CN119241093A - Preparation method for catalytic layer used to grow carbon nanotubes on glass fiber surface - Google Patents
Preparation method for catalytic layer used to grow carbon nanotubes on glass fiber surface Download PDFInfo
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C01B32/162—Preparation characterised by catalysts
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/66—Chemical treatment, e.g. leaching, acid or alkali treatment
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Abstract
本发明是关于一种用于在玻璃纤维表面生长碳纳米管的催化层的制备方法，包括以下步骤：化学自组装前驱体层制备：将二价镍盐溶于去离子水中，得到混合溶液，给混合溶液中加入有机铵盐，再调节pH为弱碱性，得到自组装络合溶液，将自组装络合溶液涂敷到玻璃纤维表面，得到涂覆有自组装前驱层的玻璃纤维；紧密催化层制备：给涂覆有自组装前驱层的玻璃纤维中加入过氧化氢，产生芬顿反应，去除化学自组装前驱体层中的有机成分，得到表面涂敷催化层的玻璃纤维。本发明的制备流程简易，工艺流程较短，适合低成本连续化生产；制备的催化层对原位生长的各类型碳纳米管具有较高兼容度，实现较高密度的碳纳米管生长，且依附强度高。The present invention relates to a method for preparing a catalytic layer for growing carbon nanotubes on the surface of glass fiber, comprising the following steps: preparation of a chemical self-assembly precursor layer: dissolving a divalent nickel salt in deionized water to obtain a mixed solution, adding an organic ammonium salt to the mixed solution, adjusting the pH to be weakly alkaline, obtaining a self-assembly complex solution, applying the self-assembly complex solution to the surface of the glass fiber, and obtaining a glass fiber coated with a self-assembly precursor layer; preparation of a compact catalytic layer: adding hydrogen peroxide to the glass fiber coated with the self-assembly precursor layer to generate a Fenton reaction, removing the organic components in the chemical self-assembly precursor layer, and obtaining a glass fiber coated with a catalytic layer on the surface. The preparation process of the present invention is simple, the process flow is short, and it is suitable for low-cost continuous production; the prepared catalytic layer has a high compatibility with various types of carbon nanotubes grown in situ, realizes the growth of carbon nanotubes with a high density, and has a high attachment strength.
Description
Technical Field
The invention relates to the field of carbon nanotube modified glass fibers, in particular to a preparation method of a catalytic layer for growing carbon nanotubes on the surface of a glass fiber.
Background
Glass Fiber (GF) is an inorganic nonmetallic material widely used, has high insulativity, high heat resistance and good mechanical strength, is commonly used for manufacturing various composite materials, but has the problems of single function, poor interface compatibility of the composite materials and the like. Carbon Nanotubes (CNT) are a novel carbon material possessing unique physical, chemical and mechanical properties that are considered to be good functional modifiers for conventional fiber materials. Research shows that the carbon nanotube and the glass fiber are compounded, so that the mechanical property of the glass fiber can be obviously improved, and the electromagnetic functionality of the glass fiber is endowed. However, the traditional mechanical mixing or physical adsorption and other modes can only obtain very limited performance improvement, and only the carbon nano tube is grown on the surface of the glass fiber in situ, so that the glass fiber can play a good functional modification role.
The key point of the preparation of the in-situ grown carbon nanotube modified glass fiber is the design of a catalytic layer on the surface of the glass fiber, generally, the closer the catalytic layer is combined with the glass fiber, the better the grown carbon nanotube has the better the adhesion, and the greater the performance improvement on the glass fiber is. The preparation method of the prior carbon nano tube modified glass fiber comprises the following steps:
Floating chemical vapor process, in which a catalyst precursor is introduced into a reaction chamber, vaporized and suspended in a gas phase, and the catalyst interacts with a carbon-containing gas to deposit carbon nanotubes on a glass fiber substrate. The catalyst particles are free floating in the reaction chamber, which is advantageous for isotropic carbon nanotube growth. The carbon nano tube grown by the floating catalyst method is relatively controllable, and can also obtain higher content, but only intermolecular van der Waals force effect exists between the carbon nano tube and the glass fiber, so that the carbon nano tube is easily separated from the surface of the glass fiber, and the method is not suitable for batch products.
The chemical grafting method for growing carbon nanotube includes surface oxidation, sulfuric acid treatment, plasma treatment and other steps to form functional base with active group on the surface of glass fiber, and chemical combination to combine glass fiber with carbon nanotube with functional group, so as to obtain carbon nanotube modified glass fiber. The chemical grafting method for growing the carbon nano-tube has high requirements on the substrate, the functional group density of the substrate determines the growth density of the carbon nano-tube, but the preparation of the highly functionalized glass fiber is extremely difficult, and the functional group utilization efficiency is not high. The method can only realize the growth of the carbon nano tube with lower density, and the content of the carbon nano tube is not more than 5 weight percent.
At present, the main preparation methods of the catalytic layer are realized on the basis of simple dipping or chemical deposition physical coating modes, and the problems of low compactness, lower attaching strength, high cost, complex flow and the like of the catalytic layer exist, so that mass production is difficult to realize.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a catalytic layer for growing carbon nanotubes on the surface of glass fiber, which can realize the growth of carbon nanotubes with higher density and has high attachment strength.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a catalytic layer for growing carbon nanotubes on the surface of glass fibers, comprising the steps of:
preparing a chemical self-assembly precursor layer:
Dissolving divalent nickel salt in deionized water to obtain a mixed solution, adding organic ammonium salt into the mixed solution, adjusting the pH value to be weak alkaline to obtain a self-assembly complexing solution, and coating the self-assembly complexing solution on the surface of the glass fiber to obtain the glass fiber coated with the self-assembly precursor layer;
Preparation of a compact catalytic layer:
and adding hydrogen peroxide solution into the glass fiber coated with the self-assembly precursor layer to generate Fenton reaction, and removing organic components in the chemical self-assembly precursor layer to obtain the glass fiber with the surface coated with the catalytic layer.
The concentration of the divalent nickel salt in deionized water is 0.02-0.2mol/L, and the ratio of the organic ammonium salt to the nickel salt is 4:1.
Further, in the compact catalytic layer on the surface of the glass fiber, at least one element of Zn, mn, fe, cu, co, si and Al is also included, and each element is in its corresponding oxidation state, exists in the form of Fe 2+、Fe3+、Cu2+、Ni2+、Co2+、Co3+、Al3+, or is reduced to the form of simple substance by reducing gas;
the mixed solution contains Zn, mn, fe, cu, co and a metal salt solution of at least one element of Al;
When the dense catalyst layer contains Si element, the glass fiber coated with the self-assembled precursor layer is recoated with a methyl siloxane ethanol solution having a concentration of 50-60 wt%.
The concentration of the metal salt solution is 0.01-0.1mol/L.
The metal salt solution is nitrate solution, sulfate solution or chloride solution;
The concentration of the hydrogen peroxide solution is 1wt% to 30wt%.
The nickel salt is nickel (II) nitrate, nickel (II) chloride, nickel (II) sulfate or nickel (II) acetate.
The organic ammonium salt is ammonium oxalate, ammonium acetate, ammonium acrylate, ammonium citrate, ammonium benzoate, ammonium tartrate or cetyl trimethyl ammonium bromide;
The pH-adjusting solution is ammonia water, the concentration of the ammonia water is 28-32wt%, and the pH is 8-9;
The glass fiber is alkali-free glass fiber, S-glass fiber, quartz fiber or high silica fiber.
The first preset time for the glass fiber to stay in the self-assembly complexing solution is 60-180s;
the application of the self-assembling complexing solution to the surface of the glass fiber includes application in the following chemically self-assembled form:
the method of spool traction is adopted, and glass fiber passes through a self-assembled complexing solution tank at a constant speed of 1-3m/min for a first preset time;
or placing the chopped glass fibers in a filter screen, directly immersing the chopped glass fibers in a self-assembly complexing solution tank, and taking out the chopped glass fibers after staying for a first preset time;
Drying the glass fiber coated with the self-assembly complexing solution for 10-15min at the temperature of 40-80 ℃ under hot air to obtain the glass fiber coated with the self-assembly precursor layer;
When the dense catalyst layer contains Si element, the glass fiber coated with the self-assembled precursor layer is coated with methyl siloxane ethanol solution with the concentration of 50-60wt% in the same way as the self-assembled complexing solution is coated on the surface of the glass fiber;
the glass fiber coated with the self-assembled precursor layer stays in the methyl siloxane ethanol solution for 30-60s.
The second preset time for the glass fiber coated with the self-assembled precursor layer to stay in the hydrogen peroxide solution is 120-180 s;
the adding hydrogen peroxide to the glass fiber coated with the self-assembled precursor layer comprises the following coating methods:
the method of spool traction is adopted, and the glass fiber coated with the self-assembled precursor layer passes through a hydrogen peroxide solution tank at a constant speed of 1-3m/min for a second preset time;
Or placing the chopped glass fiber coated with the self-assembled precursor layer in a filter screen, directly immersing the glass fiber in hydrogen peroxide solution, and taking out the glass fiber after staying for a second preset time;
and (3) drying the glass fiber subjected to Fenton reaction for 10-15min under the hot air at the temperature of 40-80 ℃ to obtain the glass fiber with the catalytic layer coated on the surface.
The invention also provides a preparation method of the in-situ grown carbon nanotube modified glass fiber, the catalytic layer is prepared according to the preparation method, and then the carbon nanotubes are grown on the surface of the catalytic layer in situ to obtain the in-situ grown carbon nanotube modified glass fiber.
The method for in-situ growth of the carbon nano tube is a chemical vapor deposition method, a flame synthesis method, an arc discharge method or a high-pressure carbon monoxide synthesis method, and the content of the carbon nano tube is 0.5-40wt%.
By means of the technical scheme, the invention has at least the following advantages:
1. The invention provides a method for arranging a compact catalytic layer on the surface of glass fiber, which is used for in-situ growth of carbon nanotubes on the surface of glass fiber, has simple preparation flow and shorter process flow, does not involve complex treatment means such as high pressure, vacuum, coating and the like, and is suitable for low-cost continuous production;
2. the catalytic layer has higher compatibility to various carbon nanotubes grown in situ and has the characteristic of high customization, and the carbon nanotube modified glass fiber prepared by the method has the carbon nanotube content of 0.1-40 wt%, preferably 0.5-40 wt% and realizes the growth of the carbon nanotubes with higher density;
3. The compact catalytic layer can provide good protection for the original glass fiber, the in-situ grown carbon nano tube on the surface of the glass fiber can not damage the fiber substrate, and the compact catalytic layer has high adhesion and can effectively enhance the mechanical property of the glass fiber.
4. According to the invention, at least one element of Zn, mn, fe, cu, co, si and Al is added into the catalytic layer generated on the surface of the glass fiber, so that the catalytic effect of the Ni-based catalytic layer is improved, the catalyst and the substrate are properly isolated, and the glass fiber substrate is protected from being damaged by the subsequent process.
The foregoing description is only an overview of the present invention, and is intended to provide a better understanding of the present invention, as it is embodied in the following description, with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
FIG. 1 is a SEM image of an in situ grown high silica fiber having a carbon nanotube content of 10wt% provided in example 1 of the present invention;
FIG. 2 is a SEM image of an alkali-free glass fiber grown in situ with a carbon nanotube content of 30wt% as provided in example 3 of the present invention;
FIG. 3 is a SEM image of an in situ grown S-glass fiber having a carbon nanotube content of 40wt% provided in example 4 of the present invention;
FIG. 4 is a SEM image of a high silica fiber grown in situ with a carbon nanotube content of 10wt% as provided in the comparative example of the present invention.
Detailed Description
In order to further describe the technical means and effects adopted for achieving the preset aim of the invention, the following detailed description refers to the specific implementation, structure, characteristics and effects of the invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "an embodiment" or "an embodiment" do not necessarily refer to the same embodiment. Furthermore, the particular features, structures, or characteristics of one or more embodiments may be combined in any suitable manner.
The invention provides a preparation method of a compact catalytic layer for carbon nanotube growth on the surface of glass fiber, which comprises the following two steps of:
preparing a chemical self-assembly precursor layer:
The proper amount of divalent nickel salt is dissolved in deionized water, the nickel salt can be any salt with proper solubility, such as nickel (II) nitrate, nickel (II) chloride, nickel (II) sulfate, nickel (II) acetate and the like, after the dissolution is completed, proper amount of organic ammonium salt is added according to a specific proportion, and the organic ammonium salt can also be any salt with proper solubility, such as ammonium oxalate, ammonium acetate, ammonium acrylate, ammonium citrate, ammonium benzoate, ammonium tartrate, hexadecyl trimethyl ammonium bromide (CTAB) and the like, and the pH is adjusted to be weak alkaline, and Ni (II) can form coordination with free NH 3 in the solution. NH 3 also bonds with the exposed free hydroxyl groups on the glass fiber surface by hydrogen bonding, so Ni (II) can bridge via NH 3 and be applied to the glass fiber surface in a chemically self-assembled form to form a precursor layer.
Preparation of a compact catalytic layer:
And then adding a proper amount of hydrogen peroxide (H 2O2) solution into the glass fiber for forming the precursor layer to generate Fenton reaction, removing organic components in the precursor, thoroughly anchoring the catalytic metal on the surface of the fiber, and finishing the step of coating the catalytic layer on the surface of the glass fiber. One or two elements Zn, mn, fe, cu, co, si, al can be additionally added into the catalytic layer generated on the surface of the glass fiber, so as to improve the catalytic effect of the Ni-based catalytic layer, properly isolate the catalyst from the glass fiber substrate and protect the glass fiber substrate from being damaged by the subsequent process. Before the in-situ growth of the carbon nanotubes, each metal element in the catalytic layer on the surface of the glass fiber may be in its corresponding oxidation state, for example, in the form of Fe 2+、Fe3+、Cu2+、Ni2+、Co2+、Co3+、Al3+, or may be reduced to a simple substance form by using a reducing gas (for example, a hydrogen-argon mixture). The catalytic layer may be applied off-line (i.e., intermittently) to the chopped fibers, or on-line (i.e., by spool pulling) to the continuous glass fibers by a specific conveyor.
The substrate to which the invention relates may be various glass fibers currently commercially available, such as alkali-free glass fibers, S-glass fibers, quartz fibers, silica-rich fibers, and the like.
The in situ grown carbon nanotubes produced by the present invention may be formed by various conventional methods such as thermal/plasma enhanced chemical vapor deposition, flame synthesis, arc discharge, high pressure carbon monoxide synthesis, etc., without limitation. However, in practice, the present invention preferably uses chemical vapor deposition because it is easier to control the in situ carbon nanotube growth process.
The invention is further illustrated by the following examples:
Example 1:
a method for disposing a FeNi catalytic layer on the surface of high silica fiber and using the method for growing 10wt% carbon nano tube in situ.
Adding 14.5g of nickel nitrate hexahydrate (Ni (NO 3)2·6H2 O) and 12.1g of ferric nitrate nonahydrate (Fe (NO 3)3·9H2 O)) into 1000mL of deionized water until the nickel nitrate is dissolved into a transparent solution with the concentration of 0.05mol/L and the concentration of 0.03mol/L, adding 72.9g of cetyltrimethylammonium bromide (CTAB) into the transparent solution until the nickel nitrate is thoroughly dissolved, and adding an appropriate amount of ammonia water with the concentration of 32wt% into the solution until the pH value of the solution is adjusted to 8.5 to obtain a self-assembled complexing solution.
The high silica fiber is left in the self-assembled complexing solution for 90s in a proper way, and the complexing component in the self-assembled complexing solution is introduced into the fiber surface in a self-assembly method:
The continuous high silica fiber is drawn by a spool, passes through a self-assembled complexing solution tank with the length of 4.5m at a constant speed of 3m/min for 90s, is placed in a filter screen, is directly immersed in the self-assembled complexing solution tank, and is taken out after being stopped for 90 s.
And then drying the high silica fiber coated with the self-assembly complexing solution for 10min under the hot air at 60 ℃ to obtain the high silica fiber coated with the self-assembly precursor layer.
The high silica fiber coated with the self-assembled precursor layer is left in a proper mode in 10wt% hydrogen peroxide solution for 180s to generate Fenton reaction, organic components in the precursor are removed, catalytic metal is thoroughly anchored on the surface of the glass fiber, and the step of coating the catalytic layer on the surface of the high silica fiber is completed comprises the following steps:
the continuous high silica fiber is drawn by a spool, and passes through a hydrogen peroxide solution tank with the length of 4.5m at a constant speed of 1.5m/min for 180s, and the chopped high silica fiber is placed in a filter screen, directly immersed in the hydrogen peroxide solution tank, and is taken out after being left for 180 s.
And drying the high silica fiber subjected to Fenton reaction for 10min under the hot air at 60 ℃ to obtain the high silica fiber with the compact catalytic layer.
The compact catalytic layer obtained by the method mainly comprises Ni and Fe metal oxides, the atomic ratio of Ni to Fe is 1:1, and a chemical vapor deposition method is adopted to grow carbon nano tubes with the content of 10wt% on the compact catalytic layer in situ.
As shown in fig. 1, from SEM images of high silica fibers grown in situ with a carbon nanotube content of 10wt%, a catalytic layer sufficient to support the carbon nanotubes with a content of 10wt% was produced on the surface of the high silica fibers after the high silica fibers were treated by the method of this example.
Example 2:
A method for arranging a NiCo catalytic layer on the surface of quartz fiber and adding an Al 2O3 protective agent is used for growing 5wt% carbon nano tubes in situ.
18.9G of nickel chloride hexahydrate (NiCl 2·6H2 O), 14.6g of cobalt nitrate hexahydrate (Co (NO 3)2·6H2 O) and 3.42g of aluminum sulfate (Al 2(SO4)3) are added into 1000mL of deionized water until the solution is dissolved into a transparent solution with the concentration of nickel chloride of 0.08mol/L, the concentration of cobalt nitrate of 0.05mol/L and the concentration of aluminum sulfate of 0.01mol/L, 77.6g of ammonium citrate is added into the transparent solution until the solution is completely dissolved, and an appropriate amount of 30wt% ammonia water is added into the solution until the pH value of the solution is adjusted to 8, so that a self-assembled complexing solution is obtained.
The quartz fiber is kept in a self-assembled complexing solution for 60s in a proper mode, and complexing components in the self-assembled complexing solution are introduced to the fiber surface in a self-assembled mode:
The continuous quartz fiber is drawn by a spool, passes through a self-assembled complexing solution tank with the length of 3m at a constant speed of 3m/min for 60s, is placed in a filter screen, is directly immersed in the self-assembled complexing solution tank, and is taken out after being left for 60 s.
And then drying the quartz fiber coated with the self-assembly complexing solution for 12min under the hot air at 40 ℃ to obtain the quartz fiber coated with the self-assembly precursor layer.
The quartz fiber coated with the self-assembled precursor layer is left in a proper mode in 5wt% hydrogen peroxide solution for 120s to generate Fenton reaction, organic components in the precursor are removed, catalytic metal is thoroughly anchored on the surface of the fiber, and the step of coating the catalytic layer on the surface of the quartz fiber is completed comprises the following steps:
the continuous quartz fiber is drawn by a spool, passes through a hydrogen peroxide solution tank with the length of 6m at a constant speed of 3m/min for 120s, is placed in a filter screen, is directly immersed in the hydrogen oxide solution tank, stays for 120s and is taken out.
And drying the quartz fiber subjected to Fenton reaction treatment for 12min under the hot air at 60 ℃ to obtain the quartz fiber with the compact catalytic layer.
The compact catalytic layer obtained by the method mainly comprises metal oxides of Ni, co and Al, wherein the atomic ratio of Ni, co and Al is 1:1:1, the Ni and Co are catalytic components, and the Al is a protective component. And (3) in-situ growing the carbon nano tube with the content of 5wt% on the compact catalytic layer by adopting a high-pressure carbon monoxide synthesis method.
Example 3:
A method for arranging a FeNiCo catalytic layer on the surface of alkali-free glass fiber and adding a Si-based protective agent is used for growing 30wt% of carbon nanotubes in situ.
Adding 14.5g of nickel nitrate hexahydrate (Ni (NO 3)2·6H2 O), 4.74g of cobalt chloride hexahydrate (CoCl 2·6H2 O) and 24.4g of ferric nitrate nonahydrate (Fe (NO 3)3·9H2 O) into 1000mL of deionized water until the nickel nitrate is dissolved into a transparent solution with the concentration of 0.05mol/L, the cobalt chloride is dissolved into the solution with the concentration of 0.02mol/L and the ferric nitrate is dissolved into the solution with the concentration of 0.06mol/L, adding 17.8g of ammonium acrylate into the transparent solution until the ammonium acrylate is thoroughly dissolved, adding an appropriate amount of 28wt% ammonia water into the solution until the pH value of the solution is adjusted to 9, and obtaining the self-assembled complexing solution.
The alkali-free glass fiber is left in the self-assembled complexing solution for 120s in a proper mode, and the complexing component in the self-assembled complexing solution is introduced to the fiber surface in a self-assembly method:
The continuous alkali-free glass fiber is drawn by a spool, passes through a self-assembled complexing solution tank with the length of 3m at a constant speed of 2m/min for 120s, is placed in a filter screen, is directly immersed in the self-assembled complexing solution tank, and is taken out after staying for 120 s.
And then drying the alkali-free glass fiber coated with the self-assembly complexing solution under the hot air at 60 ℃ for 10min, staying the alkali-free glass fiber in the methyl siloxane ethanol solution with the concentration of 50wt% for 30s in the same way, and drying the alkali-free glass fiber under the hot air at 50 ℃ for 12.5min again, thus obtaining the alkali-free glass fiber coated with the self-assembly precursor layer after drying.
The alkali-free glass fiber coated with the self-assembled precursor layer is left in a proper mode in a hydrogen peroxide solution with 20wt percent for 120s to generate Fenton reaction, organic components in the precursor are removed, catalytic metal is thoroughly anchored on the surface of the fiber, and the step of coating the catalytic layer on the surface of the alkali-free glass fiber is completed comprises the following steps:
The continuous alkali-free glass fiber is drawn by a spool, passes through a hydrogen peroxide solution tank with the length of 4m at a constant speed of 2m/min for 120s, is placed in a filter screen, is directly immersed in the hydrogen peroxide solution tank, and is taken out after staying for 120 s.
And (3) drying the alkali-free glass fiber subjected to Fenton reaction in hot air at 60 ℃ for 12.5min, and then placing the alkali-free glass fiber in hydrogen-argon mixed gas with the hydrogen volume content of 5% for annealing at 400 ℃ for 10min to obtain the alkali-free glass fiber with the compact catalytic layer.
The compact catalytic layer obtained by the method has the main components of simple metals of Ni, co and Fe and contains SiO 2 protecting components, and the atomic ratio of Ni to Co to Fe is 5:2:6. And (3) adopting a chemical vapor deposition method to grow the carbon nano tube with the content of 30 weight percent on the compact catalytic layer in situ.
As shown in fig. 2, from SEM images of alkali-free glass fibers grown in situ with a carbon nanotube content of 30wt%, it can be seen that a catalytic layer sufficient to support carbon nanotubes with a carbon nanotube content of 30wt% can be produced on the surface of the alkali-free glass fibers after the alkali-free glass fibers are treated by the method of this example.
Example 4:
A method for arranging a FeNiCo catalytic layer on the surface of S-glass fiber and adding a Si-based protective agent is used for growing 40wt% of carbon nano tubes in situ.
52.7G of nickel sulfate hexahydrate (NiSO 4·6H2 O), 5.26g of cobalt sulfate hexahydrate (Co (NO 3)2·6H2 O) and 40.3g of ferric nitrate nonahydrate (Fe (NO 3)3·9H2 O) are added into 1000mL of deionized water until the nickel nitrate is dissolved into a transparent solution with the concentration of 0.2mol/L, the cobalt chloride is dissolved into the solution with the concentration of 0.02mol/L and the ferric nitrate is dissolved into the solution with the concentration of 0.1mol/L, 99.2g of ammonium oxalate monohydrate ((NH 4)2C2O4·H2 O) is added into the transparent solution until the solution is thoroughly dissolved, a proper amount of ammonia water with the concentration of 32wt% is added into the solution until the pH of the solution is adjusted to 8.5, and a self-assembled complexing solution is obtained.
The S-glass fiber is kept in a self-assembled complexing solution for 180S in a proper mode, and complexing components in the self-assembled complexing solution are introduced to the surface of the fiber in a self-assembly method:
the continuous S-glass fiber is drawn by a spool, passes through a self-assembled complexing solution tank with the length of 3m at a constant speed of 1m/min for 180S, is placed in a filter screen, is directly immersed in the self-assembled complexing solution tank, and is taken out after being stopped for 180S.
And then drying the S-glass fiber coated with the self-assembly complexing solution for 15min under 70 ℃ hot air, staying the S-glass fiber in 55wt% methyl siloxane ethanol solution for 60S in the same way, and drying the S-glass fiber again under 80 ℃ hot air for 10min, thereby obtaining the S-glass fiber coated with the self-assembly precursor layer.
The S-glass fiber coated with the self-assembled precursor layer is left in a proper mode in 30wt% hydrogen peroxide solution for 180S to generate Fenton reaction, organic components in the precursor are removed, catalytic metal is thoroughly anchored on the surface of the fiber, and the step of coating the catalytic layer on the surface of the S-glass fiber is completed comprises the following steps:
The continuous S-glass fiber is drawn by a spool, passes through a hydrogen peroxide solution tank with the length of 3m at a constant speed of 1m/min for 180S, is placed in a filter screen, is directly immersed in the hydrogen peroxide solution tank, and is taken out after being left for 180S.
And (3) drying the S-glass fiber subjected to Fenton reaction in hot air at 70 ℃ for 15min, and then placing the S-glass fiber in hydrogen-argon mixed gas with the hydrogen volume content of 10% for annealing at 450 ℃ for 15min to obtain the S-glass fiber with the compact catalytic layer.
The compact catalytic layer obtained by the method has the main components of simple metals of Ni, co and Fe and contains SiO 2 protecting components, and the atomic ratio of Ni, co and Fe is 15:2:6. And (3) growing carbon nano tubes with the content of 40wt% on the compact catalytic layer in situ by adopting an arc discharge method.
As shown in FIG. 3, from an SEM image of an in-situ grown S-glass fiber having a carbon nanotube content of 40wt%, a catalytic layer sufficient to support the carbon nanotube content of 40wt% was produced on the surface of the S-glass fiber after the S-glass fiber was treated by the method of this example.
Example 5:
A Ni catalytic layer is arranged on the surface of the S-glass fiber and used for in-situ growth of 0.5wt% carbon nano-tubes.
Adding 5.8g of nickel nitrate hexahydrate (Ni (NO 3)2·6H2 O)) into 1000mL of deionized water until the nickel nitrate is dissolved into a transparent solution with the concentration of 0.02mol/L, adding 11.4g of ammonium oxalate monohydrate ((NH 4)2C2O4·H2 O)) into the transparent solution until the nickel nitrate is thoroughly dissolved, adding an appropriate amount of ammonia water with the concentration of 32wt% into the solution until the pH value of the solution is adjusted to 8.5, and obtaining a self-assembled complexing solution.
The S-glass fiber is left in the self-assembled complexing solution for 60S in a proper mode, and the complexing component in the self-assembled complexing solution is introduced into the fiber surface in a self-assembly method:
The continuous S-glass fiber is drawn by a spool, passes through a self-assembled complexing solution tank with the length of 3m at a constant speed of 3m/min for 60S, is placed in a filter screen, is directly immersed in the self-assembled complexing solution tank, and is taken out after being stopped for 60S.
And then drying the S-glass fiber coated with the self-assembly complexing solution for 10min under the hot air at 60 ℃, and obtaining the S-glass fiber coated with the self-assembly precursor layer after drying.
The S-glass fiber coated with the self-assembled precursor layer is left in a proper mode in a 1wt% hydrogen peroxide solution for 120S to generate Fenton reaction, organic components in the precursor are removed, catalytic metal is thoroughly anchored on the surface of the fiber, and the step of coating the catalytic layer on the surface of the S-glass fiber is completed comprises the following steps:
The continuous S-glass fiber is drawn by a spool, passes through a hydrogen peroxide solution tank with the length of 3m at a constant speed of 3m/min for 60S, is placed in a filter screen, is directly immersed in the hydrogen peroxide solution tank, and is taken out after being left for 60S.
And (3) drying the S-glass fiber subjected to Fenton reaction in hot air at 60 ℃ for 10min, and then placing the S-glass fiber in hydrogen-argon mixed gas with the hydrogen volume content of 10% and annealing the S-glass fiber at 450 ℃ for 15min to obtain the S-glass fiber with the compact catalytic layer.
The compact catalytic layer obtained by the method has the main component of metal simple substance of Ni, and carbon nano tubes with the content of 0.5 weight percent are grown on the compact catalytic layer in situ by adopting a high-pressure carbon monoxide method.
Comparative example 1:
a method for disposing a FeNi catalytic layer on the surface of high silica fiber and using the method for growing 10wt% carbon nano tube in situ.
In this example, no organic ammonium salt was added and no Fenton reaction treatment was performed, and the rest of the conditions were the same as in example 1, except that a FeNi catalyst layer was provided on the surface of the high silica fiber by a simple dipping method and used for in-situ growth of 10wt% carbon nanotubes. The specific method comprises the following steps:
14.5g of nickel nitrate hexahydrate (Ni (NO 3)2·6H2 O) and 12.1g of ferric nitrate nonahydrate (Fe (NO 3)3·9H2 O)) are added into 1000mL of deionized water until the nickel nitrate is dissolved into a transparent solution with the concentration of 0.05mol/L and the concentration of 0.03mol/L, so as to obtain an impregnating solution.
The high silica fibers were left in the impregnation solution in the proper manner for 90s, and the precursor components in the impregnation solution were introduced into the fiber surface:
The continuous high silica fiber is drawn by a spool, and passes through a dipping solution tank with the length of 4.5m at a constant speed of 3m/min for 90s, and the chopped high silica fiber is placed in a filter screen, directly immersed in the dipping solution, and taken out after being left for 90 s.
And then drying the high silica fiber coated with the impregnating solution for 10min under the hot air at 60 ℃ to obtain the high silica fiber coated with the impregnating precursor layer.
The main components of the dipping precursor layer obtained by the method are Ni and Fe metal oxides, the atomic ratio of Ni to Fe is 1:1, and a chemical vapor deposition method is adopted to grow carbon nano tubes with the content of 10wt% on the dipping precursor layer in situ.
As shown in fig. 4, as can be seen from SEM images of high silica fibers with 10wt% of carbon nanotubes grown in situ on the impregnated precursor layer, the method of the present invention, which is a self-assembly method for coating a catalyst layer on the surface of glass fibers and directly growing carbon nanotubes on the catalyst layer, has significant advantages, compared to the high silica fibers treated by adding an organic ammonium salt and a fenton reaction using a self-assembly complexing solution, in which the carbon nanotubes grown in situ on the surface have significant agglomeration and exfoliation phenomena, indicating that the adhesion of the carbon nanotubes based on the impregnated precursor layer is much weaker than that of the compact precursor layer according to the present invention.
The method has good universality on various glass fiber substrates, and can prepare a series of carbon nanotube modified glass fibers with the carbon nanotube content of 0.1-40 wt%.
The present invention is not limited to the preferred embodiments, and the present invention is described above in any way, but is not limited to the preferred embodiments, and any person skilled in the art will appreciate that the present invention is not limited to the embodiments described above, while the above disclosure is directed to various equivalent embodiments, which are capable of being modified or varied in several ways, it is apparent to those skilled in the art that many modifications, variations and adaptations of the embodiments described above are possible in light of the above teachings.
Claims (10)
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