CN113072069A - Carbide based on waste fiber textile and preparation method thereof - Google Patents
Carbide based on waste fiber textile and preparation method thereof Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/921—Titanium carbide
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
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- C01B32/949—Tungsten or molybdenum carbides
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
Abstract
The invention discloses a carbide based on waste fiber textiles and a preparation method thereof, wherein the method comprises the following steps: adding the precursor powder and a transition metal nitrate compound into an alcohol solution to obtain a precursor solution, soaking a waste fiber fabric in the precursor solution to obtain a precursor, drying the precursor to obtain a solidified precursor, placing the solidified precursor into a crucible containing the auxiliary powder, and placing the crucible into a tube furnace filled with inert gas for heat treatment to obtain the carbide. In the method, the waste fiber fabric is used as a carbon source required by the synthesis of the carbide, so that the synthesis cost is reduced, and the additional value of the waste fiber textile is improved. The metal salt in the auxiliary powder can be melted in the heat treatment process, and the particles of the precursor powder are transferred to the surface of the waste fiber fabric, so that the combination temperature of the carbon source and the precursor powder is greatly reduced, and the problem of high energy consumption for synthesizing carbide is effectively solved.
Description
Technical Field
The invention relates to the technical field of carbide preparation, in particular to a carbide based on waste fiber textiles and a preparation method thereof.
Background
The development of the circular economy, the promotion of the sustainable development of the society and the establishment of a healthy green low-carbon circular development system have reached the consensus all over the world. The comprehensive utilization of waste textiles as an important component of circular economy plays an important role in accelerating the development of renewable resource industry. The amount of waste textile clothes produced in China each year is more than 2000 million tons, and the sources of the waste textile clothes are mainly two types: firstly, waste silk and residual materials in the production process and leftovers in the garment manufacturing process; the second is waste clothes, bedding, curtains, sofa towels, carpets and the like. In 2016, the comprehensive utilization amount of waste textiles in China is about 360 ten thousand tons, and the comprehensive utilization rate is about 18 percent. The comprehensive utilization method mainly comprises the following steps: (1) the 'reuse' is realized by donation and exchange, and secondary wearing or manual operation for other use is realized; (2) "recycle" of its fiber raw material for the production of other textile products; (3) "energy utilization", i.e. recovering a part of chemical components and calorific value thereof by physical, chemical and other methods.
However, at present, most of the waste textile clothes are buried or burned on site, which wastes resources and pollutes the environment. Therefore, it is one of the problems to be solved urgently to improve the utilization rate of the waste textile clothes and expand the high value-added utilization thereof.
Over the past decades, carbides such as WC, MoC, TiC, ZrC, HfC, SiC have attracted considerable attention in industrial applications such as machining, catalysis, ceramic reinforcement, and the like. This is because carbides also have some unique advantageous properties, such as high melting point, strong corrosion resistance, good wear resistance, excellent electronic properties and good catalytic properties, compared to conventional oxides.
Generally, carbides are synthesized from a carbon source reacting with another element for a long time at high temperature (> 1500 ℃) to promote atomic diffusion of carbon atoms. However, this method has problems of high energy consumption, incomplete conversion, and long reaction time. Some approaches to the preparation of carbides that have proven effective include thermal reduction, self-propagating high temperature synthesis, sol-gel processes, and the like. In the thermal reduction method, petroleum coke or artificial graphite can be used as a carbon source, boric acid is uniformly mixed with the carbon source, and then the mixture is fired in an electric arc furnace at 1700-2300 ℃ to obtain boron carbide. However, the method requires higher preparation temperature, which not only consumes more energy, but also causes carbide decomposition at high temperature, which affects the yield. In the vapor deposition method, silicon halide, hydrocarbon and hydrogen gas are used to react with each other to form silicon carbide while being decomposed, and the temperature required is lower than that of the thermal reduction method, but the required process is complicated and harmful byproducts are easily generated. In the self-propagating high-temperature synthesis method, high-purity silicon and natural graphite can be used as raw materials and react for 3.5 hours in a graphite furnace at 1300 ℃ to obtain silicon carbide powder. However, this method still requires higher synthesis temperatures, which affects the yield. In the sol-gel method, silica sol and carbon black are used as raw materials, and a process of ammonolysis of inorganic sol-gel is adopted to obtain silicon carbide particles. However, this process requires the preparation of the gel first, which is complicated and involves high costs of the raw materials.
The waste fiber textile comprises two categories of natural fibers (including plant fibers and animal fibers) and chemical fibers (including synthetic fibers such as chinlon, terylene, acrylon, spandex, vinylon, polypropylene, polyvinyl chloride and the like). The plant fiber fabric can comprise various clothes taking plant fiber as a main component, such as cotton T-shirts, cotton casual pants and other cotton clothes; or linen clothes such as linen T-shirts, linen casual pants and the like; or cotton and hemp blended clothes. The components of the plant fiber fabric are not pure cotton or linen, and animal hair components or chemical fibers can be mixed. The plant fiber fabric is composed of three elements of carbon, hydrogen and oxygen, and mainly comprisesIs divided into (C)6H10O5) n, the carbon content is higher, for example, the carbon content of the cotton textile is up to more than 44.44 percent. The carbon material prepared from the waste fiber textiles can recycle waste substances, improve the utilization value of the waste substances and provide a carbon source for the preparation of carbon-containing compound materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method for synthesizing carbide by using a low-price waste fiber textile as a carbon source and a low-reaction-temperature molten salt method; the method can prepare the carbide material with high yield and different sizes or shapes and in the shape of particles or fibers.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the carbide based on the waste fiber textile is characterized by comprising the following preparation steps:
(1) preparing raw materials: according to mass percent, 20-80% of precursor powder, 10-70% of waste fiber fabric, 10-30% of auxiliary powder and 0-10% of transition metal nitrate compound; the auxiliary powder comprises metal salt powder and carbon black;
(2) adding the precursor powder and a transition metal nitrate compound to an alcohol solution to obtain a precursor solution;
specifically, the precursor powder may be a chemical substance composed of another synthetic element other than carbon element in the carbide to be synthesized. The alcohol solution may be mixed with the precursor powder thoroughly to form a mixed solution of the precursor powder, i.e., a precursor solution.
(3) Soaking the waste fiber fabric in the precursor solution for 2-4 h to obtain a precursor;
specifically, after a uniform precursor solution is formed, the rinsed waste clothes can be cut, and the waste fiber fabrics, namely the waste clothes, are soaked in the precursor solution for 2-4 hours, so that the waste fiber fabrics are fully soaked in the precursor solution. After sufficient soaking, a precursor loaded with a large amount of precursor powder is obtained. The waste fiber fabric is required to be immersed in the precursor solution,and the alcohol solution in the precursor solution can not be completely consumed after the full soaking. The waste fiber fabric can comprise various clothes taking waste fibers as main components, such as cotton T-shirts, cotton casual pants and other cotton clothes; or linen clothes such as linen T-shirts, linen casual pants and the like; or cotton and hemp blended clothes. In other embodiments, the waste fiber fabric may not be pure cotton or linen, and may be mixed with animal hair components or chemical fibers as long as the waste fibers are the main components. The main component of the plant fiber fabric is (C6H10O5)nBy means of the carbon element provided by the plant fiber fabric, the carbide corresponding to the precursor powder can be further grown on the plant fiber fabric, so that the aims of reducing the synthesis cost of the carbide and improving the recycling rate of the waste clothes are fulfilled.
(4) Drying the precursor at 75-110 ℃ for 2-4 h to obtain a cured precursor;
specifically, after the waste fiber fabric is fully soaked in the precursor solution in the step (2), a large amount of precursor powder is loaded on the waste fiber fabric, in the step, the waste fiber fabric can be further cured, namely, the soaked waste fiber fabric is placed at 75-110 ℃ for drying for 2-4 h, so that a cured precursor is obtained, the precursor powder can be well adhered to the waste fiber fabric, and the precursor powder cannot fall off from the waste fiber fabric in the subsequent treatment process to cause little carbide to be generated. The carbide output efficiency can be improved by the solidification treatment in this step.
(5) Placing the solidified precursor in a crucible containing the auxiliary powder;
specifically, the cured precursor obtained after the curing treatment may be placed in a crucible, and the auxiliary powder may be placed in the crucible. The crucible may be an alumina crucible or a graphite crucible. The auxiliary powder can be put into the crucible firstly, and then the solidified precursor is put on the auxiliary powder; or the solidified precursor is put into a crucible firstly, and then auxiliary powder is poured into the crucible; or pouring the auxiliary powder in several times, namely placing a part of the auxiliary powder at the bottom of the crucible, placing the solidified precursor into the crucible, and then pouring the rest of the auxiliary powder on the solidified precursor, thereby improving the yield of the carbide. By adding the auxiliary powder comprising the metal salt, the synthesis temperature can be greatly reduced, so that the carbide can be prepared into a formed carbide only at the temperature of about 1000 ℃, and the energy consumption can be effectively reduced compared with the traditional preparation method.
(6) And placing the crucible in a tube furnace filled with inert gas, heating the tube furnace from room temperature to 900-1200 ℃, preserving heat for 4-6 h, and naturally cooling to obtain the carbide.
Specifically, after the solidified precursor and the auxiliary powder are placed in the crucible, the crucible can be placed in a tubular furnace to be roasted according to a preset roasting procedure, namely, the temperature is increased to 900-1200 ℃ from room temperature and is kept for 4-6 hours, and the carbide corresponding to the precursor powder is obtained after roasting is finished. During firing, the tube furnace may be filled with an inert gas to prevent oxidation during carbide formation from the cured precursor.
Preferably, the precursor powder includes one or more of tungsten powder, molybdenum powder, silicon powder, titanium powder, zirconium powder, or hafnium powder.
Preferably, the mass of the carbon black powder in the auxiliary powder accounts for 0-20% of the total mass of the raw material components.
Preferably, the metal salt powder comprises one or more of sodium chloride, potassium chloride and sodium fluoride, and accounts for 10-30% of the total mass of the raw material components.
Preferably, the transition metal nitrate compound is one or more of nickel nitrate, iron nitrate and cobalt nitrate.
Preferably, the step (3) of soaking the waste fiber fabric in the precursor solution for 2-4 hours to obtain the precursor specifically comprises the following steps: and immersing the waste fiber fabric into the precursor solution, and stirring for 2-4 h at a constant speed in a magnetic stirring manner to obtain the precursor.
Preferably, in the step (6), the tube furnace is heated from room temperature to 900-1200 ℃ and is kept warm for 4-6 hours, and then is naturally cooled, so as to obtain the carbide, and the specific steps are as follows: and (3) heating the tubular furnace from room temperature to 600 ℃ at the heating rate of 5-10 ℃/min, heating from 600 ℃ to 900-1200 ℃ at the heating rate of 1-5 ℃/min, preserving heat for 4-6 h, and naturally cooling to obtain the carbide.
The invention also provides another technical scheme.
A carbide based on waste fiber textiles is characterized in that: the carbide comprises a waste fiber fabric and a carbide layer; and the carbonized layer takes the waste fiber fabric as a carbon source and grows on the waste fiber fabric.
Preferably, the carbide layer comprises one or more of tungsten carbide, molybdenum carbide, silicon carbide, titanium carbide, zirconium carbide or hafnium carbide.
Preferably, the carbide further comprises doped nickel particles; the waste fiber fabric comprises a plurality of waste fibers; the doped nickel particles are loaded on the waste fibers.
The carbide and the preparation method thereof have the beneficial effects that in the carbide and the preparation method thereof, waste fiber fabrics are used as carbon sources required by the synthesis of the carbide, so that the synthesis cost is reduced, and the social problem of low recovery efficiency of a large amount of waste clothes is solved. Moreover, the method places the solidified precursor in a crucible containing auxiliary powder, the auxiliary powder can be melted in the roasting process, and particles of the precursor powder are transferred to the surface of the waste fiber fabric, so that the combination temperature of the carbon source and the precursor powder is greatly reduced, and the problem that the synthesized carbide needs high energy consumption is effectively solved.
Drawings
FIG. 1 is a schematic flow chart of a method for producing a carbide according to an embodiment of the present invention;
FIG. 2 is a schematic view showing the structure of carbide in the example of the present invention;
FIG. 3 is a scanning electron micrograph of silicon carbide according to an embodiment of the present invention;
FIG. 4 is a scanning electron micrograph of titanium carbide according to an embodiment of the present invention;
FIG. 5 is a scanning electron micrograph of zirconium carbide according to an embodiment of the present invention;
FIG. 6 is a scanning electron micrograph of hafnium carbide according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1, the preparation method of the carbide based on the waste fiber textile comprises the following steps:
step S1: the raw material components by weight percentage are as follows: 20-80 wt% of precursor powder, 10-70 wt% of waste fiber fabric, 10-30 wt% of auxiliary powder and 0-10 wt% of transition metal nitrate compound; the auxiliary powder includes metal salt powder and carbon black. As shown in fig. 1, the preparation method of the carbide may include the steps of:
step S2: the precursor powder is blended in an alcohol solution to obtain a precursor solution.
In this embodiment, the precursor powder may be a chemical substance composed of another synthetic element other than carbon in the carbide to be synthesized. The alcohol solution may be mixed with the precursor powder thoroughly to form a mixed solution of the precursor powder, i.e., a precursor solution.
Step S3: and soaking the waste fiber fabric in the precursor solution for 2-4 h to obtain a precursor.
Specifically, after a uniform precursor solution is formed, the rinsed waste clothes can be cut, and the waste fiber fabrics, namely the waste clothes, are soaked in the precursor solution for 2-4 hours, so that the waste fiber fabrics are fully soaked in the precursor solution. After sufficient soaking, a precursor loaded with a large amount of precursor powder is obtained. It should be noted that, in this embodiment, it is only necessary to ensure that the waste fiber fabric can be immersed in the precursor solution, and the alcohol solution in the precursor solution is not completely consumed after the waste fiber fabric is sufficiently immersed. Specifically, the waste fiber fabric may include various clothes containing waste fibers as main components, such as cotton T-shirts, cotton casual pants, and the like(ii) a Or linen clothes such as linen T-shirts, linen casual pants and the like; or cotton and hemp blended clothes. In other embodiments, the waste fiber fabric may not be pure cotton or linen, and may be mixed with animal hair components or chemical fibers as long as the waste fibers are the main components. The main component of the plant fiber fabric is (C6H10O5)nBy means of the carbon element provided by the plant fiber fabric, the carbide corresponding to the precursor powder can be further grown on the plant fiber fabric, so that the aims of reducing the synthesis cost of the carbide and improving the recycling rate of the waste clothes are fulfilled.
Step S4: and drying the precursor at 75-110 ℃ for 2-4 h to obtain a cured precursor.
Specifically, after the waste fiber fabric is fully soaked in the precursor solution in the step S2, a large amount of precursor powder is loaded on the waste fiber fabric, and in this step, the waste fiber fabric can be further cured, that is, the soaked waste fiber fabric is dried at 75-110 ℃ for 2-4 hours, so as to obtain a cured precursor, and the precursor powder can be well adhered to the waste fiber fabric, so that the precursor powder is prevented from falling off from the waste fiber fabric in the subsequent treatment process, and the generated carbide is less. That is, the carbide yield efficiency can be improved by the solidification treatment in this step.
Step S5: the solidified precursor is placed in a crucible containing the auxiliary powder.
Specifically, the cured precursor obtained after the curing treatment may be placed in a crucible, and the auxiliary powder may be placed in the crucible. In the present embodiment, the auxiliary powder may include metal salt powder, such as single metal salt or mixed powder of multiple metal salts, e.g., sodium chloride, potassium chloride, sodium fluoride; the crucible may be an alumina crucible or a graphite crucible. The auxiliary powder can be put into the crucible firstly, and then the solidified precursor is put on the auxiliary powder; or the solidified precursor is put into a crucible firstly, and then auxiliary powder is poured into the crucible; in other embodiments, the auxiliary powder may be poured in several times, that is, a part of the auxiliary powder is placed at the bottom of the crucible, and after the solidified precursor is placed in the crucible, the rest of the auxiliary powder is poured on the solidified precursor, so as to improve the yield of the carbide. In the embodiment, the synthesis temperature can be greatly reduced by adding the auxiliary powder comprising the metal salt, so that the formed carbide can be prepared only at the temperature of about 1000 ℃, and the energy consumption can be effectively reduced compared with the traditional preparation method.
Step S6: and (3) placing the crucible in a tubular furnace filled with inert gas, heating the tubular furnace from room temperature to 900-1200 ℃, preserving heat for 4-6 h, and naturally cooling to obtain carbide.
Specifically, after the solidified precursor and the auxiliary powder are placed in the crucible, the crucible can be placed in a tubular furnace to be roasted according to a preset roasting procedure, namely, the temperature is increased to 900-1200 ℃ from room temperature and is kept for 4-6 hours, and the carbide corresponding to the precursor powder is obtained after roasting is finished. During firing, the tube furnace may be filled with an inert gas to prevent oxidation during carbide formation from the cured precursor.
In the carbide preparation method, the waste fiber fabric is used as a carbon source required by the synthesis of the carbide, so that the synthesis cost is reduced, and the social problem of low recovery efficiency of a large amount of waste clothes is solved. Moreover, the method places the solidified precursor in a crucible containing auxiliary powder, the auxiliary powder can be melted in the roasting process, and particles of the precursor powder are transferred to the surface of the waste fiber fabric, so that the combination temperature of the carbon source and the precursor powder is greatly reduced, and the problem that the synthesized carbide needs high energy consumption is effectively solved.
Based on the carbide preparation method in the above embodiments, in one embodiment, the precursor powder may include tungsten powder, molybdenum powder, silicon powder, titanium powder, zirconium powder, or hafnium powder. Corresponding tungsten carbide, molybdenum carbide, silicon carbide, titanium carbide, zirconium carbide or hafnium carbide may be produced from the precursor powder.
Based on the carbide preparation method in the above embodiment, in an embodiment, the auxiliary powder may further include carbon black powder, and the mass of the carbon black powder may be 0 to 20 wt% of the total mass of the raw material components.
Specifically, carbon black powder may be mixed with metal salt powder and placed in a crucible together with the cured precursor. Because the metal salt powder is melted in the roasting process and further transmits precursor powder particles to the surface of the waste fiber fabric, the waste fibers can be damaged in the process, namely the carbon source is lost, so that the output of carbide can be influenced. Therefore, in the embodiment, the carbon black powder is additionally supplemented in the crucible, so that in the roasting process, the carbon black powder is transferred to the surface of the waste fiber by the molten metal salt, the carbon source loss caused by the damage of the waste fiber in the process is compensated, and the output efficiency of the carbide is improved.
Based on the carbide preparation method in the above embodiment, the step of soaking the waste fiber fabric in the precursor solution for 2-4 hours to obtain the precursor may further include: and immersing the waste fiber fabric into the precursor solution, and stirring for 2-4 h at a constant speed in a magnetic stirring manner to obtain a precursor.
Specifically, after the waste fiber fabric is immersed in the precursor solution, the solution can be uniformly stirred by adopting magnetic stirring equipment, so that the waste fiber fabric can be fully immersed in the precursor solution, and precursor powder can be uniformly attached to the fabric, thereby being beneficial to the distribution of subsequent transition carbides. In one embodiment, the stirring process can be maintained for 2 hours, so that the waste fiber clothes can be fully soaked without tearing of the waste fiber fabric due to excessive stirring in a wet state.
Based on the carbide preparation method in the embodiment, the method comprises the following steps of heating the tubular furnace from room temperature to 900-1200 ℃, preserving heat for 4-6 hours, and naturally cooling to obtain the carbide: and (3) heating the tubular furnace from room temperature to 600 ℃ at the heating rate of 5-10 ℃/min, heating from 600 ℃ to 900-1200 ℃ at the heating rate of 5-10 ℃/min, preserving heat for 4-6 h, and naturally cooling to obtain the carbide.
Specifically, after the precursor is cured and the cured precursor is obtained, the cured precursor can be placed in a tube furnace for roasting, and during the roasting process, the cured precursor can be always in an argon atmosphere, so that the reaction raw materials are prevented from being oxidized at high temperature. In one embodiment, the firing parameters may be set to staged firing. In the first stage of roasting system, the temperature of the tubular furnace can be raised from room temperature to 600 ℃ at the temperature raising rate of 5-10 ℃/min, so that the temperature in the tubular furnace can be quickly close to the carbide generation temperature, and the energy consumption is reduced. In the next second stage of roasting system, the temperature of the tubular furnace can be increased from 600 ℃ to 900-1200 ℃ at the temperature increasing rate of 1-5 ℃/min, the tubular furnace is kept warm for 4-6 hours and then is naturally cooled, so that the precursor powder can fully react with the waste fiber fabric to generate sufficient carbide attached to the waste fiber, and meanwhile, the waste fiber clothes are not cracked due to serious carbonization caused by overhigh reaction temperature or overlong reaction time.
Based on the carbide preparation method in the above embodiments, in one embodiment, the raw material composition may further include nickel nitrate; the mass of the nickel nitrate accounts for 0-10 wt% of the total mass of the raw material components.
Specifically, nickel nitrate may be poured into an alcohol solution together with the precursor powder and sufficiently stirred so that the nickel nitrate may be completely dissolved in the alcohol solution. By doping nickel nitrate, nickel element can be doped into the carbide obtained subsequently, so that the performances of the carbide such as conductivity, mechanical strength and the like are improved.
As shown in fig. 2, the present embodiment provides a carbide, which may include a waste fiber fabric 2 and a carbide layer 1. Specifically, during the tube furnace roasting process, the metal salt powder in the crucible can be melted, and the melted metal salt will transport the precursor powder and transport the precursor powder to the surface of the waste fiber fabric 2. The precursor powder transported to the surface of the waste fiber fabric 2 can be further subjected to atomic bonding with the waste fiber, that is, chemical combination reaction, and finally the carbonized layer 1 which takes the waste fiber fabric 2 as a carbon source and grows on the waste fiber fabric 2 is obtained.
In the above embodiment, the waste fiber fabric may be waste fiber clothing. In the embodiment of the invention, the waste fiber clothes can comprise various clothes taking waste fibers as main components, such as cotton T-shirts, cotton casual pants and other cotton clothes; or linen clothes such as linen T-shirts, linen casual pants and the like; or cotton and hemp blended clothes. In other embodiments, the waste fiber clothing may not be pure cotton or hemp clothing, but may also be mixed with animal hair components or chemical fibers, as long as the waste fibers are the main components. Since the waste clothes are used as a source of carbon element of carbide, a large amount of waste clothes generated every year can be recycled, and thus the green development can be promoted.
In one embodiment, the carbide layer may be tungsten carbide, molybdenum carbide, silicon carbide, titanium carbide, zirconium carbide, or hafnium carbide. In this case, the precursor powder may correspond to metal tungsten powder, metal molybdenum powder, metal silicon powder, metal titanium powder, metal zirconium powder, or metal hafnium powder.
In one embodiment, the carbide may be further doped with nickel particles, and the source of the nickel element may be nickel nitrate. Further, the waste fiber fabric may have a plurality of fabric fibers, and the doped nickel particles may be supported on the waste fibers. In this embodiment, the nickel particles are loaded on the plurality of textile fibers of the waste fiber textile, so that the properties of the carbide, such as conductivity and mechanical strength, can be improved.
The preparation method of the carbide based on the waste fiber textile comprises the following specific examples:
example 1:
the preparation method of the carbide based on the waste fiber textile comprises the following steps:
step S1: preparing raw materials: the components are calculated according to the mass percentage: 20% of silicon powder (serving as precursor powder), 70% of waste fiber fabric and 10% of sodium chloride powder (serving as auxiliary powder).
Step S2: the silicon powder is poured into 100ml of alcohol solution, and the precursor solution with the suspended silicon powder is formed after full stirring.
Step S3: the waste fiber fabric is placed into the precursor solution of step S2 such that the waste fiber fabric is completely immersed in the alcohol solution. Stirring for two hours at a constant speed by using a magnetic stirring device to obtain a precursor; in the process, the waste fiber fabric can be fully loaded with silicon powder.
Step S4: and putting the precursor into an oven at 110 ℃ for 4h, and completely curing the precursor in a wet state to form a cured precursor. During the solidification process, the silicon powder attached to the waste fiber fabric is fixed on the clothes fibers of the waste fiber clothes or gaps among the clothes fibers.
Step S5: sodium chloride powder was poured into a graphite crucible, and then a cured precursor was placed on the sodium chloride powder.
Step S6: placing the graphite crucible filled with the solidified precursor and sodium chloride powder in a tubular furnace, after introducing argon gas, setting a program to heat up to 600 ℃ at a heating rate of 10 ℃/min, then heating up to 900 ℃ from 600 ℃ at a heating rate of 5 ℃/min, preserving heat for 6h, and naturally cooling to room temperature to obtain the silicon carbide. In the process, the sodium chloride powder is melted, and the silicon powder is promoted to fully react with the waste fiber fabric, so that silicon carbide as shown in figure 3 is generated on the waste fiber fabric.
Example 2:
the preparation method of the carbide based on the waste fiber textile comprises the following steps:
step S1: preparing raw materials: the components are calculated according to the mass percentage: the precursor powder comprises silicon powder and titanium powder, wherein the silicon powder accounts for 30 percent, the titanium powder accounts for 20 percent, the waste fiber fabric accounts for 40 percent, and the sodium chloride powder (serving as auxiliary powder) accounts for 10 percent.
Step S2: weighing silicon powder and titanium powder, pouring the silicon powder and the titanium powder into 100ml of alcohol solution, and fully stirring to form precursor solution in which silicon powder is suspended.
Step S3: and (3) putting the waste fiber fabric into the precursor solution, so that the waste fiber fabric is completely immersed by the alcohol solution. Stirring for 4 hours at constant speed by using a magnetic stirring device to obtain a precursor.
Step S4: and putting the precursor into a 75 ℃ oven for 4h to completely cure the precursor in a wet state so as to form a cured precursor.
Step S5: sodium chloride powder was poured into a graphite crucible, and then a cured precursor was placed on the sodium chloride powder.
Step S6: placing a graphite crucible filled with a solidified precursor and sodium chloride powder in a tubular furnace, after introducing argon gas, setting a program to heat up to 600 ℃ at a heating rate of 5 ℃/min, then heating up to 1000 ℃ from 600 ℃ at a heating rate of 5 ℃/min, and naturally cooling to room temperature after preserving heat for 5h so as to obtain a mixture of silicon carbide and titanium carbide generated on the waste fiber fabric.
Example 3
The preparation method of the carbide based on the waste fiber textile comprises the following steps:
step S1: preparing raw materials: the components are calculated according to the mass percentage: 30% of titanium powder; 30% of waste fiber fabric; the auxiliary powder comprises sodium chloride powder and carbon black powder, wherein the sodium chloride powder accounts for 10 percent, and the carbon black powder accounts for 20 percent; 10% of nickel nitrate.
Step S2: titanium powder and nickel nitrate are poured into 100ml of alcohol solution, and the precursor solution is formed after full stirring.
Step S3: and putting the waste fiber fabric into the flooding solution, so that the waste fiber fabric is completely immersed by the alcohol solution. Stirring for 2 hours at constant speed by using a magnetic stirring device to obtain a precursor.
Step S4: and putting the precursor into a 75 ℃ oven for 4h to completely cure the precursor in a wet state so as to form a cured precursor.
Step S5: sodium chloride powder and carbon black powder are fully ground and mixed to form auxiliary powder, the auxiliary powder is poured into a graphite crucible, and then a solidified precursor is placed on the auxiliary powder.
Step S6: placing the graphite crucible filled with the solidified precursor and the auxiliary powder in a tubular furnace, after introducing argon gas, setting a program to heat up to 600 ℃ at a heating rate of 5 ℃/min, then heating up to 1000 ℃ from 600 ℃ at a heating rate of 5 ℃/min, and naturally cooling to room temperature after keeping the temperature for 4h to obtain the titanium carbide shown in figure 4.
Example 4
The preparation method of the carbide based on the waste fiber textile comprises the following steps:
step S1: preparing raw materials: the components are calculated according to the mass percentage: 20% of zirconium powder; 45% of waste fiber fabric; the auxiliary powder comprises sodium chloride powder and carbon black powder, wherein the sodium chloride powder accounts for 10 percent, and the carbon black powder accounts for 20 percent; 5% of nickel nitrate.
Step S2: zirconium powder and nickel nitrate are poured into 100ml of alcohol solution, and the precursor solution is formed after full stirring.
Step S3: and putting the waste fiber fabric into the precursor solution, so that the waste fiber fabric is completely immersed by the alcohol solution. Stirring for 2 hours at constant speed by using a magnetic stirring device to obtain a precursor.
Step S4: and putting the precursor into an oven at 80 ℃ for 3h, and completely curing the precursor in a wet state to form a cured precursor.
Step S5: sodium chloride powder and carbon black powder are fully ground and mixed to form auxiliary powder, the auxiliary powder is poured into a graphite crucible, and then a solidified precursor is placed on the auxiliary powder.
Step S6: the graphite crucible containing the solidified precursor and the auxiliary powder may be placed in a tube furnace, after introducing argon gas, the temperature is raised to 600 ℃ at a heating rate of 10 ℃/min, then raised to 1000 ℃ from 600 ℃ at a heating rate of 3 ℃/min, and naturally cooled to room temperature after keeping the temperature for 4 hours, thereby obtaining zirconium carbide as shown in fig. 5.
Example 5
The preparation method of the carbide based on the waste fiber textile comprises the following steps:
step S1: preparing raw materials: the components are calculated according to the mass percentage: 30% of hafnium powder; 40% of waste fiber fabric; the auxiliary powder comprises sodium chloride powder and carbon black powder, wherein the sodium chloride powder accounts for 10 percent, and the carbon black powder accounts for 10 percent; 10% of nickel nitrate.
Step S2: hafnium powder and nickel nitrate are poured into 100ml of alcohol solution, and the precursor solution is formed after fully stirring.
Step S3: and putting the waste fiber fabric into the precursor solution, so that the waste fiber fabric is completely immersed by the alcohol solution. Stirring for 3 hours at constant speed by using a magnetic stirring device to obtain a precursor.
Step S4: and putting the precursor into an oven at 100 ℃ for 2.5h, and completely curing the precursor in a wet state to form a cured precursor.
Step S5: sodium chloride powder and carbon black powder are fully ground and mixed to form auxiliary powder, the auxiliary powder is poured into a graphite crucible, and then a solidified precursor is placed on the auxiliary powder.
Step S6: placing the graphite crucible filled with the solidified precursor and the auxiliary powder in a tube furnace, after introducing helium gas, setting a program to heat up to 600 ℃ at a heating rate of 10 ℃/min, then heating up to 1200 ℃ from 600 ℃ at a heating rate of 5 ℃/min, and naturally cooling to room temperature after keeping the temperature for 6 hours, thereby obtaining the hafnium carbide shown in fig. 6.
Example 6
The preparation method of the carbide based on the waste fiber textile comprises the following steps:
step S1: preparing raw materials: the components are calculated according to the mass percentage: 34% of tungsten powder; 34% of waste fiber fabric; the auxiliary powder comprises sodium chloride powder, potassium chloride powder and carbon black powder, wherein the sodium chloride powder accounts for 10 percent, the potassium chloride powder accounts for 10 percent, and the carbon black powder accounts for 10 percent; 2 percent of ferric nitrate.
Step S2: tungsten powder and ferric nitrate are poured into 100ml of alcohol solution, and the precursor solution is formed after the tungsten powder and the ferric nitrate are fully stirred.
Step S3: and putting the waste fiber fabric into the precursor solution, so that the waste fiber fabric is completely immersed by the alcohol solution. Stirring for 2 hours at constant speed by using a magnetic stirring device to obtain a precursor.
Step S4: and putting the precursor into a drying oven at 110 ℃ for 3h, and completely curing the precursor in a wet state to form a cured precursor.
Step S5: sodium chloride powder, potassium chloride powder and carbon black powder are fully ground and mixed to form auxiliary powder, the auxiliary powder is poured into a graphite crucible, and then a solidified precursor is placed on the auxiliary powder.
Step S6: placing the graphite crucible filled with the solidified precursor and the auxiliary powder in a tubular furnace, setting a program to heat up to 600 ℃ at a heating rate of 10 ℃/min after introducing helium gas, then heating up to 1000 ℃ from 600 ℃ at a heating rate of 3 ℃/min, preserving heat for 6h, and naturally cooling to room temperature to obtain the tungsten carbide.
Example 7
The preparation method of the carbide based on the waste fiber textile comprises the following steps:
step S1: preparing raw materials: the components are calculated according to the mass percentage: 30% of molybdenum powder; 35% of waste fiber fabric; the auxiliary powder comprises sodium chloride powder, potassium chloride powder, sodium fluoride powder and carbon black powder, wherein the sodium chloride powder is 5 percent, the potassium chloride powder is 5 percent, the sodium fluoride powder is 5 percent, and the carbon black powder is 15 percent; 5 percent of cobalt nitrate.
Step S2: molybdenum powder cobalt nitrate is poured into 100ml of alcohol solution, and the precursor solution is formed after the mixture is fully stirred.
Step S3: and putting the waste fiber fabric into the precursor solution, so that the waste fiber fabric is completely immersed by the alcohol solution. Stirring for 2 hours at constant speed by using a magnetic stirring device to obtain a precursor.
Step S4: and putting the precursor into a drying oven at 110 ℃ for 3h, and completely curing the precursor in a wet state to form a cured precursor.
Step S5: sodium chloride powder, potassium chloride powder, sodium fluoride powder and carbon black powder are fully ground and mixed to form auxiliary powder, the auxiliary powder is poured into a graphite crucible, and then a solidified precursor is placed on the auxiliary powder.
Step S6: placing the graphite crucible filled with the solidified precursor and the auxiliary powder in a tubular furnace, setting a program to heat up to 600 ℃ at a heating rate of 10 ℃/min after introducing helium gas, then heating up to 900 ℃ from 600 ℃ at a heating rate of 3 ℃/min, preserving heat for 6h, and naturally cooling to room temperature to obtain the molybdenum carbide.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of the carbide based on the waste fiber textile is characterized by comprising the following preparation steps:
(1) preparing raw materials: according to mass percent, 20-80% of precursor powder, 10-70% of waste fiber fabric, 10-30% of auxiliary powder and 0-10% of transition metal nitrate compound; the auxiliary powder comprises metal salt powder and carbon black;
(2) adding the precursor powder and a transition metal nitrate compound to an alcohol solution to obtain a precursor solution;
(3) soaking the waste fiber fabric in the precursor solution for 2-4 h to obtain a precursor;
(4) drying the precursor at 75-110 ℃ for 2-4 h to obtain a cured precursor;
(5) placing the solidified precursor in a crucible containing the auxiliary powder;
(6) and placing the crucible in a tube furnace filled with inert gas, heating the tube furnace from room temperature to 900-1200 ℃, preserving heat for 4-6 h, and naturally cooling to obtain the carbide.
2. The method for preparing carbides based on waste fiber textiles according to claim 1, characterized in that: the precursor powder comprises one or more of tungsten powder, molybdenum powder, silicon powder, titanium powder, zirconium powder or hafnium powder.
3. The method of claim 1, wherein: the mass of the carbon black powder in the auxiliary powder accounts for 0-20% of the total mass of the raw material components.
4. The method for preparing carbides based on waste fiber textiles according to claim 1, characterized in that: the metal salt powder comprises one or more of sodium chloride, potassium chloride and sodium fluoride, and accounts for 10-30% of the total mass of the raw material components.
5. The method for preparing carbides based on waste fiber textiles according to claim 1, characterized in that: the transition metal nitrate compound is one or more of nickel nitrate, ferric nitrate and cobalt nitrate.
6. The method for preparing carbides based on waste fiber textiles according to claim 1, characterized in that: the step (3) of soaking the waste fiber fabric in the precursor solution for 2-4 h to obtain the precursor comprises the following specific steps: and immersing the waste fiber fabric into the precursor solution, and stirring for 2-4 h at a constant speed in a magnetic stirring manner to obtain the precursor.
7. The method for preparing carbides based on waste fiber textiles according to claim 1, characterized in that: in the step (6), the temperature of the tube furnace is increased from room temperature to 900-1200 ℃, the temperature is kept for 4-6 hours, and then the tube furnace is naturally cooled to obtain the carbide, which comprises the following specific steps: and (3) heating the tubular furnace from room temperature to 600 ℃ at the heating rate of 5-10 ℃/min, heating from 600 ℃ to 900-1200 ℃ at the heating rate of 1-5 ℃/min, preserving heat for 4-6 h, and naturally cooling to obtain the carbide.
8. A carbide based on waste fiber textiles is characterized in that: the carbide comprises a waste fiber fabric and a carbide layer; and the carbonized layer takes the waste fiber fabric as a carbon source and grows on the waste fiber fabric.
9. The carbides based on waste fibre textiles according to claim 8, characterized in that: the carbide layer comprises one or more of tungsten carbide, molybdenum carbide, silicon carbide, titanium carbide, zirconium carbide or hafnium carbide.
10. The carbides based on waste fibre textiles according to claim 8, characterized in that: the carbide further comprises doped nickel particles; the waste fiber fabric comprises a plurality of waste fibers; the doped nickel particles are loaded on the waste fibers.
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