CN113774502B - High-frequency phase-stable PTFE (polytetrafluoroethylene) film material and manufacturing method thereof - Google Patents
High-frequency phase-stable PTFE (polytetrafluoroethylene) film material and manufacturing method thereof Download PDFInfo
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- D01D5/00—Formation of filaments, threads, or the like
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
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Abstract
The invention provides a high-frequency phase-stable PTFE (polytetrafluoroethylene) film material which comprises the following raw materials in parts by weight: 60-80 parts of PTEE powder, 5-10 parts of filling master batch, 0.5-5 parts of auxiliary agent and 0.5-5 parts of silver plating electroplating solution, wherein PTFE powder is subjected to refining treatment and then detected by a dry laser particle sizer to obtain PTFE resin with the average particle size of 0.19 mu m; and mixing the filling master batch with PTFE resin powder, adding an auxiliary agent, standing for 24 hours at 50-70 ℃ to ensure that the auxiliary agent fully permeates into the mixture of the filling master batch and the PTFE resin powder to form a material. The PTFE membrane material has high-frequency phase-stabilizing characteristic, and has much smaller deformation and smaller phase fluctuation than common PTFE membrane materials along with the temperature change; the anti-fatigue coating has the advantages of showing super-strong anti-fatigue property under high and low temperature environments, having high stability, greatly improving the working time under severe environments, prolonging the service life and enhancing the conductivity through an electroplating process.
Description
Technical Field
The invention belongs to the technical field of PTFE (polytetrafluoroethylene) membrane materials, and particularly relates to a high-frequency phase-stable PTFE membrane material and a manufacturing method thereof.
Background
Polytetrafluoroethylene (abbreviated as PTFE) is a high molecular polymer prepared by polymerizing tetrafluoroethylene as a monomer; the material has the characteristics of acid resistance, alkali resistance and resistance to various organic solutions, and is almost insoluble in all solutions; meanwhile, PTFE has the characteristic of high temperature resistance, the friction coefficient of the PTFE is extremely low, and the film made of PTFE has good light resistance and aging resistance, good tear resistance and air permeability, and is clean, colorless and transparent.
When the PTFE membrane material works under special climate and working condition conditions, good phase stability is needed under high and low temperature environment, and the existing PTFE membrane material has the problems of poor conductivity, poor high and low temperature phase stability and large deformation caused by temperature change.
Disclosure of Invention
In order to solve the technical problems, the invention provides a high-frequency phase-stable PTFE membrane material and a manufacturing method thereof, which aim to solve the problems of poor conductivity, poor high-temperature and low-temperature phase-stable performance and large deformation caused by temperature change of the existing PTFE membrane material.
Based on the above object, the present invention provides a method for producing a high-frequency phase-stable PTFE film material, comprising: the method comprises the following steps:
the PTFE powder is subjected to thinning treatment and then is detected by a dry laser particle sizer to obtain PTFE resin with the average particle size of 0.19 mu m; mixing the filling master batch with PTFE resin powder, adding an auxiliary agent, standing for 24 hours at 50-70 ℃ to ensure that the auxiliary agent fully permeates into the mixture of the filling master batch and the PTFE resin powder to form a material; and then carrying out magnetic stirring for 20-30 min, wherein the speed of a rotor of the magnetic stirring is controlled at 150-200 r/min so as to uniformly disperse PTFE powder in an aqueous medium, thus obtaining a PTFE solution subjected to infiltration treatment, and then carrying out preparation treatment on the PTFE solution, wherein the preparation treatment steps are as follows:
(1) obtaining a certain amount of PTFE solution, then uniformly stirring, and putting the uniform solution into a tank;
(2) putting the uniform solution obtained in the step (1) into a mold, and performing calendering molding under the pressure of 0.7-0.9 Mpa, wherein the pressure temperature is 20-30 ℃;
(3) then taking out the PTFE material which is formed by the rolling in the step (2), sequentially drying, cutting, hot drawing, deoiling and heat treatment setting,
drying, namely drying the rolled PTFE material to remove the lubricant, wherein the drying temperature and the drying time are 100-150 ℃ and 80-90 s;
cutting, namely introducing the dried PTFE material into a cutting mechanism for cutting, wherein the linear speed of the cutting machine is 0.8-2.0 m/min;
carrying out hot drawing, namely carrying out two working procedures of first hot drawing and second hot drawing on the cut PTFE monofilaments, wherein the temperature of the first hot drawing is controlled to be 310-330 ℃; controlling the temperature of the second hot drawing to be 330-350 ℃ to achieve the required PTFE strip;
deoiling, namely performing primary deoiling on the PTFE strips in a low-temperature deoiling stage in a low-temperature deoiling tank at the temperature of 160-200 ℃ in the low-temperature deoiling tank; carrying out secondary deoiling on the PTFE strip in a low-temperature deoiling tank at the temperature of 220-280 ℃;
stretching the deoiled strip in a single direction or a double direction at 100-390 ℃, and finally performing heat setting to clean surface garbage to prepare a PTFE microporous membrane;
the heat treatment shaping is to introduce the PTFE strip after the unidirectional stretching or the bidirectional stretching into a high-temperature shaping area, the running speed of the PTFE strip in the shaping area is 0.5m/min to 1m/min, the heat treatment shaping temperature is controlled at 360 +/-10 ℃, and meanwhile, constant tension is adopted;
(4) the PTFE membrane material comprises a surface layer and a built-in layer, the surface layer is an electroplated layer, the built-in layer is a PTFE microporous membrane after heat treatment and shaping,
carrying out micro-treatment on the PTFE microporous membrane in the step (3) by using corrosive liquid, and then placing the PTFE microporous membrane in silver plating solution for electroplating;
the PTFE membrane material with the required high-frequency stable phase is prepared by the method.
Further, the weight ratio of the filling master batch to the PTFE dispersion resin to the auxiliary agent is 0.05-0.1: 1: 0.25-0.3, and the auxiliary agent comprises one of a silane coupling agent or a thickening agent.
Further, the etching solution comprises sublimed naphthalene, tetrahydrofuran and sodium wire.
Compared with the prior art, the invention has the following beneficial effects: the PTFE membrane material has the high-frequency phase-stabilizing characteristic, and the deformation of the PTFE membrane material caused by the temperature change is much smaller than that of the common PTFE membrane material, and the phase fluctuation is smaller; the electroplating process has the advantages that the electroplating process is simple and stable, and in addition, the anti-permeability performance, the waterproof performance, the air permeability and the low temperature resistance of the electroplating process are greatly improved.
Detailed Description
The invention is further described with reference to specific examples below:
a high-frequency phase-stable PTFE membrane material has good conductivity through an electroplating process, has the characteristics of great stability and high-frequency phase stability under high-temperature and low-temperature extreme environments by adding a filling master batch and a special processing process, and has much smaller deformation and smaller phase fluctuation than common PTFE membrane materials along with temperature change; meanwhile, the PTFE membrane material can better recover the original shape after being deformed under the action of external force, thereby having higher fatigue resistance.
The first embodiment is as follows:
a high-frequency phase-stable PTFE film material comprises the following raw materials in parts by weight: 60-80 parts of PTEE powder, 5-10 parts of filling master batch, 0.5-5 parts of auxiliary agent and 0.5-5 parts of silver plating electroplating liquid.
The silver plating solution comprises an aqueous medium, an antioxidant, a grain refining agent and silver nitrate.
The filling master batch contains calcium powder and carrier resin.
A method for preparing high-frequency phase-stable PTFE membrane material comprises refining PTFE powder, and detecting with dry laser particle sizer to obtain PTFE resin with average particle size of 0.19 μm; mixing the filling master batch with PTFE resin powder, adding an auxiliary agent, and standing for 24 hours at 60 ℃, wherein when the temperature is high, the mixing effect of the filling master batch and the PTFE resin powder is better, and when the temperature is low, the mixing effect of the filling master batch and the PTFE is weakened. Fully permeating an auxiliary agent into a mixture of the filling master batch and the PTFE dispersion resin to form a material, wherein the weight ratio of the filling master batch to the PTFE dispersion resin powder to the auxiliary agent is 0.75:1: 0.275; the filling master batch contains calcium powder and carrier resin, and the auxiliary agent is a thickening agent; then, magnetic stirring is carried out for 25min, the rotor speed of the magnetic stirring is controlled to be 175min, so that the PTFE powder is uniformly dispersed in the aqueous medium, the PTFE solution subjected to infiltration treatment is obtained, and the preparation treatment is carried out on the PTFE solution: in the specific embodiment, the refined PTFE particles are subjected to laser testing through a dry laser particle size analyzer, the particle size of the PTFE particles is tested, accurate particle size test results are obtained, sampling is required to be representative at first, a sample to be tested (no matter the particle size and the distribution width) needs to be completely dispersed into single particles, and then measurement is carried out, in the embodiment, an HELOS-RODOS dry laser particle size analyzer is adopted, and the diameter of 4mm is selected for the dispersion test of the particles of 0.1-1000 microns.
The preparation treatment steps are as follows:
(1) obtaining a certain amount of PTFE solution, then uniformly stirring, and putting the uniform solution into a tank;
(2) putting the uniform solution obtained in the step (1) into a mould, and carrying out calendaring molding under the pressure of 0.8Mpa, wherein the pressure and the temperature are 25 ℃;
(3) then taking out the PTFE material which is formed by the rolling in the step (2), sequentially drying, cutting, hot drawing, deoiling and heat treatment setting,
drying, namely drying the rolled PTFE material to remove the lubricant, wherein the drying temperature and the drying time are 125 ℃ and 85 s;
cutting, namely introducing the dried PTFE material into a cutting mechanism for cutting, wherein the linear speed of the cutting machine is 1.4 m/min;
carrying out hot drawing, namely carrying out two working procedures of first hot drawing and second hot drawing on the cut PTFE monofilaments, wherein the temperature of the first hot drawing is controlled at 320 ℃; controlling the temperature of the second hot drawing at 340 ℃ to obtain the required PTFE strip;
deoiling, namely performing first deoiling on the PTFE strip in a low-temperature deoiling stage in a low-temperature deoiling tank at the temperature of 180 ℃ in the low-temperature deoiling tank; carrying out secondary deoiling on the PTFE strip in a low-temperature deoiling tank at the temperature of 250 ℃;
stretching the deoiled strip in a single direction or two directions at 245 ℃, and finally performing heat setting to clean surface garbage to prepare a PTFE microporous membrane;
the heat treatment shaping is to introduce the PTFE strips after the unidirectional stretching or the bidirectional stretching into a high-temperature shaping area, the running speed of the PTFE strips in the shaping area is 0.75m/min, the heat treatment shaping temperature is controlled at 360 ℃, and meanwhile, constant tension is adopted;
(4) the PTFE membrane material comprises a surface layer and an internal layer, wherein the surface layer is an electroplated layer, the internal layer is a PTFE microporous membrane after heat treatment and shaping, the PTFE waterproof moisture permeable microporous membrane is prepared by a special process through bidirectional stretching, each square inch of the membrane surface can reach billions of micropores, the diameter (0.3 um) of each micropore is smaller than the minimum value (60 um) of the minimum light fog in water molecules and is far larger than the diameter (0.00035 um) of water vapor molecules, water vapor can pass through but water drops cannot pass through, and the excellent waterproof moisture permeable function can be achieved by utilizing the microporous structure;
carrying out micro-treatment on the PTFE microporous membrane in the step (3) by using corrosive liquid, and then placing the PTFE microporous membrane in silver plating solution for electroplating;
the PTFE membrane material with the required high-frequency stable phase is prepared by the method.
In the step (4), the corrosive liquid comprises sublimed naphthalene, tetrahydrofuran and sodium filaments. The preparation of the corrosive liquid comprises putting 123 g of sublimed naphthalene into a three-necked flask, adding 100 g of dried tetrahydrofuran from which peroxide is removed, stirring to dissolve, slowly adding 236.5 g of fresh sodium wire or sodium sheet at room temperature, and stirring until all sodium is dissolved. The solution is black or black brown, about 1.5 hours is needed, and the whole reaction process is carried out under the protection of dry nitrogen, and the influence of oxygen and moisture is strictly prevented. Firstly, washing the surface of a PTFE microporous membrane with acetone, airing, and then placing the PTFE microporous membrane in a treatment solution at room temperature for soaking for 1-15 minutes, wherein a uniform brown or brownish black film is generated on the surface; taking out, washing in acetone or ethanol, washing with water, air drying, and bonding or placing in dry and light-proof place. The PTFE film and the material are fluorine-containing materials, the fluorine-containing materials are treated by a chemical method, and partial fluorine atoms on the surface are torn off mainly by the chemical reaction of corrosive liquid and the surface of the PTFE film; in this case, a carbonized layer and some polar groups are left on the surface, wherein the depth of the carbonized layer is preferably about 1 micron; if the surface is excessively corroded, the cohesive strength of the surface layer may be reduced because the carbonized layer generated is too thick.
In the step (4), the silver plating electroplating solution at least comprises an aqueous medium, an antioxidant, a grain refining agent and silver nitrate; the antioxidant content was 6.5 parts by weight and the grain refining agent content was 11.5 parts by weight, respectively, with respect to 10 parts by weight of the silver nitrate; the current density in the electroplating process is 23.5A/cm 2; wherein the temperature of the electroplating solution in the electroplating process is 30 ℃, and the electroplating time is 25 min.
The aqueous medium is not particularly limited, and examples thereof include water, a mixed solution of water and a known water-soluble solution, and water is preferable.
The corrosive liquid comprises sublimed naphthalene, tetrahydrofuran and sodium filaments.
Example two:
a high-frequency phase-stable PTFE film material comprises the following raw materials in parts by weight: 60-80 parts of PTEE powder, 5-10 parts of filling master batch, 0.5-5 parts of auxiliary agent and 0.5-5 parts of silver plating solution.
The silver plating solution comprises an aqueous medium, an antioxidant, a grain refining agent and silver nitrate.
The corrosive liquid comprises sublimed naphthalene, tetrahydrofuran and sodium filaments.
The filling master batch contains calcium powder and carrier resin.
A method for preparing high-frequency phase-stable PTFE membrane material comprises refining PTFE powder, and detecting with dry laser particle sizer to obtain PTFE resin with average particle size of 0.19 μm; mixing the filling master batch with PTFE resin powder, adding an auxiliary agent, and standing for 24 hours at 60 ℃, wherein when the temperature is high, the mixing effect of the filling master batch and the PTFE resin powder is better, and when the temperature is low, the mixing effect of the filling master batch and the PTFE is weakened. Fully permeating an auxiliary agent into a mixture of the filling master batch and the PTFE dispersion resin to form a material, wherein the weight ratio of the filling master batch to the PTFE dispersion resin powder to the auxiliary agent is 0.75:1: 0.275; the filling master batch contains calcium powder and carrier resin, and the auxiliary agent is a thickening agent; then, magnetic stirring is carried out for 25min, the speed of a rotor of the magnetic stirring is controlled to be 175min, so that PTFE powder is uniformly dispersed in an aqueous medium, namely, a PTFE solution subjected to infiltration treatment is obtained, and the PTFE solution is prepared: in the specific embodiment, the refined PTFE particles are subjected to laser testing through a dry laser particle size analyzer, the particle size of the PTFE particles is tested, accurate particle size test results are obtained, sampling is required to be representative at first, a sample to be tested (no matter the particle size and the distribution width) needs to be completely dispersed into single particles, and then measurement is carried out, in the embodiment, an HELOS-RODOS dry laser particle size analyzer is adopted, and the diameter of 4mm is selected for the dispersion test of the particles of 0.1-1000 microns.
The preparation treatment steps are as follows:
(1) obtaining a certain amount of PTFE solution, then uniformly stirring, and putting the uniform solution into a tank;
(2) putting the uniform solution obtained in the step (1) into a mould, and carrying out calendaring molding under the pressure of 0.7Mpa, wherein the pressure and the temperature are 20 ℃;
(3) then taking out the PTFE material which is formed by the rolling in the step (2), sequentially drying, cutting, hot drawing, deoiling and heat treatment setting,
drying, namely drying the rolled PTFE material to remove the lubricant, wherein the drying temperature and the drying time are 100 ℃ and 80 s;
cutting, namely introducing the dried PTFE material into a cutting mechanism for cutting, wherein the linear speed of the cutting machine is 0.8 m/min;
hot drawing, namely performing primary hot drawing and secondary hot drawing on the cut PTFE monofilaments, wherein the temperature of the primary hot drawing is controlled at 310 ℃; controlling the temperature of the second hot drawing to be 330 ℃ to achieve the required PTFE strip;
deoiling, namely performing primary deoiling on the PTFE strip in a low-temperature deoiling stage in a low-temperature deoiling tank at the temperature of 160 ℃ in the low-temperature deoiling tank; carrying out secondary deoiling on the PTFE strip in a low-temperature deoiling tank at the temperature of 220 ℃;
stretching the deoiled strip in a single direction or a double direction at 100 ℃, and finally performing heat setting and cleaning surface garbage to prepare a PTFE microporous membrane;
the heat treatment shaping is to introduce the PTFE strips after the unidirectional stretching or the bidirectional stretching into a high-temperature shaping area, the running speed of the PTFE strips in the shaping area is 0.5m/min, the heat treatment shaping temperature is controlled at 350 ℃, and meanwhile, constant tension is adopted;
(4) the PTFE membrane material comprises a surface layer and an internal layer, wherein the surface layer is an electroplated layer, the internal layer is a PTFE microporous membrane after heat treatment and shaping, the PTFE waterproof moisture permeable microporous membrane is prepared by a special process through bidirectional stretching, each square inch of the membrane surface can reach billions of micropores, the diameter (0.1 umum) of each micropore is smaller than the minimum value (20 umun) of the minimum light fog in water molecules, and is far larger than the diameter (0.0003 umum) of a water vapor molecule, so that water vapor can pass through but water drops cannot pass through, and the excellent waterproof moisture permeable function can be achieved by utilizing the microporous structure;
carrying out micro-treatment on the PTFE microporous membrane in the step (3) by using corrosive liquid, and then placing the PTFE microporous membrane in silver plating solution for electroplating;
the PTFE membrane material with the required high-frequency stable phase is prepared by the method.
Wherein the weight ratio of the filling master batch to the PTFE dispersion resin powder to the auxiliary agent is 0.05-0.1: 1: 0.25-0.3, and the auxiliary agent comprises one of a silane coupling agent or a thickening agent;
the filling master batch contains calcium powder and carrier resin.
In the step (4), the corrosive liquid comprises sublimed naphthalene, tetrahydrofuran and sodium filaments.
The preparation of the corrosive liquid comprises the steps of putting 118 g of sublimed naphthalene into a three-necked bottle, adding 100 g of dried tetrahydrofuran from which peroxide is removed, stirring for dissolving, then slowly adding 23 g of fresh sodium wire or sodium sheet at room temperature, and stirring until the sodium is completely dissolved. The solution is black or black brown, which takes about 1 hour, and the whole reaction process is carried out under the protection of dry nitrogen, thereby strictly preventing the influence of oxygen and moisture.
Firstly, washing the surface of a PTFE microporous membrane with acetone, airing, and then placing the PTFE microporous membrane in a treatment solution at room temperature for soaking for 1-15 minutes, wherein a uniform brown or brownish black film is generated on the surface; taking out, washing in acetone or ethanol, washing with water, air drying, and bonding or placing in dry and light-proof place. The PTFE film and the material are fluorine-containing materials, and the fluorine-containing materials are treated by a chemical method, wherein the chemical reaction is mainly carried out on the surface of the PTFE film through corrosive liquid, and partial fluorine atoms on the surface are torn off; in this case, a carbonized layer and some polar groups are left on the surface, wherein the depth of the carbonized layer is preferably about 1 micron; if the surface is excessively corroded, the cohesive strength of the surface layer may be reduced because the carbonized layer generated is too thick.
In the step (4), the silver plating solution at least comprises an aqueous medium, an antioxidant, a grain refining agent and silver nitrate.
The aqueous medium is not particularly limited, and examples thereof include water and a mixture of water and a known water-soluble solution, and water is preferred.
The antioxidant is contained in an amount of 3 parts by weight and the grain refining agent is contained in an amount of 8 parts by weight, based on 10 parts by weight of the silver nitrate; the current density in the electroplating process is 15A/cm 2; wherein the temperature of the electroplating solution in the electroplating process is 25 ℃, and the electroplating time is 20 min.
Compared with the first embodiment and the second embodiment, the second embodiment has longer processing time and slower processing speed, and the high-frequency phase stability of the PTFE material of the obtained product is higher than that of the first embodiment and the third embodiment.
Example three:
a high-frequency phase-stable PTFE film material comprises the following raw materials in parts by weight: 60-80 parts of PTEE powder, 5-10 parts of filling master batch, 0.5-5 parts of auxiliary agent and 0.5-5 parts of silver plating solution.
The silver plating solution comprises an aqueous medium, an antioxidant, a grain refining agent and silver nitrate.
The corrosive liquid comprises sublimed naphthalene, tetrahydrofuran and sodium filaments.
The filling master batch contains calcium powder and carrier resin.
A method for preparing high-frequency phase-stable PTFE membrane material comprises refining PTFE powder, and detecting with dry laser particle sizer to obtain PTFE resin with average particle size of 0.19 μm; mixing the filling master batch with PTFE resin powder, adding an auxiliary agent, and standing for 24 hours at 60 ℃, wherein when the temperature is high, the mixing effect of the filling master batch and the PTFE resin powder is better, and when the temperature is low, the mixing effect of the filling master batch and the PTFE is weakened. Fully permeating an auxiliary agent into a mixture of the filling master batch and the PTFE dispersion resin to form a material, wherein the weight ratio of the filling master batch to the PTFE dispersion resin powder to the auxiliary agent is 0.75:1: 0.275; the filling master batch contains calcium powder and carrier resin, and the auxiliary agent is a thickening agent; then, magnetic stirring is carried out for 25min, the speed of a rotor of the magnetic stirring is controlled to be 175min, so that PTFE powder is uniformly dispersed in an aqueous medium, namely, a PTFE solution subjected to infiltration treatment is obtained, and the PTFE solution is prepared: in the specific embodiment, the refined PTFE particles are subjected to laser testing through a dry laser particle size analyzer, the particle size of the PTFE particles is tested, accurate particle size test results are obtained, sampling is required to be representative at first, a sample to be tested (no matter the particle size and the distribution width) needs to be completely dispersed into single particles, and then measurement is carried out, in the embodiment, an HELOS-RODOS dry laser particle size analyzer is adopted, and the diameter of 4mm is selected for the dispersion test of the particles of 0.1-1000 microns.
The preparation treatment steps are as follows:
(1) obtaining a certain amount of PTFE solution, then uniformly stirring, and putting the uniform solution into a tank;
(2) putting the uniform solution obtained in the step (1) into a mould, and carrying out calendaring molding under the pressure of 0.9Mpa, wherein the pressure and the temperature are 30 ℃;
(3) then taking out the PTFE material which is formed by the rolling in the step (2), sequentially drying, cutting, hot drawing, deoiling and heat treatment setting,
drying, namely drying the rolled PTFE material to remove the lubricant, wherein the drying temperature and the drying time are 150 ℃ and 90 s;
cutting, namely introducing the dried PTFE material into a cutting mechanism for cutting, wherein the linear speed of the cutting machine is 2.0 m/min;
carrying out hot drawing, namely carrying out two working procedures of first hot drawing and second hot drawing on the cut PTFE monofilaments, wherein the temperature of the first hot drawing is controlled at 330 ℃; controlling the temperature of the second hot drawing to be 350 ℃ to achieve the required PTFE strip;
deoiling, namely performing primary deoiling on the PTFE strip in a low-temperature deoiling stage in a low-temperature deoiling tank at the temperature of 200 ℃ in the low-temperature deoiling tank; carrying out secondary deoiling on the PTFE strip in a low-temperature deoiling tank at the temperature of 280 ℃;
stretching the deoiled strip in a single direction or a double direction at 390 ℃, and finally performing heat setting and cleaning surface garbage to prepare a PTFE microporous membrane;
the heat treatment shaping is to introduce the PTFE strips after the unidirectional stretching or the bidirectional stretching into a high-temperature shaping area, the running speed of the PTFE strips in the shaping area is 1m/min, the heat treatment shaping temperature is controlled at 370 ℃, and meanwhile, constant tension is adopted;
(4) the PTFE membrane material comprises a surface layer and an internal layer, wherein the surface layer is an electroplated layer, the internal layer is a PTFE microporous membrane subjected to heat treatment and shaping, the PTFE waterproof moisture permeable microporous membrane is prepared by a special process through bidirectional stretching, each square inch of the membrane surface can reach billions of micropores, the diameter (0.1 um-0.5 um) of each micropore is smaller than the minimum value (20 um-100 un) of the minimum light fog in water molecules, and is far larger than the diameter (0.0003 um-0.0004 um) of water vapor molecules, so that water vapor can pass through but water drops cannot pass through, and the microporous structure can achieve an excellent waterproof moisture permeable function;
carrying out micro-treatment on the PTFE microporous membrane in the step (3) by using corrosive liquid, and then placing the PTFE microporous membrane in silver plating solution for electroplating;
the PTFE membrane material with the required high-frequency stable phase is prepared by the method.
Wherein the weight ratio of the filling master batch to the PTFE dispersion resin powder to the auxiliary agent is 0.05-0.1: 1: 0.25-0.3, and the auxiliary agent comprises one of a silane coupling agent or a thickening agent;
the filling master batch contains calcium powder and carrier resin.
In the step (4), the corrosive liquid comprises sublimed naphthalene, tetrahydrofuran and sodium filaments.
Preparation of corrosive liquid, 128 g of sublimed naphthalene is put into a three-necked bottle, 100 g of dried tetrahydrofuran which is removed of peroxide is added, 30 g of fresh sodium wire or sodium sheet is slowly added at room temperature after stirring and dissolving, and the stirring is carried out until sodium is completely dissolved. The solution is black or black brown, which takes about 2 hours, and the whole reaction process is carried out under the protection of dry nitrogen, thereby strictly preventing the influence of oxygen and moisture.
Firstly, washing the surface of a PTFE microporous membrane with acetone, airing, and then placing the PTFE microporous membrane in a treatment solution at room temperature for soaking for 1-15 minutes, wherein a uniform brown or brownish black film is generated on the surface; taking out, washing in acetone or ethanol, washing with water, air drying, and bonding immediately or placing in dry and lightproof place. The PTFE film and the material are fluorine-containing materials, the fluorine-containing materials are treated by a chemical method, and partial fluorine atoms on the surface are torn off mainly by the chemical reaction of corrosive liquid and the surface of the PTFE film; in this case, a carbonized layer, preferably about 1 μm in depth, and some polar groups are left on the surface; if the surface is excessively corroded, the cohesive strength of the surface layer may be reduced because the carbonized layer generated is too thick.
In the step (4), the silver plating solution at least comprises an aqueous medium, an antioxidant, a grain refining agent and silver nitrate.
The aqueous medium is not particularly limited, and examples thereof include water and a mixture of water and a known water-soluble solution, and water is preferred.
The content of the antioxidant is 10 parts by weight and the content of the grain refining agent is 15 parts by weight with respect to 10 parts by weight of the silver nitrate; the current density in the electroplating process is 30A/cm 2; wherein the temperature of the electroplating solution in the electroplating process is 35 ℃, and the electroplating time is 30 min.
Compared with the first embodiment, the third embodiment has shorter processing time and faster production speed, and the high-frequency phase stability of the obtained PTFE material product is lower than that of the first embodiment.
High-frequency phase stability test:
aiming at the tissue form of the PTFE membrane material, experimental research is carried out on the fatigue failure behavior and the fatigue property of the material under the high and low temperature environment, and the specific experimental steps of the fatigue failure mechanism of the PTFE membrane material are as follows:
sample preparation:
plastic sheet samples were taken on a die cutter using a standard cutter, five strips each taken longitudinally and transversely.
(2) Preparing a test environment:
the test environment temperature is realized by a temperature control system, the high temperature environment is heated and heated by a resistance wire in a high-low temperature box for regulation, the low temperature environment is realized by liquid nitrogen, and the temperature control precision is 1 ℃.
(3) And (3) clamping operation:
the tester should be provided with suitable clamps which should not cause the specimen to break at the clamps and the clamps on the tester should be immediately aligned in a line so that the long axis of the specimen coincides with the direction of the stretch through the centre line of the clamps when any load is applied. The moving speed of the test fixture meets the specified requirements.
The outer edge and the middle part of the PTFE membrane material test piece are respectively pressed on the bowl-shaped tray and one end of the middle pull rod. During dynamic test, the two ends of the clamp are connected with the upper chuck and the lower chuck of the material testing machine, and external vibration is introduced into the material through the middle pull rod, so that the PTFE membrane material generates shearing and bending deformation.
(4) Speed selection
The speed a or b should be selected when the tensile modulus is measured by selecting the speed required for the material to be measured. (a.1. + -. 0.5 mm/min; b.2. + -. 0.5 mm/min or 2.5. + -. 0.5 mm/min;)
The high and low temperature experiment is carried out on the PTFE mold material reinforced plastic by using a linear expansion coefficient measuring method to obtain the mechanical response of the material at different temperatures.
The experiment is divided into three groups of normal temperature, high temperature and low temperature, the amplitude of the applied vibration is 2.5mm, and the experimental data is shown in the following table 1.
[ TABLE 1 ]
In Table 1, F is the tensile yield force and% is the tensile value.
The PTFE membrane material is almost uniformly in a linear stage under the high-temperature and low-temperature environment, and the nonlinearity is obvious; comparing the change rule of mechanical parameters of the material at different temperatures, finding that the tensile modulus and the tensile strength of the material are highest at low temperature, and the modulus and the strength are reduced along with the temperature rise; a constitutive equation of the material at high temperature, normal temperature and low temperature is established by utilizing a Weibull function, the constitutive equation of the material is substituted into finite element analysis, the mechanical response of the material at an off-axis angle is obtained, the material fits well with experimental data, and the correctness of the constitutive equation of the material is verified.
The technical solutions of the present invention or similar technical solutions designed by those skilled in the art based on the teachings of the technical solutions of the present invention are all within the scope of the present invention.
Claims (3)
1. A manufacturing method of a high-frequency phase-stable PTFE film material is characterized by comprising the following steps: which comprises the following steps:
the PTFE powder is subjected to thinning treatment and then is detected by a dry laser particle sizer to obtain PTFE resin with the average particle size of 0.19 mu m; mixing the filling master batch with PTFE resin powder, adding an auxiliary agent, and standing for 24 hours at 50-70 ℃ to ensure that the auxiliary agent fully permeates into the mixture of the filling master batch and the PTFE resin powder to form a material; and then carrying out magnetic stirring for 20-30 min, wherein the speed of a rotor of the magnetic stirring is controlled at 150-200 r/min so as to uniformly disperse PTFE powder in an aqueous medium, thus obtaining a PTFE solution subjected to infiltration treatment, and then carrying out preparation treatment on the PTFE solution, wherein the preparation treatment steps are as follows:
(1) obtaining a certain amount of PTFE solution, then uniformly stirring to obtain uniform solution, and putting the uniform solution into a tank;
(2) putting the uniform solution obtained in the step (1) into a mold, and performing calendering molding under the pressure of 0.7-0.9 Mpa, wherein the pressure temperature is 20-30 ℃;
(3) then taking out the PTFE material which is formed by the rolling in the step (2), sequentially drying, cutting, hot drawing, deoiling and heat treatment setting,
drying, namely drying the rolled PTFE material to remove the lubricant, wherein the drying temperature and the drying time are 100-150 ℃ and 80-90 s;
cutting, namely introducing the dried PTFE material into a cutting mechanism for cutting, wherein the linear speed of the cutting machine is 0.8-2.0 m/min;
hot drawing, namely performing first hot drawing and second hot drawing on the cut PTFE monofilaments, wherein the temperature of the first hot drawing is controlled to be 310-330 ℃; controlling the temperature of the secondary hot drawing to be 330-350 ℃ to obtain the needed PTFE strips;
deoiling, namely performing primary deoiling on the PTFE strip in a low-temperature deoiling stage in a low-temperature deoiling tank at the temperature of 160-200 ℃ in the low-temperature deoiling tank; carrying out secondary deoiling on the PTFE strip in a low-temperature deoiling tank at the temperature of 220-280 ℃;
stretching the deoiled strip in a single direction or two directions at the temperature of 100-390 ℃, and finally performing heat treatment setting to clean surface garbage to prepare a PTFE microporous membrane;
the heat treatment shaping is to introduce the PTFE strip after the unidirectional stretching or the bidirectional stretching into a high-temperature shaping area, the running speed of the PTFE strip in the shaping area is 0.5m/min to 1m/min, the heat treatment shaping temperature is controlled at 360 +/-10 ℃, and meanwhile, constant tension is adopted;
(4) the PTFE membrane material comprises a surface layer and a built-in layer, the surface layer is an electroplated layer, the built-in layer is a PTFE microporous membrane after heat treatment and shaping,
carrying out micro-treatment on the PTFE microporous membrane in the step (3) by using corrosive liquid, and then placing the PTFE microporous membrane in silver plating solution for electroplating;
the needed high-frequency phase-stable PTFE film material is prepared by the method.
2. The method for manufacturing a high-frequency phase-stable PTFE film material according to claim 1, wherein:
the weight ratio of the filling master batch to the PTFE resin to the auxiliary agent is 0.05-0.1: 1: 0.25-0.3, and the auxiliary agent comprises one of a silane coupling agent or a thickening agent.
3. The method for manufacturing a high-frequency phase-stable PTFE film material according to claim 1, wherein: the corrosive liquid comprises sublimed naphthalene, tetrahydrofuran and sodium filaments.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0798333A4 (en) * | 1994-02-25 | 1998-08-19 | Daikin Ind Ltd | Process for production of polytetrafluoroethylene molding using lubricant, belt-press dehydrator, process for dehydration of solid wet matters |
| JP5135658B2 (en) * | 2001-08-02 | 2013-02-06 | ダイキン工業株式会社 | Polytetrafluoroethylene fine powder, polytetrafluoroethylene molded product obtained therefrom, and method for producing the same |
| JP3796198B2 (en) * | 2002-06-12 | 2006-07-12 | 株式会社クラレ | Manufacturing method of polarizing film |
| JP4774675B2 (en) * | 2004-04-07 | 2011-09-14 | ダイキン工業株式会社 | Modified polytetrafluoroethylene powder and method for producing tetrafluoroethylene polymer |
| JP2008522040A (en) * | 2004-11-30 | 2008-06-26 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Film limited selective electroplating on conductive surfaces |
| CN101137711A (en) * | 2005-03-10 | 2008-03-05 | 大金工业株式会社 | Polytetrafluoroethylene aqueous dispersion composition, polytetrafluoroethylene resin film and polytetrafluoroethylene resin impregnated article |
| US20100130690A1 (en) * | 2005-10-31 | 2010-05-27 | Daikin Industries, Ltd. | Method for molding polytetrafluoroethylene, polytetrafluoroethylene molded body, crosslinkable polytetrafluoroethylene, powdered polytetrafluoroethylene crosslinked body, resin blend composition of matter and resin blend molded body |
| JP2011110474A (en) * | 2009-11-25 | 2011-06-09 | Fujifilm Corp | Filter for use in filtration, and method of producing the same |
| CN101956221B (en) * | 2010-09-30 | 2012-08-29 | 深圳市信诺泰创业投资企业(普通合伙) | Continuous plating device for films and method for performing continuous plating on films |
| KR20150108744A (en) * | 2014-03-18 | 2015-09-30 | 다이요 잉키 세이조 가부시키가이샤 | Curable resin composition, dry film, cured product and printed wiring board |
| WO2017043371A1 (en) * | 2015-09-07 | 2017-03-16 | 住友電工ファインポリマー株式会社 | Polytetrafluoroethylene molded body, and manufacturing method therefor |
| EP3348610B1 (en) * | 2015-09-07 | 2021-05-26 | Sumitomo Electric Fine Polymer, Inc. | Method for manufacturing polytetrafluoroethylene molded body, and polytetrafluoroethylene molded body |
| CN108517546A (en) * | 2018-04-25 | 2018-09-11 | 芜湖航天特种电缆厂股份有限公司 | The silver-plated method of expanded microporous polytetra fluoroethylene-EPTEE film |
| EP3828208A4 (en) * | 2018-07-23 | 2022-07-13 | Daikin Industries, Ltd. | Polytetrafluoroethylene and stretched body |
| CN109133278A (en) * | 2018-09-28 | 2019-01-04 | 青岛科技大学 | A kind of complex function type dual chamber photocatalytic fuel cell device and application |
| EP3885406A4 (en) * | 2018-11-19 | 2022-08-10 | Daikin Industries, Ltd. | Composition and stretched body |
| CN109467858B (en) * | 2018-11-22 | 2021-06-29 | 南亚塑胶工业股份有限公司 | Fluororesin composition and prepreg containing same |
| CN110982203B (en) * | 2019-12-19 | 2021-11-12 | 施柏德（厦门）科技有限公司 | PTFE porous material, preparation method, product and application thereof |
| CN112339388B (en) * | 2020-11-05 | 2021-08-03 | 中国长江三峡集团有限公司 | Preparation method and application of PTFE (polytetrafluoroethylene) -based nano functional composite membrane |
| CN113201812A (en) * | 2021-05-31 | 2021-08-03 | 青岛大学 | Full-automatic production line and production process for PTFE split fiber twisted yarn |
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