CN102531657B - Method for preparing TiB2-Csf-Carbon composite material - Google Patents
Method for preparing TiB2-Csf-Carbon composite material Download PDFInfo
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- CN102531657B CN102531657B CN2012100020222A CN201210002022A CN102531657B CN 102531657 B CN102531657 B CN 102531657B CN 2012100020222 A CN2012100020222 A CN 2012100020222A CN 201210002022 A CN201210002022 A CN 201210002022A CN 102531657 B CN102531657 B CN 102531657B
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Abstract
The invention relates to a method for preparing a TiB2-Csf-Carbon composite material reinforced through chopped carbon fibers. The method for preparing the TiB2-Csf-Carbon composite material is characterized in that the method comprises the steps as follows: firstly, degumming pretreatment on a surface layer of Csf is carried out, that is, the chopped carbon fibers and acetone are mixed; secondly, materials are weighed by weight percentage, concretely, TiB2 powders account for 67.2 to 75wt percent, graphite powders account for 22.2 to 30wt percent, and the processed chopped carbon fibers account for 2.8 to 3.2wt percent; thirdly, ultrasonic dispersion, ball milling, drying and sieving are carried out so as to obtain powders that are mixed uniformly; and fourthly, the powders that are mixed uniformly are put in a graphite die, and the TiB2-Csf-Carbon composite material is obtained after sintering. The preparation method achieves simple technology and low cost; the fracture toughness of the prepared TiB2-Csf-Carbon composite material is increased by 40 percent on the premise that performance indexes such as electrical conductivity, relative density, flexural strength and the like of TiB2-Carbon composite material are not changed; and the prepared TiB2-Csf-Carbon composite material can be applied to the inert wettable cathode material in an aluminium electrolytic cell.
Description
Technical field
The present invention relates to a kind of chopped carbon fiber and strengthen TiB
2The preparation method of-carbon composite, belong to the fibre reinforced composites preparation field.
Background technology
Along with being becoming tight world energy sources day and the environmental protection requirement increasingly stringent, the high energy consumption of aluminium electrolytic industry and problem of environmental pollution more and more are subject to great attention, the focus that has now become international Aluminum circle to pay close attention to.What the tradition Aluminium Industry followed use always is the carbon anode/cathode material.There are many shortcomings in it: energy consumption is higher, and product pollution environment, carbon anode/cathode are subject to aluminium liquid erosion etc.In addition, because aluminium liquid can not wetting carbon anode/cathode, not only cause pole span to rise, current consumption is huge, and ionogen is easy to be penetrated into carbon anode/cathode inside in electrolytic process, causes the erosion of ionogen to carbon anode/cathode, finally causes electric tank cathode damaged, be forced to shutdown maintenance and change negative electrode, causing very large financial loss.In recent years, the aluminium industry member thinks that unanimously employing inert anode and inertia wenable cathode can effectively overcome the shortcoming of traditional electrolytic aluminum cathode material both at home and abroad, boosts productivity, and reaches the target of energy-conserving and environment-protective.
A lot of research both domestic and external shows: TiB2 (TiB
2) have good electroconductibility, stronger high temperature resistant, erosion resistance, good to aluminium liquid wet performance, little with the contact resistance of aluminium liquid, and absorbed electrolyte composition hardly, be the wettable cathode material of a kind of comparatively ideal inert.TiB
2Wenable cathode can make the pole span of electrolysis of aluminum foreshorten to 2mm～2.5mm, reduce simultaneously the aluminium liquid layer on negative electrode, thereby reduce the interference of magnetic field to electrolytic process, reduce the electrolytical precipitation of cell bottom, increase the aluminium amount of producing, improve current efficiency, obviously reduce the cost of electrolytic aluminum, extend bath life.But pure TiB
2Material is the high and low densified sintering product that is difficult to of spread coefficient due to fusing point, and due to the difference of chemical bond characteristics, its crystal grain is significantly higher than other direction along the axial speed of growth of C in sintering process, causes abnormal grain growth to make material property deteriorated simultaneously; On the other hand, its fragility is large, heat-shock resistance is poor, the pure TiB that has been difficult for the drawbacks limit such as processing
2Applying of cathode material.Therefore, with TiB
2Compound with carbon, prepare in conjunction with both advantages and overcome its not enough composite ceramic material, reduced TiB
2The requirement of material purity, significantly reduce costs, and good moldability is easily processed, but also can not affect the electroconductibility of material, can be used as electrolytic aluminum inertia wenable cathode material.
In recent years, the lot of domestic and foreign investigator is to TiB
2-carbon composite has carried out broad research.But be subject to the whole cathode construction of conventional aluminum electrolyzer, research work mainly concentrates on TiB
2-carbon coating aspect, this coated material preparation process is simple, can be coated in easily on the carbon materials matrix, after heat treatment can come into operation, thereby be extensively studied and use.It has the satisfactory electrical conductivity that can compare with metallographic phase, stronger anti-metal aluminium liquid and fluoride salt melt corrosive nature, and can be melted aluminium liquid good wet, thereby changes the wetting environment of cathode surface.The shortcomings such as that but it exists is easy to wear, cracky, bad mechanical strength, limited it and further applied.And the independent cathode construction of novel aluminum cell makes TiB
2The application of-carbon composite becomes possibility, and the main pressureless sintering technology that adopts prepares TiB both at home and abroad at present
2-carbon composite, and add a certain amount of resin as additive.The employing pressureless sinterings such as Li Qingyu have prepared electrolgtic aluminium TiB
2-carbon composite cathode material, wherein TiB
2Content is 70.95wt%, and compound resin is 3.5wt%.But material density is low, and mechanical property is poor, in use cracky.Large quantity research shows, introducing fiber is the effective ways of realizing the stupalith highly malleablized as wild phase, uses chopped carbon fiber as wild phase, have preparation technology simple, need not establishment and be wound around, the advantage such as preparation cost is low.Up to the present, prepare TiB for hot pressing sintering method
2-C
sfThe research of-carbon composite there is not yet report.
Summary of the invention
The purpose of this invention is to provide a kind of TiB of preparation
2-C
sfThe TiB that the method for-carbon composite, the method obtain
2-C
sfThe fracture toughness property of-carbon composite is high.
To achieve these goals, technical scheme of the present invention is: a kind of TiB of preparation
2-C
sfThe method of-carbon composite, is characterized in that it comprises the steps:
1), C
sfTop layer except the glue pre-treatment: press chopped carbon fiber (C
sf) with the volume ratio of acetone be 1: 25～30, chopped carbon fiber is mixed with acetone, fully stir, filter after standing 24～48h under room temperature (removing filtrate), with distilled water flushing chopped carbon fiber 3～5 times, then be placed in vacuum drying oven dry 24～48h under 60～80 ℃, the chopped carbon fiber after obtaining to process;
2) by the shared weight percentage of each raw material, be: TiB
2Chopped carbon fiber after powder: 67.2～75wt%, Graphite Powder 99: 22.2～30wt%, processing: 2.8～3.2wt%; Take TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and processing;
3), by wet mixing medium and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and processing is 15～20: 1, with TiB
2Add the wet mixing medium to stir ultra-sonic dispersion 1.5～2h in chopped carbon fiber after powder, Graphite Powder 99 and processing, then (ratio of grinding media to material is 4～5: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling mixes that (ball milling 10～12h), obtain slurry A; With slurry A dry 1.5～2h on Rotary Evaporators, then put into vacuum drying oven dry 24～48h under 60～80 ℃, dried powder, through grinding, is crossed 100 mesh sieves, the powder that obtains mixing;
4), the powder that will mix puts into graphite jig, be placed in vacuum sintering funace, and be filled with argon gas as protective atmosphere; sintering temperature is 1850 ℃～1950 ℃, and soaking time is 1h～1.5h, keeps 25～30MPa axle pressure to sintering to complete; then furnace cooling, obtain TiB
2-C
sf-carbon composite.
Step 1) described chopped carbon fiber is the fine carbon fiber of polypropylene (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
Step 2) described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m.
Step 3) described wet mixing medium is dehydrated alcohol, also can use water-free organic solvent, such as methyl alcohol, Virahol or toluene etc.
Step 3) frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W.
The present invention has following beneficial effect:
1, TiB2 (TiB
2) be the wettable cathode material of a kind of comparatively ideal inert, but the TiB of pressureless sintering preparation
2-carbon composite has limited its further application because of poor mechanical property, the present invention adopts hot pressing sintering method to prepare C
sfThe TiB that strengthens
2-carbon composite, do not changing TiB
2Under the prerequisite of the performance index such as-carbon composite resistivity (80 μ Ω cm), relative density (95%), bending strength (110MPa), make its fracture toughness property improve 40%, can be used as wettable inert cathode material and be applied in the New Electrolytic Aluminium groove.
2, preparation technology of the present invention is simple, and is workable, and preparation cost is low, can prepare rapidly the TiB that meets service requirements
2-C
sf-carbon composite, adopt hot-pressed sintering furnace as heat treatment furnace, has certain ubiquity, is applicable to laboratory and industrial production.
Description of drawings
Fig. 1 (a) is the SEM photo through the dried mixing raw material powder of wet mixing;
The TiB of Fig. 1 (b) for making in the embodiment of the present invention 4
2-C
sfThe section SEM photo of-carbon composite;
The TiB of Fig. 1 (c) for making in the embodiment of the present invention 6
2-C
sfThe section SEM photo of-carbon composite;
Fig. 2 is the TiB that makes in the embodiment of the present invention 4
2-C
sfThe XRD figure spectrum of-carbon composite.
Fig. 3 is prepared TiB in the embodiment of the present invention 1～6
2-C
sfThe relative density variation diagram of-carbon composite.
Fig. 4 is prepared TiB in the embodiment of the present invention 1～6
2-C
sf-carbon composite bending strength and fracture toughness property variation diagram.
Fig. 1 (a), for the SEM photo through the dried mixed powder of wet mixing, does not observe the fiber agglomeration in figure.The method for mixing that the wet mixing ball milling is described can be dispersed in chopped carbon fiber in powder equably.
Fig. 3 is prepared TiB in the embodiment of the present invention 1～6
2-C
sfThe relative density variation diagram of-carbon composite, explanation is when chopped carbon fiber content is less, fibre content is little on the relative density impact of material, and homodisperse chopped carbon fiber can play the effect of filling pore, material density is improved slightly, along with the increase of chopped carbon fiber content, due to the reinforcement of the bridge joint effect between fiber, cause the material porosity to rise, relative density sharply descends.
Fig. 4 is prepared TiB in the embodiment of the present invention 1～6
2-C
sf-carbon composite bending strength and fracture toughness property variation diagram.Explanation is along with the increase of chopped carbon fiber content, because the material porosity rises, the bending strength of material descends, and along with fibre content increases, fiber when Materials Fracture by the mechanisms consume that pulls off and extract work of rupture, significantly improved the fracture toughness property of material.But when fibre content was excessive, due to increasing of material mesoporosity, material fracture toughness descended.
Fig. 3 and Fig. 4 explanation TiB in embodiment 1～6
2-C
sfIn-carbon composite, chopped carbon fiber reinforced optimum content is 3wt%, and simultaneously further evidence is when fibre content during higher or lower than 2.8～3.2wt% content range, material over-all properties variation.
Embodiment
, in order to understand better the present invention, further illustrate content of the present invention below in conjunction with accompanying drawing, embodiment, but content of the present invention not only is confined to the following examples.
In following examples, the measurement standard of relative density, bending strength and fracture toughness property is:
(1) relative density of sample is to use the theoretical density of the volume density of sample divided by sample, and the theoretical density of sample can calculate according to the theoretical density of proportioning raw materials and each raw material self, and volume density is measured with Archimedes's method, and calculation formula is:
Wherein:
ρ is volume of sample density, m
DoFor aerial weight after the sample complete drying, m
FloatingFor the weight in water after sample use water boil 30min, ρ
WaterFor the density of water under room temperature, ρ
AirDensity for air under room temperature.
(2) bending strength of sample is measured by three-point bending method by the MTS-810 type pottery pilot system that American MTS company produces, and specimen size is 3mm * 4mm * 36mm, and span is 20mm, and loading rate is 0.5mm/min.
(3) fracture toughness property of sample is measured with the single notched beam method, and span is 16mm, and specimen size 2.5mm * 5mm * 25mm cuts a wide 0.2mm of being on the 5mm cross section, be the otch of 2.5mm deeply.
Embodiment 1 (this embodiment is comparison example, does not namely adopt chopped carbon fiber of the present invention):
With TiB
2Powder, Graphite Powder 99 are raw material, take powder by the weight percentage of each raw material: TiB
2Powder: 70wt%, Graphite Powder 99: 30wt%; Described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m; With TiB
2Powder, Graphite Powder 99 add absolute ethyl alcohol and stirring ultra-sonic dispersion 1.5～2h (to press dehydrated alcohol and TiB
2The mass ratio of powder and Graphite Powder 99 total mass is 15～20: 1, and the frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W), then (ratio of grinding media to material is 4～5: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling 10h～12h mixes, and obtains slurry A, with slurry A dry 1.5～2h on Rotary Evaporators, then put into vacuum drying oven dry 24～48h under 60～80 ℃, dried powder is through grinding, cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, be placed in vacuum sintering funace, and be filled with argon gas as protective atmosphere, sintering temperature is 1850 ℃, and pressure is 30MPa, insulation 1h, and then furnace cooling, obtain TiB
2-carbon composite.
Measure TiB
2The relative density of-carbon composite is: 95.43%, and resistivity is: 75.32 μ Ω cm, bending strength is: 107.5MPa, fracture toughness property is: 2.63MPam
1/2
Embodiment 2 (this embodiment is comparison example, does not namely adopt the amount of chopped carbon fiber of the present invention):
C
sfTop layer except the glue pre-treatment: press chopped carbon fiber (C
sf) with the volume ratio of acetone be 1: 25～30, chopped carbon fiber is mixed with acetone, fully stir, filter after standing 24～48h under room temperature (removing filtrate), with distilled water flushing chopped carbon fiber 3～5 times, then be placed in vacuum drying oven dry 24～48h under 60～80 ℃, the chopped carbon fiber after obtaining to process; Described chopped carbon fiber is the fine carbon fiber of polypropylene (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
With TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and processing is raw material, takes powder by the weight percentage of each raw material: TiB
2Powder: 70wt%, Graphite Powder 99: 29wt%, the chopped carbon fiber after processing: 1wt%; Described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m; With TiB
2Powder, Graphite Powder 99 and and process after chopped carbon fiber (C
sf) add absolute ethyl alcohol and stirring ultra-sonic dispersion 1.5～2h (to press dehydrated alcohol and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and processing is 15～20: 1, and the frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W), then (ratio of grinding media to material is 4～5: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling 10h～12h mixes, and obtains slurry A, with slurry A dry 1.5～2h on Rotary Evaporators, then put into vacuum drying oven dry 24～48h under 60～80 ℃, dried powder is through grinding, cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, be placed in vacuum sintering funace, and be filled with argon gas as protective atmosphere, sintering temperature is 1850 ℃, and pressure is 30MPa, insulation 1h, and then furnace cooling, obtain TiB
2-C
sf-carbon composite.
Measure TiB
2-C
sfThe relative density of-carbon composite is: 95.42%, and resistivity is: 78.75 μ Ω cm, bending strength is: 108.3MPa, fracture toughness property is: 2.76MPam
1/2
Embodiment 3 (this embodiment is comparison example, does not namely adopt the amount of chopped carbon fiber of the present invention):
C
sfTop layer except the glue pre-treatment: press chopped carbon fiber (C
sf) with the volume ratio of acetone be 1: 25～30, chopped carbon fiber is mixed with acetone, fully stir, filter after standing 24～48h under room temperature (removing filtrate), with distilled water flushing chopped carbon fiber 3～5 times, then be placed in vacuum drying oven dry 24～48h under 60～80 ℃, the chopped carbon fiber after obtaining to process; Described chopped carbon fiber is the fine carbon fiber of polypropylene (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
With TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and processing is raw material, takes powder by the weight percentage of each raw material: TiB
2Powder: 70wt%, Graphite Powder 99: 28wt%, the chopped carbon fiber after processing: 2wt%; Described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m; With TiB
2Powder, Graphite Powder 99 and and process after chopped carbon fiber add absolute ethyl alcohol and stirring ultra-sonic dispersion 1.5～2h (to press dehydrated alcohol and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and processing is 15～20: 1, and the frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W), then (ratio of grinding media to material is 4～5: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling 10h～12h mixes, and obtains slurry A, with slurry A dry 1.5～2h on Rotary Evaporators, then put into vacuum drying oven dry 24～48h under 60～80 ℃, dried powder is through grinding, cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, be placed in vacuum sintering funace, and be filled with argon gas as protective atmosphere, sintering temperature is 1850 ℃, and pressure is 30MPa, insulation 1h, and then furnace cooling, obtain TiB
2-C
sf-carbon composite.
Measure TiB
2-C
sfThe relative density of-carbon composite is: 95.65%, and resistivity is: 80.02 μ Ω cm, bending strength is: 112.3MPa, fracture toughness property is: 2.97MPam
1/2
Embodiment 4 (being the embodiment that adopts the amount of chopped carbon fiber of the present invention):
A kind of TiB for preparing
2-C
sfThe method of-carbon composite, it comprises the steps:
1), C
sfTop layer except the glue pre-treatment: press chopped carbon fiber (C
sf) with the volume ratio of acetone be 1: 28, chopped carbon fiber is mixed stirring with acetone, filter after standing 36h under room temperature (removing filtrate),, with distilled water flushing chopped carbon fiber 4 times, then be placed in vacuum drying oven dry 36h under 70 ℃, the chopped carbon fiber after obtaining to process;
Described chopped carbon fiber is the fine carbon fiber of polypropylene (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
2) by the shared weight percentage of each raw material, be: TiB
2Chopped carbon fiber after powder: 70wt%, Graphite Powder 99: 27wt%, processing: 3wt%; Take TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and processing;
Described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m.
3), by wet mixing medium and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and processing is 18: 1, with TiB
2Add the wet mixing medium to stir ultra-sonic dispersion 1.8h in chopped carbon fiber after powder, Graphite Powder 99 and processing, then (ratio of grinding media to material is 4.5: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling mixes (ball milling 11h), obtains slurry A; With slurry A dry 1.8h on Rotary Evaporators, then put into vacuum drying oven dry 36h under 70 ℃, dried powder, through grinding, is crossed 100 mesh sieves, the powder that obtains mixing;
Described wet mixing medium is dehydrated alcohol.The frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W.
4), the powder that will mix puts into graphite jig, is placed in vacuum sintering funace, and is filled with argon gas as protective atmosphere, sintering temperature is 1850 ℃, soaking time is 1h, keeps the 30MPa axle pressure to complete to sintering, then furnace cooling, obtain TiB
2-C
sf-carbon composite.
Measure TiB
2-C
sfThe relative density of-carbon composite is: 95.83%, and resistivity is: 82.71 μ Ω cm, bending strength is: 115.9MPa, fracture toughness property is: 3.85MPam
1/2
In the present embodiment, C
sfIf content very few (lower than 2.8wt%), to composite material toughening DeGrain, C
sf, if content is (higher than 3.2wt%) too much, cause the matrix material density to descend, mechanical properties decrease.
Embodiment 5 (this embodiment is comparison example, does not namely adopt the amount of chopped carbon fiber of the present invention):
C
sfTop layer except the glue pre-treatment: press chopped carbon fiber (C
sf) with the volume ratio of acetone be 1: 25～30, chopped carbon fiber is mixed with acetone, fully stir, filter after standing 24～48h under room temperature (removing filtrate), with distilled water flushing chopped carbon fiber 3～5 times, then be placed in vacuum drying oven dry 24～48h under 60～80 ℃, the chopped carbon fiber after obtaining to process; Described chopped carbon fiber is the fine carbon fiber of polypropylene (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
With TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and processing is raw material, takes powder by the weight percentage of each raw material: TiB
2Powder: 70wt%, Graphite Powder 99: 26wt%, the chopped carbon fiber after processing: 4wt%; Described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m; With TiB
2Powder, Graphite Powder 99 and and process after chopped carbon fiber add absolute ethyl alcohol and stirring ultra-sonic dispersion 1.5～2h (to press dehydrated alcohol and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and processing is 15～20: 1, and the frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W), then (ratio of grinding media to material is 4～5: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling 10h～12h mixes, and obtains slurry A, with slurry A dry 1.5～2h on Rotary Evaporators, then put into vacuum drying oven dry 24～48h under 60～80 ℃, dried powder is through grinding, cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, be placed in vacuum sintering funace, and be filled with argon gas as protective atmosphere, sintering temperature is 1850 ℃, and pressure is 30MPa, insulation 1h, and then furnace cooling, obtain TiB
2-C
sf-carbon composite.
Measure TiB
2-C
sfThe relative density of-carbon composite is: 95.19%, and resistivity is: 89.63 μ Ω cm, bending strength is: 99.58MPa, fracture toughness property is: 3.67MPam
1/2
Embodiment 6 (this embodiment is comparison example, does not namely adopt the amount of chopped carbon fiber of the present invention):
C
sfTop layer except the glue pre-treatment: press chopped carbon fiber (C
sf) with the volume ratio of acetone be 1: 25～30, chopped carbon fiber is mixed with acetone, fully stir, filter after standing 24～48h under room temperature (removing filtrate), with distilled water flushing chopped carbon fiber 3～5 times, then be placed in vacuum drying oven dry 24～48h under 60～80 ℃, the chopped carbon fiber after obtaining to process; Described chopped carbon fiber is the fine carbon fiber of polypropylene (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
With TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and processing is raw material, takes powder by the weight percentage of each raw material: TiB
2Powder: 70wt%, Graphite Powder 99: 25wt%, the chopped carbon fiber after processing: 5wt%; Described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m; With TiB
2Powder, Graphite Powder 99 and and process after chopped carbon fiber add absolute ethyl alcohol and stirring ultra-sonic dispersion 1.5～2h (to press dehydrated alcohol and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and processing is 15～20: 1, and the frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W), then (ratio of grinding media to material is 4～5: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling 10h～12h mixes, and obtains slurry A, with slurry A dry 1.5～2h on Rotary Evaporators, then put into vacuum drying oven dry 24～48h under 60～80 ℃, dried powder is through grinding, cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, be placed in vacuum sintering funace, and be filled with argon gas as protective atmosphere, sintering temperature is 1850 ℃, and pressure is 30MPa, insulation 1h, and then furnace cooling, obtain TiB
2-C
sf-carbon composite.
Measure TiB
2-C
sfThe relative density of-carbon composite is: 94.04%, and resistivity is: 105.6 μ Ω cm, bending strength is: 77.4MPa, fracture toughness property is: 3.39MPam
1/2
Embodiment 7 (this embodiment is comparison example, does not namely adopt chopped carbon fiber of the present invention):
With TiB
2Powder, Graphite Powder 99 are raw material, take powder by the weight percentage of each raw material: TiB
2Powder: 75wt%, Graphite Powder 99: 25wt%; Described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m; With TiB
2Powder, Graphite Powder 99 add absolute ethyl alcohol and stirring ultra-sonic dispersion 1.5～2h (to press dehydrated alcohol and TiB
2The mass ratio of powder and Graphite Powder 99 total mass is 15～20: 1, and the frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W), then (ratio of grinding media to material is 4～5: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling 10h～12h mixes, and obtains slurry A, with slurry A dry 1.5～2h on Rotary Evaporators, then put into vacuum drying oven dry 24～48h under 60～80 ℃, dried powder is through grinding, cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, be placed in vacuum sintering funace, and be filled with argon gas as protective atmosphere, sintering temperature is 1950 ℃, and pressure is 25MPa, insulation 1.5h, and then furnace cooling, obtain TiB
2-carbon composite.
Measure TiB
2-C
sfThe relative density of-carbon composite is: 96.01%, and resistivity is: 73.27 μ Ω cm, bending strength is: 100.4MPa, fracture toughness property is: 2.7MPam
1/2
Embodiment 8 (being the embodiment that adopts the amount of chopped carbon fiber of the present invention):
A kind of TiB for preparing
2-C
sfThe method of-carbon composite, it comprises the steps:
1), C
sfTop layer except the glue pre-treatment: press chopped carbon fiber (C
sf) with the volume ratio of acetone be 1: 27, chopped carbon fiber is mixed stirring with acetone, filter after standing 40h under room temperature (removing filtrate),, with distilled water flushing chopped carbon fiber 4 times, then be placed in vacuum drying oven dry 40h under 70 ℃, the chopped carbon fiber after obtaining to process;
Described chopped carbon fiber is the fine carbon fiber of polypropylene (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
2) by the shared weight percentage of each raw material, be: TiB
2Chopped carbon fiber after powder: 75wt%, Graphite Powder 99: 22.2wt%, processing: 2.8wt%; Take TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and processing;
Described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m.
3), by wet mixing medium and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and processing is 17: 1, with TiB
2Add the wet mixing medium to stir ultra-sonic dispersion 1.7h in chopped carbon fiber after powder, Graphite Powder 99 and processing, then (ratio of grinding media to material is 4.5: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling mixes (ball milling 11h), obtains slurry A; With slurry A dry 1.7h on Rotary Evaporators, then put into vacuum drying oven dry 40h under 70 ℃, dried powder, through grinding, is crossed 100 mesh sieves, the powder that obtains mixing;
Described wet mixing medium is dehydrated alcohol.
The frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W.
4), the powder that will mix puts into graphite jig, be placed in vacuum sintering funace, and be filled with argon gas as protective atmosphere; sintering temperature is 1950 ℃, and soaking time is 1.5h, keeps 25MPa axle pressure to sintering to complete; then furnace cooling, obtain TiB
2-C
sf-carbon composite.
Measure TiB
2-C
sfThe relative density of-carbon composite is: 96.27%, and resistivity is: 87.6 μ Ω cm, bending strength is: 113.37MPa, fracture toughness property is: 3.81MPam
1/2
Embodiment 9 (being the embodiment that adopts the amount of chopped carbon fiber of the present invention):
A kind of TiB for preparing
2-C
sfThe method of-carbon composite, it comprises the steps:
1), C
sfTop layer except the glue pre-treatment: press chopped carbon fiber (C
sf) with the volume ratio of acetone be 1: 25, chopped carbon fiber is mixed abundant stirring with acetone, filter after standing 24h under room temperature (removing filtrate),, with distilled water flushing chopped carbon fiber 3 times, then be placed in vacuum drying oven dry 24h under 60 ℃, the chopped carbon fiber after obtaining to process;
Described chopped carbon fiber is the fine carbon fiber of polypropylene (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
2) by the shared weight percentage of each raw material, be: TiB
2Chopped carbon fiber after powder: 67.2wt%, Graphite Powder 99: 30wt%, processing: 2.8wt%; Take TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and processing;
Described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m.
3), by wet mixing medium and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and processing is 15: 1, with TiB
2Add the wet mixing medium to stir ultra-sonic dispersion 1.5h in chopped carbon fiber after powder, Graphite Powder 99 and processing, then (ratio of grinding media to material is 4: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling mixes (ball milling 10h), obtains slurry A; With slurry A dry 1.5h on Rotary Evaporators, then put into vacuum drying oven dry 24h under 60 ℃, dried powder, through grinding, is crossed 100 mesh sieves, the powder that obtains mixing;
Described wet mixing medium is methyl alcohol.The frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W.
4), the powder that will mix puts into graphite jig, is placed in vacuum sintering funace, and is filled with argon gas as protective atmosphere, sintering temperature is 1850 ℃, soaking time is 1h, keeps the 25MPa axle pressure to complete to sintering, then furnace cooling, obtain TiB
2-C
sf-carbon composite.
Measure TiB
2-C
sfThe relative density of-carbon composite is: 95.69%, and resistivity is: 75.51 μ Ω cm, bending strength is: 110.72MPa, fracture toughness property is: 3.84MPam
1/2
Embodiment 10 (being the embodiment that adopts the amount of chopped carbon fiber of the present invention):
A kind of TiB for preparing
2-C
sfThe method of-carbon composite, it comprises the steps:
1), C
sfTop layer except the glue pre-treatment: press chopped carbon fiber (C
sf) with the volume ratio of acetone be 1: 30, chopped carbon fiber is mixed abundant stirring with acetone, filter after standing 48h under room temperature (removing filtrate),, with distilled water flushing chopped carbon fiber 5 times, then be placed in vacuum drying oven dry 48h under 80 ℃, the chopped carbon fiber after obtaining to process;
Described chopped carbon fiber is the fine carbon fiber of polypropylene (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
2) by the shared weight percentage of each raw material, be: TiB
2Chopped carbon fiber after powder: 67.2wt%, Graphite Powder 99: 29.6wt%, processing: 3.2wt%; Take TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and processing;
Described TiB
2The powder median size is 6 μ m, and Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m.
3), by wet mixing medium and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and processing is 20: 1, with TiB
2Add the wet mixing medium to stir ultra-sonic dispersion 2h in chopped carbon fiber after powder, Graphite Powder 99 and processing, then (ratio of grinding media to material is 5: 1, and ball-milling medium is ZrO to be placed in ball grinder
2Ball), ball milling mixes (ball milling 12h), obtains slurry A; With slurry A dry 2h on Rotary Evaporators, then put into vacuum drying oven dry 48h under 80 ℃, dried powder, through grinding, is crossed 100 mesh sieves, the powder that obtains mixing;
Described wet mixing medium is Virahol.The frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W.
4), the powder that will mix puts into graphite jig, be placed in vacuum sintering funace, and be filled with argon gas as protective atmosphere; sintering temperature is 1950 ℃, and soaking time is 1.5h, keeps 30MPa axle pressure to sintering to complete; then furnace cooling, obtain TiB
2-C
sf-carbon composite.
Measure TiB
2-C
sfThe relative density of-carbon composite is: 95.64%, and resistivity is: 77.9 μ Ω cm, bending strength is: 112.35MPa, fracture toughness property is: 3.84MPam
1/2
Claims (5)
1. one kind prepares TiB
2-C
sfThe method of-carbon composite, is characterized in that it comprises the steps:
1), C
sfTop layer except the glue pre-treatment: the volume ratio by chopped carbon fiber and acetone is 1: 25～30, chopped carbon fiber is mixed with acetone, stir, filter after standing 24～48h under room temperature, with distilled water flushing chopped carbon fiber 3～5 times, then be placed in vacuum drying oven dry 24～48h under 60～80 ℃, the chopped carbon fiber after obtaining to process;
2) by the shared weight percentage of each raw material, be: TiB
2Chopped carbon fiber after powder: 67.2～75wt%, Graphite Powder 99: 22.2～30wt%, processing: 2.8～3.2wt%; Take TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and processing;
3), by wet mixing medium and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and processing is 15～20: 1, with TiB
2Add the wet mixing medium to stir ultra-sonic dispersion 1.5～2h in chopped carbon fiber after powder, Graphite Powder 99 and processing, then be placed in ball grinder, ball milling mixes, and obtains slurry A; With slurry A dry 1.5～2h on Rotary Evaporators, then put into vacuum drying oven dry 24～48h under 60～80 ℃, dried powder, through grinding, is crossed 100 mesh sieves, the powder that obtains mixing;
4), the powder that will mix puts into graphite jig, be placed in vacuum sintering funace, and be filled with argon gas as protective atmosphere; sintering temperature is 1850 ℃～1950 ℃, and soaking time is 1h～1.5h, keeps 25～30MPa axle pressure to sintering to complete; then furnace cooling, obtain TiB
2-C
sf-carbon composite.
2. a kind of TiB for preparing according to claim 1
2-C
sfThe method of-carbon composite, is characterized in that: step 1) described chopped carbon fiber is polyacrylonitrile carbon fiber, and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
3. a kind of TiB for preparing according to claim 1
2-C
sfThe method of-carbon composite, is characterized in that: step 2) described TiB
2The median size of powder is 6 μ m; Graphite Powder 99 is commercially available superfine graphite powder, and median size is 15 μ m.
4. a kind of TiB for preparing according to claim 1
2-C
sfThe method of-carbon composite, is characterized in that: step 3) described wet mixing medium is dehydrated alcohol, methyl alcohol, Virahol or toluene.
5. a kind of TiB for preparing according to claim 1
2-C
sfThe method of-carbon composite, is characterized in that: step 3) frequency of described ultra-sonic dispersion is 25～30KHz, power is 1000～800W.
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| CN109053169A (en) * | 2018-07-27 | 2018-12-21 | 哈尔滨工业大学 | A kind of densification boron nitride crystal whisker enhancing vitreous silica composite ceramics and preparation method |
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| CN1807693A (en) * | 2005-12-26 | 2006-07-26 | 石忠宁 | Aluminium electrolysis cathode with titanium diboride coating and preparation process thereof |
| CN101844926A (en) * | 2010-03-24 | 2010-09-29 | 中南大学 | Pelleting method of titanium diboride powder |
| CN101876079A (en) * | 2010-06-13 | 2010-11-03 | 中国铝业股份有限公司 | Titanium boride cathode material for aluminium electrolysis and preparation method thereof |
| CN102212845A (en) * | 2011-05-24 | 2011-10-12 | 昆明冶金研究院 | Method for preparing TiB2 cathode coating for aluminium electrolysis |
| CN102304725A (en) * | 2011-09-16 | 2012-01-04 | 云南云铝润鑫铝业有限公司 | Electrolytic cathode containing titanium boride-carbon coating, and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1807693A (en) * | 2005-12-26 | 2006-07-26 | 石忠宁 | Aluminium electrolysis cathode with titanium diboride coating and preparation process thereof |
| CN101844926A (en) * | 2010-03-24 | 2010-09-29 | 中南大学 | Pelleting method of titanium diboride powder |
| CN101876079A (en) * | 2010-06-13 | 2010-11-03 | 中国铝业股份有限公司 | Titanium boride cathode material for aluminium electrolysis and preparation method thereof |
| CN102212845A (en) * | 2011-05-24 | 2011-10-12 | 昆明冶金研究院 | Method for preparing TiB2 cathode coating for aluminium electrolysis |
| CN102304725A (en) * | 2011-09-16 | 2012-01-04 | 云南云铝润鑫铝业有限公司 | Electrolytic cathode containing titanium boride-carbon coating, and preparation method thereof |
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