CN103015165A - Novel carbon fiber with spiral structure and preparation method thereof - Google Patents
Novel carbon fiber with spiral structure and preparation method thereof Download PDFInfo
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- CN103015165A CN103015165A CN2012105130619A CN201210513061A CN103015165A CN 103015165 A CN103015165 A CN 103015165A CN 2012105130619 A CN2012105130619 A CN 2012105130619A CN 201210513061 A CN201210513061 A CN 201210513061A CN 103015165 A CN103015165 A CN 103015165A
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Abstract
The invention discloses a novel carbon fiber with a spiral structure and a preparation method of the novel carbon fiber. The carbon fiber comprises a straight carbon fiber and a spiral carbon fiber, wherein the spiral carbon fiber is grown on the surface of the straight carbon fiber. The preparation method of the novel carbon fiber comprises the following steps of: (1) preparing an aqueous solution, wherein the total molar concentration of metal ions of the aqueous solution is 0.05-0.25 mol/L; (2) impregnating the carbon fiber in the aqueous solution prepared in the step (1); (3) calcinating the carbon fiber treated in the step (2) for 1-2 hours in a nitrogen or inert atmosphere at the temperature of 350-450 DEG C, and then introducing in hydrogen into the nitrogen or inert atmosphere to carry out reduction on the carbon fiber for 0.5-2 hours at the temperature of 450-550 DEG C; and (4) heating the carbon fiber treated in the step (3) to 620-750 DEG C, and feeding acetylene gas into the nitrogen or inert atmosphere to carry out reaction for 45-120 min at the pressure of 2-110 KPa, thereby obtaining a combination with a spiral carbon fiber grown on the surface of a straight carbon fiber. The carbon fiber with the spiral structure disclosed by the invention not only can improve the mechanical properties of a composite material, but also can endow the composite material with special functions. The method disclosed by the invention is advantageous to the large-scale preparation of spiral carbon fibers; and the method is simple in preparation process, easy to control, and low in cost.
Description
Technical field
The present invention relates to a kind of novel carbon fiber with helical structure and preparation method thereof.
Background technology
Coiled carbon fibers refers to have the carbon fiber of regular helix coil or torsion structure.According to the size in spiral shell footpath, it can be divided into the spiral shell footpath in micron-sized little coiled carbon fibers and spiral shell footpath at nano level spiral carbon nano-fiber.Coiled carbon fibers not only possesses the excellent performance similar to carbon nano-fiber, its distinctive helical structure is also given the characteristics such as its good elasticity, unique electromagnetism and living things catalysis, and there is potential application foreground in the fields such as catalysis, the quick material of intelligence, Microwave Absorbing Materials, high-performance and multifunctional composite of levying at miniature instrument, hand.Yet the industrial applications of present coiled carbon fibers also exist be difficult to a large amount of preparations, when preparation poor controllability and coiled carbon fibers add in the composite technological deficiency problems such as very easily reunion to.
Summary of the invention
The purpose of this invention is to provide a kind of novel carbon fiber with helical structure that can not reunite can avoid in adding composite to the time.
In order to achieve the above object, novel carbon fiber with helical structure of the present invention comprises straight carbon fiber and coiled carbon fibers, and described coiled carbon fibers is grown in straight carbon fiber surface.
Another object of the present invention provides above-mentioned novel preparation method with helical structure carbon fiber.
In order to reach this purpose, method of the present invention may further comprise the steps:
(1) preparing metal ion total mol concentration is the aqueous solution of 0.05～0.25 mol/L, at least contain in Fe, Co, the Ni metal ion one or more in this aqueous solution, follow dissolved urea in this aqueous solution, and stir, the urea molar weight is each metal cation molal quantity and its valence state sum of products 1～1.5 times in the aqueous solution;
(2) with impregnated carbon fiber in the solution that step (1) is prepared, then it is placed together closed container 120～140 ℃ of fully reactions, after its cooling, dry in the shade;
(3) carbon fiber after step (2) is processed in 350～450 ℃ of calcinings 1～2 hour, then passes into hydrogen in 450～550 ℃ of reduction 0.5～2 hour in nitrogen or inert atmosphere, obtains the carbon fiber that the surface is loaded with metal catalyst particles;
(4) carbon fiber after step (3) processing being warmed up to 620～750 ℃, passing into acetylene gas, is 2～110 KPa at pressure, reacts 45～120 min, obtains having in straight carbon fiber surface growth the combination of coiled carbon fibers.
As improvement of the present invention, the mist that passes into acetylene and hydrogen in above-mentioned steps (4) replaces the acetylene gas that passes into, and wherein the volume ratio of acetylene and hydrogen is 1 ﹕, 4～5 ﹕ 1;
As another improvement of the present invention, the mist that passes into acetylene and nitrogen in above-mentioned steps (4) replaces the acetylene gas that passes into, and wherein the volume ratio of acetylene and nitrogen is 1 ﹕, 4～5 ﹕ 1;
As another improvement of the present invention, the mist that passes into acetylene, hydrogen, nitrogen in above-mentioned steps (4) replaces the acetylene gas that passes into, and wherein the volume ratio of acetylene, hydrogen, nitrogen is respectively (1～20) ﹕, 4 ﹕ 4;
As improvement of the present invention, the metal ion in the described step (1) also contains one or more in Al ion, Cu ion, the Sn ion.
Carbon fiber with helical structure of the present invention, because coiled carbon fibers has special good mechanical property and special electromagnetic property, the combination of straight carbon fiber and coiled carbon fibers is used for reinforced composite, can avoid occur reuniting, the mechanical property that not only can improve composite can also be given the special function of composite (such as the electro-magnetic wave absorption performance etc.).The catalyst-loaded rear growth substrate as coiled carbon fibers of carbon fiber surface be conducive to a large amount of preparations of coiled carbon fibers, and preparation technology is simple, and control is with low cost easily.
Preparation method of the present invention is by being carried in composition, size and the pattern of the catalyst granules of carbon fiber surface in control step (1) to (3), and the flow ratio of acetylene, hydrogen, nitrogen can reach the purpose of control coiled carbon fibers size and helical structure in control step (4) the vapor deposition growth process.The fibre diameter of coiled carbon fibers increases with the increase of catalyst granules, add the output that an amount of Al element and Cu element can improve coiled carbon fibers in the catalyst, add the coiled carbon fibers that the Al element is conducive to obtain single coil configuration, add Cu or Sn element and be conducive to obtain spiral shell footpath and the less spiral carbon nano-fiber of fibre diameter; Reacting gas is with the increase of acetylene flow in the step (4), and the pitch of coiled carbon fibers has the trend that diminishes, and an amount of hydrogen and nitrogen flow can improve output and the purity of coiled carbon fibers, can also promote coiled carbon fibers to grow perpendicular to carbon fiber axis aspect.
Carbon fiber has the characteristics of larger specific area and little gas pressure drop, and catalyst granules is evenly distributed on carbon fiber surface, and catalyst granules can fully touch fresh reactant gas in the CVD process, can obtain high yield and highly purified coiled carbon fibers.
Adopt coaxial method to record the paraffin sample of interpolation 10 wt% coiled carbon fibers/carbon fiber conjugates in the electromagnetism parameter of 2-18 GHz scope, calculate the microwave reflection rate of sample according to transmission line theory, the result shows that coiled carbon fibers/carbon fiber conjugate has good electro-magnetic wave absorption performance.As the paraffin sample that adds 10 wt% spring type single-screw carbon fiber/carbon fiber conjugates has-10 dB bandwidth of 9.6 GHz and maximum absorption band and is the superperformance of-31 dB when 3 mm thickness.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1
(1) preparation Co
2+Concentration is 0.05 mol/L, and urea concentration is the aqueous solution of 0.1 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank to be heated to 120 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 350 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 500 ℃ of reduction 0.5 hour under hydrogen atmosphere;
(4) continue to be warmed up to 750 ℃, pass into acetylene and hydrogen as reacting gas, the reacting gas total flow is 2.0 L/min, and wherein the flow ratio of acetylene and hydrogen is 1/4, and gas pressure is 60 KPa in the maintenance CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 2
(1) preparation Ni
2+Concentration is 0.1 mol/L, and urea concentration is the aqueous solution of 0.24 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 130 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 650 ℃, pass into acetylene and hydrogen as reacting gas, the reacting gas total flow is 2.0 L/min, and wherein the flow ratio of acetylene and hydrogen is 1/3, and gas pressure is 110 KPa in the maintenance CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 3:
(1) preparation Fe
3+Concentration is 0.25 mol/L, and urea concentration is the aqueous solution of 1.125 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 140 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 450 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 550 ℃ of reductase 12s hour under hydrogen atmosphere;
(4) continue to be warmed up to 620 ℃, passing into acetylene is reacting gas, and the reacting gas total flow is 5.0 L/min, keeps gas pressure 2 KPa in the CVD body of heater.After reacting 90 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 4:
(1) preparation Ni
2+Concentration is 0.05 mol/L, Co
2+Concentration is 0.05 mol/L, and urea concentration is the aqueous solution of 0.3 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 140 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 0.5 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, passing into acetylene, hydrogen, nitrogen is reacting gas, and the reacting gas total flow is 3.0 L/min, and wherein the flow ratio of acetylene, hydrogen, nitrogen is 1 ﹕, 1 ﹕ 1, keeps that gas pressure is 110 KPa in the CVD body of heater.After reacting 45 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 5:
(1) configuration Ni
2+Concentration is 0.05 mol/L, Al
3+Concentration is 0.05 mol/L, and urea concentration is the catalyst precursor aqueous solution of 0.375 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 130 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, pass into acetylene, hydrogen and nitrogen as reacting gas, the reacting gas total flow is 3.0 L/min, and wherein the flow ratio of acetylene, hydrogen and nitrogen is 1 ﹕, 4 ﹕ 4, and gas pressure is 110 KPa in the maintenance CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 6:
(1) configuration Fe
3+Concentration is 0.2 mol/L, Sn
2+Concentration is 0.067 mol/L, and urea concentration is the catalyst precursor aqueous solution of 1.1 mol/L;
(2) with flooding 1 hour in carbon fiber plain introducing step (1) solution, then place together the hydro-thermal tank 130 ℃ of reactions 3 hours, with the carbon cloth taking-up, treat that it dries in the shade naturally after then with cold water the hydro-thermal tank being cooled off;
(3) carbon cloth after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, pass into acetylene, hydrogen and nitrogen as reacting gas, the reacting gas total flow is 20.0 L/min, and wherein the flow ratio of acetylene, hydrogen and nitrogen is 5 ﹕, 1 ﹕ 1, and gas pressure is 20 KPa in the maintenance CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 7:
(1) configuration Ni
2+Concentration is 0.08 mol/L, Al
3+Concentration is 0.05 mol/L, Cu
2+Concentration is 0.05 mol/L, and urea concentration is the aqueous solution of 0.375 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 130 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, pass into acetylene and nitrogen as reacting gas, the reacting gas total flow is 2.0 L/min, and wherein the flow ratio of acetylene and nitrogen is 1 ﹕ 4, and gas pressure is 110 KPa in the maintenance CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 8:
(1) configuration Ni
2+Concentration is 0.08 mol/L, Al
3+Concentration is 0.05 mol/L, Sn
2+Concentration is 0.03 mol/L, and urea concentration is the aqueous solution of 0.3 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 130 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, pass into acetylene and nitrogen as reacting gas, the reacting gas total flow is 2.0 L/min, and wherein the flow ratio of acetylene and nitrogen is 5 ﹕ 1, keeps gas pressure 2 KPa in the CVD body of heater.After reacting 90 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 9:
(1) configuration Ni
2+Concentration is 0.08 mol/L, Al
3+Concentration is 0.05 mol/L, Cu
2+Concentration is 0.05 mol/L, Sn
2+Concentration is 0.03 mol/L, and urea concentration is the aqueous solution of 0.35 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 130 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, pass into acetylene and nitrogen as reacting gas, the reacting gas total flow is 20 L/min, and wherein the flow ratio of acetylene and nitrogen is 2 ﹕ 1, keeps gas pressure 20 KPa in the CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 10:
(1) configuration Fe
3+Concentration is 0.1 mol/L, Cu
2+Concentration is 0.05 mol/L, Sn
2+Concentration is 0.04 mol/L, and urea concentration is the aqueous solution of 0.5 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 130 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, passing into acetylene is reacting gas, and reaction gas flow is 5 L/min, keeps gas pressure 20 KPa in the CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 11:
(1) preparation Ni
2+Concentration is 0.05 mol/L, Co
2+Concentration is 0.05 mol/L, Cu
2+Concentration is 0.05 mol/L, Sn
2+Concentration is 0.04 mol/L, and urea concentration is the aqueous solution of 0.45 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 130 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, passing into acetylene is reacting gas, and reaction gas flow is 5 L/min, keeps gas pressure 5 KPa in the CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 12:
(1) preparation Fe
3+Concentration is 0.1 mol/L, Al
3+Concentration is 0.05 mol/L, Cu
2+Concentration is 0.05 mol/L, Sn
2+Concentration is 0.05 mol/L, and urea concentration is the aqueous solution of 0.9 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 130 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, passing into acetylene and hydrogen is reacting gas, and reaction gas flow is 20 L/min, and the flow proportional of acetylene and hydrogen is 1/1, keeps gas pressure 20 KPa in the CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 13:
(1) preparation Fe
3+Concentration is 0.1 mol/L, Cu
2+Concentration is 0.05 mol/L, and urea concentration is the aqueous solution of 0.6 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 130 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, passing into acetylene and hydrogen is reacting gas, and reaction gas flow is 20 L/min, and the flow proportional of acetylene and hydrogen is 2/1, keeps gas pressure 5 KPa in the CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Embodiment 14:
(1) preparation Fe
3+Concentration is 0.1 mol/L, Al
3+Concentration is 0.05 mol/L, and urea concentration is the aqueous solution of 0.6 mol/L;
(2) carbon fiber was introduced in step (1) solution dipping 1 hour, then placed together the hydro-thermal tank 130 ℃ of reactions 3 hours, then carbon fiber is taken out after with the cooling of hydro-thermal tank with cold water, treat that it dries in the shade naturally;
(3) carbon fiber after will drying in the shade places the 400 ℃ of calcinings 1 hour under nitrogen atmosphere of CVD stove, again 450 ℃ of reduction 1 hour under hydrogen atmosphere;
(4) continue to be warmed up to 680 ℃, passing into acetylene and hydrogen is reacting gas, and reaction gas flow is 20 L/min, and the flow proportional of acetylene and hydrogen is 5/1, keeps gas pressure 2 KPa in the CVD body of heater.After reacting 60 min, blowing out, stop the supple of gas or steam, and pass into the nitrogen protection cooling.
Metal ion related in above-described embodiment all may be utilized as there being the ionic species of other valence state.Only need to guarantee that the urea molar weight is each metal cation molal quantity and its valence state sum of products 1～1.5 times in the aqueous solution, the metal ion of employing different valence state does not affect implementation result.
Claims (6)
1. a novel carbon fiber with helical structure is characterized in that, comprise straight carbon fiber and coiled carbon fibers, described coiled carbon fibers is grown in straight carbon fiber surface.
2. a novel preparation method with carbon fiber of helical structure is characterized in that, may further comprise the steps:
(1) preparing metal ion total mol concentration is the aqueous solution of 0.05～0.25mol/L, at least contain in Fe, Co, the Ni metal ion one or more in this aqueous solution, follow dissolved urea in this aqueous solution, and stir, the urea molar weight is each metal cation molal quantity and its valence state sum of products 1～1.5 times in the aqueous solution;
(2) with impregnated carbon fiber in the solution that step (1) is prepared, then it is placed together closed container 120～140 ℃ of fully reactions, after its cooling, dry in the shade;
(3) carbon fiber after step (2) is processed in 350～450 ℃ of calcinings 1～2 hour, then passes into hydrogen in 450～550 ℃ of reduction 0.5～2 hour in nitrogen or inert atmosphere, obtains the carbon fiber that the surface is loaded with metal catalyst particles;
(4) carbon fiber after step (3) processing being warmed up to 620～750 ℃, passing into acetylene gas, is 2～110KPa at pressure, reacts 45～120min, obtains having in straight carbon fiber surface growth the combination of coiled carbon fibers.
3. according to claim 2 a kind of novel preparation method with carbon fiber of helical structure, it is characterized in that, the mist that passes into acetylene and hydrogen in above-mentioned steps (4) replaces the acetylene gas that passes into, and wherein the volume ratio of acetylene and hydrogen is 1: 4～5: 1;
4. according to claim 2 a kind of novel preparation method with carbon fiber of helical structure, it is characterized in that, the mist that passes into acetylene and nitrogen in above-mentioned steps (4) replaces the acetylene gas that passes into, and wherein the volume ratio of acetylene and nitrogen is 1: 4～5: 1;
5. according to claim 2 a kind of novel preparation method with carbon fiber of helical structure, it is characterized in that, the mist that passes into acetylene, hydrogen, nitrogen in above-mentioned steps (4) replaces the acetylene gas that passes into, and wherein the volume ratio of acetylene, hydrogen, nitrogen is respectively (1～20): 4: 4;
6. according to claim 2 to 5 each a kind of novel preparation method with carbon fiber of helical structure, it is characterized in that the metal ion in the described step (1) also contains one or more in Al ion, Cu ion, the Sn ion.
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| CN104987805B (en) * | 2015-04-28 | 2018-05-11 | 江苏理工学院 | Galvanoplastic coiled carbon fibers nickel-loaded water-repellent preservation invisible coating and preparation method thereof |
| CN110306261A (en) * | 2019-03-06 | 2019-10-08 | 青岛科技大学 | A kind of preparation method of spiral nanometer carbon fiber |
| CN110306261B (en) * | 2019-03-06 | 2021-12-10 | 青岛科技大学 | Preparation method of spiral nano carbon fiber |
| CN112479730A (en) * | 2020-12-17 | 2021-03-12 | 中南大学 | Preparation method of curved carbon nanofiber reinforced C/C composite material |
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