CN110983212A - Preparation method of iron-based composite material - Google Patents
Preparation method of iron-based composite material Download PDFInfo
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- CN110983212A CN110983212A CN201911331166.0A CN201911331166A CN110983212A CN 110983212 A CN110983212 A CN 110983212A CN 201911331166 A CN201911331166 A CN 201911331166A CN 110983212 A CN110983212 A CN 110983212A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention discloses a preparation method of an iron-based composite material, and belongs to the technical field of metal materials. The invention mixes the rice hull fiber with hydrochloric acid; mixing the primary treated rice hull fiber, secondary sedimentation tank sludge, cane sugar and water, sealing and fermenting, adding a ferric nitrate solution and copper acetate, dropwise adding a potassium oxalate solution, and adding a urea solution to adjust the pH value; stirring and mixing the secondarily processed rice hull fiber and the modified chitosan solution, adding a calcium nitrate solution, and performing freeze-thaw circulation; placing the rice hull fiber subjected to the third treatment in a carbonization furnace, gradually heating and carbonizing to obtain modified rice hull fiber; mixing and ball-milling modified rice hull fiber, organic silicon resin, a curing agent, nano iron powder, an emulsifier, organic acid, oyster shell powder, starch and deionized water to obtain a ball grinding material, hot-pressing and molding the ball grinding material, demolding to obtain a blank, placing the blank in a sintering furnace, gradually heating, and filling nitrogen for sintering to obtain the iron-based composite material. The iron-based composite material provided by the invention has excellent mechanical properties.
Description
Technical Field
The invention discloses a preparation method of an iron-based composite material, and belongs to the technical field of metal materials.
Background
The carbon fiber reinforced metal matrix composite material is used as a representative of light, heat-resistant, high-strength and deformable processing materials, and has wider application prospect in the field of aerospace. Various carbon fiber composite material samples are prepared by a powder metallurgy method, a hot rolling method and a hot pressing method, the microstructure and the interface bonding condition of the composite material samples are observed by combining an optical microscope, a scanning electron microscope and the like, the related performance of the composite material samples is tested and analyzed, a plurality of simple methods for preparing the carbon fiber composite material are preliminarily discussed, and preliminary experiment bases are provided for preparing the carbon fiber composite material under different processing conditions.
Carbon fiber and iron powder are used as raw materials, and a powder metallurgy method is adopted to prepare the carbon fiber reinforced iron-based composite material and the carbon fiber reinforced iron-based composite material. The result shows that after the carbon fiber and the iron-based powder are sintered, the carbon fiber part keeps the original shape, a large amount of iron-carbon compounds are not formed, the bonding area with the matrix is less, the distribution is not uniform, and the iron-based composite material has pores, so that the material performance is poor; the original appearance of the carbon fiber is kept less after the titanium-based composite material is sintered, and an interface reaction occurs in the sintering process, so that the performance of the composite material is enhanced. Meanwhile, the carbon fiber content is increased, the wear resistance of the composite material is improved, and the hardness is increased.
Disclosure of Invention
The invention aims to provide a preparation method of an iron-based composite material, which aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
an iron-based composite material comprises the following raw materials in parts by weight: 2-3 parts of rice hull fiber, 3-5 parts of a curing agent, 100-120 parts of nano iron powder, 2-3 parts of an emulsifier, 1-2 parts of an organic acid, 1-2 parts of oyster shell powder and 10-20 parts of deionized water.
The iron-based composite material also comprises the following raw materials in parts by weight: 20-30 parts of organic silicon resin and 3-5 parts of starch.
The emulsifier is any one of alkylphenol polyoxyethylene, high-carbon fatty alcohol polyoxyethylene, coconut oleic acid, fatty acid or diethanol amine; the organic acid is any one of stearic acid, oleic acid or linoleic acid; the organic silicon resin is any one of polymethyl organic silicon resin, polyethyl organic silicon resin or polyaryl organic silicon resin; the starch is any one of glutinous rice starch, corn starch, sweet potato starch, potato starch or wheat starch.
The iron-based composite material comprises the following raw materials in parts by weight: 3 parts of rice hull fiber, 5 parts of a curing agent, 120 parts of nano iron powder, 3 parts of an emulsifier, 2 parts of organic acid, 2 parts of oyster shell powder, 20 parts of deionized water, 30 parts of organic silicon resin and 5 parts of starch.
A preparation method of an iron-based composite material comprises the following specific preparation steps:
(1) treating rice hull fiber for one time;
(2) carrying out secondary treatment on the product obtained in the step (1);
(3) treating the substance obtained in the step (2) for three times;
(4) modifying the product obtained in the step (3);
(5) mixing materials;
(6) hot-pressing the product obtained in the step (5) for forming;
(7) and (4) sintering the product obtained in the step (6).
The iron-based composite material is prepared by the following specific steps:
(1) mixing and stirring the rice hull fiber and hydrochloric acid, standing, filtering, washing and drying to obtain the once-treated rice hull fiber, and treating with hydrochloric acid to improve the permeability of the rice hull fiber and enable more water to permeate into the fiber;
(2) mixing the primary treated rice hull fiber, secondary sedimentation tank sludge, cane sugar and water, sealing and fermenting, then adding ferric nitrate solution and copper acetate, then dropwise adding potassium oxalate solution, then adding urea solution to adjust pH, filtering, freezing, ball-milling, sieving and drying to obtain secondary treated rice hull fiber, wherein in the fermentation process, firstly, anaerobic respiration of microorganisms generates ethanol which is helpful for dissolving copper acetate in a system, then, dropwise adding potassium oxalate solution, potassium oxalate can react with copper acetate in the system to generate copper oxalate precipitate which is deposited in the fiber, secondly, because the bacterial cell wall has negative charge, iron ions with positive charge can be attracted, then, through dropwise adding urea, hydroxide ions generated by urea hydrolysis are utilized to precipitate iron ions in the system to generate ferric hydroxide, and in addition, nitrate ions are combined with another hydrolysis product ammonium ions of urea, generating ammonium nitrate, freezing to form ice crystals among fiber cells, ball milling to break the ice crystals to break the fibers into micro-nano fiber whiskers, straightening the micro-nano fiber whiskers in the system, and ensuring that the micro-nano fiber whiskers are not easy to wind in the mixing process and have good dispersion performance;
(3) stirring and mixing the secondary treated rice hull fiber and the modified chitosan solution, then adding a calcium nitrate solution, performing freeze-thaw cycle, filtering, washing and drying to obtain a tertiary treated rice hull fiber, introducing calcium ions into the system by adding the calcium nitrate, wherein the calcium ions can promote the modified chitosan in the system to be crosslinked to form a three-dimensional network, and then improving the strength of a modified chitosan film formed on the surface of the fiber through the freeze-thaw cycle;
(4) placing the rice hull fiber subjected to the three-time treatment in a carbonization furnace, gradually heating and carbonizing to obtain a modified rice hull fiber, wherein in the carbonization process, firstly, ammonium nitrate deposited in the fiber is heated and decomposed to generate gas, the gas is stored in a system due to the existence of a modified chitosan film on the surface of the fiber, copper oxalate deposited in the fiber is heated and decomposed along with the gradual rise of the temperature of the system to generate carbon dioxide and copper oxide, secondly, organic matters in the system start to be carbonized, organic matters in the fiber are carbonized and shrunk, but a hard siliceous layer exists on the surface of the rice hull fiber to block the carbonization and shrinkage of the organic matters in the fiber, so that the rice hull fiber is spirally curled to form the rice hull fiber in a spiral curling shape, the carbonized rice hull fiber in the spiral curling shape can be well dispersed in the ball milling process, and simultaneously, the gas in the system is under the pressure generated by the spiral curling, the expansion is generated, copper oxide particles and iron oxide particles in the system are extruded by expansion pressure, so that a large number of bulges are formed on the surface of the fiber, and partial copper oxide particles and iron oxide particles are even extruded out, so that pores appear on the surface of the fiber, the contact bonding area between the modified rice hull fiber and the matrix is increased, so that the mechanical property of the system is further improved, and meanwhile, the defects or the pores exist, so that in the later-stage sintering process, part of molten iron permeates into the fiber from the defects or the pores on the surface of the fiber, so that the interface bonding strength between the modified fiber and the matrix is further improved, and the mechanical property of the system is improved;
(5) mixing and ball-milling modified rice hull fiber, a curing agent, nano iron powder, an emulsifier, organic acid, oyster shell powder, deionized water, organic silicon resin and starch to obtain a ball grinding material, wherein the starch is added, so that the structure and the particle morphology of a starch crystallization area are damaged in the ball-milling process, and the crystallinity is effectively reduced, so that the fluidity of activated starch in a system is enhanced, and all components in the system can be fully mixed;
(6) hot-pressing the ball-milled material, and demolding to obtain a blank;
(7) the blank is placed in a sintering furnace, the temperature is raised step by step, nitrogen is filled for sintering, the iron-based composite material is obtained, organic silicon resin is added into the system, in the nitrogen filling sintering process, the organic silicon resin is heated and decomposed, and the residual radicals obtained by decomposition can be combined with the simple substance iron in the system, so that the modified rice hull fiber and the matrix metal form precise combination, the density of the system is improved, and the mechanical property of the system is further improved.
The iron-based composite material is prepared by the following specific preparation process:
(1) placing the rice hull fiber and hydrochloric acid in a No. 1 beaker according to a mass ratio of 1: 10-1: 20, mixing and stirring for 40-60 min under the condition that the rotating speed is 300-500 r/min, standing for 3-5 h, filtering to obtain No. 1 filter residue, washing the No. 1 filter residue with glacial acetic acid until the washing liquid is neutral, then placing the washed No. 1 filter residue in an oven, and drying to constant weight under the condition that the temperature is 105-110 ℃ to obtain the primary treated rice hull fiber;
(2) mixing 20-30 parts by weight of primary treated rice hull fiber, 1-2 parts by weight of secondary sedimentation tank sludge, 0.3-0.5 part by weight of sucrose and 30-50 parts by weight of water, placing the mixture in a fermentation kettle, hermetically fermenting for 3-5 days at the temperature of 30-35 ℃, adding a ferric nitrate solution with the mass fraction of 10-20% and 0.03-0.05 times by weight of the primary treated rice hull fiber into the fermentation kettle, dropwise adding a potassium oxalate solution with the mass fraction of 8-10% into the fermentation kettle by a rubber head dropper, adding a urea solution with the mass fraction of 8-10% into the fermentation kettle, adjusting the pH value to 7.4-7.6, filtering to obtain No. 2 filter residue, placing the No. 2 filter residue in liquid nitrogen for freezing to obtain a frozen material, placing the frozen material in a ball mill, sieving by a 320-mesh sieve, obtaining ball-milling frozen material, then placing the ball-milling frozen material in an oven, and drying the ball-milling frozen material to constant weight under the condition that the temperature is 105-110 ℃ to obtain secondary treated rice hull fiber;
(3) placing the secondary-treatment rice hull fiber and the modified chitosan solution in a mixer according to a mass ratio of 1: 10-1: 20, stirring and mixing for 40-60 min under the condition that the rotating speed is 600-800 r/min, then adding a calcium nitrate solution with a mass fraction of 10-20% and 0.1-0.2 times of the mass of the secondary-treatment rice hull fiber into the mixer to obtain a mixed solution, then placing the mixed solution into a refrigerator, freezing for 6-8 h at the temperature of-1-10 ℃ to obtain a frozen block, then placing the frozen block at room temperature until the frozen block is completely melted, performing freeze-thaw cycle for 5-8 times, filtering to obtain No. 3, then washing the No. 3 filter residue with deionized water for 5-8 times, then placing the washed No. 3 filter residue into an oven, and drying to constant weight at the temperature of 105-110 ℃ to obtain tertiary-treatment rice hull fiber;
(4) placing the rice hull fiber subjected to the tertiary treatment in a carbonization furnace, introducing nitrogen into the carbonization furnace at the speed of 100-120 mL/min, heating to 650-750 ℃ at the speed of 8-10 ℃/min, carbonizing for 3-5 hours at the temperature of 650-750 ℃, and cooling to room temperature along with the furnace to obtain modified rice hull fiber;
(5) according to the weight parts, 2-3 parts of modified rice hull fiber, 3-5 parts of curing agent, 100-120 parts of nano iron powder, 2-3 parts of emulsifier, 1-2 parts of organic acid, 1-2 parts of oyster shell powder, 10-20 parts of deionized water, 20-30 parts of organic silicon resin and 3-5 parts of starch are placed in a ball mill, and mixed and ball-milled for 40-60 min to obtain a ball grinding material;
(6) pouring the ball-milling material into a mold, then performing hot press molding in a molding machine in the mold under the conditions that the temperature is 130-140 ℃ and the pressure is 20-30 MPa, and demolding to obtain a blank;
(7) and placing the blank in a sintering furnace, filling nitrogen into the sintering furnace at the speed of 100-120 mL/min, heating to 1450-1550 ℃ at the speed of 10-15 ℃/min, filling nitrogen to sinter for 3-5 h at the temperature of 1450-1550 ℃, and cooling to room temperature along with the furnace to obtain the iron-based composite material.
The preparation process of the modified shell polysaccharide liquid in the step (3) is as follows: placing chitosan and water in a No. 2 beaker according to a mass ratio of 1: 50-1: 100, stirring for 10-20 min by using a glass rod, standing and swelling for 3-5 h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, heating, stirring and dissolving for 40-60 min at a temperature of 90-95 ℃ and a rotating speed of 500-600 r/min, cooling to 30-35 ℃, adding chitosanase with a mass of 0.01-0.02 times of that of the chitosan into the No. 2 beaker, heating, stirring and carrying out enzymolysis for 40-60 min at a temperature of 30-35 ℃ and a rotating speed of 300-500 r/min, and then heating to 90-95 ℃ to inactivate the enzyme to obtain the modified chitosan liquid.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the preparation process, firstly, in the fermentation process, anaerobic respiration of microorganisms generates ethanol which is helpful for dissolving copper acetate in a system, then potassium oxalate solution is dripped, potassium oxalate can react with the copper acetate in the system to generate copper oxalate precipitate to be deposited in fibers, secondly, because bacterial cell walls have negative charges, iron ions with positive charges can be attracted, then urea is dripped, hydroxide ions generated by urea hydrolysis are utilized to precipitate the iron ions in the system to generate ferric hydroxide, in addition, nitrate ions are combined with ammonium ions of another hydrolysis product of the urea to generate ammonium nitrate, thirdly, freezing is carried out to form ice crystals among fiber cells, and then ball milling and ice crystal cracking are carried out to split the fibers into fiber whiskers with micro-nano scale which can be straightened in the system, the micro-nano fibers have larger specific surface area than common fibers and can be fully combined with matrix metal, so that the mechanical property of the system is further improved; finally, in the carbonization process, the ammonium nitrate deposited in the fiber is heated and decomposed to generate gas, the gas is stored in the system due to the existence of the modified chitosan film on the surface of the fiber, the copper oxalate deposited in the fiber is heated and decomposed to generate carbon dioxide and copper oxide, then, organic matters in the system start to be carbonized, the organic matters in the fiber are carbonized and shrunk, but the carbonization shrinkage of the organic matters in the fiber is hindered due to the existence of a hard silica layer on the surface of the rice hull fiber, so that the rice hull fiber is spirally curled to form the spirally curled rice hull fiber, the spirally curled carbonized rice hull fiber can be well dispersed in the ball milling process, meanwhile, the gas in the system expands under the pressure generated by the spiral curling, and the copper oxide particles and the iron oxide particles in the system are extruded by expansion pressure to form a large number of bulges on the surface of the fiber, partial copper oxide particles and iron oxide particles are even extruded out, so that pores appear on the surface of the fiber, the contact bonding area between the modified rice hull fiber and the matrix is increased, the mechanical property of the system is further improved, and meanwhile, the defects or the pores exist, so that in the later sintering process, part of molten iron permeates into the fiber from the defects or the pores on the surface of the fiber, the interface bonding strength between the modified fiber and the matrix is further improved, and the mechanical property of the system is improved;
(2) according to the invention, by adding starch, in the ball milling process, the structure of a starch crystallization area and the appearance of particles are damaged, and the crystallinity is effectively reduced, so that the fluidity of activated starch in a system is enhanced, all components in the system can be fully mixed, the dispersibility of modified rice hull fiber in the system is improved, and the mechanical property of the system is further improved;
(3) according to the invention, by adding the organic silicon resin, in the nitrogen-filled sintering process, the organic silicon resin is heated and decomposed, and the residual radicals obtained by decomposition can be combined with the simple substance iron in the system, so that the modified rice hull fiber and the matrix metal form precise combination, the density of the system is improved, and the mechanical property of the system is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to more clearly illustrate the method provided by the present invention, the following examples are given, and the test methods for each index of the iron-based composite material manufactured in the following examples are as follows:
mechanical properties: a static tensile load is applied to the sample in the hot rolling direction by a WDW-200 microcomputer controlled electronic universal tensile testing machine to break the sample, and the yield strength and elongation of the sample are obtained by measuring the yield strength, breaking force and elongation of the sample spacing.
Example 1
The iron-based composite material comprises the following raw materials in parts by weight: 3 parts of rice hull fiber, 5 parts of a curing agent, 120 parts of nano iron powder, 3 parts of an emulsifier, 2 parts of organic acid, 2 parts of oyster shell powder, 20 parts of deionized water, 30 parts of organic silicon resin and 5 parts of starch.
The emulsifier is alkylphenol polyoxyethylene.
The organic acid is stearic acid.
The organic silicon resin is polymethyl organic silicon resin.
The starch is glutinous rice starch.
The iron-based composite material is prepared by the following specific preparation process:
(1) placing the rice hull fiber and hydrochloric acid in a No. 1 beaker according to a mass ratio of 1:20, mixing and stirring for 60min under the condition that the rotating speed is 500r/min, standing for 5h, filtering to obtain No. 1 filter residue, washing the No. 1 filter residue with glacial acetic acid until the washing liquid is neutral, then placing the washed No. 1 filter residue in an oven, and drying at the temperature of 110 ℃ to constant weight to obtain the primary-treated rice hull fiber;
(2) mixing 30 parts of primary treated rice hull fiber, 2 parts of secondary sedimentation tank sludge, 0.5 part of cane sugar and 50 parts of water, placing the mixture in a fermentation kettle, hermetically fermenting for 5 days at the temperature of 35 ℃, adding a ferric nitrate solution with the mass fraction of 20 percent and 0.5 time of the mass fraction of the primary treated rice hull fiber into the fermentation kettle, adding a potassium oxalate solution with the mass fraction of 10 percent, which is 0.2 time of the mass fraction of the primary treated rice hull fiber, into the fermentation kettle through a rubber head dropper, adding a urea solution with the mass fraction of 10 percent into the fermentation kettle, adjusting the pH value to 7.6, filtering to obtain No. 2 filter residue, placing the No. 2 filter residue in liquid nitrogen for freezing to obtain a frozen material, placing the frozen material in a ball mill for ball milling, sieving by a 320-mesh sieve to obtain a ball-milled frozen material, placing the ball-milled frozen material in a baking oven at the temperature of 110 ℃, drying to constant weight to obtain secondary treated rice hull fiber;
(3) placing the secondary-treated rice hull fiber and the modified chitosan solution in a mixer according to a mass ratio of 1:20, stirring and mixing for 60min at a rotating speed of 800r/min, adding a calcium nitrate solution with a mass fraction of 20% and 0.2 times of the mass of the secondary-treated rice hull fiber into the mixer to obtain a mixed solution, placing the mixed solution into a refrigerator, freezing for 8h at a temperature of-10 ℃ to obtain a frozen block, placing the frozen block at room temperature to be completely melted, performing freeze-thaw cycle for 8 times, filtering to obtain No. 3 filter residue, washing the No. 3 filter residue with deionized water for 8 times, placing the washed No. 3 filter residue into an oven, and drying to constant weight at a temperature of 110 ℃ to obtain the three-time-treated rice hull fiber;
(4) placing the rice hull fiber subjected to the three-time treatment in a carbonization furnace, introducing nitrogen into the carbonization furnace at the speed of 120mL/min, heating to 750 ℃ at the speed of 10 ℃/min, carbonizing for 5 hours at the temperature of 750 ℃, and cooling to room temperature along with the furnace to obtain modified rice hull fiber;
(5) putting 3 parts of modified rice hull fiber, 5 parts of curing agent, 120 parts of nano iron powder, 3 parts of emulsifier, 2 parts of organic acid, 2 parts of oyster shell powder, 20 parts of deionized water, 30 parts of organic silicon resin and 5 parts of starch in a ball mill, and mixing and ball-milling for 60min to obtain a ball grinding material;
(6) pouring the ball-milled material into a mould, then carrying out hot press forming in a forming machine in the mould under the conditions that the temperature is 140 ℃ and the pressure is 30MPa, and demoulding to obtain a blank;
(7) and placing the blank in a sintering furnace, filling nitrogen into the sintering furnace at the speed of 120mL/min, heating to 1550 ℃ at the speed of 15 ℃/min, filling nitrogen, sintering for 5 hours at the temperature of 1550 ℃, and cooling to room temperature along with the furnace to obtain the iron-based composite material.
The preparation process of the modified shell polysaccharide liquid in the step (3) is as follows: placing chitosan and water in a No. 2 beaker according to the mass ratio of 1:100, stirring for 20min by a glass rod, standing and swelling for 5h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, heating, stirring and dissolving for 60min at the temperature of 95 ℃ and the rotating speed of 600r/min, then cooling to 35 ℃, then adding chitosanase with the mass of 0.02 time of that of the chitosan into the No. 2 beaker, heating, stirring and performing enzymolysis for 60min at the temperature of 35 ℃ and the rotating speed of 500r/min, and then heating to 95 ℃ to inactivate the enzyme, thus obtaining the modified chitosan liquid.
Example 2
The iron-based composite material comprises the following raw materials in parts by weight: 3 parts of rice hull fiber, 5 parts of a curing agent, 120 parts of nano iron powder, 3 parts of an emulsifier, 2 parts of organic acid, 2 parts of oyster shell powder, 20 parts of deionized water, 30 parts of organic silicon resin and 5 parts of starch.
The emulsifier is alkylphenol polyoxyethylene.
The organic acid is stearic acid.
The organic silicon resin is polymethyl organic silicon resin.
The starch is glutinous rice starch.
The iron-based composite material is prepared by the following specific preparation process:
(1) putting 3 parts of modified rice hull fiber, 5 parts of curing agent, 120 parts of nano iron powder, 3 parts of emulsifier, 2 parts of organic acid, 2 parts of oyster shell powder, 20 parts of deionized water, 30 parts of organic silicon resin and 5 parts of starch in a ball mill, and mixing and ball-milling for 60min to obtain a ball grinding material;
(2) pouring the ball-milled material into a mould, then carrying out hot press forming in a forming machine in the mould under the conditions that the temperature is 140 ℃ and the pressure is 30MPa, and demoulding to obtain a blank;
(3) and placing the blank in a sintering furnace, filling nitrogen into the sintering furnace at the speed of 120mL/min, heating to 1550 ℃ at the speed of 15 ℃/min, filling nitrogen, sintering for 5 hours at the temperature of 1550 ℃, and cooling to room temperature along with the furnace to obtain the iron-based composite material.
Example 3
The iron-based composite material comprises the following raw materials in parts by weight: 3 parts of rice hull fiber, 5 parts of a curing agent, 120 parts of nano iron powder, 3 parts of an emulsifier, 2 parts of organic acid, 2 parts of oyster shell powder, 20 parts of deionized water and 5 parts of starch.
The emulsifier is alkylphenol polyoxyethylene.
The organic acid is stearic acid.
The starch is glutinous rice starch.
The iron-based composite material is prepared by the following specific preparation process:
(1) placing the rice hull fiber and hydrochloric acid in a No. 1 beaker according to a mass ratio of 1:20, mixing and stirring for 60min under the condition that the rotating speed is 500r/min, standing for 5h, filtering to obtain No. 1 filter residue, washing the No. 1 filter residue with glacial acetic acid until the washing liquid is neutral, then placing the washed No. 1 filter residue in an oven, and drying at the temperature of 110 ℃ to constant weight to obtain the primary-treated rice hull fiber;
(2) mixing 30 parts of primary treated rice hull fiber, 2 parts of secondary sedimentation tank sludge, 0.5 part of cane sugar and 50 parts of water, placing the mixture in a fermentation kettle, hermetically fermenting for 5 days at the temperature of 35 ℃, adding a ferric nitrate solution with the mass fraction of 20 percent and 0.5 time of the mass fraction of the primary treated rice hull fiber into the fermentation kettle, adding a potassium oxalate solution with the mass fraction of 10 percent, which is 0.2 time of the mass fraction of the primary treated rice hull fiber, into the fermentation kettle through a rubber head dropper, adding a urea solution with the mass fraction of 10 percent into the fermentation kettle, adjusting the pH value to 7.6, filtering to obtain No. 2 filter residue, placing the No. 2 filter residue in liquid nitrogen for freezing to obtain a frozen material, placing the frozen material in a ball mill for ball milling, sieving by a 320-mesh sieve to obtain a ball-milled frozen material, placing the ball-milled frozen material in a baking oven at the temperature of 110 ℃, drying to constant weight to obtain secondary treated rice hull fiber;
(3) placing the secondary-treated rice hull fiber and the modified chitosan solution in a mixer according to a mass ratio of 1:20, stirring and mixing for 60min at a rotating speed of 800r/min, adding a calcium nitrate solution with a mass fraction of 20% and 0.2 times of the mass of the secondary-treated rice hull fiber into the mixer to obtain a mixed solution, placing the mixed solution into a refrigerator, freezing for 8h at a temperature of-10 ℃ to obtain a frozen block, placing the frozen block at room temperature to be completely melted, performing freeze-thaw cycle for 8 times, filtering to obtain No. 3 filter residue, washing the No. 3 filter residue with deionized water for 8 times, placing the washed No. 3 filter residue into an oven, and drying to constant weight at a temperature of 110 ℃ to obtain the three-time-treated rice hull fiber;
(4) placing the rice hull fiber subjected to the three-time treatment in a carbonization furnace, introducing nitrogen into the carbonization furnace at the speed of 120mL/min, heating to 750 ℃ at the speed of 10 ℃/min, carbonizing for 5 hours at the temperature of 750 ℃, and cooling to room temperature along with the furnace to obtain modified rice hull fiber;
(5) putting 3 parts of modified rice hull fiber, 5 parts of curing agent, 120 parts of nano iron powder, 3 parts of emulsifier, 2 parts of organic acid, 2 parts of oyster shell powder, 20 parts of deionized water and 5 parts of starch into a ball mill according to parts by weight, and mixing and ball-milling for 60min to obtain a ball grinding material;
(6) pouring the ball-milled material into a mould, then carrying out hot press forming in a forming machine in the mould under the conditions that the temperature is 140 ℃ and the pressure is 30MPa, and demoulding to obtain a blank;
(7) and placing the blank in a sintering furnace, filling nitrogen into the sintering furnace at the speed of 120mL/min, heating to 1550 ℃ at the speed of 15 ℃/min, filling nitrogen, sintering for 5 hours at the temperature of 1550 ℃, and cooling to room temperature along with the furnace to obtain the iron-based composite material.
The preparation process of the modified shell polysaccharide liquid in the step (3) is as follows: placing chitosan and water in a No. 2 beaker according to the mass ratio of 1:100, stirring for 20min by a glass rod, standing and swelling for 5h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, heating, stirring and dissolving for 60min at the temperature of 95 ℃ and the rotating speed of 600r/min, then cooling to 35 ℃, then adding chitosanase with the mass of 0.02 time of that of the chitosan into the No. 2 beaker, heating, stirring and performing enzymolysis for 60min at the temperature of 35 ℃ and the rotating speed of 500r/min, and then heating to 95 ℃ to inactivate the enzyme, thus obtaining the modified chitosan liquid.
Example 4
The iron-based composite material comprises the following raw materials in parts by weight: 3 parts of rice hull fiber, 5 parts of a curing agent, 120 parts of nano iron powder, 3 parts of an emulsifier, 2 parts of organic acid, 2 parts of oyster shell powder, 20 parts of deionized water and 30 parts of organic silicon resin.
The emulsifier is alkylphenol polyoxyethylene.
The organic acid is stearic acid.
The organic silicon resin is polymethyl organic silicon resin.
The iron-based composite material is prepared by the following specific preparation process:
(1) placing the rice hull fiber and hydrochloric acid in a No. 1 beaker according to a mass ratio of 1:20, mixing and stirring for 60min under the condition that the rotating speed is 500r/min, standing for 5h, filtering to obtain No. 1 filter residue, washing the No. 1 filter residue with glacial acetic acid until the washing liquid is neutral, then placing the washed No. 1 filter residue in an oven, and drying at the temperature of 110 ℃ to constant weight to obtain the primary-treated rice hull fiber;
(2) mixing 30 parts of primary treated rice hull fiber, 2 parts of secondary sedimentation tank sludge, 0.5 part of cane sugar and 50 parts of water, placing the mixture in a fermentation kettle, hermetically fermenting for 5 days at the temperature of 35 ℃, adding a ferric nitrate solution with the mass fraction of 20 percent and 0.5 time of the mass fraction of the primary treated rice hull fiber into the fermentation kettle, adding a potassium oxalate solution with the mass fraction of 10 percent, which is 0.2 time of the mass fraction of the primary treated rice hull fiber, into the fermentation kettle through a rubber head dropper, adding a urea solution with the mass fraction of 10 percent into the fermentation kettle, adjusting the pH value to 7.6, filtering to obtain No. 2 filter residue, placing the No. 2 filter residue in liquid nitrogen for freezing to obtain a frozen material, placing the frozen material in a ball mill for ball milling, sieving by a 320-mesh sieve to obtain a ball-milled frozen material, placing the ball-milled frozen material in a baking oven at the temperature of 110 ℃, drying to constant weight to obtain secondary treated rice hull fiber;
(3) placing the secondary-treated rice hull fiber and the modified chitosan solution in a mixer according to a mass ratio of 1:20, stirring and mixing for 60min at a rotating speed of 800r/min, adding a calcium nitrate solution with a mass fraction of 20% and 0.2 times of the mass of the secondary-treated rice hull fiber into the mixer to obtain a mixed solution, placing the mixed solution into a refrigerator, freezing for 8h at a temperature of-10 ℃ to obtain a frozen block, placing the frozen block at room temperature to be completely melted, performing freeze-thaw cycle for 8 times, filtering to obtain No. 3 filter residue, washing the No. 3 filter residue with deionized water for 8 times, placing the washed No. 3 filter residue into an oven, and drying to constant weight at a temperature of 110 ℃ to obtain the three-time-treated rice hull fiber;
(4) placing the rice hull fiber subjected to the three-time treatment in a carbonization furnace, introducing nitrogen into the carbonization furnace at the speed of 120mL/min, heating to 750 ℃ at the speed of 10 ℃/min, carbonizing for 5 hours at the temperature of 750 ℃, and cooling to room temperature along with the furnace to obtain modified rice hull fiber;
(5) putting 3 parts of modified rice hull fiber, 5 parts of curing agent, 120 parts of nano iron powder, 3 parts of emulsifier, 2 parts of organic acid, 2 parts of oyster shell powder, 20 parts of deionized water and 30 parts of organic silicon resin into a ball mill according to parts by weight, and mixing and ball-milling for 60min to obtain a ball grinding material;
(6) pouring the ball-milled material into a mould, then carrying out hot press forming in a forming machine in the mould under the conditions that the temperature is 140 ℃ and the pressure is 30MPa, and demoulding to obtain a blank;
(7) and placing the blank in a sintering furnace, filling nitrogen into the sintering furnace at the speed of 120mL/min, heating to 1550 ℃ at the speed of 15 ℃/min, filling nitrogen, sintering for 5 hours at the temperature of 1550 ℃, and cooling to room temperature along with the furnace to obtain the iron-based composite material.
The preparation process of the modified shell polysaccharide liquid in the step (3) is as follows: placing chitosan and water in a No. 2 beaker according to the mass ratio of 1:100, stirring for 20min by a glass rod, standing and swelling for 5h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, heating, stirring and dissolving for 60min at the temperature of 95 ℃ and the rotating speed of 600r/min, then cooling to 35 ℃, then adding chitosanase with the mass of 0.02 time of that of the chitosan into the No. 2 beaker, heating, stirring and performing enzymolysis for 60min at the temperature of 35 ℃ and the rotating speed of 500r/min, and then heating to 95 ℃ to inactivate the enzyme, thus obtaining the modified chitosan liquid.
Example 5
The iron-based composite material comprises the following raw materials in parts by weight: 3 parts of rice hull fiber, 5 parts of a curing agent, 120 parts of nano iron powder, 3 parts of an emulsifier, 2 parts of oyster shell powder, 20 parts of deionized water, 30 parts of organic silicon resin and 5 parts of starch.
The emulsifier is alkylphenol polyoxyethylene.
The organic silicon resin is polymethyl organic silicon resin.
The starch is glutinous rice starch.
The iron-based composite material is prepared by the following specific preparation process:
(1) placing the rice hull fiber and hydrochloric acid in a No. 1 beaker according to a mass ratio of 1:20, mixing and stirring for 60min under the condition that the rotating speed is 500r/min, standing for 5h, filtering to obtain No. 1 filter residue, washing the No. 1 filter residue with glacial acetic acid until the washing liquid is neutral, then placing the washed No. 1 filter residue in an oven, and drying at the temperature of 110 ℃ to constant weight to obtain the primary-treated rice hull fiber;
(2) mixing 30 parts of primary treated rice hull fiber, 2 parts of secondary sedimentation tank sludge, 0.5 part of cane sugar and 50 parts of water, placing the mixture in a fermentation kettle, hermetically fermenting for 5 days at the temperature of 35 ℃, adding a ferric nitrate solution with the mass fraction of 20 percent and 0.5 time of the mass fraction of the primary treated rice hull fiber into the fermentation kettle, adding a potassium oxalate solution with the mass fraction of 10 percent, which is 0.2 time of the mass fraction of the primary treated rice hull fiber, into the fermentation kettle through a rubber head dropper, adding a urea solution with the mass fraction of 10 percent into the fermentation kettle, adjusting the pH value to 7.6, filtering to obtain No. 2 filter residue, placing the No. 2 filter residue in liquid nitrogen for freezing to obtain a frozen material, placing the frozen material in a ball mill for ball milling, sieving by a 320-mesh sieve to obtain a ball-milled frozen material, placing the ball-milled frozen material in a baking oven at the temperature of 110 ℃, drying to constant weight to obtain secondary treated rice hull fiber;
(3) placing the secondary-treated rice hull fiber and the modified chitosan solution in a mixer according to a mass ratio of 1:20, stirring and mixing for 60min at a rotating speed of 800r/min, adding a calcium nitrate solution with a mass fraction of 20% and 0.2 times of the mass of the secondary-treated rice hull fiber into the mixer to obtain a mixed solution, placing the mixed solution into a refrigerator, freezing for 8h at a temperature of-10 ℃ to obtain a frozen block, placing the frozen block at room temperature to be completely melted, performing freeze-thaw cycle for 8 times, filtering to obtain No. 3 filter residue, washing the No. 3 filter residue with deionized water for 8 times, placing the washed No. 3 filter residue into an oven, and drying to constant weight at a temperature of 110 ℃ to obtain the three-time-treated rice hull fiber;
(4) placing the rice hull fiber subjected to the three-time treatment in a carbonization furnace, introducing nitrogen into the carbonization furnace at the speed of 120mL/min, heating to 750 ℃ at the speed of 10 ℃/min, carbonizing for 5 hours at the temperature of 750 ℃, and cooling to room temperature along with the furnace to obtain modified rice hull fiber;
(5) putting 3 parts of modified rice hull fiber, 5 parts of curing agent, 120 parts of nano iron powder, 3 parts of emulsifier, 2 parts of oyster shell powder, 20 parts of deionized water, 30 parts of organic silicon resin and 5 parts of starch in a ball mill, and mixing and ball-milling for 60min to obtain a ball grinding material;
(6) pouring the ball-milled material into a mould, then carrying out hot press forming in a forming machine in the mould under the conditions that the temperature is 140 ℃ and the pressure is 30MPa, and demoulding to obtain a blank;
(7) and placing the blank in a sintering furnace, filling nitrogen into the sintering furnace at the speed of 120mL/min, heating to 1550 ℃ at the speed of 15 ℃/min, filling nitrogen, sintering for 5 hours at the temperature of 1550 ℃, and cooling to room temperature along with the furnace to obtain the iron-based composite material.
The preparation process of the modified shell polysaccharide liquid in the step (3) is as follows: placing chitosan and water in a No. 2 beaker according to the mass ratio of 1:100, stirring for 20min by a glass rod, standing and swelling for 5h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, heating, stirring and dissolving for 60min at the temperature of 95 ℃ and the rotating speed of 600r/min, then cooling to 35 ℃, then adding chitosanase with the mass of 0.02 time of that of the chitosan into the No. 2 beaker, heating, stirring and performing enzymolysis for 60min at the temperature of 35 ℃ and the rotating speed of 500r/min, and then heating to 95 ℃ to inactivate the enzyme, thus obtaining the modified chitosan liquid.
Example 6
The iron-based composite material comprises the following raw materials in parts by weight: 3 parts of rice hull fiber, 5 parts of a curing agent, 120 parts of nano iron powder, 3 parts of an emulsifier, 2 parts of organic acid, 20 parts of deionized water, 30 parts of organic silicon resin and 5 parts of starch.
The emulsifier is alkylphenol polyoxyethylene.
The organic acid is stearic acid.
The organic silicon resin is polymethyl organic silicon resin.
The starch is glutinous rice starch.
The iron-based composite material is prepared by the following specific preparation process:
(1) placing the rice hull fiber and hydrochloric acid in a No. 1 beaker according to a mass ratio of 1:20, mixing and stirring for 60min under the condition that the rotating speed is 500r/min, standing for 5h, filtering to obtain No. 1 filter residue, washing the No. 1 filter residue with glacial acetic acid until the washing liquid is neutral, then placing the washed No. 1 filter residue in an oven, and drying at the temperature of 110 ℃ to constant weight to obtain the primary-treated rice hull fiber;
(2) mixing 30 parts of primary treated rice hull fiber, 2 parts of secondary sedimentation tank sludge, 0.5 part of cane sugar and 50 parts of water, placing the mixture in a fermentation kettle, hermetically fermenting for 5 days at the temperature of 35 ℃, adding a ferric nitrate solution with the mass fraction of 20 percent and 0.5 time of the mass fraction of the primary treated rice hull fiber into the fermentation kettle, adding a potassium oxalate solution with the mass fraction of 10 percent, which is 0.2 time of the mass fraction of the primary treated rice hull fiber, into the fermentation kettle through a rubber head dropper, adding a urea solution with the mass fraction of 10 percent into the fermentation kettle, adjusting the pH value to 7.6, filtering to obtain No. 2 filter residue, placing the No. 2 filter residue in liquid nitrogen for freezing to obtain a frozen material, placing the frozen material in a ball mill for ball milling, sieving by a 320-mesh sieve to obtain a ball-milled frozen material, placing the ball-milled frozen material in a baking oven at the temperature of 110 ℃, drying to constant weight to obtain secondary treated rice hull fiber;
(3) placing the secondary-treated rice hull fiber and the modified chitosan solution in a mixer according to a mass ratio of 1:20, stirring and mixing for 60min at a rotating speed of 800r/min, adding a calcium nitrate solution with a mass fraction of 20% and 0.2 times of the mass of the secondary-treated rice hull fiber into the mixer to obtain a mixed solution, placing the mixed solution into a refrigerator, freezing for 8h at a temperature of-10 ℃ to obtain a frozen block, placing the frozen block at room temperature to be completely melted, performing freeze-thaw cycle for 8 times, filtering to obtain No. 3 filter residue, washing the No. 3 filter residue with deionized water for 8 times, placing the washed No. 3 filter residue into an oven, and drying to constant weight at a temperature of 110 ℃ to obtain the three-time-treated rice hull fiber;
(4) placing the rice hull fiber subjected to the three-time treatment in a carbonization furnace, introducing nitrogen into the carbonization furnace at the speed of 120mL/min, heating to 750 ℃ at the speed of 10 ℃/min, carbonizing for 5 hours at the temperature of 750 ℃, and cooling to room temperature along with the furnace to obtain modified rice hull fiber;
(5) putting 3 parts of modified rice hull fiber, 5 parts of curing agent, 120 parts of nano iron powder, 3 parts of emulsifier, 2 parts of organic acid, 20 parts of deionized water, 30 parts of organic silicon resin and 5 parts of starch in a ball mill, and mixing and ball-milling for 60min to obtain a ball grinding material;
(6) pouring the ball-milled material into a mould, then carrying out hot press forming in a forming machine in the mould under the conditions that the temperature is 140 ℃ and the pressure is 30MPa, and demoulding to obtain a blank;
(7) and placing the blank in a sintering furnace, filling nitrogen into the sintering furnace at the speed of 120mL/min, heating to 1550 ℃ at the speed of 15 ℃/min, filling nitrogen, sintering for 5 hours at the temperature of 1550 ℃, and cooling to room temperature along with the furnace to obtain the iron-based composite material.
The preparation process of the modified shell polysaccharide liquid in the step (3) is as follows: placing chitosan and water in a No. 2 beaker according to the mass ratio of 1:100, stirring for 20min by a glass rod, standing and swelling for 5h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, heating, stirring and dissolving for 60min at the temperature of 95 ℃ and the rotating speed of 600r/min, then cooling to 35 ℃, then adding chitosanase with the mass of 0.02 time of that of the chitosan into the No. 2 beaker, heating, stirring and performing enzymolysis for 60min at the temperature of 35 ℃ and the rotating speed of 500r/min, and then heating to 95 ℃ to inactivate the enzyme, thus obtaining the modified chitosan liquid.
Comparative example
The iron-based composite material comprises the following raw materials in parts by weight: 3 parts of rice hull fiber, 5 parts of a curing agent, 120 parts of nano iron powder, 3 parts of an emulsifier and 20 parts of deionized water.
The iron-based composite material is prepared by the following specific preparation process:
(1) putting 3 parts of modified rice hull fiber, 5 parts of curing agent, 120 parts of nano iron powder, 3 parts of emulsifier and 20 parts of deionized water in a ball mill according to parts by weight, and mixing and ball-milling for 60min to obtain a ball grinding material;
(2) pouring the ball-milled material into a mould, then carrying out hot press forming in a forming machine in the mould under the conditions that the temperature is 140 ℃ and the pressure is 30MPa, and demoulding to obtain a blank;
(3) and placing the blank in a sintering furnace, filling nitrogen into the sintering furnace at the speed of 120mL/min, heating to 1550 ℃ at the speed of 15 ℃/min, filling nitrogen, sintering for 5 hours at the temperature of 1550 ℃, and cooling to room temperature along with the furnace to obtain the iron-based composite material.
Performance test table:
table 1:
as can be seen from table 1, by comparing example 1, example 2 and the comparative example, the modified rice hull fiber is spirally curled through a series of modifications to the rice hull fiber, and a large number of protrusions, defects or pores are formed on the surface of the modified rice hull fiber, so that the contact area between the modification and the matrix metal is increased, and meanwhile, in the sintering process, metal iron in the system can permeate into the rice hull fiber through the defects and pores on the surface of the rice hull fiber, so that the interface bonding strength between the modified rice hull fiber and the matrix metal is increased, and the mechanical property of the system is further improved; compared with the examples 1, 3 and the comparative example, the organic silicon resin is added, the organic silicon resin is heated and decomposed in the nitrogen-filled sintering process, and the residual radicals obtained by decomposition can be combined with the simple substance iron in the system, so that the modified rice hull fiber and the matrix metal are tightly combined, the density of the system is improved, and the mechanical property of the system is further improved; as can be seen by comparing the example 1 with the example 4 with the comparative example, in the ball milling process, the structure of the starch crystallization area and the appearance of the particles are damaged, and the crystallinity is effectively reduced, so that the mobility of the activated starch in the system is enhanced, the components in the system can be fully mixed, the dispersibility of the modified rice hull fiber in the system is improved, and the mechanical property of the system is further improved.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (1)
1. A preparation method of an iron-based composite material is characterized by comprising the following steps: the preparation process comprises the following steps:
(1) placing the rice hull fiber and hydrochloric acid in a No. 1 beaker according to a mass ratio of 1: 10-1: 20, mixing and stirring for 40-60 min under the condition that the rotating speed is 300-500 r/min, standing for 3-5 h, filtering to obtain No. 1 filter residue, washing the No. 1 filter residue with glacial acetic acid until the washing liquid is neutral, then placing the washed No. 1 filter residue in an oven, and drying to constant weight under the condition that the temperature is 105-110 ℃ to obtain the primary treated rice hull fiber;
(2) mixing 20-30 parts by weight of primary treated rice hull fiber, 1-2 parts by weight of secondary sedimentation tank sludge, 0.3-0.5 part by weight of sucrose and 30-50 parts by weight of water, placing the mixture in a fermentation kettle, hermetically fermenting for 3-5 days at the temperature of 30-35 ℃, adding a ferric nitrate solution with the mass fraction of 10-20% and 0.03-0.05 times by weight of the primary treated rice hull fiber into the fermentation kettle, dropwise adding a potassium oxalate solution with the mass fraction of 8-10% into the fermentation kettle by a rubber head dropper, adding a urea solution with the mass fraction of 8-10% into the fermentation kettle, adjusting the pH value to 7.4-7.6, filtering to obtain No. 2 filter residue, placing the No. 2 filter residue in liquid nitrogen for freezing to obtain a frozen material, placing the frozen material in a ball mill, sieving by a 320-mesh sieve, obtaining ball-milling frozen material, then placing the ball-milling frozen material in an oven, and drying the ball-milling frozen material to constant weight under the condition that the temperature is 105-110 ℃ to obtain secondary treated rice hull fiber;
(3) placing the secondary-treatment rice hull fiber and the modified chitosan solution in a mixer according to a mass ratio of 1: 10-1: 20, stirring and mixing for 40-60 min under the condition that the rotating speed is 600-800 r/min, then adding a calcium nitrate solution with a mass fraction of 10-20% and 0.1-0.2 times of the mass of the secondary-treatment rice hull fiber into the mixer to obtain a mixed solution, then placing the mixed solution into a refrigerator, freezing for 6-8 h at the temperature of-1-10 ℃ to obtain a frozen block, then placing the frozen block at room temperature until the frozen block is completely melted, performing freeze-thaw cycle for 5-8 times, filtering to obtain No. 3, then washing the No. 3 filter residue with deionized water for 5-8 times, then placing the washed No. 3 filter residue into an oven, and drying to constant weight at the temperature of 105-110 ℃ to obtain tertiary-treatment rice hull fiber; the preparation process of the modified shell polysaccharide liquid comprises the following steps: placing chitosan and water in a No. 2 beaker according to a mass ratio of 1: 50-1: 100, stirring for 10-20 min by using a glass rod, standing and swelling for 3-5 h, placing the No. 2 beaker in a digital display speed measurement constant-temperature magnetic stirrer, heating, stirring and dissolving for 40-60 min at a temperature of 90-95 ℃ and a rotating speed of 500-600 r/min, then cooling to 30-35 ℃, adding chitosanase with a mass of 0.01-0.02 times of that of the chitosan into the No. 2 beaker, heating, stirring and carrying out enzymolysis for 40-60 min at a temperature of 30-35 ℃ and a rotating speed of 300-500 r/min, and then heating to 90-95 ℃ to inactivate the enzyme to obtain a modified chitosan liquid;
(4) placing the rice hull fiber subjected to the tertiary treatment in a carbonization furnace, introducing nitrogen into the carbonization furnace at the speed of 100-120 mL/min, heating to 650-750 ℃ at the speed of 8-10 ℃/min, carbonizing for 3-5 hours at the temperature of 650-750 ℃, and cooling to room temperature along with the furnace to obtain modified rice hull fiber;
(5) putting 3 parts of modified rice hull fiber, 5 parts of curing agent, 120 parts of nano iron powder, 3 parts of emulsifier, 2 parts of organic acid, 2 parts of oyster shell powder, 20 parts of deionized water, 30 parts of organic silicon resin and 5 parts of starch into a ball mill, and mixing and ball-milling for 40-60 min to obtain a ball grinding material; the emulsifier is any one of alkylphenol polyoxyethylene, high-carbon fatty alcohol polyoxyethylene, coconut oleic acid, fatty acid or diethanol amine; the organic acid is any one of stearic acid, oleic acid or linoleic acid; the organic silicon resin is any one of polymethyl organic silicon resin, polyethyl organic silicon resin or polyaryl organic silicon resin; the starch is any one of glutinous rice starch, corn starch, sweet potato starch, potato starch or wheat starch;
(6) pouring the ball-milling material into a mold, then performing hot press molding in a molding machine in the mold under the conditions that the temperature is 130-140 ℃ and the pressure is 20-30 MPa, and demolding to obtain a blank;
(7) and placing the blank in a sintering furnace, filling nitrogen into the sintering furnace at the speed of 100-120 mL/min, heating to 1450-1550 ℃ at the speed of 10-15 ℃/min, filling nitrogen to sinter for 3-5 h at the temperature of 1450-1550 ℃, and cooling to room temperature along with the furnace to obtain the iron-based composite material.
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| CN109940161B (en) | 2019-12-31 |
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