CN112406139A - Thermoplastic composite material wire (rod) and preparation method and application thereof - Google Patents
Thermoplastic composite material wire (rod) and preparation method and application thereof Download PDFInfo
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- CN112406139A CN112406139A CN202011091514.4A CN202011091514A CN112406139A CN 112406139 A CN112406139 A CN 112406139A CN 202011091514 A CN202011091514 A CN 202011091514A CN 112406139 A CN112406139 A CN 112406139A
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- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
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- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Reinforced Plastic Materials (AREA)
- Moulding By Coating Moulds (AREA)
Abstract
The invention provides a thermoplastic composite wire (bar) and a preparation method and application thereof, belonging to the field of thermoplastic composite wires or bars, wherein the structure comprises the following two parts: the composite core material comprises a thermoplastic hybrid fiber reinforced core part and a thermoplastic hybrid fiber winding surface layer, wherein the thermoplastic hybrid fiber reinforced core part is formed by mixing high-modulus carbon fibers as main bodies and high-toughness fibers, and a composite core material is formed by heating and infiltrating specific thermoplastic resin in the continuous yarn running process of unidirectional pultrusion fibers by a hot-melt method through a pultrusion process; after the core material is formed, the hybrid fiber is wound on the surface of the core material by adopting a spiral winding process, and the winding fiber is composed of the hybrid high-toughness fiber taking high-strength carbon fiber as a main body. The composite layered thermoplastic composite material bar or rod can be subjected to secondary thread machining on the surface, and is suitable for application of composite material bars or rods with thread structures.
Description
Technical Field
The invention belongs to a thermoplastic composite material wire or rod, and particularly relates to a thermoplastic composite material wire or rod with a pultrusion fiber structure and a winding fiber structure.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the development of secondary recycling of composite materials becoming more and more extensive, thermoplastic composite materials have increasingly extensive application prospects, various continuous fiber reinforced thermoplastic resin matrix composite materials are continuously researched and developed, wherein the pultrusion process is simple, the production efficiency is high, and the continuous fiber reinforced thermoplastic resin matrix composite material is suitable for production of composite bars or rods of continuous fibers and thermoplastic resin. The thermoplastic pultrusion fiber composite material is mainly applied to rod-shaped and rod-shaped materials in the fields of oil fields, industry and the like. With the increasing upgrading of the performance of composite rods or rod processing parts, the secondary processing of thermoplastic composite rods and rods becomes the processing trend of the main composite materials, and the thread processing of the rods or rods becomes the main processing mode, but the inventor finds that: for the pultruded fiber composite material, the mechanical property anisotropy of the fiber is large in the axial tensile strength and weak in the radial tensile strength, so that the radial damage of the fiber is easily caused in the thread processing process of the pultruded bar or rod.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention provides a bar or rod structure made of thermoplastic composite material, which comprises the following two parts: the composite core material comprises a thermoplastic hybrid fiber reinforced core part and a thermoplastic hybrid fiber winding surface layer, wherein the thermoplastic hybrid fiber reinforced core part is formed by mixing high-modulus carbon fibers as main bodies and high-toughness fibers, and a composite core material is formed by heating and infiltrating specific thermoplastic resin in the continuous yarn running process of unidirectional pultrusion fibers by a hot-melt method through a pultrusion process; after the core material is formed, the hybrid fiber is wound on the surface of the core material by adopting a spiral winding process, and the winding fiber is composed of the hybrid high-toughness fiber taking high-strength carbon fiber as a main body. The composite layered thermoplastic composite material bar or rod can be subjected to secondary thread machining on the surface, and is suitable for application of composite material bars or rods with thread structures.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the invention, a thermoplastic composite wire/rod is provided comprising a thermoplastic hybrid fiber reinforced core and a thermoplastic hybrid fiber wound surface layer; the thermoplastic hybrid fiber wound surface layer is wound around the thermoplastic hybrid fiber reinforced core surface.
In order to improve the secondary thread processing performance of the bar or rod of the thermoplastic composite material, the fiber reinforced structure of the pultrusion thermoplastic composite material needs to be further reinforced, on the basis of pultrusion, the pultrusion fiber reinforced and spiral winding molded fiber reinforced secondary composite structure thermoplastic composite material wire or bar is formed through a spiral winding process, the anti-damage characteristic of the radial composite material is improved through spiral winding, and therefore the thread processing capacity of the bar or rod composite material is improved.
In a second aspect of the present invention, there is provided a method of preparing a thermoplastic composite wire/rod comprising:
mixing high-modulus carbon fibers and high-toughness fibers;
arranging fibers by adopting a one-way pultrusion process to form one-way pultrusion hybrid fibers;
the thermoplastic resin melt is infiltrated into the unidirectional pultrusion hybrid fiber in a heating, pressurizing and melting mode, and molding is carried out, so as to obtain the thermoplastic hybrid fiber reinforced core;
mixing high-strength carbon fiber and high-toughness fiber;
wrapping hybrid fibers in two dimensions around the surface of the thermoplastic hybrid fiber reinforced core;
and (3) impregnating the thermoplastic hot-melt resin aqueous emulsion, drying and forming a thermoplastic hybrid fiber winding surface layer to obtain the composite material.
The preparation method disclosed by the invention is simple, excellent in mechanical property, strong in practicability and easy to popularize.
In a third aspect of the invention, the thermoplastic composite wire/rod material is applied to the oil field and industrial fields.
The rod-shaped or rod-shaped composite material prepared by the method has better anti-damage property, so that the rod-shaped or rod-shaped composite material is expected to be widely applied to the oil field and the industrial field.
The invention has the beneficial effects that:
(1) on the basis of pultrusion, the invention forms the thermoplastic composite material wire rod or rod material with the secondary composite structure of pultrusion fiber reinforcement and spiral winding fiber reinforcement by a spiral winding process, and improves the anti-damage characteristic of the radial composite material by spiral winding, thereby improving the thread processing capability of the rod-shaped or rod-shaped composite material.
(2) The invention has the advantages of simple structure, excellent mechanical property, strong practicability and easy popularization.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a schematic view of a thermoplastic composite rod or bar structure comprising two parts: a thermoplastic hybrid fiber reinforced core 1 and a thermoplastic hybrid fiber wound surface layer 2.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
A structure of a thermoplastic composite rod or bar, the structure comprising two parts: the composite core material comprises a thermoplastic hybrid fiber reinforced core part and a thermoplastic hybrid fiber winding surface layer, wherein the thermoplastic hybrid fiber reinforced core part is formed by mixing high-modulus carbon fibers as main bodies and high-toughness fibers, and a composite core material is formed by heating and infiltrating specific thermoplastic resin in the continuous yarn running process of unidirectional pultrusion fibers by a hot-melt method through a pultrusion process; after the core material is formed, the hybrid fiber is wound on the surface of the core material by adopting a spiral winding process, and the winding fiber is composed of the hybrid high-toughness fiber taking high-strength carbon fiber as a main body. The composite layered thermoplastic composite material bar or rod can be subjected to secondary thread machining on the surface, and is suitable for application of composite material bars or rods with thread structures.
The high-modulus carbon fiber adopted by the thermoplastic hybrid fiber reinforced core can be any one of M40, M40J, M55, M55J, M60 and M60J, the high-tenacity fiber can be any one of aramid fiber, UHMWPE fiber, PBO fiber and the like, and the hybrid ratio of the two fibers can be flexibly adjusted according to the use requirement. So as to take account of the rigidity and the toughness of the material and lead the reinforced core to have better supporting and tensile functions.
The specific type of the thermoplastic resin matrix of the thermoplastic hybrid fiber reinforced core is not particularly limited, and any one of polyethylene, polypropylene, polycarbonate, thermoplastic polyester, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyamide, polyimide, and the like can be selected, and the content of the resin matrix is controlled within the range of 40-60% to facilitate the distribution of the fibers and the impregnation of the resin.
The thermoplastic hybrid fiber reinforced core is characterized in that after hybrid fibers are arranged in a single direction and pass through a cavity die with a certain diameter, a thermoplastic resin melt is infiltrated into the single-direction pultrusion hybrid fibers by adopting a heating, pressurizing and melting mode, the heating and pressurizing temperature is controlled within the range of 180-290 ℃, and the pressurizing pressure is controlled within the range of 2-8 MPa. The diameter of the finally formed thermoplastic hybrid fiber reinforced core is controlled in the range of 1-10mm and flexibly adjusted according to application requirements.
The thermoplastic hybrid fiber winding surface layer is prepared by adopting a two-dimensional winding process on the surface of the thermoplastic hybrid fiber reinforced core after the thermoplastic hybrid fiber reinforced core is prepared, and can be formed by adopting high-strength carbon fiber and high-toughness fiber in a hybrid winding way, wherein the high-strength carbon fiber can be any one of T300, T700, T800 and T1000 carbon fibers, the high-toughness fiber can be any one of aramid fiber, UHMWPE fiber, PBO fiber and the like, the mixing ratio of the two fibers can be flexibly adjusted according to the design requirement, the winding process adopts any winding mode of hoop winding, spiral winding, longitudinal winding and the like, wherein the winding angle of the circumferential winding is controlled within the range of 85-90 degrees, the winding angle of the spiral winding is controlled within the range of 45-70 degrees, and the winding angle of the longitudinal winding is not more than 25 degrees, so that the anti-damage property and the thread processing capability of the radial composite material are better improved.
The preparation of the thermoplastic hybrid fiber winding surface layer is characterized in that the hybrid fiber is wound on the surface of the core part in a two-dimensional mode and then is impregnated with thermoplastic hot melt resin aqueous emulsion, the type of the hot melt adhesive can be flexibly designed according to the type of powder to be coated later, the concentration of the hot melt adhesive aqueous emulsion is controlled to be 3% -10%, and the wound surface layer is impregnated with the hot melt adhesive with the concentration and then is dried at 80-120 ℃ so as to improve the interface shear strength and the comprehensive mechanical property of the composite material.
The specific composition of the thermoplastic resin matrix emulsion of the thermoplastic hybrid fiber winding surface layer is not particularly limited, and any one of polyethylene, polypropylene, polycarbonate, thermoplastic polyester, polyphenylene sulfide, polyether ether ketone, polyether ketone, polyamide, polyimide and the like can be selected, and the content of the resin matrix is controlled within the range of 40-60%, so that better dispersibility and stability are obtained, and the interfacial shear strength of the composite material and the resin matrix is effectively improved.
With the increase of the thickness of the thermoplastic hybrid fiber winding surface layer, the radial anti-damage capability and the thread processing capability of the composite material are improved, but if the thickness of the thermoplastic hybrid fiber winding surface layer exceeds 5mm, the improvement of the radial anti-damage capability by continuously increasing the thickness is not large, and the integral mechanical property of the composite material is also influenced. Thus, in some embodiments, the thickness of the thermoplastic hybrid fiber wound surface layer is controlled to be in the range of 1-5 mm.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
A thermoplastic composite material bar or rod specifically comprises a thermoplastic hybrid fiber reinforced core 1 and a thermoplastic hybrid fiber wound surface layer 2, wherein M40 carbon fiber and aramid K49 fiber are mixed according to the mixing ratio of 5:1, the fibers are arranged by adopting a one-way pultrusion process, and then a thermoplastic Polyester (PET) matrix with the resin content of 55% is compounded inside fiber monofilaments at the temperature of 220 ℃ and the pressure of 2MPa in an infiltration mode to form the reinforced core 1 with the diameter of 4 mm. After the thermoplastic hybrid fiber reinforced core 1 is prepared, mixing the T300 carbon fiber and the PBO fiber at a ratio of 5:2 on the surface, and processing the surface reinforcing layer 2 by a hoop winding process with a winding angle of 85-90 degrees. While winding the hybrid fiber, the winding fiber is impregnated with 10% thermoplastic polypropylene emulsion, and then dried and molded at 120 ℃ for 2 hours to prepare a surface reinforcing layer 2 with a thickness of 3mm and a resin content of 55%.
The composite material has good radial anti-damage property and thread processing capability.
Example 2
A thermoplastic composite material bar or rod specifically comprises a thermoplastic hybrid fiber reinforced core 1 and a thermoplastic hybrid fiber wound surface layer 2, wherein M60 carbon fiber and aramid K129 fiber are mixed according to the mixing ratio of 5:3, the fibers are arranged by adopting a one-way pultrusion process, and then a polypropylene matrix with the resin content of 50% is compounded inside fiber monofilaments at the temperature of 200 ℃ and the pressure of 4MPa in an infiltration mode to form the reinforced core 1 with the diameter of 3 mm. After the thermoplastic hybrid fiber reinforced core 1 is prepared, mixing the T700 carbon fiber and the UHMWPE fiber at the ratio of 3:2 on the surface, and processing the surface reinforcing layer 2 by a spiral winding process with the winding angle of 45-70 degrees. And (3) winding the hybrid fiber, simultaneously soaking the winding fiber into thermoplastic polyurethane emulsion with the concentration of 10%, and then drying and molding the winding fiber at 110 ℃ for 3 hours to prepare the surface reinforcing layer 2 with the thickness of 4mm and the resin content of 55%.
The composite material has good radial anti-damage property and thread processing capability.
Example 3
A thermoplastic composite material bar or rod specifically comprises a thermoplastic hybrid fiber reinforced core 1 and a thermoplastic hybrid fiber wound surface layer 2, wherein M40J carbon fibers and aramid K29 fibers are mixed according to the mixing ratio of 6:1, the fibers are arranged by adopting a unidirectional pultrusion process, and then a thermoplastic Polyester (PET) matrix with the resin content of 53% is compounded inside fiber monofilaments at the temperature of 250 ℃ and the pressure of 5MPa in an infiltration mode to form the reinforced core 1 with the diameter of 3 mm. After the thermoplastic hybrid fiber reinforced core 1 is prepared, mixing the T1000 carbon fiber and the PBO fiber at a ratio of 7:2 on the surface, and processing the surface reinforcing layer 2 by a longitudinal winding process with a winding angle not more than 15 degrees. While the hybrid fiber is wound again, the wound fiber is impregnated with a thermoplastic PET emulsion having a concentration of 6%, and then dried and molded at 140 ℃ for 4 hours to prepare a surface reinforcing layer 2 having a thickness of 3mm and a resin content of 55%.
The composite material has good radial anti-damage property and thread processing capability.
Example 4
A thermoplastic composite material bar or rod specifically comprises a thermoplastic hybrid fiber reinforced core 1 and a thermoplastic hybrid fiber wound surface layer 2, wherein M60J carbon fibers and aramid K129 fibers are mixed according to the mixing ratio of 3:1, the fibers are arranged by adopting a unidirectional pultrusion process, and then a thermoplastic Polyester (PET) matrix with the resin content of 52% is compounded inside fiber monofilaments at the temperature of 240 ℃ and the pressure of 6MPa in an infiltration mode to form the reinforced core 1 with the diameter of 5 mm. After the thermoplastic hybrid fiber reinforced core 1 is prepared, mixing T800 carbon fiber and PBO fiber in a ratio of 5:1 on the surface, and processing the surface reinforcing layer 2 by a hoop winding process with a winding angle of 85-90 degrees. While the hybrid fiber is wound again, the wound fiber is impregnated with a thermoplastic polyolefin emulsion having a concentration of 8%, and then dried and molded at 120 ℃ for 5 hours to prepare a surface reinforcing layer 2 having a thickness of 1mm and a resin content of 65%.
The composite material has good radial anti-damage property and thread processing capability.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A thermoplastic composite wire/rod characterized by comprising a thermoplastic hybrid fiber reinforced core and a thermoplastic hybrid fiber wound surface layer; the thermoplastic hybrid fiber wound surface layer is wound around the thermoplastic hybrid fiber reinforced core surface.
2. The thermoplastic composite wire/rod of claim 1 wherein the winding is any one of hoop winding, spiral winding, longitudinal winding.
3. The thermoplastic composite wire/rod of claim 2 wherein the hoop winding has a winding angle of 85-90 °.
4. The thermoplastic composite wire/rod of claim 2 wherein the helically wound wrap angle is 45-70 °.
5. The thermoplastic composite wire/rod of claim 2 wherein the longitudinal wind has a wind angle of no more than 25 °.
6. The thermoplastic composite wire/rod of claim 1 wherein the thermoplastic hybrid fiber reinforced core has a diameter of 1-10 mm.
7. The thermoplastic composite wire/rod of claim 1 wherein the thermoplastic hybrid fiber wound surface layer has a thickness of 1-5 mm.
8. The thermoplastic composite wire/rod of claim 1 wherein the thermoplastic hybrid fiber reinforced core is hybrid of high modulus carbon fibers, high tenacity fibers;
preferably, the high modulus carbon fiber is any one of M40, M40J, M55, M55J, M60 and M60J
Preferably, the high-toughness fiber can be any one of aramid fiber, UHMWPE fiber, PBO fiber and the like;
or the thermoplastic hybrid fiber winding surface layer is formed by hybrid winding of high-strength carbon fibers and high-toughness fibers;
preferably, the high-strength carbon fiber is any one of T300, T700, T800 and T1000 carbon fiber;
preferably, the high-tenacity fibers used may be any one of aramid fibers, UHMWPE fibers, PBO fibers, and the like.
9. A method of making a thermoplastic composite wire/rod comprising:
mixing high-modulus carbon fibers and high-toughness fibers;
arranging fibers by adopting a one-way pultrusion process to form one-way pultrusion hybrid fibers;
the thermoplastic resin melt is infiltrated into the unidirectional pultrusion hybrid fiber in a heating, pressurizing and melting mode, and molding is carried out, so as to obtain the thermoplastic hybrid fiber reinforced core;
mixing high-strength carbon fiber and high-toughness fiber;
wrapping hybrid fibers in two dimensions around the surface of the thermoplastic hybrid fiber reinforced core;
and (3) impregnating the thermoplastic hot-melt resin aqueous emulsion, drying and forming a thermoplastic hybrid fiber winding surface layer to obtain the composite material.
10. Use of the thermoplastic composite wire/rod according to any one of claims 1 to 8 in the oilfield, industrial field.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112549694A (en) * | 2020-12-21 | 2021-03-26 | 赵培翔 | Wide fiber web reinforced plastic laminated composite sheet |
CN113997458A (en) * | 2021-11-01 | 2022-02-01 | 深圳市栢迪科技有限公司 | Manufacturing method of composite bar, composite bar and application of composite bar |
-
2020
- 2020-10-13 CN CN202011091514.4A patent/CN112406139A/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112549694A (en) * | 2020-12-21 | 2021-03-26 | 赵培翔 | Wide fiber web reinforced plastic laminated composite sheet |
CN113997458A (en) * | 2021-11-01 | 2022-02-01 | 深圳市栢迪科技有限公司 | Manufacturing method of composite bar, composite bar and application of composite bar |
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