linear velocity is 5 to 15m/min, and the rolling thickness is 0.05 to 0.3 mm.
9. The production method according to claim 1 or 2, wherein the step S5 includes: and (3) degreasing the membrane material at 100-200 ℃, and then shaping at 350-400 ℃.
10. A polytetrafluoroethylene/carbon fiber composite release film characterized by being prepared by the preparation method of any one of claims 1 to 9.
11. The use of the polytetrafluoroethylene/carbon fiber composite release film according to claim 10 in a coating process of a composite proton exchange membrane.
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