CN111303472A - Method for modifying polytetrafluoroethylene based on laser welding - Google Patents

Method for modifying polytetrafluoroethylene based on laser welding Download PDF

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CN111303472A
CN111303472A CN202010193614.1A CN202010193614A CN111303472A CN 111303472 A CN111303472 A CN 111303472A CN 202010193614 A CN202010193614 A CN 202010193614A CN 111303472 A CN111303472 A CN 111303472A
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ptfe
laser
nano
laser welding
nano material
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何明平
吕亮
何家望
石为慈
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Quzhou University
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Quzhou University
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/14—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation
    • B29C65/16—Laser beams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J2327/12—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 containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/011—Nanostructured additives
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract

The invention discloses a method for modifying polytetrafluoroethylene based on laser welding. The method adopts laser irradiation to weld nano materials on the surface of a Polytetrafluoroethylene (PTFE) sheet, thereby achieving the purposes of improving the wear resistance, the thermal conductivity, the hydrophilicity and the like. The method sequentially comprises the following steps: 1) placing a PTFE sheet in a mould, laying a layer of nano material on the surface of the PTFE sheet, and then carrying out mould pressing at a certain pressure to embed the nano material into the surface of the PTFE sheet to obtain a parison; 2) and (3) carrying out laser irradiation on the surface of the obtained parison, instantly melting the irradiated micro area on the surface of the plastic substrate by using the heat effect of the laser beam, surrounding the nano material adhered to the surface of the area by the melt, and anchoring the nano material on the surface of the PTFE sheet when the melt is cooled and solidified, so that the effective welding of the powder material and the surface of the PTFE sheet is realized, and the aim of modification is fulfilled. The laser welding method adopted by the invention has the advantages of simple process and low cost, and can effectively improve the surface performance of the PTFE sheet.

Description

Method for modifying polytetrafluoroethylene based on laser welding
Technical Field
The invention relates to a method for modifying polytetrafluoroethylene based on laser welding, in particular to a method for welding a nano material on the surface of a polytetrafluoroethylene sheet by utilizing laser thermal effect.
Background
The Polytetrafluoroethylene (PTFE) film is prepared from polytetrafluoroethylene suspension resin by cold pressing, sintering, turning and rolling. Of PTFE molecules-CF2The repeating units are arranged in a zigzag shape, and since the fluorine atom radius is slightly larger than that of the hydrogen atom, the adjacent-CF2The units cannot be completely oriented in the trans-cross direction, but form a twisted chain in a helical shape, with the fluorine atoms covering almost the entire surface of the polymer chain, and this almost gapless steric barrier prevents any atoms or groups from entering the interior of its structure and destroying the carbon chain. The PTFE has excellent self-lubricating property, chemical stability, high and low temperature resistance, good electrical insulation property, weather resistance and non-combustible property due to the structural characteristics of the PTFE.
However, the molecular structure characteristics of the PTFE film also cause the defects of small specific surface area, low surface energy, poor adhesion performance with other materials and the like of the PTFE film, are not beneficial to printing, coating and adhesion, and also influence the application of the PTFE film in the aspects of biocompatibility and the like.
In recent years, researchers at home and abroad aim to improve the relevant performance of the PTFE film by performing surface modification treatment on the PTFE film. The surface modification of the polytetrafluoroethylene film is mainly to improve the surface hydrophilicity and improve the bonding performance with other materials. The PTFE film surface modification techniques are widely used, and include sodium-naphthalene complex chemical treatment, laser irradiation modification, ion implantation modification, high-temperature melting method, high-energy irradiation graft modification, and plasma modification. These methods, however, have corresponding disadvantages. The sodium-naphthalene complex treating agent is toxic and corrosive, the surface of the treated sodium-naphthalene complex is discolored, and the adhesive property is seriously reduced after the sodium-naphthalene complex treating agent is exposed to light for a long time; the laser radiation modification method has strict requirements on the used laser source and needs to meet the following conditions: the oscillation wavelength of the laser beam can be absorbed by PTFE, and the photon energy of the laser beam is larger than the C-F bond energy of the PTFE; the ion implantation modification is to inject high-energy ion beams into the material, and the ion beams and atoms or molecules in the material generate a series of physical and chemical reactions to change the structure and the performance of the material, but the processing equipment is expensive; the disadvantages of the high temperature melting method are that the polytetrafluoroethylene has poor dimensional stability at high temperature, is difficult to keep the shape, and the high temperature may cause damage to the material body; the high-energy radiation modification problem is that radiation not only can act on the surface, but also can damage the body, polytetrafluoroethylene is not resistant to radiation, degradation and mechanical property reduction can be caused, and radiation can also have adverse effects on operators, and protective measures need to be taken; the plasma modification has the defects of high price of treatment equipment, short effect maintaining time after treatment and the like. Therefore, constructing a simple, cheap and stable PTFE membrane surface modification process is an important challenge for improving the performance of PTFE membranes.
Laser welding is an efficient precision welding method using a laser beam with high energy density as a heat source. The laser welding has the characteristics of large depth ratio, small heat affected zone, good surface forming and the like. The welding method can be applied to welding metal, plastic or the combination of plastic and metal. However, the existing laser welding basically welds the bulk materials, and there are few reports on the welding between the bulk materials and the nano-powder materials.
According to the problems in the prior art, in order to improve the bonding property of PTFE and improve the wear resistance, the heat conductivity and the like of PTFE, the invention utilizes the laser thermal effect to weld the nano material on the surface of the polytetrafluoroethylene sheet for modification: 1) Placing a PTFE sheet in a mould, laying a layer of nano material on the surface of the PTFE sheet, then carrying out mould pressing at a certain pressure, and pressing nano powder into the surface of PTFE; 2) and (3) carrying out laser irradiation on the surface of the obtained parison, instantly melting the irradiated micro area on the surface of the plastic substrate by using the heat effect of the laser beam, surrounding the powder material adhered to the surface of the area by the melt, and anchoring the powder material on the surface of the PTFE film when the melt is cooled and solidified, so that the effective welding of the powder material and the surface of the PTFE film is realized, and the purpose of modification is achieved. The laser welding method adopted by the invention has simple process, can be carried out in the air atmosphere, has low equipment price and stable modification treatment effect.
Disclosure of Invention
The invention aims to provide a method for modifying polytetrafluoroethylene by welding a nano material on the surface of the polytetrafluoroethylene by utilizing the thermal effect of laser.
The method is characterized by comprising the following steps:
(1) embedding of nanomaterials on PTFE surfaces
Putting a PTFE sheet into a die, weighing a certain amount of nano powder, spreading the nano powder on the surface of the PTFE, carrying out die pressing under a certain pressure, and maintaining the pressure for a period of time.
(2) Welding of nano material on PTFE surface
And (2) placing the parison obtained in the step (1) under a laser engraving machine, adjusting a laser spot of the laser engraving machine to focus the laser spot, irradiating the PTFE surface at a certain laser power and engraving depth, instantly melting irradiated micro areas on the surface of the plastic substrate by using the heat effect of a laser beam, surrounding the powder material adhered to the surface of the micro areas by using the melt, and anchoring the powder material on the surface of the PTFE film when the melt is cooled and solidified, so that the powder material and the surface of the PTFE film are effectively welded, and the aim of modification is fulfilled.
The method for modifying the polytetrafluoroethylene based on laser welding is characterized by comprising the following steps: the nano material is one of a carbon nano tube, a hexagonal boron nitride nanosheet, a graphite nanosheet, nano molybdenum disulfide, nano aluminum oxide and nano silicon dioxide.
The method for modifying the polytetrafluoroethylene based on laser welding is characterized by comprising the following steps: the polytetrafluoroethylene is a sheet.
The method for modifying the polytetrafluoroethylene based on laser welding is characterized by comprising the following steps: in the step 1), the cold pressing pressure is 100-140 MPa.
The method for modifying the polytetrafluoroethylene based on laser welding is characterized by comprising the following steps: in the step 2), the laser power is 0.1-1W.
The method for modifying the polytetrafluoroethylene based on laser welding is characterized by comprising the following steps: in the step 2), the irradiation concentration of the laser is 1-10 mm.
Detailed Description
The invention is further described below with reference to specific examples.
Wherein the thermal conductivity is tested according to GB/T10297-2015; the wear performance was tested in accordance with GB/T5478-2008.
Example 1
The preparation method of the embodiment comprises the following steps:
(1) cutting a PTFE sheet into a wafer with the diameter of 10 cm, putting the wafer into a mold, weighing 10g of carbon nano tube, spreading the carbon nano tube on the surface of the PTFE, carrying out mold pressing under the pressure of 100 MPa, and maintaining the pressure for a period of time.
(2) And (2) placing the parison obtained in the step (1) under a laser engraving machine, adjusting a laser spot of the laser engraving machine to focus the parison, adjusting the laser power to be 0.1W and the engraving depth to be 1 mm, irradiating the PTFE surface, instantly melting an irradiated micro area of the PTFE surface by using the heat effect of a laser beam, surrounding the carbon nanotube adhered to the surface of the area by a melt, and anchoring the carbon nanotube on the surface of the PTFE film when the melt is cooled and solidified, so that the carbon nanotube and the surface of the PTFE film are effectively welded, and the purpose of modification is achieved.
The composite material sample prepared above was tested and had a water contact angle of 76.5 °, a wear loss of 0.0146 g, and a thermal conductivity of 0.4317W/(m.k).
Example 2
The preparation method of the embodiment comprises the following steps:
(1) cutting a PTFE sheet into a wafer with the diameter of 10 cm, putting the wafer into a mold, weighing 10g of hexagonal boron nitride nanosheet, spreading the hexagonal boron nitride nanosheet on the surface of the PTFE, carrying out mold pressing under the pressure of 120 MPa, and maintaining the pressure for a period of time.
(2) And (2) placing the parison obtained in the step (1) under a laser engraving machine, adjusting a laser spot of the laser engraving machine to focus the parison, adjusting the laser power to be 0.2W and the engraving depth to be 2 mm, irradiating the PTFE surface, instantly melting an irradiated micro area of the PTFE surface by using the heat effect of a laser beam, enclosing the hexagonal boron nitride nanosheet adhered to the surface of the area by a melt, and anchoring the hexagonal boron nitride nanosheet to the surface of the PTFE film when the melt is cooled and solidified, so that the effective welding of the hexagonal boron nitride nanosheet and the surface of the PTFE film is realized, and the purpose of modification is achieved.
The composite material sample prepared in the above way is tested, the water contact angle is 69.6 degrees, the abrasion loss is 0.0113 g, and the thermal conductivity is 0.4341W/(m.k).
Example 3
The preparation method of the embodiment comprises the following steps:
(1) cutting a PTFE sheet into a wafer with the diameter of 10 cm, putting the wafer into a mold, weighing 10g of graphite nanosheet, spreading the graphite nanosheet on the surface of the PTFE, carrying out mold pressing under the pressure of 120 MPa, and maintaining the pressure for a period of time.
(2) And (2) placing the parison obtained in the step (1) under a laser engraving machine, adjusting a laser spot of the laser engraving machine to focus the parison, adjusting the laser power to be 1W and the engraving depth to be 1 mm, irradiating the PTFE surface, instantly melting an irradiated micro area of the PTFE surface by using the heat effect of a laser beam, enclosing the graphite nanosheet adhered to the surface of the area by a melt, and anchoring the graphite nanosheet to the surface of the PTFE film when the melt is cooled and solidified, so that the graphite nanosheet is effectively welded to the surface of the PTFE film, and the purpose of modification is achieved.
The composite material sample prepared above was tested, and it had a water contact angle of 67.3 °, a wear loss of 0.0197 g, and a thermal conductivity of 0.4378W/(m.k).
Example 4
The preparation method of the embodiment comprises the following steps:
(1) cutting a PTFE sheet into a wafer with the diameter of 10 cm, putting the wafer into a die, weighing 10g of nano molybdenum disulfide, spreading the nano molybdenum disulfide on the surface of the PTFE, carrying out die pressing under the pressure of 100 MPa, and maintaining the pressure for a period of time.
(2) And (2) placing the parison obtained in the step (1) under a laser engraving machine, adjusting a laser spot of the laser engraving machine to focus the parison, adjusting the laser power to be 0.5W and the engraving depth to be 1.5mm, irradiating the PTFE surface, instantly melting an irradiated micro area of the PTFE surface by using the heat effect of a laser beam, surrounding a carbon nanotube adhered to the surface of the area by a melt, and anchoring the nano molybdenum disulfide on the surface of the PTFE film when the melt is cooled and solidified, so that the effective welding of the nano molybdenum disulfide and the surface of the PTFE film is realized, and the purpose of modification is achieved.
The composite material sample prepared in the above way is tested, the water contact angle is 60.5 degrees, the abrasion loss is 0.0106 g, and the thermal conductivity is 0.4728W/(m.k).
Example 5
The preparation method of the embodiment comprises the following steps:
(1) cutting a PTFE sheet into a wafer with the diameter of 10 cm, putting the wafer into a mold, weighing 10g of nano silicon dioxide, spreading the nano silicon dioxide on the surface of the PTFE, carrying out mold pressing under the pressure of 100 MPa, and maintaining the pressure for a period of time.
(2) And (2) placing the parison obtained in the step (1) under a laser engraving machine, adjusting a laser spot of the laser engraving machine to focus the parison, adjusting the laser power to be 1W and the engraving depth to be 1 mm, irradiating the PTFE surface, instantly melting an irradiated micro area of the PTFE surface by using the heat effect of a laser beam, surrounding the carbon nanotube adhered to the surface of the area by using a melt, and anchoring the nano silicon dioxide on the surface of the PTFE film when the melt is cooled and solidified, so that the effective welding of the nano silicon dioxide and the surface of the PTFE film is realized, and the purpose of modification is achieved.
The composite material sample prepared above was tested, and it had a water contact angle of 61.5 °, a wear loss of 0.0128g, and a thermal conductivity of 0.4697W/(m.k).
Example 6
The preparation method of the embodiment comprises the following steps:
(1) cutting a PTFE sheet into a wafer with the diameter of 10 cm, putting the wafer into a die, weighing 10g of nano alumina, spreading the nano alumina on the surface of the PTFE, carrying out die pressing under the pressure of 100 MPa, and maintaining the pressure for a period of time.
(2) And (2) placing the parison obtained in the step (1) under a laser engraving machine, adjusting a laser spot of the laser engraving machine to focus the parison, adjusting the laser power to be 1W and the engraving depth to be 1 mm, irradiating the PTFE surface, instantly melting an irradiated micro area of the PTFE surface by using the heat effect of a laser beam, surrounding the carbon nanotube adhered to the surface of the area by using a melt, and anchoring the nano aluminum oxide on the surface of the PTFE film when the melt is cooled and solidified, so that the effective welding of the nano aluminum oxide and the surface of the PTFE film is realized, and the purpose of modification is achieved.
The composite material sample prepared above was tested, and it had a water contact angle of 63.2 °, a wear loss of 0.0134g, and a thermal conductivity of 0.4926W/(m.k).
The embodiments described above are intended to facilitate the understanding and appreciation of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (6)

1. A method for modifying polytetrafluoroethylene based on laser welding is characterized by comprising the following steps: the laser irradiation method is adopted to weld the nano material on the surface of the Polytetrafluoroethylene (PTFE), thereby achieving the modification purposes of improving the wear resistance, the thermal conductivity, the hydrophilicity and the like. The method comprises the following specific steps:
(1) embedding of nanomaterials on PTFE surfaces
Placing a PTFE sheet in a mould, laying a layer of nano material on the surface of the PTFE sheet, and then carrying out mould pressing at a certain pressure to embed the nano material into the surface of the PTFE sheet to obtain a parison;
(2) welding of nano material on PTFE surface
And (3) carrying out laser irradiation on the surface of the obtained parison, instantly melting the irradiated micro area on the surface of the plastic substrate by using the heat effect of the laser beam, surrounding the powder material adhered to the surface of the area by the melt, and anchoring the powder material on the surface of the PTFE film when the melt is cooled and solidified, so that the effective welding of the powder material and the surface of the PTFE film is realized, and the purpose of modification is achieved.
2. The method of modifying polytetrafluoroethylene based on laser welding according to claim 1, characterized in that: the nano material is one of a carbon nano tube, a hexagonal boron nitride nanosheet, a graphite nanosheet, nano molybdenum disulfide, nano aluminum oxide and nano silicon dioxide.
3. The method of modifying polytetrafluoroethylene based on laser welding according to claim 1, characterized in that: the polytetrafluoroethylene is a sheet.
4. The method of modifying polytetrafluoroethylene based on laser welding according to claim 1, characterized in that: in the step (1), the cold pressing pressure is 100-140 MPa.
5. The method of modifying polytetrafluoroethylene based on laser welding according to claim 1, characterized in that: in the step (2), the laser power is 0.1-1W.
6. The method of modifying polytetrafluoroethylene based on laser welding according to claim 1, characterized in that: in the step (2), the thickness of the laser welding is 1-10 mm.
CN202010193614.1A 2020-03-18 2020-03-18 Method for modifying polytetrafluoroethylene based on laser welding Pending CN111303472A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111957976A (en) * 2020-07-06 2020-11-20 番禺得意精密电子工业有限公司 Method for manufacturing composite board

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111957976A (en) * 2020-07-06 2020-11-20 番禺得意精密电子工业有限公司 Method for manufacturing composite board
CN111957976B (en) * 2020-07-06 2022-09-16 番禺得意精密电子工业有限公司 Method for manufacturing composite board

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