Carbon fiber reinforced vinyl ester composite material and preparation method thereof

Abstract

The invention relates to the technical field of composite material preparation, in particular to a carbon fiber reinforced vinyl ester composite material and a preparation method thereof. The invention discloses a carbon fiber reinforced vinyl ester composite material and a preparation method thereof. The preparation method comprises the following steps: S100, putting a carbon fiber fabric into a drying oven for drying; s200, adding a curing agent and an accelerant, adding an amino-containing macromolecular polymer, uniformly stirring, and fully standing for defoaming for later use; s300, a pipeline of the vacuum infusion equipment is sealed through a vacuum bag film; s400, curing and demolding: adding an amino-containing macromolecular polymer into the resin matrix to prepare a carbon fiber / vinyl ester composite material system; and S500, the composite material is treated. The carbon fiber reinforced vinyl ester composite material and the preparation method thereof have the advantages that the compatibility and the interface bonding strength are improved, the interlaminar shear strength of a composite material product is improved, the influence on the comprehensive mechanical property and the long-term durability of the composite material is avoided, and the long-period use requirement of a ship can be met.

Description

Technical Field

[0001] The invention relates to the technical field of composite material preparation, and in particular to a carbon fiber reinforced vinyl ester composite material and a preparation method thereof. Background Art

[0002] At present, carbon fiber reinforced resin-based composite materials have been widely used in aviation, aerospace, navigation, rail transportation and other fields due to their excellent specific stiffness and specific strength. Carbon fiber reinforced vinyl ester composite materials have the advantages of good resistance to marine environment, strong functional designability, light weight, and easy molding of complex structures. At present, they have been widely used in many parts of ships, and all-composite yachts and high-speed passenger ships have been prepared both at home and abroad, significantly reducing the weight of the hull and increasing the speed of the hull.

[0003] In the field of ships, in order to strengthen carbon fiber composite materials, various research institutions have done a lot of work in the interface modification of composite materials and invented a variety of preparation methods. For example, the Chinese invention patent with publication number CN104877150A discloses a method for preparing carbon fiber composite materials by interface modification. The interface modification is to modify both the carbon fiber and the epoxy vinyl ester resin, and introduce functional groups matching the epoxy vinyl ester resin matrix on the surface of the carbon fiber, which can improve the compatibility and affinity with the epoxy vinyl ester resin, improve the compatibility and affinity of the modified carbon fiber with the epoxy vinyl ester resin, and improve the bonding strength of the interface between the modified carbon fiber and the epoxy vinyl ester resin. The preparation method includes oxidation treatment of the carbon fiber, preparation of a coupling agent solution, modification of the carbon fiber, drying, preparation of a modified epoxy vinyl ester resin, and preparation of a carbon fiber composite material. However, compared with the carbon fiber reinforced epoxy resin system, the interface of the current carbon fiber reinforced vinyl ester resin composite material still has poor compatibility and low interface bonding strength. The interlaminar shear strength of the prepared composite products is low, which in turn affects the comprehensive mechanical properties and long-term durability of the composite material, making it difficult to meet the long-term use requirements of ships. Summary of the invention

[0004] In view of this, the present invention aims to provide a carbon fiber reinforced vinyl ester composite material and a preparation method thereof, wherein a carbon fiber reinforced vinyl ester composite material with excellent interface performance is prepared by directly adding a macromolecular polymer containing an amino group into a vinyl ester resin. The modification mechanism is speculated to be based on the migration effect and plays a "bridging" role between the resin matrix and the carbon fiber surface, thereby improving the interface bonding strength between the two, solving the problems of poor compatibility, low interface bonding strength, and low interlaminar shear strength of the prepared composite material product, thereby affecting the comprehensive mechanical properties and long-term durability of the composite material, and making it difficult to meet the long-term use requirements of ships.

[0005] In order to solve the above problems, the present invention provides a carbon fiber reinforced vinyl ester composite material and a preparation method thereof, comprising:

[0006] S100, cutting the carbon fiber fabric according to the size required by the process, and drying it in an oven at 60-120°C for 0.5-4 hours;

[0007] S200, add 1% to 2% by mass of curing agent and 0 to 0.4% by mass of accelerator to vinyl ester resin, then add 1 to 20% by mass of amino-containing macromolecular polymer based on the mass fraction of vinyl ester resin, stir evenly and let stand for defoaming for later use;

[0008] S300, setting up a vacuum perfusion device, and sealing the pipeline of the vacuum perfusion device by using a vacuum bag film;

[0009] S400, curing and demoulding: curing and post-curing treatment are performed according to the curing process, and a macromolecular polymer containing amino groups is added to the resin matrix to play a role of connecting the resin matrix and the carbon fiber surface based on the migration effect to prepare a carbon fiber / vinyl ester composite material system;

[0010] S500, processing the prepared carbon fiber / vinyl ester composite material to form a finished product.

[0011] Furthermore, the preparation environment temperature is 15~35°C and the humidity is 25%~75%.

[0012] Furthermore, the preparation environment maintains a constant temperature.

[0013] Furthermore, the carbon fiber fabric is polyacrylonitrile-based carbon fiber fabric or asphalt-based carbon fiber fabric.

[0014] Furthermore, the polypropylene carbon fiber fabric is at least one of T300, T700, T800, T1000, M40, M45, M50 and 48k large tow.

[0015] Furthermore, the type of vinyl ester resin is at least one of high-strength vinyl ester resin, high-toughness vinyl ester resin, aging-resistant vinyl ester resin and flame-retardant vinyl ester resin epoxy resin.

[0016] Furthermore, the amino-containing macromolecular polymer is at least one of linear polysiloxane, branched polysiloxane, linear polyamino ester, branched polyamino ester, linear polyamidoamine, and dendritic polyamide.

[0017] Furthermore, the macromolecular polymer has a molecular weight ≥ 1000 g / mol.

[0018] Further, in step S500, the method for treating the prepared carbon fiber / vinyl ester composite material includes removing vacuum auxiliary materials and flash edges.

[0019] Furthermore, after the prepared carbon fiber / vinyl ester composite material is processed, the composite material is inspected to ensure that there are no bubbles and no glue deficiency.

[0020] Compared with the prior art, the carbon fiber reinforced vinyl ester composite material and the preparation method thereof described in the present invention have the following advantages:

[0021] The advantage of this technical solution is that a carbon fiber reinforced vinyl ester composite material with excellent interface performance is prepared by directly adding an amino-containing macromolecular polymer into a vinyl ester resin. The modification mechanism is speculated to be based on the migration effect, which plays a "bridging" role between the resin matrix and the carbon fiber surface, thereby improving the interface bonding strength between the two, improving the compatibility and interface bonding strength, and improving the interlaminar shear strength of the prepared composite product, avoiding the impact on the comprehensive mechanical properties and long-term durability of the composite material, and being able to meet the long-term use requirements of ships. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a schematic diagram of the structure of the amino-containing macromolecular polymer described in an embodiment of the present invention. DETAILED DESCRIPTION

[0023] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, specific embodiments of the present invention are described in detail below with reference to the accompanying drawings.

[0024] In the present invention, the descriptions involving "first", "second", "upper", "lower", etc. are only used for descriptive purposes and cannot be understood as indicating or implying their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first", "second", "upper", "lower" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various embodiments can be combined with each other, but it must be based on the ability of ordinary technicians in the field to implement. When the technical solutions between the embodiments can be combined, they are all within the protection scope required by the present invention.

[0025] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0026] A carbon fiber reinforced vinyl ester composite material and a preparation method thereof, comprising:

[0027] The preparation environment temperature is 15~35℃, and the humidity is 25%~75%. It is best to carry out molding in a constant temperature workshop.

[0028] The carbon fiber fabric is a polyacrylonitrile-based carbon fiber fabric or a pitch-based carbon fiber fabric. The polyacrylonitrile carbon fiber fabric is at least one of T300, T700, T800, T1000, M40, M45, M50 and 48k large tow.

[0029] The type of vinyl ester resin is at least one of high-strength vinyl ester resin, high-toughness vinyl ester resin, aging-resistant vinyl ester resin and flame-retardant vinyl ester resin epoxy resin.

[0030] like Figure 1 As shown, the amino-containing macromolecular polymer is at least one of linear polysiloxane, branched polysiloxane, linear polyamino ester, branched polyamino ester, linear polyamidoamine, and dendritic polyamide.

[0031] Furthermore, the macromolecular polymer has a molecular weight ≥ 1000 g / mol.

[0032] S100, cutting the carbon fiber fabric according to the size required by the process, and drying it in an oven at 60-120°C for 0.5-4 hours;

[0033] S200, add 1% to 2% by mass of curing agent and 0 to 0.4% by mass of accelerator to vinyl ester resin, then add 1 to 20% by mass of amino-containing macromolecular polymer based on the mass fraction of vinyl ester resin, stir evenly and let stand for defoaming for later use;

[0034] S300, setting up a vacuum perfusion device, and sealing the pipeline of the vacuum perfusion device by using a vacuum bag film;

[0035] S400, curing and demoulding: curing and post-curing treatment are performed according to the curing process, and a macromolecular polymer containing amino groups is added to the resin matrix to play a role of connecting the resin matrix and the carbon fiber surface based on the migration effect to prepare a carbon fiber / vinyl ester composite material system;

[0036] S500, processing the prepared carbon fiber / vinyl ester composite material to form a finished product.

[0037] The method for treating the prepared carbon fiber / vinyl ester composite material includes removing vacuum auxiliary materials and flash

[0038] Furthermore, after the prepared carbon fiber / vinyl ester composite material is processed, the composite material is inspected to ensure that there are no bubbles and no glue deficiency.

[0039] The above preparation method is described below with several specific examples, and the effects are compared with those of comparative examples.

[0040] Example 1

[0041] Confirm the environmental conditions for composite material molding. The ambient temperature of the site should be between 15-35°C and the humidity should be controlled between 25%-75%. If conditions permit, it is best to carry out molding in a constant temperature workshop;

[0042] S100, cut T700 grade carbon fiber fabric according to the size required by the process, and place it in an oven at 60-120°C to dry for 0.5-4 hours;

[0043] S200, resin configuration: select high-strength vinyl ester resin and methyl ethyl ketone peroxide as curing agent, add 2% amino-containing macromolecular polymer by mass fraction of vinyl ester resin, stir evenly and let stand for defoaming for later use;

[0044] S300, preparation process: use vacuum infusion process for pipeline setting and vacuum bag film sealing, pay attention to air tightness inspection;

[0045] S400, curing and demoulding: perform curing and post-curing treatment according to the curing process recommended by the resin.

[0046] S500, after the preparation is completed, remove the vacuum auxiliary materials and flash;

[0047] S600, check the molding quality of the test piece to ensure that there are no defects such as bubbles and glue deficiency, and obtain the required carbon fiber reinforced vinyl ester composite material system.

[0048] Example 2

[0049] Confirm the environmental conditions for composite material molding. The ambient temperature of the site should be between 15-35°C and the humidity should be controlled between 25%-75%. If conditions permit, it is best to carry out molding in a constant temperature workshop;

[0050] S100, cut T800 grade carbon fiber fabric according to the size required by the process, and place it in an oven at 60-120°C to dry for 0.5-4 hours;

[0051] S200, resin configuration: select high-toughness vinyl ester resin and benzoyl peroxide as curing agent, add 6% amino-containing macromolecular polymer by mass fraction of vinyl ester resin, stir evenly and let stand for defoaming for later use;

[0052] S300, preparation process: use vacuum infusion process to set up pipelines and seal vacuum bag film, pay attention to air tightness inspection;

[0053] S400, curing and demoulding: perform curing and post-curing treatment according to the curing process recommended by the resin.

[0054] S500, after the preparation is completed, remove the vacuum auxiliary materials and flash;

[0055] S600, check the molding quality of the test piece to ensure that there are no defects such as bubbles and glue deficiency, and obtain the required carbon fiber reinforced vinyl ester composite material system.

[0056] Example 3

[0057] Confirm the environmental conditions for composite material molding. The ambient temperature of the site should be between 15-35°C and the humidity should be controlled between 25%-75%. If conditions permit, it is best to carry out molding in a constant temperature workshop;

[0058] S100, cutting the large tow carbon fiber fabric according to the size required by the process, and drying it in an oven at 60-120°C for 0.5-4 hours;

[0059] S200, resin configuration: select high-strength vinyl ester resin and methyl ethyl ketone peroxide as curing agent, add 5% amino-containing macromolecular polymer by mass fraction of vinyl ester resin, stir evenly and let stand for defoaming for later use;

[0060] S300, preparation process: use vacuum infusion process to set up pipelines and seal vacuum bag film, pay attention to air tightness inspection;

[0061] S400, curing and demoulding: perform curing and post-curing treatment according to the curing process recommended by the resin.

[0062] S500, after the preparation is completed, remove the vacuum auxiliary materials and flash;

[0063] S600, check the molding quality of the test piece to ensure that there are no defects such as bubbles and glue deficiency, and obtain the required carbon fiber reinforced vinyl ester composite material system.

[0064] Example 4

[0065] Confirm the environmental conditions for composite material molding. The ambient temperature of the site should be between 15-35°C and the humidity should be controlled between 25%-75%. If conditions permit, it is best to carry out molding in a constant temperature workshop;

[0066] S100, cutting the asphalt-based carbon fiber fabric according to the size required by the process, and drying it in an oven at 60-120°C for 0.5-4 hours;

[0067] S200, resin configuration: select high-toughness vinyl ester resin and methyl ethyl ketone peroxide as curing agent, add 8% amino-containing macromolecular polymer by mass fraction of vinyl ester resin, stir evenly and let stand for defoaming for later use;

[0068] S300, preparation process: use vacuum infusion process to set up pipelines and seal vacuum bag film, pay attention to air tightness inspection;

[0069] S400, curing and demoulding: perform curing and post-curing treatment according to the curing process recommended by the resin.

[0070] S500, after the preparation is completed, remove the vacuum auxiliary materials and flash;

[0071] S600, check the molding quality of the test piece to ensure that there are no defects such as bubbles and glue deficiency, and obtain the required carbon fiber reinforced vinyl ester composite material system.

[0072] Example 5

[0073] Confirm the environmental conditions for composite material molding. The ambient temperature of the site should be between 15-35°C and the humidity should be controlled between 25%-75%. If conditions permit, it is best to carry out molding in a constant temperature workshop;

[0074] S100, cut T700 grade carbon fiber fabric according to the size required by the process, and place it in an oven at 60-120°C to dry for 0.5-4 hours;

[0075] S200, resin configuration: select high-toughness vinyl ester resin and methyl ethyl ketone peroxide as curing agent, add 6% amino-containing macromolecular polymer by mass fraction of vinyl ester resin, stir evenly and let stand for defoaming for later use;

[0076] S300, preparation process: use vacuum infusion process to set up pipelines and seal vacuum bag film, pay attention to air tightness inspection;

[0077] S400, curing and demoulding: perform curing and post-curing treatment according to the curing process recommended by the resin.

[0078] S500, after the preparation is completed, remove the vacuum auxiliary materials and flash;

[0079] S600, check the molding quality of the test piece to ensure that there are no defects such as bubbles and glue deficiency, and obtain the required carbon fiber reinforced vinyl ester composite material system.

[0080] Comparative Example 1

[0081] Confirm the environmental conditions for composite material molding. The ambient temperature of the site should be between 15-35°C and the humidity should be controlled between 25%-75%. If conditions permit, it is best to carry out molding in a constant temperature workshop;

[0082] S100, cut T700 grade carbon fiber fabric according to the size required by the process, and place it in an oven at 60-120°C to dry for 0.5-4 hours;

[0083] S200, resin configuration: select high-strength vinyl ester resin and methyl ethyl ketone peroxide as curing agent, stir evenly and let stand to defoam for later use;

[0084] S300, preparation process: use vacuum infusion process to set up pipelines and seal vacuum bag film, pay attention to air tightness inspection;

[0085] S400, curing and demoulding: perform curing and post-curing treatment according to the curing process recommended by the resin.

[0086] S500, after the preparation is completed, remove the vacuum auxiliary materials and flash;

[0087] S600, check the molding quality of the test piece to ensure that there are no defects such as bubbles and glue deficiency, and obtain the required carbon fiber reinforced vinyl ester composite material system.

[0088] Comparative Example 2

[0089] Confirm the environmental conditions for composite material molding. The ambient temperature of the site should be between 15-35°C and the humidity should be controlled between 25%-75%. If conditions permit, it is best to carry out molding in a constant temperature workshop;

[0090] S100, cut T700 grade carbon fiber fabric according to the size required by the process, and place it in an oven at 60-120°C to dry for 0.5-4 hours;

[0091] S200, resin configuration: select high-strength vinyl ester resin and methyl ethyl ketone peroxide as curing agent, add 4% vinyl-containing macromolecular polymer by mass fraction of vinyl ester resin, stir evenly and let stand for defoaming for later use;

[0092] S300, preparation process: use vacuum infusion process to set up pipelines and seal vacuum bag film, pay attention to air tightness inspection;

[0093] S400, curing and demoulding: perform curing and post-curing treatment according to the curing process recommended by the resin.

[0094] S500, after the preparation is completed, remove the vacuum auxiliary materials and flash;

[0095] S600, check the molding quality of the test piece to ensure that there are no defects such as bubbles and glue deficiency, and obtain the required carbon fiber reinforced vinyl ester composite material system.

[0096] The comparison of shear strength between different systems is shown in Table 1 below:

[0097] Table 1

[0098] system Interlaminar shear strength (MPa) Example 1 42.2 Example 2 52.9 Example 3 49.9 Example 4 46.8 Example 5 56.1 Comparative Example 1 35.7 Comparative Example 2 35.2

[0099] It can be seen from the comparison results shown in Table 1 above that the carbon fiber reinforced vinyl ester composite material prepared by the preparation method of the present invention effectively improves the interlaminar shear strength compared with the composite material prepared by the traditional method.

[0100] Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the scope defined by the claims.

Claims

1. A carbon fiber reinforced vinyl ester composite material and a preparation method thereof, characterized in that: include: S100, cutting the carbon fiber fabric according to the size required by the process, and drying it in an oven at 60-120°C for 0.5-4 hours; S200, add 1% to 2% by mass of curing agent and 0 to 0.4% by mass of accelerator to vinyl ester resin, then add 1 to 20% by mass of amino-containing macromolecular polymer based on the mass fraction of vinyl ester resin, stir evenly and let stand for defoaming for later use; S300, setting up a vacuum perfusion device, and sealing the pipeline of the vacuum perfusion device by using a vacuum bag film; S400, curing and demoulding: curing and post-curing treatment are performed according to the curing process, and a macromolecular polymer containing amino groups is added to the resin matrix to play a role of connecting the resin matrix and the carbon fiber surface based on the migration effect to prepare a carbon fiber / vinyl ester composite material system; S500, processing the prepared carbon fiber / vinyl ester composite material to form a finished product.

2. The carbon fiber reinforced vinyl ester composite material and the preparation method thereof according to claim 1, characterized in that: The preparation environment temperature is 15~35℃ and the humidity is 25%~75%.

3. The carbon fiber reinforced vinyl ester composite material and the preparation method thereof according to claim 2, characterized in that: The preparation environment maintains a constant temperature.

4. The carbon fiber reinforced vinyl ester composite material and the preparation method thereof according to claim 1, characterized in that: The carbon fiber fabric is a polyacrylonitrile-based carbon fiber fabric or a pitch-based carbon fiber fabric.

5. The carbon fiber reinforced vinyl ester composite material and the preparation method thereof according to claim 4, characterized in that: The polypropylene carbon fiber fabric is at least one of T300, T700, T800, T1000, M40, M45, M50 and 48k large tow.

6. The carbon fiber reinforced vinyl ester composite material and the preparation method thereof according to claim 1, characterized in that: The type of vinyl ester resin is at least one of high-strength vinyl ester resin, high-toughness vinyl ester resin, aging-resistant vinyl ester resin and flame-retardant vinyl ester resin epoxy resin.

7. The carbon fiber reinforced vinyl ester composite material and the preparation method thereof according to claim 1, characterized in that: The amino-containing macromolecular polymer is at least one of linear polysiloxane, branched polysiloxane, linear polyamino ester, branched polyamino ester, etc., linear polyamidoamine, and dendritic polyamide.

8. The carbon fiber reinforced vinyl ester composite material and the preparation method thereof according to claim 7, characterized in that: The molecular weight of macromolecular polymers is ≥1000 g / mol.

9. The carbon fiber reinforced vinyl ester composite material and the preparation method thereof according to claim 1, characterized in that: In step S500, the method for treating the prepared carbon fiber / vinyl ester composite material includes removing vacuum auxiliary materials and flash.

10. The carbon fiber reinforced vinyl ester composite material and the preparation method thereof according to claim 1, characterized in that: After the prepared carbon fiber / vinyl ester composite material is processed, the composite material is inspected to ensure that there are no bubbles and no glue deficiency.

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