CN107619279A - A kind of carbon nanometer high-temperature ceramic and preparation method thereof - Google Patents

A kind of carbon nanometer high-temperature ceramic and preparation method thereof Download PDF

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CN107619279A
CN107619279A CN201710777764.5A CN201710777764A CN107619279A CN 107619279 A CN107619279 A CN 107619279A CN 201710777764 A CN201710777764 A CN 201710777764A CN 107619279 A CN107619279 A CN 107619279A
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walled carbon
powder
temperature
ceramic
nanometer high
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崔从文
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WEIHAI WENRUN MEASURE & CONTROL EQUIPMENT Co Ltd
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WEIHAI WENRUN MEASURE & CONTROL EQUIPMENT Co Ltd
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Abstract

The invention provides a kind of carbon nanometer high-temperature ceramic and preparation method thereof, the present invention is improved traditional earthenware, prepare a kind of carbon nanometer high-temperature ceramic for including multi-walled carbon nanotube matrix, intermediate layer and ceramic powder last layer successively from inside to outside, described intermediate layer is Ni Al powder, and ceramic powder last layer is by being distributed with TiO2And Al2O3The composite ceramic powder spraying that the intermetallic compound base body grinding of particle forms forms；There is the carbon nanometer high-temperature ceramic of the present invention high temperature resistant, acid and alkali-resistance, hardness height, good toughness, pore size filter to reach nano level advantage, it can be widely applied in the products such as refractory ceramics dust removal filter, indoor air filter, manufacturing process is easy, and operationally, when the absorption of carbon nanometer high-temperature ceramic reaches saturation, dust is directly discharged by the air effect of brushing by fluid passage, is not in the generation of clogging, is reduced the generation of harm.

Description

A kind of carbon nanometer high-temperature ceramic and preparation method thereof
Technical field
The present invention relates to a kind of silicon rubber, more particularly to a kind of carbon nanometer high-temperature ceramic and preparation method thereof.
Background technology
The 80's of 20th century porous ceramic micro filter and hyperfiltration technique initially enter industrial applications field, due to ceramics Material has that corrosion-resistant, high temperature resistant, long lifespan, easily regeneration, filter efficiency are high, the characteristic such as mechanical strength height thus be widely used In in chemical industry, food, water process, etc. field, and be also widely applied in some working condition rugged environments, It is mainly used in separation of solid and liquid or solid and gas separation.
Traditional porous ceramic film is made of ceramic powders such as carborundum, silicon nitride, mullite, cordierites, its hole source The intergranular gap formed when particle packing, thus the porosity of this kind of porous ceramic pipe, the big fluid in aperture is when passing through Resistance it is higher, filtering particle diameter be unsatisfactory for requiring, be not suitable for the application under low-pressure or high flux；Although furthermore ceramic material Possessing numerous materials can not be than the superiority of analogy, but its fatal weakness is his fragility, and ceramic material is all by ion Key or the more of covalent bond composition can promote the system that material slides through mechanism, its shortage, and material once receives additional load, then It is difficult the presence of the microdefect formed in material surface avoided plus ceramic process, they are likely to form formation of crack, Stress can be concentrated at the tip of these crackles, again without other systems that can consume extraneous energy in ceramic material, only Exchanged with new free energy, such result results in the Quick Extended of crackle, shows as the brittle fracture of material, this meeting The physical life of material is substantially reduced, while also limit the extension in materials application field.
CNT (CNTs) be the class graphite plane being made up of carbon hexatomic ring be curled into seamless tubular nanoscale it is hollow Pipe, wherein each carbon atom occurs to be bonded completely by 3 carbon atoms of sp hydridization and surrounding.According to the layer for forming tube wall carbon atom Number is different, can be single-walled carbon nanotube (SWCNTs) and multi-walled carbon nanotube (MWCNTs) by CNTs points.Multi-walled carbon nanotube is A kind of carbon nanomaterial of hollow columnar structures, it is connected by C-C covalent bonds between atom, there is good mechanical property and Zi Run Slip, its average Young's modulus is 1.8 TPa, and bending strength is up to 14.2 GPa.Multi-walled carbon nanotube, using fluidized-bed reaction Prepared by device batch, carbon pipe mean outside diameter 8 ~ 15 nm, the um of average length 10 ~ 30, specific surface area are more than 233m2/ g, due to its tool There is special tube pile structure and have many abnormal mechanics, electricity and chemical properties and receive significant attention.
The content of the invention
The invention aims to solve above-mentioned prior art deficiency, there is provided a kind of carbon nanometer high-temperature ceramic and its system Preparation Method, the present invention traditional earthenware is improved, prepare a kind of carbon nanometer high-temperature ceramic, its have high temperature resistant, Acid and alkali-resistance, hardness height, good toughness, pore size filter reach nanoscale, have simple in construction, easy for installation, the advantages of production cost is low.
A kind of carbon nanometer high-temperature ceramic, include multi-walled carbon nanotube matrix, intermediate layer and pottery successively from inside to outside Porcelain powder bed, described intermediate layer are Ni-Al powder, and Ni weight fraction is 60% ~ 80%, preferably 65% in Ni-Al powder ~ 80%, more preferably 70% ~ 80%, most preferably 72% ~ 75% remaining be Al powder；Described ceramic powder last layer is by being distributed with TiO2With Al2O3The composite ceramic powder spraying that the intermetallic compound base body grinding of particle forms is formed, and the composite ceramic powder is put down Equal particle diameter is 5 μm ~ 20 μm, preferably 5 μm ~ 19 μm, most preferably 5 μm ~ 18 μm.
Further, multi-walled carbon nanotube matrix of the present invention is burnt by amino multi-walled carbon nano-tube powder as matrix phase Knot forms, and the amino multi-walled carbon nano-tube surface is coated with Ni-P alloy layers, and thickness of coating is 2nm ~ 8nm, and preferably 2nm ~ 5nm, most preferably 5nm；The intermetallic compound includes NiAl, NiTi and TiAl.
A kind of preparation method of carbon nanometer high-temperature ceramic, comprises the following steps：
1) preparation of multi-walled carbon nanotube matrix：A. the preparation of CNT：The silicon chip immersion medium that surface is coated with to iron film is molten In liquid, silicon chip is connected with dc source, to silicon chip electrified regulation to 500~1000 DEG C, CNT is made in conduction time 2h, The iron film thickness is 2nm ~ 30nm, preferably 6nm ~ 24nm, most preferably 8nm ~ 15nm, and described medium solution is ethanol or methanol Any of solution, described medium solution exclude inner air using the preceding nitrogen that is first passed through, prepared in aforementioned manners CNT pipe shaft structure smooth uniform, wall defects are few, and external diametrical extent has helical form carbon nanometer up to 13~26 nm Pipe, is grown on silicon chip base terminal and is emitted for openend, other end end emits completely enclosed.
B. acid treatment：In concentrated nitric acid and the mixed liquor of the concentrated sulfuric acid that multi-walled carbon nanotube is placed in, flowed back at 100 DEG C 6h is stirred, the concentration of above-mentioned concentrated nitric acid is 16molL-1, the concentration of the concentrated sulfuric acid is 18molL-1, concentrated nitric acid and the concentrated sulfuric acid Volume ratio 3:1, above-mentioned mixed liquor is cooled to room temperature, filtered using deionized water rinsing, until filtrate is into neutrality, in above-mentioned Property filtrate uses 0.1 ~ 0.5um, preferably 0.1 ~ 0.3um, more preferably 0.15 ~ 0.25 um, most preferably 0.2 ~ 0.25um poly- carbonic acid Ester film is filtrated to get black solid, and 12h is soaked during the black solid is soaked in hydrochloric acid solution, will after filtering again Gained solid obtains functionalized multi-wall carbonnanotubes, after aoxidizing filtration method to CNT processing using nitration mixture in 60 DEG C of drying Benefit cost it is relatively low, disclosure satisfy that the requirement of Technological Economy, there is good application prospect.
C. the functionalized multi-wall carbonnanotubes in above-mentioned steps b are mixed into 12h with thionyl chloride at room temperature, obtained To chloride product, then it is mixed with equivalent trien and TEPA respectively, stirs 24h at room temperature, Amino multi-walled carbon nano-tube is finally given, amino multi-walled carbon nano-tube cost is low for this, saves pre-treatment step, technique letter It is single；Cleaning, environmental protection, energy consumption are low, and the three wastes are few.
d：Amino multi-walled carbon nano-tube in step c is put into mould cold pressing, helped using zirconium disilicide powder as sintering Agent, the internal diameter that finally sintering is prepared into circular tube shaped is 4 ~ 6mm, preferably 5mm, and pipe thickness is 1.5 ~ 2.5mm, and preferably 2mm's is more Wall carbon nano tube matrix, the multi-walled carbon nanotube matrix use two step hot pressing sintering methods：First with 4 ~ 6 DEG C/min heating rates Temperature is risen to as 1300 DEG C, sintering pressure is 12 ~ 35MPa, heat-insulation pressure keeping 8 ~ 12 minutes；Then with 11 ~ 16 DEG C/min heating It is 1500 ~ 1700 DEG C, 12 ~ 35MPa of sintering pressure, 4 ~ 9min of heat-insulation pressure keeping that speed, which rises to sintering temperature, and whole sintering process is High vacuum environment.In the present invention sintering temperature of material, sintering pressure, sintering time be below existing hot pressing and sintering technique will Ask；The additive for improving material inside organization structure is used as using multi-walled carbon nanotube, it will be apparent that the crystallite dimension of material is reduced, 6.98MPa ﹒ m1/2 are arrived into the fracture toughness lifting of material.The present invention uses two step hot pressing and sintering techniques, with quick, low temperature spy Point prepares the tubular matrix with higher-density and mechanical property..
2) preparation of carbon nanometer high-temperature ceramic：E. substrate pretreated：Removed using the process of blasting treatment above-mentioned Greasy dirt to surface of multi-walled carbon nanotube matrix in step d, oxide skin, the surface roughness 37.1 μm~48.4 of described matrix μm。
F. intermediate layer sprays：By substrate preheating to 150~200 DEG C, voltage be 80V, electric current 400A, spray away from guarantor Hold 85~100mm, powder sending quantity be 0.6kg/h under conditions of, 0.05~0.15mm thickness intermediate layer Ni-Al powder is sprayed to it End, Ni mass fraction is 60wt% ~ 80wt%, preferably 65wt% ~ 80wt% in the Ni-Al powder, more preferably 70wt% ~ 80wt%, most preferably 72wt% ~ 75wt%, remaining is Al powder.
G. ceramic powder last layer is prepared and sprayed：NiH by weight fraction for 45wt% Ni, 15wt% Al, 30wt%2、 10wt% Al2O3Ethanol wet-mixing is added, reacts to be formed between NiAl, NiTi, TiAl metal by SHS process Compound group into matrix in Dispersed precipitate have TiO2And Al2O3The composite of particle, described composite grinding is made The average grain diameter of composite ceramic powder described in composite ceramic is 5um ~ 20um, preferably 5 ~ 19um, most preferably 5 ~ 18um, continues to protect Above-mentioned matrix uniform rotation is held, ensures powder particle dissolve fully, rotating speed 1.3m/s, is back and forth moved along axis of workpiece using spray gun Ceramic coated powder is moved, spray gun axial reciprocating translational speed is 0.08 ~ 0.15m/s, preferably 0.08 ~ 0.12 m/s, most preferably 0.1m/s, spray gun circumference translational speed are 0.45 ~ 0.58m/s, preferably 0.45 ~ 0.52m/s, most preferably 0.5m/s, powder feeding gas 1.5 ~ 2.2kg/h of flow, preferably 1.8 ~ 2.2 kg/h, most preferably 2kg/h, flow 0.8 ~ 1.5kg/h of working gas is more excellent 0.8 ~ 1.2 kg/h, most preferably 1 kg/h are selected, the advantage that the spraying method sprayed using axial reciprocating has speed control is reduced Firing rate, product cost is reduced, reduce product thermic load.
3) post-process：The carbon nanometer high-temperature ceramic of above-mentioned preparation is put into progress ultrasonic disperse 30min in 50 DEG C of water, then The microwave treatment 15min for being 500W with power under the conditions of 90 DEG C.
Further, the present invention is molten using the nitration mixture of sulfuric acid and nitric acid to the amino multi-walled carbon nano-tube obtained in step c Liquid purifies, and eliminates influence of the impurity to Composite Coatings process, and sulfuric acid and nitric acid volume ratio are 3 in the mixed acid solution：1, purifying Amino multi-walled carbon nano-tube is washed to neutrality and is dried in vacuo using deionized water afterwards, by purifying, dried amination Multi-walled carbon nanotube carries out surface modification, its surface is obtained one layer of Ni-P alloy layer uniformly, fine and close.
Further, the present invention using planetary ball mill by amino multi-walled carbon nano-tube wet-milling 6h after purification, then Carry out being dried in vacuo again standby, reduce multi-walled carbon nanotube winding in the plating solution and agglomeration.
Further, when the present invention carries out surface modification to amino multi-walled carbon nano-tube, the composition of basic bath is： NiSO4•6H2O 30 g/L, NaH2PO2•H2O 25 g/L, CH3COONa•3H2O 15 g/L, Na3C6H5O7•2H2O (citric acids Sodium) 15 g/L, the mg/L of lactic acid 25, lead acetate l5 mg/L, 2h is aged after above-mentioned basic bath is prepared, will have been pre-processed 1g/L amino multi-walled carbon nano-tube after wet-milling, added simultaneously in basic bath with 0.5 g/L citric acids, ultrasonic wave scattered 30 Min, Composite Coatings are then carried out in thermostat water bath, temperature is (85 soil 1) DEG C during Composite Coatings, and PH is 4.5~4.7, is stirred The r/min of speed 200, the h of time 2 are mixed, is not reacted to each other between plating each composition of agent；It is small to the corrosiveness of matrix；It can remove The oxide on surface, effectively protects matrix；Cost is cheap.
Further, the multi-walled carbon nanotube after acid treatment in above-mentioned steps b is scattered in by the present invention by ultrasonic dispersion In Ludox, ground at 120 DEG C after vacuum drying chamber drying, multi-walled carbon nanotube and SiO is made2Mass ratio is 1：1 answers Adsorbent CS50 is closed, the Composite material transparent is good, viscosity little Yi cast, has that electrical loss is small, magnetic loss is small concurrently, is more than or less than Viscosity little Yi should not be poured into a mould during this value, and electrical loss is big, magnetic loss is big.
The aperture of untreated CNT focuses mostly between 0~3 nm, and Pass through above-mentioned technical proposal is received in addition Material shows mesoporous and pore characteristics after rice Ludox grain, and nanometer titanium dioxide silicon particle is used as when strengthening phase, with more walls Good cooperative effect, the SiO of generation be present in CNT2Gluing layer effectively reduces the agglomerate behavior between carbon pipe, improves Be used alone multi-walled carbon nanotube and nanometer titanium dioxide silicon particle be used as adsorbent adsorption capacity it is not good enough the shortcomings that, formed Specific surface area is big, the uniform mesoporous-micropore double hole channel carbon nano-composite material of pore.
Further, working gas used in step g of the present invention is Ar, N2And H2Mixed gas, H in mixed gas2's Volume ratio is 5%~10%, and remaining is Ar and N2Mixed gas, wherein H2Purity >=99.95%, Ar and N2Purity is all higher than 99.999%, the arc voltage and arc length and hot entropy of ion arc can be improved, the direct benefit brought to product reaches health discharge will Ask, and purification efficiency is high, cleaning equipment high temperature resistant, service life length；With simple in construction, easy to use, processing cost is low.
Further, the carbon nanometer high-temperature ceramic that prepared by the present invention is applied to refractory ceramics dust removal filter.
Further, the carbon nanometer high-temperature ceramic that prepared by the present invention is applied to indoor air filter.
The present invention applies to be used in refractory ceramics dust removal filter and indoor air filter as filter core, can be filtered Particle diameter is smaller, and structural strength is big, and when the absorption of carbon nanometer high-temperature ceramic reaches saturation, dust is straight by the air effect of brushing Fluid passage discharge was connected, is not in the generation of clogging, reduces the generation of harm.
The beneficial effects of the present invention are：Carbon nanometer high-temperature ceramic high temperature resistant, acid and alkali-resistance, the hardness of the present invention is high, tough The good, pore size filter of property reaches nanoscale, and simple in construction, can be widely used in refractory ceramics dust removal filter and indoor air filtration Device field, due to the carbon nanometer high-temperature ceramic of the present invention also have the advantages that intensity is high, wearability is good, anti-Qu Qiangdu therefore can To adapt to the application of various environment extensively, and service life is grown, and replacement cycle length, comparatively greatly reduces use cost.
Brief description of the drawings
Fig. 1 is Ni-P-MWNTS coating surface morphology figures in embodiment 3.
When Fig. 2 is that to be Normal stress in embodiment 3 be 10N, shape appearance figure after the friction of Ni-P-MWNTS coating.
Embodiment
Embodiment 1
25 nm iron film is plated in silicon chip matrix, silicon chip is immersed in the container for filling ethanol or methanol solution, silicon chip and direct current Power supply connects, and after the air in nitrogen stripping container, to silicon chip electrified regulation to 850 DEG C, carbon can be made after 2 h by, which continuing, receives Mitron, the multi-walled carbon nanotube pipe shaft structure smooth uniform prepared, wall defects are few, and external diametrical extent exists up to 15 nm Spiral carbon nano pipe, it is grown on silicon chip base terminal and is emitted for openend, other end end emits completely enclosed.
1）500 mg multi-walled carbon nanotubes are placed in concentrated nitric acid (225ml, 16 mol L-1) and the concentrated sulfuric acid (75ml, 18 mol•L-1) mixed liquor in, the return stirring 6h at 100 DEG C.After mixed solution is cooled to room temperature, rushed repeatedly using deionized water Wash filter, until filtrate is filtered into after neutrality using 0.22um polycarbonate films, will filtering gained black solid in hydrochloric acid (12mol•L-1) in immersion 12h, again filter after, by gained solid in 60 DEG C drying, obtain functionalized multi-wall carbonnanotubes (CNT-COOH).Again by its at room temperature with SOCl2Stir 12h, obtain chloride product, then by its respectively with equivalent Sanya Tetramine and TEPA mixing, stir 24h, finally give amino multi-walled carbon nano-tube at room temperature；By amination Multi-walled carbon nanotube is put into mould cold pressing, and using zirconium disilicide powder as sintering aid, finally sintering is prepared into circular tube shaped Internal diameter is 5mm, and pipe thickness is 2mm multi-walled carbon nanotube matrix.The multi-walled carbon nanotube matrix sintering process is：First Temperature is risen to as 1300 DEG C using 4 ~ 6 DEG C/min heating rates, sintering pressure is 12 ~ 35MPa, heat-insulation pressure keeping 8 ~ 12 minutes, then Sintering temperature is risen to as 1500 ~ 1700 DEG C using 11 ~ 16 DEG C/min heating rate, 12 ~ 35MPa of sintering pressure, heat-insulation pressure keeping 4 ~ 9min, whole sintering process are high vacuum environment.
Greasy dirt, the oxide skin on amino multi-walled carbon nano-tube surface, the surface roughness of matrix are removed using sandblasting means 37.1 μm~48.4 μm, then by substrate preheating to 150~200 DEG C, voltage be 80V, electric current 400A, spray away from keep 85~ Under conditions of 100mm, powder sending quantity are 0.6kg/h, it is sprayed among the refractory ceramics finishing coat of 0.05~0.15mm thickness Transition zone Ni-Al powder, Ni weight fraction is 75wt% in the Ni-Al powder.
By Al, 30wt% that weight fraction is Ni, 15wt% for being 45wt% by weight fraction NiH2, 10wt% Al2O3Add Enter ethanol wet-mixing, the base to be formed in NiAl, NiTi, TiAl intermetallic compound composition is reacted by SHS process Dispersed precipitate has TiO in body2And Al2O3The composite of particle, described composite grinding is made described in composite ceramic The average grain diameter of composite ceramic powder is 5 μm ~ 18 μm, ensures powder particle dissolve fully, continues to keep above-mentioned matrix at the uniform velocity to turn Dynamic, rotating speed 1.3m/s, spray gun moves back and forth along axis of workpiece, and spray gun axial reciprocating translational speed is：0.1m/s, spray gun are circumferential Translational speed：0.5m/s, ceramic powders are ejected into workpiece substrate surface, the coating formed every time is not easy blocked up, prevents workpiece Overheat.The flow 2kg/h of powder feeding gas and the kg/h of flow 1 of working gas, used working gas are：In Ar and N2Gas The H of 5%~10% volume ratio is added in body2Gas, H2>=99.95%, Ar, N299.999% is all higher than, the arc voltage of ion arc can be improved With arc length and hot entropy.
The amino multi-walled carbon nano-tube of ceramic coated powder is finally put into progress ultrasonic disperse 30min in 50 DEG C of water, The microwave treatment 15min for being again 500W with power under the conditions of 90 DEG C.
Embodiment 2
The present embodiment 2 and the difference of embodiment 1 are：Multi-walled carbon nanotube after the step b acid treatments of embodiment 1 is passed through Ultrasonic dispersion is scattered in Ludox, is ground after being placed at 120 DEG C vacuum drying chamber drying, be made multi-walled carbon nanotube with SiO2Multi-walled carbon nanotube/SiO of mass ratio2Compound adsorbent CS50, formation specific surface area is big, the uniform mesoporous-micropore of pore Double hole channel carbon nano-composite material.
Embodiment 3
The present embodiment 3 and the difference of embodiment 1 are：The amino multi-walled carbon nano-tube obtained in the step c of embodiment 1 is used The mixed acid solution of sulfuric acid and nitric acid purifies, and the sulfuric acid and nitric acid volume ratio are 3：1, make to be washed with deionized to neutrality, directly To filtrate pH close to neutrality, it is subsequently placed in vacuum drying chamber and dries, using planetary ball mill by the multi-wall carbon nano-tube of purifying The h of pipe wet-milling 6, cut out it is short, vacuum drying chamber drying after it is standby.Surface is carried out to the amino multi-walled carbon nano-tube after processing It is modified, its surface is obtained one layer of Ni-P alloy layer uniformly, fine and close, basic bath composition is：NiSO4 •6H2O 30 g/ L, NaH2PO2 • H2O 25 g/L, CH3COONa•3H2O 15 g/L, Na3C6H5O7The g/L of 2O 15, the mg/L of lactic acid 25, acetic acid The mg/L of lead 15, the basic bath are aged 2h after preparing, by the 1 g/L amino multi-walled carbon nano-tube located in advance with 0.5g/L citric acids are added in basic bath simultaneously, and ultrasonic wave disperses 30 min, and Composite Coatings are then carried out in thermostat water bath, Temperature is (85 soil 1) DEG C during Composite Coatings, and PH is 4.5~4.7, stir speed (S.S.) 200 r/min, time 2h.
The difference of embodiment 4 and embodiment 1 is that the present invention uses two step hot pressing and sintering techniques, first with 5 DEG C/min liters It is 1300 DEG C, sintering pressure 30MPa that warm speed, which rises to temperature, heat-insulation pressure keeping 8 ~ 12 minutes, then with 15 DEG C/min heating Speed rises to sintering temperature as 1500 ~ 1700 DEG C, sintering pressure 30MPa, 4 ~ 9min of heat-insulation pressure keeping, and whole sintering process is Gao Zhen Altitude.Zirconium diboride ceramics base composite wood with higher-density and mechanical property is prepared with the characteristics of quick, low temperature Material, facilitate its follow-up large-scale production and prepare and fiber reinforced technology.
Hardness detection method is using HV-1000 digital display type microhardnesses instrument measurement Ni-P-MWNTs composite deposites in table 1 Microhardness, carry pressure 0.98 N, load time 10s；Utilize the thickness of the digital cladding thickness measurer measurement composite deposites of epoch TT260 Degree.Microhardness and thickness are that each sample surveys 5 points, are averaged.
Multi-walled carbon nanotube anti-wear performance detects in table 1, using MFT-4000 multifunction surface ability meters (Lanzhou Micro-nano instrument Science and Technology Ltd.）Carry out reciprocal dry wear test, the Si that pin sample is diameter 5mm3N4Ball, workpiece try for research Sample, normal load 10N, reciprocating friction distance is 5mm, and friction speed is 100mm/min, experiment duration 10 min.
During abrasion test, part MWNTs is destroyed, come off after, rolling friction occurs in wear surface, reduces The friction factor and wear rate of coating, so as to improving the wear resistance of composite deposite.
Table 1.
Material wear ability refers to the ability that certain material resists abrasion under certain friction condition.Generally, it is with wear rate Inverse represents.I.e.
ε=1/w
The wearability of ε-material in formula；
W-material is in unit interval or unit motion apart from interior caused wear extent, i.e. wear rate.
Relative wear rate ε=ε samples/ε standards can also be used
Using the phase structure of German Bruker D8 Advance X-ray diffractometers (XRD) analysis coating.
The surface topography of forward and backward coating is worn with Nova NanoSEM450 SEM (SEM) observation.Ni-P- MWNTs composite deposites surface is made up of blistered particle, and non-structure cell is smaller, and MWNTs is network-like to be embedded in nickel phosphorus non-crystal born of the same parents In, be advantageous to its abundant dispersion-strengthened action to composite deposite, and then improve the structure of composite deposite.
Fig. 1 is Ni-P-MWNTS coating surface morphologies in embodiment 3, when Fig. 2 is that to be Normal stress in embodiment 3 be 10N, Shape appearance figure after the friction of Ni-P-MWNTS coating, surface is without obvious plow vestige, and the abrasive dust to come off is less, and surface is still smooth. Multi-walled carbon nanotube is uniformly distributed in Ni-P-MWNTs composite deposites, and is connected together with nickel phosphorus structure cell.Tried in fretting wear In testing, it is embedded into and is gradually come off in the MWNTs of matrix coating from coating, and be attached to wear surface, is effectively reduced coating Direct contact with friction pin reduces frictional resistance, reduces the friction factor and wear rate of coating.
The surface of Ni-P-MWNTs composite deposites as shown in Figure 1 is uniform, fine and close, overall smoother.
As shown in Fig. 2 during abrasion test, part MWNTs is destroyed, come off after, rolled in wear surface Dynamic friction, the friction factor and wear rate of coating are reduced, so as to improve the wear resistance of composite deposite.This paper's Under test condition, the microhardness of Ni-P-MWNTs composite deposites reaches 935HV, and wear rate is 9.6 × 10-12m3/（N••m）, Average friction factor is 0.08.

Claims (10)

  1. A kind of 1. carbon nanometer high-temperature ceramic, it is characterised in that：Include multi-walled carbon nanotube matrix, middle mistake successively from inside to outside Crossing layer and ceramic powder last layer, described intermediate layer is Ni-Al powder, and Ni weight fraction is 60 ~ 80% in Ni-Al powder, Remaining is Al powder；Described ceramic powder last layer is by being distributed with TiO2And Al2O3The intermetallic compound base body grinding of particle forms Composite ceramic powder spraying form, the average grain diameter of the composite ceramic powder is 5 μm ~ 20 μm.
  2. A kind of 2. carbon nanometer high-temperature ceramic according to claim 1, it is characterised in that：The multi-walled carbon nanotube matrix Formed by amino multi-walled carbon nano-tube powder as matrix phase sintering, the amino multi-walled carbon nano-tube surface is coated with Ni-P Alloy layer, thickness of coating are 2nm ~ 8nm；The intermetallic compound includes NiAl, NiTi and TiAl.
  3. A kind of 3. preparation method of carbon nanometer high-temperature ceramic, it is characterised in that：Comprise the following steps：
    1）The preparation of multi-walled carbon nanotube matrix：A. the preparation of CNT：The silicon chip immersion medium that surface is coated with to iron film is molten In liquid, silicon chip is connected with dc source, to silicon chip electrified regulation to 500~1000 DEG C, CNT is made in conduction time 2h, The iron film thickness is 2 ~ 30nm, and described medium solution is any of ethanol or methanol solution, described medium solution Inner air is excluded using the preceding nitrogen that is first passed through；B. acid treatment：Concentrated nitric acid that multi-walled carbon nanotube is placed in and the concentrated sulfuric acid it is mixed Close in liquid, the return stirring 6h at 100 DEG C, the concentration of above-mentioned concentrated nitric acid is 16molL-1, the concentration of the concentrated sulfuric acid is 18mol L-1, the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 3:1, above-mentioned mixed liquor is cooled to room temperature, filtered using deionized water rinsing, directly To filtrate into neutrality, above-mentioned neutral filtrate is filtrated to get black solid using 0.1 ~ 0.5um polycarbonate film, by described in Black solid soaks 12h in being soaked in hydrochloric acid solution, after filtering again, by gained solid in 60 DEG C of drying, obtain carboxylated Multi-walled carbon nanotube；C. the functionalized multi-wall carbonnanotubes in above-mentioned steps b are mixed with thionyl chloride at room temperature 12h, chloride product is obtained, then it is mixed with equivalent trien and TEPA respectively, stirred at room temperature 24h is mixed, finally gives amino multi-walled carbon nano-tube；d：Amino multi-walled carbon nano-tube in step c is put into mould cold pressing, Using zirconium disilicide powder as sintering aid, the internal diameter that finally sintering is prepared into circular tube shaped be 4 ~ 6mm, pipe thickness for 1.5 ~ 2.5mm multi-walled carbon nanotube matrix, the multi-walled carbon nanotube matrix sintering process are：Heated up first with 4 ~ 6 DEG C/min fast Rate rises to temperature as 1300 DEG C, and sintering pressure is 12 ~ 35MPa, heat-insulation pressure keeping 8 ~ 12 minutes, then with 11 ~ 16 DEG C/min liter It is 1500 ~ 1700 DEG C, 12 ~ 35MPa of sintering pressure, 4 ~ 9min of heat-insulation pressure keeping that warm speed, which rises to sintering temperature, whole sintering process For high vacuum environment；
    2）The preparation of carbon nanometer high-temperature ceramic：E. substrate pretreated：Above-mentioned step is removed using the Process method of blasting treatment Greasy dirt to surface of multi-walled carbon nanotube matrix in rapid d, oxide skin, the μ of surface roughness 37.1 μm~48.4 of described matrix m；F. intermediate layer sprays：By substrate preheating to 150~200 DEG C, voltage be 80V, electric current 400A, spray away from keep 85 Under conditions of~100mm, powder sending quantity are 0.6kg/h, 0.05~0.15mm thickness intermediate layer Ni-Al powder is sprayed to it, Ni weight fraction is 60 ~ 80% in the Ni-Al powder, and remaining is Al powder, and g. ceramic powder last layers prepare and spraying：Will weight Measure Ni, 15wt% that fraction is 45wt% Al, 30wt% NiH2, 10wt% Al2O3Ethanol wet-mixing is added, by from climing Prolong high―temperature nuclei react to be formed NiAl, NiTi, TiAl intermetallic compound composition matrix in Dispersed precipitate have TiO2With Al2O3The composite of particle, composite ceramic is made in described composite grinding, the composite ceramic powder is averaged Particle diameter is 5 μm ~ 20 μm, continues to keep above-mentioned matrix uniform rotation, rotating speed 1.3m/s, is back and forth moved along axis of workpiece using spray gun Ceramic coated powder is moved, ensures powder particle dissolve fully, spray gun axial reciprocating translational speed is 0.08 ~ 0.15m/s, and spray gun is all It is 0.45 ~ 0.58m/s, 1.5 ~ 2.2kg/h of flow of powder feeding gas and 0.8 ~ 1.5kg/ of flow of working gas to translational speed h；
    3）Post processing：The carbon nanometer high-temperature ceramic of above-mentioned preparation is put into progress ultrasonic disperse 30min in 50 DEG C of water, then 90 The microwave treatment 15min for being 500W with power under the conditions of DEG C.
  4. A kind of 4. preparation method of carbon nanometer high-temperature ceramic according to claim 3, it is characterised in that：To in step c Obtained amino multi-walled carbon nano-tube is purified using the mixed acid solution of sulfuric acid and nitric acid, sulfuric acid and nitric acid in the mixed acid solution Volume ratio is 3：1, amino multi-walled carbon nano-tube is washed to neutrality and is dried in vacuo using deionized water after purification, will be pure Change, the progress surface modification of dried amino multi-walled carbon nano-tube, its surface is obtained one layer of Ni-P alloy uniformly, fine and close Coating.
  5. A kind of 5. preparation method of carbon nanometer high-temperature ceramic according to claim 4, it is characterised in that：Using planetary Amino multi-walled carbon nano-tube wet-milling 6h after purification is then carried out being dried in vacuo standby by ball mill again.
  6. A kind of 6. preparation method of carbon nanometer high-temperature ceramic according to claim 4 or 5, it is characterised in that：To amino When multi-walled carbon nano-tube carries out surface modification, the composition of basic bath is：NiSO4•6H2O 30g/L、NaH2PO2• H2O 25g/L, CH3COONa•3H2O 15g/L、Na3C6H5O7•2H2O (sodium citrate) 15g/L, lactic acid 25mg/L, lead acetate 15mg/L, 2h is purified after above-mentioned basic bath is prepared, 1g/L amino multi-walled carbon nano-tubes after wet-milling will have been pre-processed, Added simultaneously in basic bath with 0.5g/L citric acids, ultrasonic wave disperses 30min, is then carried out in thermostat water bath compound Plate, temperature is 85 1 DEG C of soil during Composite Coatings, and PH is 4.5~4.7, stir speed (S.S.) 200r/min, time 2h.
  7. A kind of 7. preparation method of carbon nanometer high-temperature ceramic according to claim 3 or 4, it is characterised in that：Will be above-mentioned Multi-walled carbon nanotube in step b after acid treatment is scattered in Ludox by ultrasonic dispersion, the vacuum drying chamber at 120 DEG C Ground after drying, multi-walled carbon nanotube and SiO is made2Mass ratio is 1：1 compound adsorbent CS50.
  8. A kind of 8. preparation method of carbon nanometer high-temperature ceramic according to claim 3 or 4, it is characterised in that：Step g institutes The working gas used is Ar, N2And H2Mixed gas, H in mixed gas2Volume ratio be 5%~10%, remaining be Ar and N2Mixed gas, wherein H2Purity >=99.95%, Ar and N2Purity is all higher than 99.999%.
  9. A kind of 9. preparation method of carbon nanometer high-temperature ceramic according to claim 3 or 4, it is characterised in that：It is prepared Carbon nanometer high-temperature ceramic be applied to refractory ceramics dust removal filter.
  10. A kind of 10. preparation method of carbon nanometer high-temperature ceramic according to claim 3 or 4, it is characterised in that：It is prepared Carbon nanometer high-temperature ceramic be applied to indoor air filter.
CN201710777764.5A 2017-09-01 2017-09-01 A kind of carbon nanometer high-temperature ceramic and preparation method thereof Pending CN107619279A (en)

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CN110204063A (en) * 2019-06-04 2019-09-06 成都纳海川环境工程有限公司 The preparation method of heavy passenger's motortruck engine water circulation inorganic particle scale dispersing agent
CN110698201A (en) * 2019-11-05 2020-01-17 湘潭大学 Ceramic and preparation method thereof
CN111943717A (en) * 2020-08-14 2020-11-17 南方科技大学 Silver-loaded diatom shell antibacterial ceramic filter element and preparation method thereof

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CN103088337A (en) * 2013-01-31 2013-05-08 南昌航空大学 Method for laser-induction hybrid cladding of copper composite coating dispersedly strengthened by carbon nanotubes (CNTs)
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US8895189B2 (en) * 2012-02-03 2014-11-25 Nanotek Instruments, Inc. Surface-mediated cells with high power density and high energy density
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CN110204063A (en) * 2019-06-04 2019-09-06 成都纳海川环境工程有限公司 The preparation method of heavy passenger's motortruck engine water circulation inorganic particle scale dispersing agent
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