Plasma-modified glass fiber reinforced polyether ether ketone-based composites and methods of making the same

Abstract

This invention provides a plasma-modified glass fiber reinforced polyetheretherketone (PEEK) composite material and its preparation method, belonging to the field of glass fiber reinforced materials. The composite material is prepared by treating a PEEK film and glass fiber cloth with glow discharge plasma, followed by hot pressing, resulting in a composite material with good compatibility between PEEK and glass fiber. This method can significantly improve the interfacial bonding strength between glass fiber and PEEK resin, thereby improving the mechanical properties of the composite laminate. The interlaminar shear strength of the composite material is increased by 43% compared to the untreated composite material. Furthermore, this method also has the advantages of energy saving, environmental protection, short processing time, and high efficiency.

Description

Technical Field

[0001] This invention belongs to the field of glass fiber reinforced materials, specifically relating to a plasma-modified glass fiber reinforced polyether ether ketone-based composite material and its preparation method. Background Technology

[0002] Glass fiber reinforced resin matrix composites not only possess excellent mechanical properties and good recyclability, but their reinforcing glass fiber is also inexpensive, giving them a significant competitive advantage and making them an indispensable basic material in production and daily life. However, due to the poor interfacial compatibility between polyetheretherketone (PEEK) resin and glass fiber, the mechanical properties of PEEK / glass fiber composite laminates are not ideal, limiting the development and application of PEEK / glass fiber composites. Therefore, it is necessary to modify the PEEK film and glass fiber cloth to improve their interfacial compatibility, thereby enhancing the mechanical properties of PEEK / glass fiber composite laminates and enabling them to be developed and applied more broadly.

[0003] There are many ways to modify polyetheretherketone (PEEK) films and glass fibers, such as coupling agent treatment, acid and alkali treatment, and plasma treatment. Considering the advantages of plasma treatment, such as energy saving, environmental friendliness, short processing time, high efficiency, and the fact that it only treats the material surface without damaging the material's inherent properties, this method is highly recommended. Summary of the Invention

[0004] This invention provides a plasma-modified glass fiber reinforced polyether ether ketone-based composite material and its preparation method. The composite material has good compatibility and excellent mechanical properties.

[0005] This invention first provides a method for preparing plasma-modified glass fiber reinforced polyether ether ketone-based composite materials, comprising:

[0006] Step a: Select glass fiber cloth as the reinforcing material, and use glow discharge plasma to treat the glass fiber cloth to obtain the treated glass fiber cloth;

[0007] Step b: Select polyetheretherketone film as resin matrix, and use glow discharge plasma to treat polyetheretherketone film to obtain treated polyetheretherketone film.

[0008] Step c: Stack the treated fiberglass cloth and polyetheretherketone film;

[0009] Step d: The stacked materials are cured by a vacuum hot press to obtain plasma-modified glass fiber reinforced polyether ether ketone composite material.

[0010] Preferably, in steps a and b, the atmosphere for glow discharge plasma treatment is at least one of O2, N2, or Ar.

[0011] Preferably, in steps a and b, the gas flow rate for glow discharge plasma treatment is 40-200 ml / min.

[0012] Preferably, in steps a and b, the glow discharge plasma treatment time is 2-8 minutes.

[0013] Preferably, in step b, before plasma treatment, the polyetheretherketone film is immersed in a cleaning solution for 20-60 minutes, and then dried in a vacuum drying oven at a temperature of 50-80°C for 30-60 minutes to clean and dry the polyetheretherketone film.

[0014] Preferably, the cleaning solution is at least one of distilled water, anhydrous ethanol, or acetone.

[0015] Preferably, in step c, the glass fiber cloth comprises 5-15 parts and the polyetheretherketone film comprises 5-15 parts by volume.

[0016] Preferably, in step c, the stacking is done in an interval manner.

[0017] Preferably, in step d, the curing process includes: curing at 330-350℃ for 5-15 minutes, then heating to 350-370℃ for 5-15 minutes, and finally heating to 390-420℃ for 40-80 minutes, with a curing pressure of 5-25 MPa.

[0018] The present invention also provides a plasma-modified glass fiber reinforced polyether ether ketone-based composite material obtained by the above preparation method.

[0019] Beneficial effects of the present invention

[0020] This invention provides a plasma-modified glass fiber reinforced polyetheretherketone (PEEK) composite material and its preparation method. The composite material is prepared by treating a PEEK film and glass fiber cloth with glow discharge plasma, followed by hot pressing, resulting in a composite material with good compatibility between PEEK and glass fiber. This method significantly improves the interfacial bonding strength between glass fiber and PEEK resin, thereby enhancing the mechanical properties of the composite laminate. The interlaminar shear strength of the composite material is increased by 43% compared to the untreated composite material. Furthermore, this method offers advantages such as energy saving, environmental friendliness, short processing time, and high efficiency. Attached Figure Description

[0021] Figure 1 The graph shows the results of the glass fiber / polyetheretherketone resin microdroplet debonding test (interfacial shear stress) used in Examples 1-3 and Comparative Example 1 of this invention. Detailed Implementation

[0022] This invention first provides a method for preparing plasma-modified glass fiber reinforced polyether ether ketone-based composite materials, comprising:

[0023] Step a: Select glass fiber cloth as the reinforcing material, and treat the glass fiber cloth with glow discharge plasma to obtain the treated glass fiber cloth. The treatment process preferably includes: cutting the sample to be treated to a suitable size, preferably 10cm × 15cm, placing it on a sample tray, horizontally placing it into the plasma cleaner chamber, closing the chamber, inputting the treatment time as 120S-480S, preferably 240S, turning on the instrument switch, starting vacuuming, and after 35S, when the machine alerts you, turning on the air inlet knob and adjusting the air inlet flow rate to 40ml / min-200ml / min, preferably 40-100ml / min, to begin plasma treatment of the sample. The atmosphere for the glow discharge plasma treatment is preferably at least one of O2, N2, or Ar.

[0024] Step b: Select polyetheretherketone film as resin matrix. Preferably, the polyetheretherketone film is first immersed in cleaning solution for 20-60 minutes, and then dried in vacuum drying oven at 50-80°C for 30-60 minutes to clean and dry the polyetheretherketone film. The cleaning solution is preferably at least one of distilled water, anhydrous ethanol or acetone.

[0025] Then, the polyetheretherketone (PEEK) film is subjected to plasma treatment using glow discharge plasma to obtain a treated PEEK film. The treatment process preferably includes: cutting the sample to be treated to a suitable size, preferably 10cm × 15cm, placing it on a sample tray, horizontally placing it into the plasma cleaner chamber, closing the chamber, inputting the treatment time as 120s-480s, preferably 240s, turning on the instrument switch, starting vacuuming, and after 35s, when the machine alerts you, turning on the air inlet knob and adjusting the air inlet flow rate to 40ml / min-200ml / min, preferably 40-100ml / min, to begin plasma treatment of the sample. The atmosphere for the glow discharge plasma treatment is preferably at least one of O2, N2, or Ar.

[0026] In steps a and b, the glass fiber cloth cut to the correct size and the selected cleaned polyetheretherketone film are subjected to plasma treatment. This process creates etching marks and grooves on the surface of the sample, increasing the surface roughness of the material. This facilitates the formation of a mechanical interlocking structure between the glass fiber and the polyetheretherketone, thereby increasing the interfacial bonding strength. Simultaneously, plasma treatment introduces oxygen-containing active functional groups, such as hydroxyl and carboxyl groups, onto the sample surface, increasing the surface energy of the sample and facilitating the formation of stable chemical bonds between the samples, thus improving the interfacial bonding strength of the composite material.

[0027] According to this invention, the mechanism by which glow discharge plasma treatment introduces oxygen-containing active functional groups onto the sample surface is as follows: Different gases are used as the gas atmosphere during plasma treatment. During the treatment process, the plasma cleaner chamber is in a vacuum state. In this vacuum state (approximately 10–100 Pa), an electric field is applied to the gas. Under the energy provided by the electric field, the gas transforms from a gaseous state to a plasma state (also known as the "fourth state of matter"), which contains a large number of active particles such as electrons, ions, photons, and various free radicals. These particles are more diverse and more reactive than those produced by ordinary chemical reactions, making them more likely to react with the contacted material surface. Plasma surface modification technology utilizes these high-energy and active particles to undergo physical or chemical reactions with the material surface, thereby altering the surface properties of the material. Using oxygen as the atmosphere during the treatment process, the oxygen plasma contains abundant oxygen-containing particles with high chemical activity. These particles react chemically on the glass fiber surface, introducing oxygen-containing groups such as OC=O onto the glass fiber surface.

[0028] Step c: Stack the treated fiberglass cloth and polyetheretherketone film in a hot press mold, preferably in an alternating stacking manner to ensure that the material is wrinkle-free. The fiberglass cloth and polyetheretherketone film, by volume, comprise 5-15 parts of fiberglass cloth and 5-15 parts of polyetheretherketone film. More preferably, they comprise 7-9 parts of fiberglass cloth and 11-13 parts of polyetheretherketone film.

[0029] Step d: The stacked materials are cured using a vacuum hot press to obtain plasma-modified glass fiber reinforced polyether ether ketone (PEEK) composite material. The curing process preferably includes: curing at 330-350℃ for 5-15 minutes, then increasing the temperature to 350-370℃ for 5-15 minutes, and finally increasing the temperature to 390-420℃ for 40-80 minutes, with a curing pressure of 5-25 MPa.

[0030] According to the present invention, the method further includes post-processing the prepared composite laminate in accordance with conventional methods in the art, such as demolding, trimming, cutting, and polishing, so as to facilitate performance testing of the composite material.

[0031] The present invention will be further described in detail below with reference to the embodiments and comparative examples. All raw materials involved in the embodiments are commercially available.

[0032] Example 1

[0033] Place a 10cm x 15cm glass fiber cloth into the plasma cleaner, set the treatment time to 120 seconds, turn on the start button to begin vacuuming, and after 35 seconds, wait for the plasma cleaner to alert you. Then, adjust the air inlet knob to create an oxygen atmosphere in the chamber, with an air inlet flow rate of 40ml / min, and begin processing the sample. Once the instrument alerts you that the processing is complete, switch to the other side of the glass fiber cloth for further processing.

[0034] Cut the polyetheretherketone (PEEK) film into 10cm x 15cm pieces, clean them with anhydrous ethanol, and air dry them naturally. Then, place them in a plasma cleaner, set the treatment time to 120 seconds, turn on the start button, and begin vacuuming. After 35 seconds, wait for the plasma cleaner to alert you, then adjust the air inlet knob to create an oxygen atmosphere in the chamber. Set the air inlet flow rate to 40ml / min and begin processing the sample. Once the instrument alerts you that the processing is complete, switch to the other side of the PEEK film for further processing.

[0035] By volume, 7 parts of glass fiber cloth and 13 parts of polyetheretherketone (PEEK) film were sequentially and evenly placed into a mold. The mold was then placed in a vacuum hot press, and a vacuum was evacuated until the display reading was below 20. The hot pressing program was set, and the vacuum hot press was operated according to the program to obtain a PEEK / glass fiber composite laminate. The hot pressing program was as follows: pre-pressing at 340℃ for 10 minutes at a pressure of 5 MPa; then pre-pressing at 360℃ for 10 minutes at a pressure of 5 MPa; finally, hot pressing at 400℃ for 60 minutes at a curing pressure of 25 MPa. The interfacial shear stress diagram of the prepared composite material is shown below. Figure 1 As shown.

[0036] Example 2

[0037] Place a 10cm x 15cm glass fiber cloth into the plasma cleaner, set the treatment time to 240 seconds, turn on the start button to begin vacuuming, and after 35 seconds, wait for the plasma cleaner to alert you. Then, adjust the air inlet knob to create an oxygen atmosphere in the chamber, with an air inlet flow rate of 60ml / min, and begin processing the sample. Once the instrument alerts you that the processing is complete, switch to the other side of the glass fiber cloth for further processing.

[0038] Cut the polyetheretherketone (PEEK) film into 10cm x 15cm pieces, clean them with anhydrous ethanol, and air dry them naturally. Then, place them in a plasma cleaner, set the treatment time to 240 seconds, turn on the start button, and begin vacuuming. After 35 seconds, wait for the plasma cleaner to alert you, then adjust the air inlet knob to create an oxygen atmosphere in the chamber. Set the air inlet flow rate to 60ml / min and begin processing the sample. Once the instrument alerts you that the processing is complete, switch to the other side of the PEEK film for further processing.

[0039] By volume, 8 parts of glass fiber cloth and 12 parts of polyetheretherketone (PEEK) film were sequentially and evenly placed into a mold. The mold was then placed in a vacuum hot press, and a vacuum was drawn until the display reading was below 20. The hot pressing program was set, and the vacuum hot press was operated according to the program to obtain the desired PEEK / glass fiber composite laminate of this embodiment. The hot pressing program was as follows: pre-pressing at 340°C for 10 minutes at a pressure of 5 MPa; then pre-pressing at 360°C for 10 minutes at a pressure of 5 MPa; finally, hot pressing at 400°C for 60 minutes at a curing pressure of 25 MPa. The interfacial shear stress diagram of the prepared composite material is shown below. Figure 1 As shown.

[0040] Example 3

[0041] Place a 10cm x 15cm glass fiber cloth into the plasma cleaner, set the treatment time to 360 seconds, turn on the start button to begin vacuuming, and after 35 seconds, wait for the plasma cleaner to alert you. Then, adjust the air inlet knob to create an oxygen atmosphere in the chamber, with an air inlet flow rate of 100ml / min, and begin processing the sample. Once the instrument alerts you that the processing is complete, switch to the other side of the glass fiber cloth for further processing.

[0042] Cut the polyetheretherketone (PEEK) film into 10cm x 15cm pieces, clean them with anhydrous ethanol, and air dry them naturally. Then, place them in a plasma cleaner, set the treatment time to 360 seconds, turn on the start button, and begin vacuuming. After 35 seconds, wait for the plasma cleaner to alert you, then adjust the air inlet knob to create an oxygen atmosphere in the chamber. Set the air inlet flow rate to 100ml / min and begin processing the sample. Once the instrument alerts you that the processing is complete, switch to the other side of the PEEK film for further processing.

[0043] By volume, 9 parts of glass fiber cloth and 11 parts of polyetheretherketone (PEEK) film were sequentially and evenly placed into a mold. The mold was then placed in a vacuum hot press, and a vacuum was drawn until the display reading was below 20. The hot pressing program was set, and the vacuum hot press was operated according to the program to obtain the desired PEEK / glass fiber composite laminate of this embodiment. The hot pressing program was as follows: pre-pressing at 340°C for 10 minutes at a pressure of 5 MPa; then pre-pressing at 360°C for 10 minutes at a pressure of 5 MPa; finally, hot pressing at 400°C for 60 minutes at a curing pressure of 25 MPa. The interfacial shear stress diagram of the prepared composite material is shown below. Figure 1 As shown.

[0044] Comparative Example 1

[0045] This embodiment provides a blank polyetheretherketone (PEEK) / glass fiber composite laminate sample as a blank control compared to the PEEK / glass fiber composite laminate provided in Example 1. The preparation method of this blank PEEK / glass fiber composite laminate sample is the same as in Example 1, except that the PEEK film and glass fiber cloth are not subjected to plasma treatment. The interfacial shear stress diagram of the prepared composite material is shown below. Figure 1 As shown.

[0046] The mechanical properties of the composite materials obtained in Examples 1-3 and Comparative Example 1 were tested, as shown in Table 1:

[0047] Table 1

[0048]

[0049]

[0050] As can be seen from Table 1, compared with the blank polyetheretherketone / glass fiber composite laminate provided in Comparative Example 1, the interlaminar shear strength of the polyetheretherketone / glass fiber composite laminate provided in Example 1 is increased by 16%, the interlaminar shear strength of the polyetheretherketone / glass fiber composite laminate provided in Example 2 is increased by 43%, and the interlaminar shear strength of the polyetheretherketone / glass fiber composite laminate provided in Example 3 is increased by 20%.

[0051] As described above, the embodiments of the present invention effectively enhance the interfacial bonding strength between polyetheretherketone (PEEK) and glass fiber by plasma treatment of glass fiber cloth and polyetheretherketone (PEEK) film, while also improving the mechanical properties of the composite laminate. However, the treatment time should be selected within an appropriate range. For the activity and polarity of the fiber surface, excessively long treatment times may damage newly generated polar functional groups, thereby reducing the fiber surface modification effect and causing a decrease in mechanical properties.

[0052] The above description is only a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing plasma-modified glass fiber reinforced polyetheretherketone (PEEK) based composite material, characterized in that, include: Step a: Select glass fiber cloth as the reinforcing material, and use glow discharge plasma to treat the glass fiber cloth to obtain the treated glass fiber cloth; Step b: Select polyetheretherketone film as resin matrix, and use glow discharge plasma to treat polyetheretherketone film to obtain treated polyetheretherketone film. Step c: Stack the treated fiberglass cloth and polyetheretherketone film; Step d: The stacked materials are cured by a vacuum hot press to obtain plasma-modified glass fiber reinforced polyether ether ketone composite material.

2. The method for preparing a plasma-modified glass fiber reinforced polyetheretherketone (PEEK) composite material according to claim 1, characterized in that, In steps a and b, the atmosphere for glow discharge plasma treatment is at least one of O2, N2, or Ar.

3. The method for preparing a plasma-modified glass fiber reinforced polyetheretherketone (PEEK) composite material according to claim 1, characterized in that, In steps a and b, the gas flow rate for glow discharge plasma treatment is 40-200 ml / min.

4. The method for preparing a plasma-modified glass fiber reinforced polyetheretherketone (PEEK) composite material according to claim 1, characterized in that, In steps a and b, the glow discharge plasma treatment time is 2-8 minutes.

5. The method for preparing a plasma-modified glass fiber reinforced polyetheretherketone (PEEK) composite material according to claim 1, characterized in that, In step b, before plasma treatment, the polyetheretherketone film is immersed in a cleaning solution for 20-60 minutes, and then dried in a vacuum drying oven at 50-80°C for 30-60 minutes to clean and dry the polyetheretherketone film.

6. The method for preparing a plasma-modified glass fiber reinforced polyether ether ketone-based composite material according to claim 5, characterized in that, The cleaning solution is at least one of distilled water, anhydrous ethanol, or acetone.

7. The method for preparing a plasma-modified glass fiber reinforced polyetheretherketone (PEEK) composite material according to claim 1, characterized in that, In step c, by volume, the glass fiber cloth is 5-15 parts and the polyetheretherketone film is 5-15 parts.

8. The method for preparing a plasma-modified glass fiber reinforced polyetheretherketone (PEEK) composite material according to claim 1, characterized in that, In step c, the stacking is done in an interval manner.

9. The method for preparing a plasma-modified glass fiber reinforced polyetheretherketone (PEEK) composite material according to claim 1, characterized in that, In step d, the curing process includes: curing at 330-350℃ for 5-15 minutes, then heating to 350-370℃ for 5-15 minutes, and finally heating to 390-420℃ for 40-80 minutes, with a curing pressure of 5-25 MPa.

10. The plasma-modified glass fiber reinforced polyether ether ketone-based composite material obtained by the preparation method according to claim 1.

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