CN101585534B - Sol-gel method-based method for preparing composite nano diamond thin films - Google Patents
Sol-gel method-based method for preparing composite nano diamond thin films Download PDFInfo
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- CN101585534B CN101585534B CN2009100229698A CN200910022969A CN101585534B CN 101585534 B CN101585534 B CN 101585534B CN 2009100229698 A CN2009100229698 A CN 2009100229698A CN 200910022969 A CN200910022969 A CN 200910022969A CN 101585534 B CN101585534 B CN 101585534B
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Abstract
The invention relates to the field of diamond thin film preparation and discloses a sol-gel method-based method for preparing composite nano diamond thin films, which comprises the following steps: a,preparing composite nano diamond slurry; b, whirl coating by using a sol-gel method; c, performing thermal sintering treatment after whirl coating; and d, performing surface treatment and annealing treatment. The method is simple in process and low in cost; the prepared composite nano diamond thin film is stable and uniform; and the method is suitable to be used in application fields of frictional wear, cold cathode field emission, micro electro mechanical system (MEMs), electrochemical inert electrode, optical coating and the like.
Description
Technical field
The present invention relates to the preparation field of diamond thin, be specially a kind of preparation method of the composite nano-diamond film based on sol-gel method.
Background technology
Diamond crystal has hardness the highest in the existing material of nature, its Mohs' hardness is 10.Adamantine fusing point is 4000 ℃; It also has very high thermal conductivity, and the thermal conductivity under the natural II quasi-diamond room temperature is 26W/ (CMK), is 5 times of copper.Thermal conductivity under the natural I quasi-diamond room temperature is 9W/ (CMK), thermal conductivity under the artificial high-quality single-crystal diamond room temperature is 18～20W/ (CMK), thermal conductivity under the general defective artificial single-crystal diamond room temperature is 4.5～6.5W/ (CMK), and the thermal conductivity under the general synthetic polycrystalline diamond room temperature is 4～10W/ (CMK).Diamond energy gap numerical value is 5.3～5.5eV, DIELECTRIC CONSTANT r is 5.58 ± 0.03, the resistivity of natural diamond is 1010 Ω CM, resistivity under the natural II quasi-diamond room temperature is 1～108 Ω CM, the acceptor level of its boron is positioned at about 0.37eV on the valence band, has very high saturated carrier velocity.Adamantine breaking down field strength is up to 100 * 105V/cm.Diamond has good chemical stability, and is acidproof corrosion-resistant.Even at high temperature various acid are worked hardly to diamond, in the air diamond crystal of large-size below 600～700 ℃ and the diadust crystal all be very stable below 450～500 ℃.Though adamantine work function is up to 5.8eV, diamond has negative electron affinity.The broad stopband can reduce the quantity that produces electric charge, has determined the diamond device to have microwave property, and high breaking down field strength combines with high thermal conductivity, and its power bearing ability improves greatly, diamond is become need the preferred material of the electron emission source that Rapid Thermal spreads.Therefore, diamond thin film electron emitting cathode has broad application prospects, and can be used for making energy-conservation cold light source, indicating meter, transmitter, semiconductor electronic source, can be adapted to the abominable Working environment of polar expedition, aerospace etc.The microstructure characteristic of nano-diamond film and mechanics, electricity and optical property make it in fields such as frictional wear, cold-cathode field emission, MEMS (micro electro mechanical system) (MEMs), electrochemistry noble electrode and optical coatings extraordinary application prospect be arranged.
At present, the main flow processing method of preparation diamond thin has chemical vapour deposition (MOCVD), hot wire process MPCVD method, and the radio frequency discharge method, plasma torch method etc., reliable than the explosion method cleaning of early stage High Temperature High Pressure, but and the film of depositing high-quality.Though it is a variety of that the preparation method of diamond thin has, these growth methods all can not obtain the fine diamond thin of the uniform field emission performance of big area, and complex process, the cost height.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the composite nano-diamond film based on sol-gel method, can obtain the uniform composite nano-diamond film of big area, and technology is simple, cost is low.
For achieving the above object, the present invention is achieved by the following technical solutions.
A kind of preparation method of the composite nano-diamond film based on sol-gel method is characterized in that, may further comprise the steps:
A, grind Nano diamond and nano-graphite respectively, its coacervate that scatters, then with nano-graphite, Nano diamond, ethyl cellulose by weight 1: 3: 4 mixed as solute;
B, by weight 1: 20 to 1: 15 ratio solute is added in the Terpineol 350 solvent, ultra-sonic dispersion 2-3 hour, heated and stirred under 380-400K was crossed the 400-450 mesh sieve then again, naturally cools to room temperature at last, the Nano diamond slurry is stand-by;
C, drop on the substrate, select 5000-7000 rev/min rotating speed with the Nano diamond slurry of glass stick with preparation, utilize collosol and gel machine whirl coating after, carry out thermal sintering processing;
When d, thermal sintering handle, kept 25-30 minute after being warming up to 333K earlier, kept 120-140 minute after being warming up to 400K again, kept 60-80 minute after being warming up to 600K then, naturally cooling, the thermal sintering rear film;
The organism of e, removal thermal sintering rear film surface sediment is 600K-620K in temperature then, and the time is to carry out anneal under the 10-20min condition, promptly gets composite nano-diamond film.
Further improvement of the present invention and characteristics are:
When (1) making solute, ethyl cellulose through after grinding, is mixed with Nano diamond, nano-graphite.
(2) organism of described removal thermal sintering rear film surface sediment, be specially: the organism of drawing stripping sintering rear film surface sediment with the thick polytetrafluoroethylene film sheet of 100 μ m-200 μ m, paste the organism on thermal sintering rear film surface then with the blue film of faint viscose glue, blow the residue of leaving over off with wind-force at last.
The present invention adopts the Prepared by Sol Gel Method composite nano-diamond film, not only reduces operation and saves time, and save the Nano diamond raw material.Therefore, technology is simple, and cost is low.
The present invention adopts the composite nano-diamond film of Prepared by Sol Gel Method, and not only chemical stability height, operating temperature range are big but also corrosion-resistant, and therefore, Application Areas is extensive.Sintered-carbide die, bearing, the precision instrumentation part that can adopt this composite nano-diamond film to make as coating; Cold-cathode field emission cold light source, indicating meter, the electronic source device that also can adopt this composite nano-diamond film coating to make; Optical element, biosensor and the MEMs that can also adopt this composite nano-diamond film to make as protective layer, not only long service life can be used for the work of environment such as polar expedition, aerospace.Therefore, in the present invention, substrate can be bearing, conductive glass, stainless steel substrates, optical element etc.
The present invention mixes Nano diamond with nano-graphite, and the composite nano-diamond film of collosol and gel preparation has improved electrical and thermal conductivity performance; Because Nano diamond not only chemical stability height, operating temperature range is big but also corrosion-resistant, so the electron device that adopts the transmitter that this composite nano-diamond film makes, energy-conservation cold light source, indicating meter, electron source is long service life not only, and can be used for the work of environment such as polar expedition, aerospace.
Because nano particle is agglomerated into the larger-size coacervate that has some weak linkage interfaces easily, influence the homogeneity of film, before pulp preparation, respectively nanometer Buddha's warrior attendant and nano-graphite are ground, its coacervate granularity of scattering is diminished.Simultaneously, ethyl cellulose is ground, make it mix more abundant with nanometer Buddha's warrior attendant, nano-graphite.
The slurry of Prepared by Sol Gel Method composite Nano Buddha's warrior attendant film of the present invention is rarer, so the thermal sintering curve comprises 3 temperature rise periods, 3 constant temperature stages and 1 temperature-fall period.First section constant temperature: kept 25-30 minute the oven dry composite nano-diamond film after being warming up to 333K; Second section constant temperature: kept 120-140 minute after being warming up to 400K, make composite nano-diamond printed layers surface more evenly with smooth by the capillary of slurry itself from the modification effect, and make the printed layers thorough drying; The 3rd section constant temperature: kept 60-80 minute after being warming up to 600K, make dried pulping material at high temperature decompose volatilization.Thermal sintering is handled two purposes: can make film drying on the one hand and be bonded in securely on the substrate, can make on the other hand that contained pulping material decomposition evaporation falls in the film.
Embodiment
Embodiment 1
The preparation method of a kind of composite nano-diamond film based on sol-gel method of the present invention specifically may further comprise the steps:
A, grind Nano diamond, nano-graphite and ethyl cellulose respectively, its coacervate that scatters, then with nano-graphite, Nano diamond, ethyl cellulose by weight 1: 3: 4 mixed as solute;
B, solute is added in the Terpineol 350 solvent by weight 1: 20 ratio, ultra-sonic dispersion 2 hours, heated and stirred under 380K is crossed 400 mesh sieves then again, naturally cools to room temperature at last, the Nano diamond slurry is stand-by;
C, drop on the Conducting Glass, select 5000 rev/mins rotating speed with the Nano diamond slurry of glass stick with preparation, utilize collosol and gel machine whirl coating after, carry out thermal sintering processing;
When d, thermal sintering handle, kept 30 minutes after being warming up to 333K earlier, kept 120 minutes after being warming up to 400K again, kept 60 minutes after being warming up to 600K then, naturally cooling, the thermal sintering rear film;
E, at first draw the organism of stripping sintering rear film surface sediment with the thick polytetrafluoroethylene film sheet of 100 μ m-200 μ m, then, then blow the residue of leaving over off with wind-force with the organism on the blue film stickup thermal sintering rear film surface of faint viscose glue; Be 600K in temperature then, the time is to carry out anneal under the 20min condition, promptly gets composite nano-diamond film.
Embodiment 2:
The preparation method of a kind of composite nano-diamond film based on sol-gel method of the present invention specifically may further comprise the steps:
A, grind Nano diamond, nano-graphite and ethyl cellulose respectively, its coacervate that scatters, then with nano-graphite, Nano diamond, ethyl cellulose by weight 1: 3: 4 mixed as solute;
B, solute is added in the Terpineol 350 solvent by weight 1: 18 ratio, ultra-sonic dispersion 2.5 hours, heated and stirred under 390K is crossed 450 mesh sieves then again, naturally cools to room temperature at last, the Nano diamond slurry is stand-by;
C, drop on the Conducting Glass, select 6000 rev/mins rotating speed with the Nano diamond slurry of glass stick with preparation, utilize collosol and gel machine whirl coating after, carry out thermal sintering processing;
When d, thermal sintering handle, kept 25 minutes after being warming up to 333K earlier, kept 130 minutes after being warming up to 400K again, kept 70 minutes after being warming up to 600K then, naturally cooling, the thermal sintering rear film;
E, at first draw the organism of stripping sintering rear film surface sediment with the thick polytetrafluoroethylene film sheet of 100 μ m-200 μ m, then, then blow the residue of leaving over off with wind-force with the organism on the blue film stickup thermal sintering rear film surface of faint viscose glue; Be 610K in temperature then, the time is to carry out anneal under the 18min condition, promptly gets composite nano-diamond film.
Embodiment 3:
The preparation method of a kind of composite nano-diamond film based on sol-gel method of the present invention specifically may further comprise the steps:
A, grind Nano diamond, nano-graphite and ethyl cellulose respectively, its coacervate that scatters, then with nano-graphite, Nano diamond, ethyl cellulose by weight 1: 3: 4 mixed as solute;
B, solute is added in the Terpineol 350 solvent by weight 1: 15 ratio, ultra-sonic dispersion 3 hours, heated and stirred under 400K is crossed 450 mesh sieves then again, naturally cools to room temperature at last, the Nano diamond slurry is stand-by;
C, drop on the stainless steel, select 7000 rev/mins rotating speed with the Nano diamond slurry of glass stick with preparation, utilize collosol and gel machine whirl coating after, carry out thermal sintering processing;
When d, thermal sintering handle, kept 30 minutes after being warming up to 333K earlier, kept 140 minutes after being warming up to 400K again, kept 80 minutes after being warming up to 600K then, naturally cooling, the thermal sintering rear film;
E, at first draw the organism of stripping sintering rear film surface sediment with the thick polytetrafluoroethylene film sheet of 100 μ m-200 μ m, then, then blow the residue of leaving over off with wind-force with the organism on the blue film stickup thermal sintering rear film surface of faint viscose glue; Be 620K in temperature then, the time is to carry out anneal under the 10min condition, promptly gets composite nano-diamond film.
The foregoing description, as radiator, nano-graphite is as conductive medium with the little point of Nano diamond, the composite nano-diamond film of Prepared by Sol Gel Method, by thermal sintering, the surface treatment of thermal sintering rear film, anneal, improved the homogeneity and the stability of composite nano-diamond film.This composite nano-diamond film is applicable to the electron emitting cathode of electron device preparations such as transmitter, cold light source, indicating meter, electron source, have corrosion-resistant, advantages such as chemical stability is high, operating temperature range is big, long service life, can be used for fields such as polar expedition, aerospace.
The present invention changes substrate, the composite nano-diamond film of preparation can make it in fields such as frictional wear, cold-cathode field emission, MEMS (micro electro mechanical system) (MEMs), electrochemistry noble electrode and optical coatings extraordinary application prospect be arranged because of its microstructure characteristic and mechanics, electricity and optical property.
(1) frictional wear field: the composite nano-diamond film that can on complex-shaped workpieces, prepare, its friction and wear behavior excellence, frictional coefficient is low, do not need the expensive polishing operation of extremely wasting time and energy, as: composite nano-diamond film as the carbamide tool of coating, sintered-carbide die, bearing, precision instrumentation part etc.
(2) optical coating field: composite nano-diamond film has only very little photoabsorption, all has the good optical through performance in most ultraviolet region to most infrared region.As crucial optical material ZnS, Ge, MgF2 and opticglass etc. technically, in order to improve weathering and sand cutting or the scratch resistance ability resisted, or need when radiation of extreme burn into or hot environment work, must apply the nano-diamond film supercoat,
(3) cold-cathode field emission field: diamond has negative electron affinity, high breaking down field strength combines with high thermal conductivity, power bearing ability improves greatly, Nano diamond is become needs the preferred material of the electron emission source of Rapid Thermal diffusion, can be used for making energy-conservation cold light source, indicating meter, transmitter, the semiconductor electronic source of working under the abominable Working environment of polar expedition, aerospace etc., therefore have broad application prospects.
(4) electrochemical applications field: various biosensors and bio-medical transmitter; The long-range circumstances monitoring sensor; The transmitter of using in fused salt or the high radioactivity environment; The electrode that uses in extreme corrosive environment it is as the anode degraded of electrolysis of fluorides, organic waste water, ozonizer, fused salt electrolysis, active metal reduction etc.The conductive channel that the grain boundary structure of corrosion resistant nano-diamond film provides has and the similar semiconducting behavior in micron diamond film boron doping back it, does not need to mix and just can directly use as electrode.Owing to smooth surface, therefore more can pile up by the anti-soil thing simultaneously than micron diamond membrane electrode.The nano-diamond membrane counter electrode body material of even compact can provide better anticorrosive protection.
(5) moving parts of MEMS (micro electro mechanical system): MEMs and primary structure member, particularly those devices that need big power consumption or must under the high corrosion environment, work.The diamond frictional coefficient is extremely low, and Young's modulus and physical strength are very high, adds splendid unreactiveness (not with any acid-alkali medium reaction), therefore is the ideal material of making the MEMs element.Nano-diamond membrane crystal grain is tiny, and the surface is extremely smooth, therefore can directly deposit to make small MEMs element.
Claims (3)
1. the preparation method based on the composite nano-diamond film of sol-gel method is characterized in that, may further comprise the steps:
A, grind Nano diamond and nano-graphite respectively, its coacervate that scatters, then with nano-graphite, Nano diamond, ethyl cellulose by weight 1: 3: 4 mixed as solute;
B, by weight 1: 20 to 1: 15 ratio solute is added in the Terpineol 350 solvent, ultra-sonic dispersion 2-3 hour, heated and stirred under 380-400K was crossed the 400-450 mesh sieve then again, naturally cools to room temperature at last, the Nano diamond slurry is stand-by;
C, drop on the substrate, select 5000-7000 rev/min rotating speed with the Nano diamond slurry of glass stick with preparation, utilize collosol and gel machine whirl coating after, carry out thermal sintering processing;
When d, thermal sintering handle, kept 25-30 minute after being warming up to 333K earlier, kept 120-140 minute after being warming up to 400K again, kept 60-80 minute after being warming up to 600K then, naturally cooling, the thermal sintering rear film;
The organism of e, removal thermal sintering rear film surface sediment is 600K-620K in temperature then, and the time is to carry out anneal under the 10-20min condition, promptly gets composite nano-diamond film.
2. the preparation method of a kind of composite nano-diamond film based on sol-gel method according to claim 1 is characterized in that, when making solute, ethyl cellulose through after grinding, is mixed with Nano diamond, nano-graphite.
3. the preparation method of a kind of composite nano-diamond film based on sol-gel method according to claim 1, it is characterized in that, the organism of described removal thermal sintering rear film surface sediment, be specially: the organism of drawing stripping sintering rear film surface sediment with the thick polytetrafluoroethylene film sheet of 100 μ m-200 μ m, paste the organism on thermal sintering rear film surface then with the blue film of faint viscose glue, blow the residue of leaving over off with wind-force at last.
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| CN106380612B (en) * | 2016-09-10 | 2019-11-19 | 上海大学 | Transparent nanofiber element-Nano diamond heat conduction composite membrane and preparation method thereof |
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| CN101428975A (en) * | 2008-12-10 | 2009-05-13 | 北方民族大学 | Processing method for thermal sintering in producing composite nano-diamond film on electrically conducting glass substrate |
| CN101439934A (en) * | 2008-12-15 | 2009-05-27 | 北方民族大学 | Slurry for printing composite nano diamond thin film on glass substrate and preparation thereof |
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| CN101428975A (en) * | 2008-12-10 | 2009-05-13 | 北方民族大学 | Processing method for thermal sintering in producing composite nano-diamond film on electrically conducting glass substrate |
| CN101439934A (en) * | 2008-12-15 | 2009-05-27 | 北方民族大学 | Slurry for printing composite nano diamond thin film on glass substrate and preparation thereof |
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