CN111705391B - Carbon nanotube fiber hybrid fabric, preparation method thereof and reinforced composite material - Google Patents
Carbon nanotube fiber hybrid fabric, preparation method thereof and reinforced composite material Download PDFInfo
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- CN111705391B CN111705391B CN202010511388.7A CN202010511388A CN111705391B CN 111705391 B CN111705391 B CN 111705391B CN 202010511388 A CN202010511388 A CN 202010511388A CN 111705391 B CN111705391 B CN 111705391B
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- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
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- D03D13/008—Woven fabrics characterised by the special disposition of the warp or weft threads, e.g. with curved weft threads, with discontinuous warp threads, with diagonal warp or weft characterised by weave density or surface weight
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Abstract
The invention relates to a carbon nanotube fiber hybrid fabric, a preparation method thereof and a reinforced composite material. The preparation method of the carbon nanotube fiber hybrid fabric comprises the following steps: spinning the carbon nanotube array to prepare carbon nanotube fiber yarns; treating the carbon nano tube fiber yarn by adopting an acid solution, and drafting the carbon nano tube fiber yarn; combining the carbon nanotube fiber yarns to prepare a carbon nanotube fiber bundle; mixing the carbon nano tube fiber bundle with the high-performance fiber to prepare a mixed fiber bundle; then weaving at least two of the carbon nano tube fiber bundle, the high-performance fiber and the mixed fiber bundle, or weaving the mixed fiber bundle to prepare the carbon nano tube fiber hybrid fabric. The preparation method of the carbon nanotube fiber hybrid fabric can prepare the carbon nanotube fiber hybrid fabric with high strength, good impact resistance, good creep resistance and good humidity, heat and aging resistance.
Description
Technical Field
The invention relates to the field of fiber materials, in particular to a carbon nanotube fiber hybrid fabric, a preparation method thereof and a reinforced composite material.
Background
The fibers used in the traditional bulletproof material are aramid fibers, carbon fibers and ultra-high molecular weight polyethylene fibers. The aramid fiber has high modulus, higher elongation and good impact resistance, but the aramid fiber has poor dimensional stability and ultraviolet irradiation resistance, high water absorption and poor damp-heat aging resistance, so that the service life of the product is influenced. Although carbon fibers have high strength, the greatest disadvantage is brittleness, i.e., low impact resistance, which limits their application in ballistic materials. The ultra-high molecular weight polyethylene fiber has low density, excellent performances of high strength, high modulus, impact resistance, cutting resistance and the like, and the manufactured body armor is lighter and better in weight than aramid fiber body armor. However, the ultra-high molecular weight polyethylene fiber has poor creep resistance, is easy to deform irreversibly under long-time stress, is not high-temperature resistant, and can affect the use of bulletproof products to a certain extent.
Disclosure of Invention
Based on the above, there is a need for a method for preparing a carbon nanotube fiber hybrid fabric which has good resistance to wet heat aging, impact resistance and creep and can be used in a bulletproof material.
In addition, there is a need to provide a carbon nanotube fiber hybrid fabric and a reinforced composite.
A preparation method of a carbon nanotube fiber hybrid fabric comprises the following steps:
spinning the carbon nanotube array to prepare carbon nanotube fiber yarns;
treating the carbon nano tube fiber yarn by adopting an acid solution, and drafting the carbon nano tube fiber yarn;
combining the carbon nanotube fiber yarns to prepare a carbon nanotube fiber bundle;
mixing the carbon nano tube fiber bundle with high-performance fibers to prepare a mixed fiber bundle; and a process for the preparation of a coating,
weaving at least two of the carbon nanotube fiber bundle, the high-performance fiber and the mixed fiber bundle, or weaving the mixed fiber bundle to prepare the carbon nanotube fiber hybrid fabric.
In one embodiment, in the preparation process of the carbon nanotube fiber hybrid fabric, the volume ratio of the carbon nanotube fibers to the high-performance fibers is 1: 1-1: 10.
In one embodiment, the high performance fibers are selected from at least one of aramid fibers, ultra-high molecular weight polyethylene fibers, and carbon fibers.
In one embodiment, the method of mixing the carbon nanotube fiber bundle with the high performance fiber is a doubling method, a stranding method or a core-spun method.
In one embodiment, the carbon nanotube fiber hybrid fabric is a woven fabric, a warp knit fabric or a weft knit fabric, and the yarn for weaving the carbon nanotube fiber hybrid fabric is selected from at least one of the carbon nanotube fiber bundle, the high performance fiber and the hybrid fiber bundle.
In one embodiment, the carbon nanotube fiber hybrid fabric has a grammage of 50g/m2～200g/m2。
In one embodiment, the warp and weft density of the carbon nanotube fiber hybrid fabric is 20 pieces/10 cm-200 pieces/10 cm.
In one embodiment, the acid solution is selected from one of a nitric acid solution and a chlorosulfonic acid solution.
In one embodiment, in the step of drawing the carbon nanotube fiber filament, the drawing ratio is 1-1.1.
In one embodiment, the step of spinning the carbon nanotube array to prepare the carbon nanotube fiber yarn comprises: and drawing a film with the width of 0.1-20 cm from the carbon nano tube array, twisting and spinning the film to prepare the carbon nano tube fiber yarn.
In one embodiment, in the step of twisting spun filaments, the twist is in the range of 100tpm to 15000 tpm.
In one embodiment, in the step of spinning the carbon nanotube array to prepare the carbon nanotube fiber, the length of the carbon nanotubes in the carbon nanotube array is 100 μm to 1000 μm, and the diameter of the carbon nanotubes in the carbon nanotube array is 6nm to 15 nm.
In one embodiment, in the step of combining the carbon nanotube fibers to prepare the carbon nanotube fiber bundles, the number of the combined carbon nanotube fibers in each bundle is 10 to 100.
The carbon nanotube fiber hybrid fabric is prepared by the preparation method of the carbon nanotube fiber hybrid fabric.
The raw materials for preparing the reinforced composite material comprise the carbon nanotube fiber hybrid fabric.
In one embodiment, the raw material for preparing the reinforced composite material further comprises a resin matrix, and the volume fraction of the carbon nanotube fiber hybrid fabric in the raw material is 50-55%.
The preparation method of the carbon nanotube fiber hybrid fabric comprises the steps of preparing the carbon nanotube fiber yarns by spinning the carbon nanotube array, and then adopting acid solution treatment and drafting treatment to increase the functional groups on the surface of the carbon nanotube fiber yarns and arrange the carbon nanotube fiber yarns in order to enhance the strength of the carbon nanotube fiber yarns. And then combining the carbon nanotube fiber yarns to obtain carbon nanotube fiber bundles, mixing and weaving the carbon nanotube fiber bundles with other high-performance fibers, wherein the addition of the carbon nanotube fibers improves the performance defects of the traditional aramid fibers, carbon fibers and ultrahigh molecular weight polyethylene fibers, so that the carbon nanotube fiber hybrid fabric with high strength, good impact resistance, good creep resistance and good humidity and heat aging resistance is obtained, and can be used for preparing reinforced composite materials such as bulletproof materials.
Drawings
FIG. 1 is a process flow diagram of a method for preparing a carbon nanotube fiber hybrid fabric according to one embodiment;
FIG. 2 is a schematic diagram of the carbon nanotube fiber filament with excessive twist in step S110 in the process flow diagram of FIG. 1;
FIG. 3 is a schematic view of a carbon nanotube fiber filament with proper twist in step S110 of the process flow diagram shown in FIG. 1;
FIG. 4 is a schematic illustration of the hybrid fabric produced in step S140 of the process flow diagram of FIG. 1 as a plied yarn;
fig. 5 is a schematic view of the hybrid fabric prepared in step S140 of the process flow diagram of fig. 1 as a core spun yarn.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description taken in conjunction with the accompanying drawings. The detailed description sets forth the preferred embodiments of the invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Referring to fig. 1, a method for preparing a carbon nanotube fiber hybrid fabric according to an embodiment includes the following steps:
step S110: and spinning the carbon nanotube array to prepare the carbon nanotube fiber.
Wherein, in the carbon nano tube array, the length of the carbon nano tube is 100-1000 μm, and the diameter is 6-15 nm. Further, the length of the carbon nanotube is 300 μm to 600 μm. The carbon nanotubes in the carbon nanotube array have proper length and diameter, so that the prepared carbon nanotube fiber has high strength.
Specifically, step S110 includes: and drawing a film with the width of 0.1-20 cm from the carbon nano tube array, twisting and spinning the film to prepare the carbon nano tube fiber yarn. Further, the width of the drawn film is 0.1cm to 5 cm. In one embodiment, the twist is in the range of 100 to 15000tpm during twist spinning of the filaments. Further, the twist is 2000 to 15000 tpm. The thin film drawn from the carbon nano tube array is orderly arranged, the length and the diameter are uniform, and the carbon nano tube fiber yarn obtained by twisting and spinning the thin film has better mechanical property.
During the process of twisting and spinning into filaments, if the twist is too large, the carbon nanotube fiber filaments will form a spiral shape, as shown in fig. 2. The carbon nanotube fiber is seriously deformed in the axial direction of the fiber due to excessive twisting, and when the fiber is stressed in the axial direction, the bearing capacity of the carbon nanotube fiber in the axial direction of the fiber is reduced due to the deformation, so that the mechanical property of the whole carbon nanotube fiber is reduced. When the twist is too small, the carbon nanotube film is not completely twisted, and the carbon nanotube film is still in a film state in some places or the carbon nanotubes are not tightly cohered to form weak nodes, so that the carbon nanotube film is firstly broken when the fiber is stressed. As shown in fig. 3, under the optimal twist, the carbon nanotubes are tightly cohered, the carbon nanotube fiber is not seriously deformed in the axial direction of the fiber, and the carbon nanotube fiber has excellent mechanical properties and is suitable for the next processing and weaving.
Step S120: and (3) treating the carbon nano tube fiber yarn by adopting an acid solution, and drafting the carbon nano tube fiber yarn.
Specifically, the acid solution is selected from one of a nitric acid solution and a chlorosulfonic acid solution. In one embodiment, the mass concentration of the acid solution is 10% to 50%. The carbon nanotube fiber is subjected to surface treatment by adopting the acid solution, and functional groups on the surface of the carbon nanotube fiber are increased, so that the interface combination with a resin matrix is improved when the reinforced composite material is prepared, and the strength of the composite material is enhanced.
In one embodiment, in the step of performing the surface treatment on the carbon nanotube fiber filament with the acid solution, the carbon nanotube fiber filament is soaked in the acid solution. The soaking time is 1 min-120 min. In practical application, the specific time is determined according to the type and concentration of the acid solution, and the carbon nano tube in the fiber cannot be well drawn due to too short time, so that the surface modification of the fiber is not obvious; over time, the carbon nanotube structure is destroyed, thereby reducing the fiber strength.
In addition, the carbon nanotube fiber is drawn to ensure that the carbon nanotubes are more orderly and parallel in the fiber, thereby increasing the strength of the carbon nanotube fiber. Specifically, the draft ratio is 1 to 1.1.
Step S130: and combining the carbon nanotube fiber yarns to prepare the carbon nanotube fiber bundle.
In the present embodiment, the order of step S120 and step S130 may not be changed. The phenomenon of mutual adhesion and entanglement can occur when a plurality of untreated carbon nanotube fibers are combined together, so that part of fibers and an acid solution cannot be in full contact reaction; and the adhesion and the interlacing phenomena can cause uneven fiber tension in the fiber bundle, so that the tension is more uneven during drafting, and the later use and the mechanical property are influenced. Therefore, in order to make the fibers react with the acid solution in a sufficient contact manner and to make each fiber filament be well drawn, in the present embodiment, the acid treatment and the drawing treatment are performed on the individual fiber filaments, and then the treated fiber filaments are combined to obtain the fiber bundle.
Specifically, the number of the combined root in each bundle is 10 to 100. Furthermore, the number of the combined root in each bundle is 10-50.
Carbon nanotube fibers are a new generation of high performance fibers formed by the axial alignment of numerous carbon nanotubes, with the tubes being connected by van der waals forces. The carbon nanotube fiber has the advantages of light weight, high strength, high temperature resistance, corrosion resistance, long service life, small occupied space, flexibility, random bending, no easy flying during weaving and suitability for being made into fabrics, and is not easy to deform at high temperature, and the heat dissipation is fast. However, the conventional carbon nanotube fiber has a disadvantage of low strength when applied to a bulletproof fiber material, and in this embodiment, the carbon nanotube fiber bundle prepared by the above method can improve the strength of the carbon nanotube fiber bundle, thereby improving the strength of the prepared carbon nanotube fiber hybrid fabric.
Step S140: the carbon nanotube fiber bundle is mixed with high performance fibers to prepare a mixed fiber bundle.
Step S150: weaving at least two of the carbon nanotube fiber bundle, the high-performance fiber and the mixed fiber bundle, or weaving the mixed fiber bundle to prepare the carbon nanotube fiber hybrid fabric.
Specifically, the high-performance fiber is at least one selected from aramid fiber, ultra-high molecular weight polyethylene fiber, and carbon fiber.
In the preparation process of the carbon nanotube fiber hybrid fabric, the volume ratio of the carbon nanotube fiber bundle to the high-performance fiber is 1: 1-1: 10. Further, the volume ratio of the carbon nanofiber bundle to the high-performance fibers is 1: 1-1: 5. When the volume ratio of the carbon nanofiber bundle to the high-performance fiber exceeds the above ratio, the performance of the prepared hybrid fabric is reduced, and the effect of adding the carbon nanotube fiber is not obvious.
Specifically, the method of mixing the carbon nanotube fiber bundle with the high performance fiber is a doubling method, a stranding method or a core-spun method. Therefore, the carbon nanotube fiber bundles are mixed with the high performance fibers to obtain the yarn, the twisted yarn or the core-spun yarn. In one embodiment, referring to fig. 4, when the carbon nanotube fiber bundles and the high performance fibers are mixed by a stranding method, 1 carbon nanotube fiber bundle and 1 to 3 high performance fiber bundles are mixed, wherein the volume of 1 carbon nanotube fiber bundle is the same as that of 1 high performance fiber bundle. Referring to fig. 5, in the core-spun method, carbon nanotube fibers are used as the outer layer to wrap the fibers, and high performance fibers are used as the inner layer core yarn fibers. In the core-spun method, the high-performance fiber can be used as an outer layer wrapping fiber, and the carbon nano tube fiber is used as an inner layer core yarn fiber.
The weaving mode is weaving, warp knitting and weft knitting. Thus, the carbon nanotube fiber hybrid fabric is a woven fabric, a warp knit fabric, or a weft knit fabric. The yarns for weaving the carbon nanotube fiber hybrid fabric are selected from at least one of carbon nanotube fiber bundles, high-performance fibers and mixed fiber bundles.
Specifically, when woven, the weave may be plain, twill, satin, or other more complex weaves. In the embodiment, the weaving is single-layer fabric, and the warp yarn and the weft yarn can be pure carbon nano tube fiber bundles, pure high-performance fiber bundles or mixed fiber bundles of the pure carbon nano tube fiber bundles and the pure high-performance fiber bundles.
Wherein the square meter gram weight of the carbon nano tube fiber hybrid fabric is 50g/m2～200g/m2. The gram weight of the woven fabric is determined by the density of warp and weft yarns and the density of blended yarns. Specifically, the warp and weft density of the carbon nanotube fiber hybrid fabric is 20/10 cm-200/10 cm. The density of the blended yarn is 5tex to 250 tex.
Specifically, when the fabric is woven by warp knitting, the fabric texture can be chain knitting, warp flat knitting, axial warp knitting or other more complex textures, and the yarns are mixed fiber bundles. Wherein the square meter gram weight of the carbon nano tube fiber hybrid fabric is 50g/m2～200g/m2The grammage of the warp knit fabric is determined by the loop length and the density of the blended yarn. Specifically, the coil length is 2mm &5mm, and the density of the blended yarn is 5 tex-250 tex.
Specifically, when the fabric is woven by weft knitting, the fabric texture can be plain stitch, rib, links or other more complex textures, and the yarns are mixed fiber bundles. Wherein the square meter gram weight of the carbon nano tube fiber hybrid fabric is 50g/m2～200g/m2The grammage of weft-knitted fabrics is determined by the stitch length and the density of the blended yarns. Specifically, the coil length is 2 mm-5 mm, and the density of the blended yarn is 5 tex-250 tex.
The preparation method of the carbon nanofiber hybrid fabric at least has the following advantages:
(1) the preparation method of the carbon nanotube fiber hybrid fabric comprises the steps of preparing the carbon nanotube fiber yarns by spinning the carbon nanotube array, and then adopting acid solution treatment and drafting treatment to increase the functional groups on the surface of the carbon nanotube fiber yarns and arrange the carbon nanotube fiber yarns in order to enhance the strength of the carbon nanotube fiber yarns. And then combining the carbon nanotube fiber yarns to obtain carbon nanotube fiber bundles, mixing and weaving the carbon nanotube fiber bundles with other high-performance fibers, wherein the addition of the carbon nanotube fibers improves the performance defects of the traditional aramid fibers, carbon fibers and ultrahigh molecular weight polyethylene fibers, so that the carbon nanotube fiber hybrid fabric with high strength, good impact resistance, good creep resistance and good humidity and heat aging resistance is obtained, and can be used for preparing reinforced composite materials such as bulletproof materials.
(2) The preparation method of the carbon nanotube fiber hybrid fabric is simple in process and easy for industrial production.
The carbon nanofiber hybrid fabric according to an embodiment is prepared by the above method for preparing a carbon nanotube fiber hybrid fabric. The carbon nanotube fiber hybrid fabric has high strength, good impact resistance, good creep resistance and good damp-heat aging resistance, and can be used for preparing reinforced composite materials such as bulletproof materials.
In one embodiment, the raw material for preparing the reinforced composite material includes the carbon nanotube fiber hybrid fabric.
Specifically, the raw materials for preparing the reinforced composite material also comprise a resin matrix. For example, the resin matrix may be an epoxy resin. It is to be understood that any resin matrix commonly used in the art may be used as the resin matrix of the present embodiment. In the raw materials, the volume fraction of the carbon nanotube fiber hybrid fabric is 50-55%.
In one embodiment, the reinforced composite is a ballistic resistant material. In another embodiment, the reinforced composite material may be a bridge reinforcing material or a building reinforcing material.
Specifically, the preparation process of the reinforced composite material may be a process commonly used in the art, such as a VARTM (vacuum assisted resin transfer molding) process, and will not be described herein.
The reinforced composite material has high strength, good impact resistance, good creep resistance and good damp-heat aging resistance.
The following are specific examples:
examples 1 to 1
The preparation process of the carbon nanotube fiber hybrid fabric of the embodiment is specifically as follows:
(1) a film of 10cm width was drawn from a carbon nanotube array of 500 μm length and 10nm diameter, and then spun into filaments with a twist of 2000tpm to obtain carbon nanotube filaments.
(2) And (2) soaking the carbon nanotube fiber yarn obtained in the step (1) in a nitric acid solution with the mass concentration of 20% for treatment for 30min, and drawing the carbon nanotube fiber yarn, wherein the drawing multiple is 1.06.
(3) And (3) combining the 50 carbon nanotube fibers treated in the step (2) into a bundle of carbon nanotube fiber.
(4) Mixing the carbon nano tube fiber bundles treated in the step (3) with aramid fibers by adopting a core-spun method, wherein the outer layer wrapping fibers are carbon nano tube fiber bundles, the inner layer core yarns are aramid fibers, the volume ratio of the carbon nano tube fiber bundles to the aramid fibers is 1:5, weaving is carried out in a weaving mode, the warp and weft yarns are all mixed fiber bundles, the warp and weft density is 30 pieces/10 cm, and the gram weight is 200g/m2。
Examples 1 to 2
The preparation process of the carbon nanotube fiber hybrid fabric of the embodiment is specifically as follows:
(1) a film with the width of 10cm is pulled out from a carbon nano tube array with the length of 500 mu m and the diameter of 10nm, and the film is twisted and spun into filaments with the twist of 2000tpm to obtain the carbon nano tube fiber filaments.
(2) And (2) soaking the carbon nanotube fiber yarn obtained in the step (1) in a nitric acid solution with the mass concentration of 20% for treatment for 30min, and drawing the carbon nanotube fiber yarn, wherein the drawing multiple is 1.06.
(3) And (3) combining the 50 carbon nanotube fibers treated in the step (2) into a bundle of carbon nanotube fiber.
(4) Mixing the carbon nano tube fiber bundles treated in the step (3) with the ultrahigh molecular weight polyethylene fibers by adopting a core-spun method, wherein the outer wrapping fibers are carbon nano tube fibers, the inner core yarns are ultrahigh molecular weight polyethylene fibers, the volume ratio of the carbon nano tube fiber bundles to the ultrahigh molecular weight polyethylene fibers is 1:5, then weaving in a weaving mode, the warp and weft yarns are mixed fiber bundles, the warp and weft density is 30/10 cm, and the gram weight is 200g/m2。
Examples 1 to 3
The preparation process of the carbon nanotube fiber hybrid fabric of the embodiment is specifically as follows:
(1) a film of 10cm width was drawn from a carbon nanotube array of 500 μm length and 10nm diameter, and spun into a filament with a twist of 2000tpm to obtain a carbon nanotube fiber filament.
(2) And (2) soaking the carbon nanotube fiber yarn obtained in the step (1) in a nitric acid solution with the mass concentration of 20% for treatment for 30min, and drawing the carbon nanotube fiber yarn, wherein the drawing multiple is 1.06.
(3) Combining the 50 carbon nanotube fibers processed in the step (2) into a bundle of carbon nanotube fibers.
(4) Mixing the carbon nanotube fiber bundles processed in the step (3) with carbon fibers by adopting a core-spun method, wherein the outer layer wrapping fibers are carbon nanotube fibers, the inner layer core yarns are carbon fibers, the volume ratio of the carbon nanotube fiber bundles to the carbon fibers is 1:5, then weaving in a weaving mode, the warp and weft yarns are both mixed fiber bundles, the warp and weft density is 30/10 cm,the gram weight is 200g/m2。
Examples 1 to 4
The preparation process of the carbon nanotube fiber hybrid fabric of the present embodiment is specifically as follows:
(1) a film of 10cm width was drawn from a carbon nanotube array of 500 μm length and 10nm diameter, and spun into a filament with a twist of 2000tpm to obtain a carbon nanotube fiber filament.
(2) And (2) soaking the carbon nanotube fiber yarn obtained in the step (1) in a nitric acid solution with the mass concentration of 20% for treatment for 30min, and drawing the carbon nanotube fiber yarn, wherein the drawing multiple is 1.06.
(3) And (3) combining the 50 carbon nanotube fibers processed in the step (2) into a bundle of carbon nanotube fibers.
(4) Mixing the carbon nanotube fiber bundles treated in the step (3) with carbon fibers and aramid fibers by adopting a core-spun method, wherein the outer layer wrapping fibers are carbon nanotube fibers, the inner layer core yarns are the carbon fibers and the aramid fibers, the ratio of the volume of the carbon nanotube fiber bundles to the carbon fibers and the aramid fibers is 1:1:4, then weaving in a weaving mode, the warp and weft yarns are mixed fiber bundles, the density of the warp and weft yarns is 30/10 cm, and the gram weight is 200g/m2。
Examples 1 to 5
The preparation process of the carbon nanotube fiber hybrid fabric of the embodiment is specifically as follows:
(1) a film of 10cm width was drawn from a carbon nanotube array of 500 μm length and 10nm diameter, and spun into a filament with a twist of 2000tpm to obtain a carbon nanotube fiber filament.
(2) And (2) soaking the carbon nanotube fiber yarn obtained in the step (1) in a nitric acid solution with the mass concentration of 20% for treatment for 30min, and drawing the carbon nanotube fiber yarn, wherein the drawing multiple is 1.06.
(3) And (3) combining the 50 carbon nanotube fibers processed in the step (2) into a bundle of carbon nanotube fibers.
(4) Mixing the carbon nano tube fiber bundles treated in the step (3) with aramid fibers and ultra-high molecular weight polyethylene fibers by adopting a stranding method, wherein the volume of the carbon nano tube fiber bundles is equal to that of the aramid fibersThe volume ratio of aramid fiber to ultra-high molecular weight polyethylene fiber is 1:1:4, then weaving is carried out in a weaving mode, the warp and weft yarns are all mixed fiber bundles, the density of the warp and weft yarns is 30/10 cm, and the gram weight is 200g/m2。
Examples 1 to 6
The preparation process of the carbon nanotube fiber hybrid fabric of the embodiment is specifically as follows:
(1) a film of 10cm width was drawn from a carbon nanotube array of 500 μm length and 10nm diameter, and spun into a filament with a twist of 2000tpm to obtain a carbon nanotube fiber filament.
(2) And (2) soaking the carbon nanotube fiber yarn obtained in the step (1) in a nitric acid solution with the mass concentration of 20% for treatment for 30min, and drawing the carbon nanotube fiber yarn, wherein the drawing multiple is 1.06.
(3) And (3) combining the 50 carbon nanotube fibers processed in the step (2) into a bundle of carbon nanotube fibers.
(4) Mixing the carbon nanotube fiber bundles treated in the step (3) with carbon fibers and ultrahigh molecular weight polyethylene fibers by adopting a doubling method, wherein the ratio of the volume of the carbon nanotube fiber bundles to the volume of the carbon fibers and the ultrahigh molecular weight polyethylene fibers is 1:5, weaving in a weaving mode, wherein warp and weft yarns are the mixed fiber bundles, the density of the warp and weft yarns is 30/10 cm, and the gram weight is 200g/m2。
Examples 1 to 7
The preparation process of the carbon nanotube fiber hybrid fabric of the embodiment is specifically as follows:
(1) a film with the width of 10cm is pulled out from a carbon nano tube array with the length of 500 mu m and the diameter of 10nm, and the film is twisted and spun into filaments with the twist of 2000tpm to obtain the carbon nano tube fiber filaments.
(2) And (2) soaking the carbon nanotube fiber yarn obtained in the step (1) in a nitric acid solution with the mass concentration of 20% for treatment for 30min, and drawing the carbon nanotube fiber yarn, wherein the drawing multiple is 1.06.
(3) And (3) combining the 50 carbon nanotube fibers processed in the step (2) into a bundle of carbon nanotube fibers.
(4) The carbon nano treated in the step (3) is addedMixing the rice-tube fiber bundles with carbon fibers, aramid fibers and ultra-high molecular weight polyethylene fibers by a stranding method, wherein the ratio of the volume of the carbon nano-tube fiber bundles to the sum of the volumes of the carbon fibers, the aramid fibers and the ultra-high molecular weight polyethylene fibers is 1:5, weaving in a weaving mode, wherein warp and weft yarns are all mixed fiber bundles, the density of the warp and weft yarns is 30/10 cm, and the gram weight is 200g/m2。
Examples 1 to 8
The preparation process of the carbon nanotube fiber hybrid fabric of the embodiment is specifically as follows:
(1) a film having a width of 0.1cm was drawn from a carbon nanotube array having a length of 100 μm and a diameter of 6nm, and then spun into a filament by twisting at a twist of 15000tpm to obtain a carbon nanotube fiber filament.
(2) And (2) soaking the carbon nano tube fiber yarn obtained in the step (1) in a chlorosulfonic acid solution with the mass concentration of 10% for treatment for 120min, and drawing the carbon nano tube fiber yarn with the drawing multiple of 1.
(3) Combining the 100 carbon nanotube fibers treated in the step (2) into a bundle of carbon nanotube fiber.
(4) Mixing the carbon nanotube fiber bundles treated in the step (3) with aramid fibers by adopting a core-spun method, wherein the outer-layer wrapping fibers are carbon nanotube fiber bundles, the inner-layer core yarns are aramid fibers, the volume ratio of the carbon nanotube fiber bundles to the aramid fibers is 1:1, and then weaving in a weaving mode to obtain the carbon nanotube fiber hybrid fabric, the fabric weave is plain, the warp and weft density is 200 pieces/10 cm, and the gram weight is 50g/m2。
Examples 1 to 9
The preparation process of the carbon nanotube fiber hybrid fabric of the embodiment is specifically as follows:
(1) a film of 20cm width was drawn from a carbon nanotube array of 1000 μm length and 15nm diameter, and then spun into filaments with a twist of 100tpm to obtain carbon nanotube filaments.
(2) And (2) soaking the carbon nano tube fiber yarn obtained in the step (1) in a chlorosulfonic acid solution with the mass concentration of 50% for 1min, and drafting the carbon nano tube fiber yarn with the drafting multiple of 1.1.
(3) And (3) combining the 10 carbon nanotube fibers treated in the step (2) into a bundle of carbon nanotube fiber.
(4) Mixing the carbon nanotube fiber bundles treated in the step (3) with aramid fibers by adopting a core-spun method, wherein the outer-layer wrapping fibers are carbon nanotube fiber bundles, the inner-layer core yarns are aramid fibers, the volume ratio of the carbon nanotube fiber bundles to the aramid fibers is 1:10, and then weaving in a weaving mode to obtain the carbon nanotube fiber hybrid fabric, the fabric weave is plain, the warp and weft density is 20/10 cm, and the gram weight is 200g/m2。
Example 2-1 to example 2-9
The reinforced composite material of example 2-1 to example 2-9 was prepared as follows:
(1) the carbon nanotube fiber hybrid fabrics prepared in examples 1-1 to 1-9 were used.
(2) And mixing the carbon nanotube fiber hybrid fabric with epoxy resin, and preparing the reinforced composite material according to a VARTM (vacuum transfer molding) process, wherein the volume fraction of the carbon nanotube fiber hybrid fabric is 52%.
Comparative examples 1 to 1
The fabric of comparative example 1-1 was prepared as follows:
weaving carbon fibers by a weaving mode, wherein warp and weft yarns are the carbon fibers, the density of the warp and weft yarns is 30/10 cm, and the gram weight is 200g/m2。
Comparative examples 1 to 2
The fabric of comparative examples 1-2 was prepared as follows:
weaving the ultra-high molecular weight polyethylene fiber in a weaving mode, wherein the warp and weft are all the ultra-high molecular weight polyethylene fiber, the warp and weft density is 30/10 cm, and the gram weight is 200g/m2。
Comparative examples 1 to 3
The fabric of comparative examples 1-3 was prepared as follows:
the aramid fiber is woven in a weaving mode, the warp is the aramid fiber, the warp and weft are the aramid fiber, the density of the warp and the weft is 30 pieces/10 cm, and the gram weight is 200g/m2。
Comparative examples 1 to 4
The carbon nanotube fiber hybrid fabric of comparative examples 1 to 4 was prepared in a similar manner to the carbon nanotube fiber hybrid fabric of example 1 to 1, except that comparative examples 1 to 4 did not include the step (2), i.e., the carbon nanotube fiber filaments were not subjected to the acid treatment and the drawing treatment.
Comparative examples 1 to 5
The preparation process of the carbon nanotube fiber hybrid fabric of comparative examples 1 to 5 is similar to that of the carbon nanotube fiber hybrid fabric of example 1 to 1, except that the step (2) of comparative examples 1 to 5 is: and (2) soaking the carbon nano tube fiber yarn obtained in the step (1) in a nitric acid solution with the mass concentration of 100% for treatment for 30 min.
Comparative examples 1 to 6
The preparation process of the carbon nanotube fiber hybrid fabric of comparative examples 1 to 6 is similar to that of the carbon nanotube fiber hybrid fabric of example 1 to 1, except that the step (2) of comparative examples 1 to 6 is: and (2) drafting the carbon nano tube fiber yarn obtained in the step (1) with the drafting multiple of 1.2.
Comparative examples 1 to 7
The carbon nanotube fiber hybrid fabric of comparative examples 1 to 7 was prepared in a similar process to that of example 1 to 1, except that the volume ratio of the carbon nanotube fiber bundles to the aramid fiber bundles in step (4) of comparative examples 1 to 7 was 5: 1.
Comparative examples 1 to 8
The manufacturing process of the carbon nanotube fiber hybrid fabric of comparative examples 1 to 8 is similar to that of the carbon nanotube fiber hybrid fabric of example 1 to 1 except that the twist is 20000tpm in step (1) of comparative examples 1 to 8.
Comparative examples 1 to 9
The preparation process of the carbon nanotube fiber hybrid fabric of comparative examples 1 to 9 is similar to that of the carbon nanotube fiber hybrid fabric of example 1 to 1, except that the step (4) of comparative examples 1 to 9 is: weaving the carbon nano tube fiber bundles treated in the step (3) and aramid fibers in a weaving mode, wherein the warp and weft yarns are mixed fiber bundles, and the warp and weft density is 60 root/10 cm, gram weight 400g/m2。
Comparative examples 2-1 to 2-9
The reinforced composite materials of comparative examples 2-1 to 2-9 were prepared as follows:
(1) the carbon nanotube fiber hybrid fabrics of comparative examples 1-1 to 1-9 were taken, respectively.
(2) And mixing the carbon nanotube fiber hybrid fabric with epoxy resin, and preparing the reinforced composite material according to a VARTM (vacuum transfer molding) process, wherein the volume fraction of the carbon nanotube fiber hybrid fabric is 52%.
The performance data for each of the fibers used in the examples and comparative examples are shown in table 1 below.
TABLE 1 Properties of fibers used in examples and comparative examples
The impact, creep and wet heat aging resistance data of the reinforced composite materials prepared in examples 2-1 to 2-9 and comparative examples 2-1 to 2-9 are shown in Table 2. The impact property is obtained by testing according to an ASTM D7136 method, the creep strain is obtained by testing according to a GB11546-89 method, and the bending strength retention rate after 100 hours of hydrothermal treatment at 50 ℃ is obtained by testing according to an ASTM D7264 method.
TABLE 2 Properties of the reinforced composites of the examples and comparative examples
As can be seen from Table 2, the combination properties of the hybrid fabric are improved after the other high performance fibers are mixed and woven with the carbon nanotube fibers. As can be seen from the comparison between example 2-1 and comparative example 2-3, the addition of the carbon nanotube fiber improves the disadvantage of the aramid fiber that the resistance to wet heat aging is poor. As can be seen from the comparison of example 2-2 and comparative example 2-1, the addition of the carbon nanotube fiber greatly improves the impact resistance of the carbon fiber. As can be seen from the comparison of examples 2-3 and comparative examples 2-2, the addition of the carbon nanotube fiber reduces the creep strain of the ultra-high molecular weight polyethylene fiber, i.e., improves the creep resistance.
From the experimental results, it can be seen that the carbon nanotube fiber as a reinforcing fiber mixed in the high-performance fiber fabric can improve the original defects of the high-performance fiber fabric and enhance the original advantages of each fiber, so that the mixed fabric has good humidity, heat and aging resistance, good impact resistance and good creep resistance, and can be applied to the preparation of bulletproof materials.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (11)
1. A preparation method of a carbon nanotube fiber hybrid fabric is characterized by comprising the following steps:
spinning the carbon nanotube array to prepare carbon nanotube fiber yarns;
treating the carbon nano tube fiber yarn by adopting an acid solution, and drafting the carbon nano tube fiber yarn;
combining the drafted carbon nanotube fibers to prepare a carbon nanotube fiber bundle;
mixing the carbon nano tube fiber bundle with high-performance fibers by adopting a stranding method to prepare a mixed fiber bundle; mixing 1 carbon nanotube fiber bundle and 1-3 high-performance fiber bundles, wherein the volume of the 1 carbon nanotube fiber bundle is the same as that of the 1 high-performance fiber bundle;
weaving the mixed fiber bundle to prepare a carbon nano tube fiber hybrid fabric;
the square meter gram weight of the carbon nano tube fiber hybrid fabric is 50g/m2～200g/m2The warp and weft density is 20 pieces/10 cm-200 pieces/10 cm.
2. The method of claim 1, wherein the high performance fiber is at least one selected from the group consisting of aramid fiber, ultra-high molecular weight polyethylene fiber, and carbon fiber.
3. The method of claim 1, wherein the carbon nanotube fiber hybrid fabric is a woven fabric, a warp knit fabric, or a weft knit fabric.
4. The method for preparing a carbon nanotube fiber hybrid fabric according to any one of claims 1 to 3, wherein the blended yarn density of the carbon nanotube fiber hybrid fabric is 5tex to 250 tex.
5. The method for producing a carbon nanotube fiber hybrid fabric according to claim 1, wherein the carbon nanotube fiber is drawn at a draw ratio of 1 to 1.1.
6. The method for preparing the carbon nanotube fiber hybrid fabric according to any one of claims 1 to 3, wherein the step of spinning the carbon nanotube array to prepare the carbon nanotube fiber yarn comprises: and drawing a film with the width of 0.1-20 cm from the carbon nano tube array, twisting and spinning the film to prepare the carbon nano tube fiber yarn.
7. The method for preparing a carbon nanotube fiber hybrid fabric according to claim 6, wherein in the step of twisting and spinning the yarn, the twist is 100 to 15000 tpm; and/or the presence of a gas in the gas,
the length of the carbon nano tube in the carbon nano tube array is 100-1000 mu m, and the diameter is 6-15 nm.
8. The method of claim 1 or 7, wherein the step of combining the carbon nanotube fibers to produce the carbon nanotube fiber bundles comprises combining the carbon nanotube fibers in an amount of 10 to 100 pieces per bundle.
9. A carbon nanotube fiber hybrid fabric, characterized by being prepared by the method for preparing a carbon nanotube fiber hybrid fabric according to any one of claims 1 to 8.
10. A reinforced composite material, characterized in that a raw material for preparing the reinforced composite material comprises the carbon nanotube fiber hybrid fabric of claim 9.
11. The reinforced composite of claim 10, wherein the raw material from which the reinforced composite is made further comprises a resin matrix, wherein the volume fraction of the carbon nanotube fiber hybrid fabric in the raw material is 50% to 55%.
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