CN102531657A - Method for preparing TiB2-Csf-Carbon composite material - Google Patents
Method for preparing TiB2-Csf-Carbon composite material Download PDFInfo
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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 belongs 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 receive great attention, the focus that has at present become international Aluminum circle to pay close attention to.What the industry of tradition electrolytic aluminum 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; Compelled shutdown maintenance and replacing negative electrode cause very big financial loss.In recent years, the aluminium industry member is consistent both at home and abroad thinks that employing inert anode and inertia wettability negative electrode can effectively overcome the shortcoming of traditional electrolytic aluminum cathode material, 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
2The wettability negative electrode can make the pole span of electrolysis of aluminum foreshorten to 2mm～2.5mm; Reduce the aluminium liquid layer on the negative electrode simultaneously, thereby reduce the interference of magnetic field, reduce the electrolytical deposition of cell bottom electrolytic process; Increase the aluminium amount of producing; Improve current efficiency, obviously reduce the cost of electrolytic aluminum, prolong bath life.But pure TiB
2Material is the high and low densified sintering product that is difficult to of spread coefficient owing to fusing point, and owing to the difference of chemical bond characteristic, its crystal grain is significantly higher than other direction along the axial speed of growth of C in sintering process, causes crystal grain to be grown up unusually and makes the material property deterioration simultaneously; On the other hand, its fragility is big, heat-shock resistance is poor, the pure TiB that has been difficult for drawbacks limit such as processing
2Applying of cathode material.Therefore, with TiB
2Compound with carbon, prepare and combine both advantages and overcome its insufficient composite ceramic material, reduced TiB
2The requirement of material purity significantly reduces cost, and good moldability is prone to processing, but also can not influence the electroconductibility of material, can be used as electrolytic aluminum inertia wettability 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, it is simple that this coated material prepares process, can be coated in easily on the carbon materials matrix, after heat treatment can come into operation, thereby studied widely and use.It has can with the satisfactory electrical conductivity of metallographic phase analogy, stronger anti-metal aluminium liquid and fluoride salt melt corrosive nature, and can be melted aluminium liquid good wet, thereby change the wetting environment of cathode surface.Many shortcomings such as that but it exists is easy to wear, cracky, bad mechanical strength have limited it and have further applied.And the independent cathode construction of novel aluminum cell makes TiB
2The application of-carbon composite becomes possibility, and main both at home and abroad at present employing pressureless sintering technology prepares TiB
2-carbon composite, and add a certain amount of resin as additive.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 relatively poor, in use cracky.Big quantity research shows that 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 twine, 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 does not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of preparation TiB
2-C
SfThe method of-carbon composite, the TiB that this method obtains
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 preparation TiB
2-C
SfThe method of-carbon composite is characterized in that it comprises the steps:
1), C
SfThe top layer remove 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, leave standstill 24～48h after-filtration (removing filtrating) under the room temperature, with distilled water flushing chopped carbon fiber 3～5 times; Place vacuum drying oven in 60～80 ℃ of down dry 24～48h then, the chopped carbon fiber after obtaining to handle;
2), be: TiB by the shared weight percentage of each raw material
2Chopped carbon fiber after powder: 67.2～75wt%, Graphite Powder 99: 22.2～30wt%, the processing: 2.8～3.2wt%; Take by weighing TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and the processing;
3), by wet mixing medium and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and the processing is 15～20: 1, with TiB
2Add the wet mixing medium in the chopped carbon fiber after powder, Graphite Powder 99 and the processing and stir ultra-sonic dispersion 1.5～2h, (ball-to-powder weight ratio is 4～5: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), evenly (ball milling 10～12h) obtains slurry A to ball mill mixing; With slurry A dry 1.5～2h on Rotary Evaporators, put into vacuum drying oven then in 60～80 ℃ of down dry 24～48h, dried powder is crossed 100 mesh sieves, the powder that obtains mixing through grinding;
4), the powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into 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 accomplish; Furnace cooling obtains TiB then
2-C
Sf-carbon composite.
The described chopped carbon fiber of step 1) is the fine thomel of Vestolen PP 7052 (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.
The described wet mixing medium of step 3) is an absolute ethyl alcohol, also can use water-free organic solvent, for example methyl alcohol, Virahol or toluene etc.
The frequency of the described ultra-sonic dispersion of step 3) 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
SfEnhanced TiB
2-carbon composite is not changing TiB
2Under the prerequisite of-carbon composite resistivity (80 μ Ω cm), specific density (95%), bending strength performance index such as (110MPa), make its fracture toughness property improve 40%, can be used as wettable inert cathode material and be applied in the novel electrolytic aluminum groove.
2, preparation technology of the present invention is simple, and is workable, and preparation cost is low, can prepare the TiB that meets request for utilization rapidly
2-C
Sf-carbon composite adopts 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 invention 4
2-C
SfThe section SEM photo of-carbon composite;
The TiB of Fig. 1 (c) for making in the embodiment of the invention 6
2-C
SfThe section SEM photo of-carbon composite;
The TiB of Fig. 2 for making in the embodiment of the invention 4
2-C
SfThe XRD figure spectrum of-carbon composite.
Fig. 3 is prepared TiB in the embodiment of the invention 1～6
2-C
SfThe specific density variation diagram of-carbon composite.
Fig. 4 is prepared TiB in the embodiment of the invention 1～6
2-C
Sf-carbon composite bending strength and fracture toughness property variation diagram.
Fig. 1 (a) does not observe the fiber agglomeration for the SEM photo through the dried mixed powder of wet mixing among the figure.The method for mixing that the wet mixing ball milling is described can be dispersed in chopped carbon fiber in the powder equably.
Fig. 3 is prepared TiB in the embodiment of the invention 1～6
2-C
SfThe specific density variation diagram of-carbon composite is explained at chopped carbon fiber content more after a little while, and fibre content is little to the specific density influence 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, because the reinforcement of the bridge joint effect between the fiber; Cause the material porosity to rise, specific density sharply descends.
Fig. 4 is prepared TiB in the embodiment of the 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 material ruptures through 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, owing to increasing of material mesoporosity, material fracture toughness descended.
Fig. 3 and Fig. 4 explanation TiB in embodiment 1～6
2-C
SfThe short-and-medium carbon fiber reinforced optimum content of cutting of-carbon composite is 3wt%, further proves when fibre content is higher than or be lower than 2.8～3.2wt% content range material over-all properties variation simultaneously.
Embodiment
In order to understand the present invention better, 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 following embodiment.
In following examples, the measurement standard of specific density, bending strength and fracture toughness property is:
(1) specific density of sample is with the volume density of the sample theoretical density 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 with Archimedes's method mensuration, and calculation formula is:
Wherein:
ρ is a volume of sample density, m
DoBe aerial weight behind the sample complete drying, m
FloatingFor sample with water boil 30min after weight in water, ρ
WaterBe the density of water under the room temperature, ρ
AirDensity for air under the room temperature.
(2) bending strength of sample is measured through 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 SENB 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 a comparison example, does not promptly adopt chopped carbon fiber of the present invention):
With TiB
2Powder, Graphite Powder 99 are raw material, take by weighing 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 and (press absolute ethyl 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), and (ball-to-powder weight ratio is 4～5: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), ball milling 10h～12h mixes, and obtains slurry A; With slurry A dry 1.5～2h on Rotary Evaporators, put into vacuum drying oven then in 60～80 ℃ of down dry 24～48h, dried powder is through grinding; Cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into argon gas as protective atmosphere, sintering temperature is 1850 ℃, and pressure is 30MPa, insulation 1h, and furnace cooling obtains TiB then
2-carbon composite.
Measure TiB
2The specific 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 a comparison example, does not promptly adopt the amount of chopped carbon fiber of the present invention):
C
SfThe top layer remove 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, leave standstill 24～48h after-filtration (removing filtrating) under the room temperature, with distilled water flushing chopped carbon fiber 3～5 times; Place vacuum drying oven in 60～80 ℃ of down dry 24～48h then, the chopped carbon fiber after obtaining to handle; Described chopped carbon fiber is the fine thomel of Vestolen PP 7052 (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 the processing is a raw material, takes by weighing powder by the weight percentage of each raw material: TiB
2Powder: 70wt%, Graphite Powder 99: 29wt%, the chopped carbon fiber after the 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 handle after chopped carbon fiber (C
Sf) add absolute ethyl alcohol and stirring ultra-sonic dispersion 1.5～2h and (press absolute ethyl alcohol and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and the processing is 15～20: 1, and the frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W), and (ball-to-powder weight ratio is 4～5: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), ball milling 10h～12h mixes, and obtains slurry A; With slurry A dry 1.5～2h on Rotary Evaporators, put into vacuum drying oven then in 60～80 ℃ of down dry 24～48h, dried powder is through grinding; Cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into argon gas as protective atmosphere, sintering temperature is 1850 ℃, and pressure is 30MPa, insulation 1h, and furnace cooling obtains TiB then
2-C
Sf-carbon composite.
Measure TiB
2-C
SfThe specific 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 a comparison example, does not promptly adopt the amount of chopped carbon fiber of the present invention):
C
SfThe top layer remove 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, leave standstill 24～48h after-filtration (removing filtrating) under the room temperature, with distilled water flushing chopped carbon fiber 3～5 times; Place vacuum drying oven in 60～80 ℃ of down dry 24～48h then, the chopped carbon fiber after obtaining to handle; Described chopped carbon fiber is the fine thomel of Vestolen PP 7052 (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 the processing is a raw material, takes by weighing powder by the weight percentage of each raw material: TiB
2Powder: 70wt%, Graphite Powder 99: 28wt%, the chopped carbon fiber after the 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 handle after chopped carbon fiber add absolute ethyl alcohol and stirring ultra-sonic dispersion 1.5～2h and (press absolute ethyl alcohol and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and the processing is 15～20: 1, and the frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W), and (ball-to-powder weight ratio is 4～5: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), ball milling 10h～12h mixes, and obtains slurry A; With slurry A dry 1.5～2h on Rotary Evaporators, put into vacuum drying oven then in 60～80 ℃ of down dry 24～48h, dried powder is through grinding; Cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into argon gas as protective atmosphere, sintering temperature is 1850 ℃, and pressure is 30MPa, insulation 1h, and furnace cooling obtains TiB then
2-C
Sf-carbon composite.
Measure TiB
2-C
SfThe specific 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 preparation TiB
2-C
SfThe method of-carbon composite, it comprises the steps:
1), C
SfThe top layer remove 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; Leave standstill 36h after-filtration (removing filtrating) under the room temperature; With distilled water flushing chopped carbon fiber 4 times, place vacuum drying oven then in 70 ℃ of dry 36h down, the chopped carbon fiber after obtaining to handle;
Described chopped carbon fiber is the fine thomel of Vestolen PP 7052 (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
2), be: TiB by the shared weight percentage of each raw material
2Chopped carbon fiber after powder: 70wt%, Graphite Powder 99: 27wt%, the processing: 3wt%; Take by weighing TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and the 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 the processing is 18: 1, with TiB
2Add the wet mixing medium in the chopped carbon fiber after powder, Graphite Powder 99 and the processing and stir ultra-sonic dispersion 1.8h, (ball-to-powder weight ratio is 4.5: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), ball mill mixing is (ball milling 11h) evenly, obtains slurry A; With slurry A dry 1.8h on Rotary Evaporators, put into vacuum drying oven dry 36h under 70 ℃ then, dried powder is crossed 100 mesh sieves, the powder that obtains mixing through grinding;
Described wet mixing medium is an absolute ethyl alcohol.The frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W.
4), the powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into argon gas as protective atmosphere, sintering temperature is 1850 ℃, and soaking time is 1h, keeps the 30MPa axle pressure to accomplish to sintering, and furnace cooling obtains TiB then
2-C
Sf-carbon composite.
Measure TiB
2-C
SfThe specific 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
SfContent is as if very few (being lower than 2.8wt%), then to composite material toughening DeGrain, C
SfContent is if too much (being higher than 3.2wt%) then causes the matrix material density to descend mechanical properties decrease.
Embodiment 5 (this embodiment is a comparison example, does not promptly adopt the amount of chopped carbon fiber of the present invention):
C
SfThe top layer remove 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, leave standstill 24～48h after-filtration (removing filtrating) under the room temperature, with distilled water flushing chopped carbon fiber 3～5 times; Place vacuum drying oven in 60～80 ℃ of down dry 24～48h then, the chopped carbon fiber after obtaining to handle; Described chopped carbon fiber is the fine thomel of Vestolen PP 7052 (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 the processing is a raw material, takes by weighing powder by the weight percentage of each raw material: TiB
2Powder: 70wt%, Graphite Powder 99: 26wt%, the chopped carbon fiber after the 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 handle after chopped carbon fiber add absolute ethyl alcohol and stirring ultra-sonic dispersion 1.5～2h and (press absolute ethyl alcohol and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and the processing is 15～20: 1, and the frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W), and (ball-to-powder weight ratio is 4～5: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), ball milling 10h～12h mixes, and obtains slurry A; With slurry A dry 1.5～2h on Rotary Evaporators, put into vacuum drying oven then in 60～80 ℃ of down dry 24～48h, dried powder is through grinding; Cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into argon gas as protective atmosphere, sintering temperature is 1850 ℃, and pressure is 30MPa, insulation 1h, and furnace cooling obtains TiB then
2-C
Sf-carbon composite.
Measure TiB
2-C
SfThe specific 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 a comparison example, does not promptly adopt the amount of chopped carbon fiber of the present invention):
C
SfThe top layer remove 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, leave standstill 24～48h after-filtration (removing filtrating) under the room temperature, with distilled water flushing chopped carbon fiber 3～5 times; Place vacuum drying oven in 60～80 ℃ of down dry 24～48h then, the chopped carbon fiber after obtaining to handle; Described chopped carbon fiber is the fine thomel of Vestolen PP 7052 (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 the processing is a raw material, takes by weighing powder by the weight percentage of each raw material: TiB
2Powder: 70wt%, Graphite Powder 99: 25wt%, the chopped carbon fiber after the 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 handle after chopped carbon fiber add absolute ethyl alcohol and stirring ultra-sonic dispersion 1.5～2h and (press absolute ethyl alcohol and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and the processing is 15～20: 1, and the frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W), and (ball-to-powder weight ratio is 4～5: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), ball milling 10h～12h mixes, and obtains slurry A; With slurry A dry 1.5～2h on Rotary Evaporators, put into vacuum drying oven then in 60～80 ℃ of down dry 24～48h, dried powder is through grinding; Cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into argon gas as protective atmosphere, sintering temperature is 1850 ℃, and pressure is 30MPa, insulation 1h, and furnace cooling obtains TiB then
2-C
Sf-carbon composite.
Measure TiB
2-C
SfThe specific 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 a comparison example, does not promptly adopt chopped carbon fiber of the present invention):
With TiB
2Powder, Graphite Powder 99 are raw material, take by weighing 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 and (press absolute ethyl 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), and (ball-to-powder weight ratio is 4～5: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), ball milling 10h～12h mixes, and obtains slurry A; With slurry A dry 1.5～2h on Rotary Evaporators, put into vacuum drying oven then in 60～80 ℃ of down dry 24～48h, dried powder is through grinding; Cross 100 mesh sieves, the powder that obtains mixing; The powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into argon gas as protective atmosphere, sintering temperature is 1950 ℃, and pressure is 25MPa, insulation 1.5h, and furnace cooling obtains TiB then
2-carbon composite.
Measure TiB
2-C
SfThe specific 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 preparation TiB
2-C
SfThe method of-carbon composite, it comprises the steps:
1), C
SfThe top layer remove 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; Leave standstill 40h after-filtration (removing filtrating) under the room temperature; With distilled water flushing chopped carbon fiber 4 times, place vacuum drying oven then in 70 ℃ of dry 40h down, the chopped carbon fiber after obtaining to handle;
Described chopped carbon fiber is the fine thomel of Vestolen PP 7052 (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
2), be: TiB by the shared weight percentage of each raw material
2Chopped carbon fiber after powder: 75wt%, Graphite Powder 99: 22.2wt%, the processing: 2.8wt%; Take by weighing TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and the 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 the processing is 17: 1, with TiB
2Add the wet mixing medium in the chopped carbon fiber after powder, Graphite Powder 99 and the processing and stir ultra-sonic dispersion 1.7h, (ball-to-powder weight ratio is 4.5: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), ball mill mixing is (ball milling 11h) evenly, obtains slurry A; With slurry A dry 1.7h on Rotary Evaporators, put into vacuum drying oven dry 40h under 70 ℃ then, dried powder is crossed 100 mesh sieves, the powder that obtains mixing through grinding;
Described wet mixing medium is an absolute ethyl alcohol.
The frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W.
4), the powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into argon gas as protective atmosphere, sintering temperature is 1950 ℃, and soaking time is 1.5h, keeps the 25MPa axle pressure to accomplish to sintering, and furnace cooling obtains TiB then
2-C
Sf-carbon composite.
Measure TiB
2-C
SfThe specific 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 preparation TiB
2-C
SfThe method of-carbon composite, it comprises the steps:
1), C
SfThe top layer remove 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; Leave standstill 24h after-filtration (removing filtrating) under the room temperature; With distilled water flushing chopped carbon fiber 3 times, place vacuum drying oven then in 60 ℃ of dry 24h down, the chopped carbon fiber after obtaining to handle;
Described chopped carbon fiber is the fine thomel of Vestolen PP 7052 (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
2), be: TiB by the shared weight percentage of each raw material
2Chopped carbon fiber after powder: 67.2wt%, Graphite Powder 99: 30wt%, the processing: 2.8wt%; Take by weighing TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and the 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 the processing is 15: 1, with TiB
2Add the wet mixing medium in the chopped carbon fiber after powder, Graphite Powder 99 and the processing and stir ultra-sonic dispersion 1.5h, (ball-to-powder weight ratio is 4: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), ball mill mixing is (ball milling 10h) evenly, obtains slurry A; With slurry A dry 1.5h on Rotary Evaporators, put into vacuum drying oven dry 24h under 60 ℃ then, dried powder is crossed 100 mesh sieves, the powder that obtains mixing through grinding;
Described wet mixing medium is a methyl alcohol.The frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W.
4), the powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into argon gas as protective atmosphere, sintering temperature is 1850 ℃, and soaking time is 1h, keeps the 25MPa axle pressure to accomplish to sintering, and furnace cooling obtains TiB then
2-C
Sf-carbon composite.
Measure TiB
2-C
SfThe specific 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 preparation TiB
2-C
SfThe method of-carbon composite, it comprises the steps:
1), C
SfThe top layer remove 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; Leave standstill 48h after-filtration (removing filtrating) under the room temperature; With distilled water flushing chopped carbon fiber 5 times, place vacuum drying oven then in 80 ℃ of dry 48h down, the chopped carbon fiber after obtaining to handle;
Described chopped carbon fiber is the fine thomel of Vestolen PP 7052 (PAN), and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
2), be: TiB by the shared weight percentage of each raw material
2Chopped carbon fiber after powder: 67.2wt%, Graphite Powder 99: 29.6wt%, the processing: 3.2wt%; Take by weighing TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and the 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 the processing is 20: 1, with TiB
2Add the wet mixing medium in the chopped carbon fiber after powder, Graphite Powder 99 and the processing and stir ultra-sonic dispersion 2h, (ball-to-powder weight ratio is 5: 1, and ball-milling medium is ZrO to place ball grinder again
2Ball), ball mill mixing is (ball milling 12h) evenly, obtains slurry A; With slurry A dry 2h on Rotary Evaporators, put into vacuum drying oven dry 48h under 80 ℃ then, dried powder is crossed 100 mesh sieves, the powder that obtains mixing through grinding;
Described wet mixing medium is a Virahol.The frequency of described ultra-sonic dispersion is 25～30KHz, and power is 1000～800W.
4), the powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into argon gas as protective atmosphere, sintering temperature is 1950 ℃, and soaking time is 1.5h, keeps the 30MPa axle pressure to accomplish to sintering, and furnace cooling obtains TiB then
2-C
Sf-carbon composite.
Measure TiB
2-C
SfThe specific 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
SfThe top layer remove 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, leave standstill 24～48h after-filtration under the room temperature, with distilled water flushing chopped carbon fiber 3～5 times; Place vacuum drying oven in 60～80 ℃ of down dry 24～48h then, the chopped carbon fiber after obtaining to handle;
2), be: TiB by the shared weight percentage of each raw material
2Chopped carbon fiber after powder: 67.2～75wt%, Graphite Powder 99: 22.2～30wt%, the processing: 2.8～3.2wt%; Take by weighing TiB
2Chopped carbon fiber after powder, Graphite Powder 99 and the processing;
3), by wet mixing medium and TiB
2The mass ratio of the chopped carbon fiber total mass after powder, Graphite Powder 99 and the processing is 15～20: 1, with TiB
2Add the wet mixing medium in the chopped carbon fiber after powder, Graphite Powder 99 and the processing and stir ultra-sonic dispersion 1.5～2h, place ball grinder again, ball mill mixing is even, obtains slurry A; With slurry A dry 1.5～2h on Rotary Evaporators, put into vacuum drying oven then in 60～80 ℃ of down dry 24～48h, dried powder is crossed 100 mesh sieves, the powder that obtains mixing through grinding;
4), the powder that mixes is put into graphite jig, place in the vacuum heating-press sintering stove, and charge into 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 accomplish; Furnace cooling obtains TiB then
2-C
Sf-carbon composite.
2. a kind of preparation TiB according to claim 1
2-C
SfThe method of-carbon composite is characterized in that: the described chopped carbon fiber of step 1) is the fine thomel of Vestolen PP 7052, and specification is 6K, and mean length is 2mm, and Fibre diameter is 7 μ m.
3. a kind of preparation TiB 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 preparation TiB according to claim 1
2-C
SfThe method of-carbon composite is characterized in that: the described wet mixing medium of step 3) is absolute ethyl alcohol, methyl alcohol, Virahol or toluene.
5. a kind of preparation TiB according to claim 1
2-C
SfThe method of-carbon composite is characterized in that: the frequency of the described ultra-sonic dispersion of step 3) is 25～30KHz, and power is 1000～800W.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105702320A (en) * | 2014-11-28 | 2016-06-22 | 湖南利德电子浆料股份有限公司 | Silver conductive paste for radio frequency identification tag and preparation method thereof |
| 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 |
| CN109752398A (en) * | 2019-02-25 | 2019-05-14 | 广州能源检测研究院 | A method of detection lithium titanate purity |
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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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Patent Citations (5)
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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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| CN105702320A (en) * | 2014-11-28 | 2016-06-22 | 湖南利德电子浆料股份有限公司 | Silver conductive paste for radio frequency identification tag and preparation method thereof |
| 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 |
| CN109752398A (en) * | 2019-02-25 | 2019-05-14 | 广州能源检测研究院 | A method of detection lithium titanate purity |
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