CN106637912B - Iron-based alloy composite fiber and preparation method thereof - Google Patents
Iron-based alloy composite fiber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an iron-based alloy composite fiber and a preparation method thereof. The invention also provides a preparation method of the iron-based alloy fiber coated by the graphene layer. The method comprises the steps of combining a microwave technology of rapid heating with a microwave absorption characteristic of a graphene derivative and a microwave eddy current heating characteristic of the surface of an iron-based alloy fiber, coating the graphene derivative layer on the surface of the iron-based alloy fiber to form a composite fiber, enabling the composite fiber to move through a microwave heating area at a set speed in a set atmosphere, enabling the graphene derivative layer on the surface of the composite fiber to be converted into a graphene layer by microwave heating treatment at a set time, enabling the composite fiber to leave the microwave heating area and to be cooled, and finally enabling the composite fiber to be extruded to obtain the composite iron-based alloy fiber with good conductivity and corrosion resistance.
Description
Technical Field
The invention belongs to the field of materials, and relates to an iron-based alloy composite fiber and a preparation method thereof, in particular to an iron-based alloy composite fiber which has good conductive capability and good corrosion resistance by using graphene with good conductive capability and sealing effect to coat the iron-based alloy fiber.
Background
With the development of society, fibers of iron-based alloys including iron, steel, stainless steel, etc. have been widely used in a wide range of fields including engineering and construction, electromagnetic protection, etc. due to their numerous advantages such as good mechanical properties, low price, etc. However, the iron-based alloy fiber has problems of corrosion and conductivity to be improved, which limits further popularization and application. Therefore, the coating modification of the iron-based alloy fiber is highly concerned and rapidly develops in the aspects of polymer coating, iron-based alloy compounding and the like. On the other hand, graphene as a two-dimensional conductive material has excellent mechanical properties (Young modulus up to 1.0TPa) and electrical properties (electron mobility up to 10)6cm2.v-1s-1) Thermal properties (thermal conductivity up to 5000 w.m)-1.k-1) Optical properties (the visible light absorption of single-layer graphene is only 2.3 percent and the excellent mode locking characteristic), and ultra-large theoretical specific surface area (2630 m)2.g-1) So that the application potential of the metal surface modifier is highly concerned. Researches show that the graphene layer coated copper wire prepared by the vapor deposition method on the surface of the copper wire not only has good corrosion resistance, but also has excellent conductivity. Due to the catalytic properties required for graphene vapor deposition, the metal materials for growing graphene by vapor deposition are limited to a few metal materials such as copper and nickel. In addition, graphene oxide produced on the basis of graphite or reduction thereof has been developedThe product is reduced graphene oxide. The graphene oxide or reduced graphene oxide solution can be coated layer by layer to form a film in a manner that a graphene basal plane is parallel to a coating substrate, but the graphene oxide or reduced graphene oxide solution has poor electric conductivity and small holes formed on the graphene basal plane due to oxidation have certain substance passing capacity, so that the wide application of the graphene oxide or reduced graphene oxide solution in a wider range is influenced. Graphene powder with a high reduction degree prepared from graphene oxide based on high-temperature reduction has improved conductivity, but due to poor dispersion performance, people can only coat the surface of a material in a powder electrostatic spraying manner at present. However, in the electrostatic powder spraying, due to the agglomeration of graphene powder, it is difficult to spread a uniform coating material on a graphene base surface, and thus the excellent performance of the graphene material cannot be exerted. For this reason, graphene anticorrosive coatings containing graphene-based materials including graphene oxide powder, reduced graphene oxide powder, and graphene powder have also been developed. On one hand, other materials including the polymer material added in the anticorrosive coating affect the performances of the graphene including the electric conductivity and the heat conductivity, and on the other hand, the influence of basal plane pores existing in the graphene oxide and the reduced graphene oxide on the anticorrosive capability and the characteristic that the graphene powder is difficult to uniformly disperse and coat make the performance of the anticorrosive coating obtained by coating the graphene anticorrosive coating further need to be improved through development. Therefore, there is an urgent need to develop a new technology capable of effectively coating graphene layers on the surface of a material. Therefore, the invention firstly proposes that the graphene layer is coated on the surface of the iron-based alloy fiber internationally to obtain the composite iron-based alloy fiber with good electric conductivity and corrosion resistance. The invention also provides a preparation method for preparing the graphene layer coated iron-based alloy composite fiber, namely the graphene derivative layer coated iron-based alloy composite fiber is obtained by coating the graphene derivative solution on the iron-based alloy fiber, the composite fiber moves through a microwave heating zone at a set speed under a set atmosphere condition, and the oxidized graphene derivative layer or the graphene edge derivative layer and the iron-based alloy fiber are enabled to be oxidized by utilizing the microwave absorption capacity of the graphene micro-zone in the graphene derivative and the metal eddy current heating characteristic of the surface of the iron-based alloy fiber with the depth of several micronsThe alloy surface layer is rapidly heated up due to the microwave action and reduces the oxidized graphene derivative or removes the edge functional group of the graphene edge derivative to convert the graphene derivative layer into the graphene layer. Because the graphene derivative layer coated by the solution is coated on the iron-based alloy fiber layer by layer in a form that a graphene base surface is spread, the graphene layer obtained by high-temperature treatment can keep better electric conduction, heat conduction and mechanical properties due to the interaction between pi electron clouds among different graphene layer layers. On the other hand, the composite fiber moves through the microwave heating zone at a set speed, so that not only can the heating time of the composite fiber be accurately controlled, for example, the heating time of a common microwave oven is set to be a plurality of grades with a unit of 30 seconds, but experiments show that heating one whole grade under a protective atmosphere can cause the coated graphene derivative layer to be scattered or even fall off due to too fast temperature rise, even if the microwave pulse length can be set by the precise microwave oven, the possibly optimal heating time such as 1.2 seconds can not be easily set, and the composite fiber passes through the microwave heating zone at the set speed, so that the accurate optimal heating time can be easily obtained according to the size of the microwave heating zone. The composite fiber passes through the microwave heating area at a set speed, and uneven heating caused by different heating effects of different areas of the microwave heating area can be avoided. In fact, the composite fiber is placed in a microwave oven to be heated for a period of time, and after the composite fiber is taken out, the heating effect of the composite fiber placed in different heating areas can be obviously different, which is related to the uniformity of a heating electric field in the microwave oven. While passing the composite fiber through the entire microwave heating zone at a set speed achieves a consistent heating effect as all composite fibers pass through the entire heating zone. Of course, the composite fiber can pass through the whole microwave heating area at a set speed, and the cooling time can be accurately controlled, so that the optimization of the process is facilitated. The method of passing the composite fiber through the entire microwave heating zone at a set speed is also compatible with the fiber processing process, thereby facilitating mass production of the iron-based alloy composite fiber. And microwave heating (usually in seconds) due to selective heating of the graphene derivative layer and the iron-based alloy fiberThe surface is maintained, high energy consumption caused by heat transfer and the like during other heating (usually within hours) can be avoided, and the graphene layer coated iron-based alloy composite fiber can be rapidly cooled after leaving a microwave heating area, so that the processing time is greatly shortened.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide an iron-based alloy composite fiber and a preparation method thereof, namely, a graphene layer is coated on the surface of the iron-based alloy fiber to obtain a novel composite fiber with good conductivity and corrosion resistance. The invention also provides a preparation method of the iron-based alloy fiber coated by the graphene layer, and the iron-based alloy composite fiber coated by the graphene layer can be conveniently and quickly prepared, so that the further development and application of the iron-based alloy composite fiber are facilitated.
The technical scheme is as follows: according to the iron-based alloy composite fiber, the graphene layer is coated on the surface of the iron-based alloy fiber. The graphene layer has a carbon content greater than 90%. The iron-based alloy includes iron, steel and stainless steel.
The preparation method of the iron-based alloy composite fiber provided by the invention is realized by coating a graphene layer on the surface of an iron-based alloy through the following method: firstly, preparing a graphene derivative solution, then coating the graphene derivative solution on the surface of a selected iron-based alloy fiber to form an iron-based alloy composite fiber coated with a graphene derivative layer, then enabling the iron-based alloy composite fiber to pass through a microwave heating zone at a set speed under a set atmosphere so that the iron-based alloy composite fiber is subjected to microwave heating high-temperature treatment and the graphene derivative layer on the surface of the iron-based alloy composite fiber is converted into a graphene layer, then enabling the iron-based alloy composite fiber to leave the microwave heating zone and be cooled, and then performing extrusion treatment to obtain the iron-based alloy composite fiber coated with the graphene layer.
The graphene derivative refers to graphene oxide which is an oxide of graphene, and reduced graphene oxide and graphene edge derivatives.
The set atmosphere refers to inert atmosphere, reducing atmosphere or vacuum state; the inert atmosphere refers to a gas which does not react with the graphene derivative, such as nitrogen, helium, argon; the reducing atmosphere refers to a gas containing a gas capable of reducing the graphene derivative, such as hydrogen, alcohols, and alkane gases; the vacuum state refers to the air pressure less than 4KPa (relative vacuum degree less than-20 KPa);
the iron-based alloy composite fiber exits the microwave heating zone and is cooled by passing through a cold atmosphere or by additionally applying a cold gas fluid.
The graphene derivative layer is converted into the graphene layer, namely oxidized graphene is reduced at high temperature and converted into graphene, and the graphene edge derivative is subjected to high-temperature edge functional group removal and converted into graphene.
The composite fiber moves through the microwave heating area at a set speed, and the heating time is controlled according to the size of the microwave heating area.
The microwave heating high-temperature treatment of the iron-based alloy composite fiber can be repeated to high-temperature treat the graphene derivative layer for multiple times.
The graphene derivative solution is coated on the surface of the selected iron-based alloy fiber to form the iron-based alloy composite fiber coated with the graphene derivative layer, the composite fiber moves at a set speed under a set atmosphere through a microwave heating area to enable the iron-based alloy composite fiber to be subjected to microwave heating high-temperature treatment and convert the graphene derivative layer on the surface of the iron-based alloy composite fiber into the graphene layer, the iron-based alloy composite fiber leaves the microwave heating area and is cooled, and then the series of processes of extrusion treatment can be repeated, namely the graphene derivative can be coated for multiple times and subjected to microwave high-temperature treatment to obtain the thickened graphene layer.
The coating comprises dip coating, spray coating, brush coating, foam coating, layer-by-layer assembly coating and contact coating.
Has the advantages that: compared with the prior art, the invention has the following advantages:
the two-dimensional graphene material with good conductive capability and sealing capability is used for coating the iron-based alloy fiber to form the composite iron-based alloy fiber with good conductive capability and corrosion resistance for the first time. Meanwhile, the novel iron-based alloy composite fiber with good conductivity and corrosion resistance can be obtained conveniently, quickly and with low energy consumption by coating the graphene derivative solution, selectively heating the graphene derivative layer and the iron-based alloy fiber surface at a set speed by the composite fiber through a microwave heating area and microwaves to treat the graphene derivative layer at a high temperature and convert the graphene derivative layer and the iron-based alloy fiber surface into a graphene layer. The method can make a contribution to the further development and application of the iron-based alloy fiber and the graphene material.
Drawings
FIG. 1 is a schematic diagram of a process for preparing an iron-based alloy composite fiber.
FIG. 2 is a schematic view of a fiber passing around a metal baffle by a guide wheel.
The figure shows that: 1. iron-based alloy fibers; 2. an immersion liquid pool 2a for solution; 3. a liquid squeezing roller; 4. a drying room; 5. a metal baffle plate 5a and a small hole; 6. a microwave heating furnace 6a, microwave input 6b and a heating cavity; 7. an atmosphere cavity 7a, a gas inlet 7b, a gas outlet; 8. a rear temperature control part 8a, a temperature control fluid inlet 8b and a temperature control fluid outlet; 9. a guide wheel; 10. and (4) extruding the roller.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Firstly, an iron-based alloy fiber 1 passes through a solution 2a in a soaking tank 2 by a guide wheel 9 to be coated with a graphene derivative solution, then the iron-based alloy composite fiber coated with a graphene derivative layer is squeezed to remove redundant solution by a squeezing roller 3, then the composite fiber is dried by a drying room 4, and then the composite fiber enters a microwave oven 6 protected by a metal baffle 5 with small holes 5 a. An atmosphere chamber 7 is provided in a heating zone of a microwave oven, and an atmosphere surrounding the iron-based alloy composite fiber in the microwave heating zone is controlled by a gas inlet 7a and a gas outlet 7 b. Then, microwave is input through a microwave input 6a, the graphene derivative layer on the iron-based alloy composite fiber is subjected to microwave heating under a set atmosphere environment, then the graphene derivative layer leaves the microwave oven 6 through a metal baffle plate with small holes and enters a rear temperature control region 8, temperature of the iron-based alloy composite fiber subjected to microwave heating treatment is controlled by setting temperature circulating fluid through a temperature control fluid inlet 8a and a temperature control fluid outlet 8b, and then the iron-based alloy composite fiber subjected to microwave heating treatment is extruded through an extrusion roller 10 to obtain the iron-based alloy composite fiber coated by the graphene layer.
The iron-based alloy baffle 5 can be changed from small holes 5a which are beneficial to the continuous operation of the fibers to a guide wheel 9 which is beneficial to the microwave blocking and the protection of the human body by guiding the fibers to continuously run by bypassing the iron-based alloy baffle. As shown in fig. 2.
The graphene derivative layer coated on the surface of the iron-based alloy fiber is converted into the graphene layer, which is a challenge to be solved. Except for the long-time treatment at the extremely high temperature, the carbon content of the graphene derivative treated by the common chemical reduction and high-temperature reduction method hardly exceeds 90 percent, and the long-time treatment at the extremely high temperature not only consumes large energy, but also damages the thin-layer structure of the graphene derivative. There is therefore an urgent need to develop new techniques to convert graphene derivative layers into graphene layers. Therefore, the invention firstly utilizes the characteristic that the graphene derivative has microwave absorption characteristic and the characteristic that the microwave has rapid temperature rise internationally, and the graphene derivative layer passes through the microwave heating zone at a set speed in a set atmosphere, so that the graphene derivative layer is heated and processed under the conditions of accurately controlling the heating time and avoiding uneven heating, and the graphene derivative layer is converted into the graphene layer. In fact, there have been some related studies on the application of microwave treatment to graphene-related materials. For example, one method for preparing graphene oxide is to microwave-treat graphite oxide, and separate few layers or even single layers of graphene oxide from each other by microwave heating to a high temperature of more than two thousand degrees celsius, which causes a large amount of gas to be generated inside the graphite oxide. And the graphene oxide can be almost completely reduced at high temperature of more than two thousand degrees centigrade to be converted into graphene. Our experiments show that graphene derivatives including graphene oxide, reduced graphene oxide and graphene edge derivatives can be efficiently converted into graphene by microwave heating treatment in a non-oxidizing atmosphere. The problem is that the common microwave heating treatment has high local temperature due to centralized heating, so that severe reaction generates gas and the structure of the graphene derivative material is damaged, and the graphene derivative layer becomes fragments, so that the microwave heating process must be effectively controlled to effectively treat the graphene derivative at high temperature and avoid the damage of the severe reaction to the structure of the graphene derivative material. Our experiments show that the graphene derivatives can be effectively converted into graphene by short-time microwave heating for less than 3 seconds under a set atmosphere, but since rapid expansion of gases including moisture generated by reduction is an important pushing hand for causing structural damage of the graphene derivatives, we have generated an idea of avoiding rapid expansion, such as water vapor generated by reduction due to rapid cooling. Experiments show that the structure of the graphene derivative material can be well maintained and the graphene derivative material can be finally converted into the graphene material due to the fact that the graphene derivative material is rapidly heated by microwaves and gas generated by rapid cooling reduction under the condition of introducing cold nitrogen. Of course, heating the material while cooling with the introduction of cooled nitrogen gas is still desired from the viewpoint of energy consumption. Another problem of microwave heating treatment of graphene derivative materials is the problem of uneven heating of a microwave heating area, which is related to the uniformity of a heating electric field in a microwave oven, and although the uniformity of heating in the microwave oven can be improved by designing a curved antenna structure, the uneven heating of the electric field is difficult to avoid, and the effect of uneven heating causes the effect of converting graphene derivative materials into graphene to be different in different areas and affects the overall performance, and if the heating time is prolonged, it may happen that a part of graphene derivative materials are damaged due to overheating, and another part of graphene derivative materials may not be well reduced. Therefore, in order to reduce the increase of energy consumption caused by the cooling of the cooling fluid while microwave heating and improve the uniformity of the microwave heating treatment, a method is considered in which the graphene derivative material is heated by a microwave heating zone at a set speed under a set atmosphere to accurately control the heating time, and then is rapidly cooled, so that the graphene derivative in all the zones can be relatively uniformly heated by the whole microwave heating zone, and after the microwave heating is finished, the graphene derivative is cooled at room temperature unless the temperature is specially reduced, and then is cooled by a cooling device after leaving the microwave oven, so that the energy consumption of the cooling is reduced. Experiments show that the method has good effect, the content of carbon in the graphene layer exceeds 90% for the graphene derivative layer to be converted into the graphene layer, and the common graphite is nearly completely reduced due to the fact that 3% of oxygen is adsorbed by the common graphite, and the graphene derivative layer has good electrical property.
The present invention will be further described with reference to the following examples.
The first embodiment is as follows:
firstly, preparing graphene oxide powder and reduced graphene oxide powder. 30 g of graphite are mixed with 15g of sodium nitrate and 750 ml of concentrated sulfuric acid. The mixture was cooled to 0 ℃ in an ice bath and stirred for 2h, then 90 g of potassium permanganate were slowly added, keeping the temperature of the mixture below 5 ℃ during mixing. The mixture was stirred for an additional hour and warmed to room temperature by removing the ice bath. To the mixture was added 1 liter of distilled water and the temperature in the oil bath was increased to 90 ℃. An additional 300 ml of water was added and stirred for another half an hour. The color of the mixture turned brown. The mixture was then treated and diluted with 30% 300 ml hydrogen peroxide and 30 l hot water. The mixture was further washed with an excess of water until the pH of the filtrate was almost neutral to obtain graphene oxide. And then, carrying out freeze drying on the graphene oxide to obtain graphene oxide powder. The graphene oxide powder was then dispersed in water and reduced with hydrazine hydrate at 80 degrees celsius for 12 hours. Reduced graphene oxide formed as a black precipitate, collected by filtration through a 0.45 μm PTFE membrane, and rinsed with copious amounts of water. The product was further purified by soxhlet extraction with methanol, Tetrahydrofuran (THF) and water. Finally, the obtained reduced graphene oxide is freeze-dried at-120 ℃ under a vacuum environment of 0.05 mm Hg. Then 0.5 mg/ml of an aqueous solution of reduced graphene oxide was prepared with deionized water.
Then, a SWH82B steel wire with a diameter of 0.5 mm was obtained. Then the above-mentionedThe steel wire is coated through a 0.5 mg/ml reduced graphene oxide aqueous solution immersion tank at the speed of 60 m/min to form the composite steel wire with the surface coated with the reduced graphene oxide layer, then the composite steel wire is subjected to liquid squeezing roller with the line pressure of 200N/cm and the hardness of 90 degrees to remove redundant solution, and then the composite steel wire enters a drying room with the temperature of 150 ℃ to be dried, so that the composite steel wire with the surface coated with the reduced graphene oxide layer is obtained. Then the composite steel wire enters a microwave heating area protected by argon through a stainless steel baffle plate with a small hole. The microwave heating zone is formed by connecting 10 microwave ovens with the power of 1000W, the length of the heating zone reaches 1 meter, then the composite steel wire is heated by the microwave ovens for about 1 second, then enters the rear temperature control zone through a small hole on the steel baffle plate and is cooled by cold air controlled by circulating cooling water, and then the composite steel wire is extruded by an extrusion roller with the line pressure of 1200N/cm. Repeating the coating, microwave heating, cooling and extruding processes for three times to obtain the graphene layer with the carbon content of more than 90 percent and the conductivity of more than 5000Sm-1The graphene layer is coated on the composite steel wire. The composite steel wire has no obvious corrosion phenomenon in 1M sulfuric acid solution for one week under the condition that the exposed head end is not exposed, and shows excellent corrosion resistance.
Example two:
first, a SWRM10 steel wire having a diameter of 3 mm was taken, and then the steel wire was passed through a 10 mg/ml graphene oxide aqueous solution having a length of 30 cm at a speed of 0.1 m/s, and dried to obtain a composite steel wire having a graphene oxide layer coated on the surface thereof. The composite steel wire is heated for about 1 second in a heating zone with the diameter of 10 cm of a microwave oven with the power of 1000W under the protection of a reducing atmosphere with the ratio of nitrogen to hydrogen of 55:1 at the room temperature at the speed of 0.1 m/s, then enters a room temperature zone again for cooling, then the composite steel wire is extruded by an extrusion roller with the linear pressure of 1000N/cm, and the microwave heating-cooling-extrusion process is repeated for 20 times. The obtained graphene layer has carbon content of more than 90 percent and conductivity of more than 5000Sm-1The graphene layer is coated on the composite steel wire. The composite steel wire has no obvious corrosion phenomenon in 1M nitric acid solution for one week under the condition of not exposing the exposed head end, and shows excellent corrosion resistanceAnd (5) carrying out characterization.
Example three:
first, edge carboxylated graphene sheets are prepared. 5 grams of graphite and 100 grams of dry ice were added to an iron-based alloy capsule containing 1000 grams of iron-based alloy balls of 5 mm diameter. The vessel was sealed and fixed in a planetary ball mill (F-P4000) and stirred at 500rpm for 48 hours. Subsequently, the internal pressure is slowly released through a gas outlet. After the ball milling is finished, the container cover is opened in the air, and the carboxylate is initiated to generate violent hydration reaction by the moisture in the air to generate carboxylic acid so as to flash. The product obtained is subjected to soxhlet extraction with a 1M hydrochloric acid solution to thoroughly acidify the carboxylate and remove possible impurities of the iron-based alloy. And finally, freeze-drying the graphene nano sheet at-120 ℃ for 48 hours under a vacuum environment of 0.05 mm Hg to obtain dark black powder of the edge carboxylated graphene nano sheet. The edge carboxylated graphene nanoplatelets were sonicated in isopropanol for 30 minutes to obtain a 0.1 wt% solution that was uniformly dispersed.
Then 6 x 29Fi + FC steel cords of 2 cm diameter were obtained. The steel wire rope is then passed through a 50 cm long 0.1 wt% edge-carboxylated graphene isopropanol solution at a speed of 0.1 m/s, and dried to obtain a composite steel wire rope with the surface coated with the edge-carboxylated graphene layer. The composite steel wire rope is heated for about 2 seconds in a helium protection state at a speed of 0.05 m/s in a room temperature state through a heating zone with the diameter of 10 cm of a microwave oven with the power of 1000W, then enters a room temperature area again for cooling, then the composite steel wire rope is extruded through an extrusion roller with the linear pressure of 1300N/cm, and the solution coating-microwave heating-cooling-extrusion process is repeated for 3 times. The obtained graphene layer has carbon content of more than 90 percent and conductivity of more than 5000Sm-1The graphene layer is coated on the composite steel wire rope. The composite steel wire rope has no obvious corrosion phenomenon even in 1M sulfuric acid solution for one week under the condition that the exposed head end is not exposed, and shows excellent corrosion resistance characteristic.
Example four:
firstly, preparing an edge halogenated graphene nanosheet. 5g of graphite was added to an iron-based alloy capsule containing 1000 g of iron-based alloy balls having a diameter of 5 mm. The capsules were then sealed and filled and evacuated with argon for five cycles under vacuum pressure of 0.05 mm hg. Thereafter, chlorine gas was added from the gas inlet through the cylinder pressure of 8.75 atm. The vessel was sealed and fixed in a planetary ball mill (F-P4000) and stirred at 500rpm for 48 hours. The obtained product is subjected to Soxhlet extraction by using methanol and 1M hydrochloric acid solution in sequence to thoroughly remove small-molecular organic impurities and possible iron-based alloy impurities. And finally, freeze-drying the graphene nano sheets for 48 hours at-120 ℃ under a vacuum environment of 0.05 mm Hg to obtain dark black powder of the edge chlorinated graphene nano sheets. Then 0.1 mg/ml of N, N' -dimethylformamide DMF solution of edge chlorinated graphene is prepared.
Then, a 301 type stainless steel wire having a diameter of 100 μm was obtained. Then, the stainless steel wire is passed through a 40 cm long 0.1 mg/ml solution of chlorinated graphene N, N' -dimethylformamide DMF at a speed of 0.5 m/s, and after drying, a composite stainless steel wire with the surface coated with a layer of chlorinated graphene at the edge is obtained. The composite stainless steel wire was heated at a speed of 0.02 m/s under a nitrogen atmosphere containing 5% hydrogen gas for about 5 seconds at room temperature through a heating zone of 1000W in a microwave oven having a diameter of 10 cm, followed by cooling with circulating cooling water, and then the composite stainless steel wire was subjected to an extrusion treatment through an extrusion roll having a linear pressure of 500N/cm, and the above solution coating-microwave heating-cooling-extrusion treatment process was repeated 8 times. The obtained graphene layer has carbon content of more than 90 percent and conductivity of more than 5000Sm-1The graphene layer is coated on the composite stainless steel wire. The composite stainless steel wire has no obvious corrosion phenomenon even in 1M nitric acid solution for one week under the condition that the exposed head end is not exposed, and shows excellent corrosion resistance characteristic.
EXAMPLE five
First a 6 x 19+ FC wire rope of 2 mm diameter was taken. Then, the steel wire rope is operated at the speed of 1 dm/s, the steel wire rope is allowed to be 6 cm away from a nozzle of an electrostatic sprayer, 8KV voltage is applied to the nozzle of the electrostatic sprayer, 0.5 mg/ml reduced graphene oxide aqueous solution is sprayed onto the steel wire rope through the nozzle at the speed of 200 μ l/min, and then the steel wire rope is dried at room temperature, and the electrostatic spraying and the drying at room temperature are repeated for 10 times, so that the reduced graphene oxide layer-coated steel wire composite rope is obtained. The composite rope was vacuum dried at 50 degrees celsius for 10 hours. And then heating the composite fiber at the room temperature of 0.05M/S for about 2S through a heating zone with the diameter of 1000W of a microwave oven at the room temperature under the protection of nitrogen, then cooling the composite fiber in the room temperature zone, extruding the composite steel wire rope through an extrusion roller with the line pressure of 500N/cm, repeating the microwave heating-cooling-extrusion process for 5 times, and then extruding the composite steel wire rope through the extrusion roller with the line pressure of 1300N/cm to obtain the graphene layer coated steel wire composite rope with the graphene layer carbon content of more than 90% and the conductivity of more than 5000S/M. The composite steel wire rope has no obvious corrosion phenomenon even in a 1M nitric acid solution for one week under the condition that the exposed head end is not exposed, and shows excellent corrosion resistance.
EXAMPLE six
First, an iron wire having a diameter of 0.914 mm was taken, and then the iron wire was passed through a 1 mg/ml aqueous reduced graphene oxide solution having a length of 40 cm at a speed of 0.1 m/s, and dried to obtain a composite iron wire having a surface coated with a reduced graphene oxide layer. The composite iron wire is heated for about 5 seconds at the room temperature by a heating zone with the diameter of 10 cm of a microwave oven with the power of 800W at the speed of 0.02 m/s under the vacuum environment of 2KPa, and then enters a room temperature area again for cooling, the microwave heating-cooling process is repeated for 5 times, and then the composite iron wire is extruded by an extrusion roller with the linear pressure of 800N/cm. The obtained graphene layer has carbon content of more than 90 percent and conductivity of more than 5000Sm-1The graphene layer is coated with the composite iron wire. The composite iron wire has no obvious corrosion phenomenon even in 1M hydrochloric acid solution for one week under the condition that the exposed head end is not exposed, and shows excellent corrosion resistance.
EXAMPLE seven
First, a 3 mm diameter 7 x 7 wire rope was taken. The iron wire rope was then passed through a 30 cm-long 10 mg/ml aqueous graphene oxide solution at a speed of 0.1 m/s, and dried to obtain a graphene oxide layer-coated composite iron wire rope. The composite iron wire rope is coated with 10 mg/ml graphene oxide aqueous solution circularly and dried for 2 times, and then is treated in hydrazine hydrate steam at 95 ℃ for 24 hours to reduce the graphene oxide layer, so that the composite iron wire rope with the surface coated with the reduced graphene oxide is obtained. And then heating the composite iron wire rope for about 2 seconds through a heating zone with the diameter of 10 cm of a microwave oven with the power of 1000W at the speed of 0.05M/S under the protection of nitrogen at room temperature, then cooling the composite iron wire rope in the room temperature zone again, repeating the cooling-microwave heating-cooling process for 10 times, and then extruding the composite iron wire rope for three times through an extrusion roller under the linear pressure of 800N/cm to obtain the graphene layer coated composite iron wire rope with the carbon content of the graphene derivative layer being more than 90% and the electric conductivity being more than 5000S/M. The composite iron wire rope has no obvious corrosion phenomenon in 1M hydrochloric acid solution for one week under the condition that the exposed head end is not exposed, and shows excellent corrosion resistance.
Claims (8)
1. A preparation method of an iron-based alloy composite fiber is characterized in that the surface of the iron-based alloy fiber is coated with a graphene layer, and the preparation method comprises the following steps: firstly, preparing a graphene derivative solution, then coating the graphene derivative solution on the surface of a selected iron-based alloy fiber to form an iron-based alloy composite fiber coated by a graphene derivative layer, then enabling the iron-based alloy composite fiber to move through a microwave heating zone at a set speed under a set atmosphere so that the iron-based alloy composite fiber is subjected to heating high-temperature treatment by microwaves within 1-3 seconds, converting the graphene derivative layer on the surface of the iron-based alloy composite fiber into a graphene layer, then enabling the iron-based alloy composite fiber to leave the microwave heating zone and be cooled, then performing extrusion treatment, and repeating the coating-microwave heating-cooling-extrusion process for multiple times to obtain the iron-based alloy composite fiber coated by the graphene layer; the microwave heating power is 800W or 1000W.
2. The method according to claim 1, wherein the predetermined atmosphere is an inert atmosphere, a reducing atmosphere, or a vacuum state.
3. The method of claim 1, wherein the graphene layer has a carbon content of greater than 90%.
4. The method of claim 1, wherein the iron-based alloy is steel.
5. The method of claim 1, wherein the graphene derivative is graphene oxide, reduced graphene oxide, or a graphene edge derivative.
6. The method according to claim 1, wherein the predetermined atmosphere is an inert atmosphere, a reducing atmosphere, or a vacuum state; the inert atmosphere refers to a gas that does not react with the graphene derivative; the reducing atmosphere is gas containing graphene derivatives capable of being reduced; the vacuum state refers to the air pressure of less than 4 KPa.
7. The method of claim 1, wherein the iron-based alloy composite fiber is cooled by passing the iron-based alloy composite fiber out of a microwave heating zone and cooling the iron-based alloy composite fiber through a cold atmosphere or by additionally applying a cold gas.
8. The method of claim 1, wherein the graphene derivative layer is converted into a graphene layer by reducing oxidized graphene at high temperature, and the graphene edge derivative is converted into graphene by removing edge functional groups at high temperature.
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| CN102502611A (en) * | 2011-11-15 | 2012-06-20 | 东南大学 | Method for rapidly preparing graphene in large quantities by utilizing graphite oxides |
| CN103209505A (en) * | 2013-03-19 | 2013-07-17 | 苏州格瑞丰纳米科技有限公司 | High temperature resistance microwave equipment and production method of thin-layer two-dimensional materials |
| CN104419228A (en) * | 2013-08-29 | 2015-03-18 | 通用电气公司 | Coating, coating method, and coated article |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102502611A (en) * | 2011-11-15 | 2012-06-20 | 东南大学 | Method for rapidly preparing graphene in large quantities by utilizing graphite oxides |
| CN103209505A (en) * | 2013-03-19 | 2013-07-17 | 苏州格瑞丰纳米科技有限公司 | High temperature resistance microwave equipment and production method of thin-layer two-dimensional materials |
| CN104419228A (en) * | 2013-08-29 | 2015-03-18 | 通用电气公司 | Coating, coating method, and coated article |
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