CN102268655A - Preparation method and device of nanocrystalline carbon nitride film - Google Patents
Preparation method and device of nanocrystalline carbon nitride film Download PDFInfo
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- CN102268655A CN102268655A CN 201110213134 CN201110213134A CN102268655A CN 102268655 A CN102268655 A CN 102268655A CN 201110213134 CN201110213134 CN 201110213134 CN 201110213134 A CN201110213134 A CN 201110213134A CN 102268655 A CN102268655 A CN 102268655A
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Abstract
The invention belongs to the technical field of the nanometer material and particularly relates to a preparation method and device of a nanocrystalline carbon nitride film. The preparation method comprises the following steps: placing a pretreated substrate in a high temperature tubular furnace, injecting the air of a carrier gas-discharging reaction system, pumping working solution containing the carbon nitride component in a premixing tube, mixing with carrier gas, ensuring that the temperature of the premixing tube is higher than the boiling point of the working solution and the vapor of the working solution and the carrier gas enter the high temperature tubular furnace, and performing high temperature pyrolytic deposition to obtain the nanocrystalline carbon nitride film. The nanocrystalline carbon nitride film synthesized by the method is uniform and dense and has no impurities and good crystallinity and excellent tribological properties. The experimental device is simple, the temperature is stable and reliable, the repeatability is high and the preparation method is suitable for industrial production.
Description
Technical field
The invention belongs to technical field of nano material, particularly a kind of preparation method of nanocrystalline carbon-nitrogen film and device.
Background technology
Since Cohen etc. early 1990s prophesy in C-N system, may exist hardness to surpass adamantine β-C
3N
4After, started one synthetic β-C immediately in the world
3N
4Research boom.People competitively adopt the whole bag of tricks to attempt to synthesize the β-C of pure phase
3N
4Crystal or crystalline film, and its structure studied and discuss.Main preparation method has laser ablation method, sputtering method (comprising radio-frequency sputtering, magnetron sputtering, ion beam sputtering etc.), the high pressure synthesis method, sedimentation (comprising plasma activated chemical vapour deposition, vacuum arc deposition, electrochemical deposition etc.), ion implantation etc.From the academic paper of having delivered as can be seen, these methods in most cases, what obtain all is a kind of amorphous carbon-nitrogen film; Film forming density is poor, and is impure; Composition does not reach the requirement of N/C=1.33.
The situation that apply for a patent in this field is as follows: the patented invention (Japanese Patent J03240959) of SUME SUMITPMO ELEC IND KK, utilize voltage of alternating current plasma discharge deposit carbon nitrogen film, but only synthesized carbon-nitrogen film, do not obtained the carbonitride of crystalline phase; People's such as Chen Yan and king's grace brother invention " crystalline alpha mutually with beta-phase carbon nitride thin film material and preparation method thereof " (Chinese patent CN1151386A) is with the synthetic Crystalline Carbon Nitride Films of the auxiliary hot filament CVD of negative bias, but this method purity is difficult to guarantee.People's such as Tanaka's Zhuo and Yuan Lei invention " microwave plasma CVD synthesizes the crystalline phase carbon-nitrogen film " (Chinese patent CN1219604A) feeds microwave in the working chamber, thereby makes geseous discharge produce the plasma body deposit film.From these patents of invention as can be seen, the presoma that is used to prepare carbon-nitrogen film is gas mostly, as CH
4, CO, C
2H
2, N
2, NH
3Deng, these reactant gasess are in chemical vapor deposition processes, after needing earlier the chemical bond rupture with itself, therefore regeneration C-N key needs to adopt some supplementary meanss such as strong negative bias, microwave plasma, magnetron sputtering etc. to improve its chemical reactivity.This just needs some expensive utility appliance, or consumes more energy and improve its chemically reactive, and conversion unit is huger in the application process of reality, and chemical reaction process is more loaded down with trivial details.
Summary of the invention
The object of the present invention is to provide a kind of preparation method and device thereof of nanocrystalline carbon-nitrogen film, overcome present preparation method's reaction process complexity, to the demanding defective of conversion unit.
The technical solution used in the present invention is as follows:
A kind of preparation method of nanocrystalline carbon-nitrogen film, the substrate that pre-treatment is good is put into high temperature process furnances, feed after carrier gas drains air in the reactive system, the working fluid of the carbon containing nitrogen component of liquid state is pumped into pre-mixing Guan Zhongyu carrier gas to be mixed, after treating that pre-mixing pipe temperature surpasses the boiling temperature of working fluid, working fluid steam and carrier gas enter in the high temperature process furnances high temperature pyrolysis and deposit and obtain nanocrystalline carbon-nitrogen film.
The working fluid of the carbon containing nitrogen component of described liquid state is the liquid phase carboritride or is the mixed solution of carbon containing and/or nitrogenous compound and carboritride that the volume ratio of carbon containing and/or nitrogen component and carboritride is 1:0.05～20.
Described liquid phase carboritride is a methylamine, ethamine, thyl methyl amine, dimethylamine, quadrol, diethylamine, propylamine, propylene diamine, butylamine, butanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, the first Isopropylamine, aniline, N-methyl-N-ethylaniline, pyridine, acetonitrile, cyanobenzene, adjacent toluic nitrile, hydrazine, between tolylhydrazine, tryptamines, pentanoic, vulkacit H, trimeric cyanamide, polyamines, alkaloid, aliphatic amide, the water of aromatic amine or one or more the mixture in the organic solution; Carbon compound is one or more in benzene, toluene, ethylbenzene, dimethylbenzene, diethylbenzene or first and second benzene, and nitrogenous compound is an ammoniacal liquor.
Working fluid steam and carrier gas enter in the high temperature process furnances back 700～1100 ℃ of following pyrolytic reaction 15min～10 hour, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.
Preferably, behind 700～1100 ℃ of following high temperature pyrolysis reaction 15min～5 hour, close the working fluid sampling device, continue to feed carrier gas in the reactive system, the carboritride that obtains again same roasting temperature 15min～5 hours, is naturally cooled to room temperature, obtain nanocrystalline carbon-nitrogen film.
In deposition process, the flow control of mixing steam is at 5～300 standard cm
3/ min(SCCM).
Enter the pre-mixing pipe by the peristaltic pump pumps working fluid, extraction speed is 0.05～10ml/min.
The carrier gas of feeding system is Ar, He, N
2Or H
2, its flow is not more than 1000 standard cm
3/ min.
Described substrate is Pt, and pre-treatment comprises matting, polishing and annealing, and described annealing conditions is: protection of inert gas, 800～1000 ℃ of temperature, time 10～30min.About choice of substrate, also can adopt Si, SiO
2, Mo, Ni metal or semiconductor material, insulating material such as quartz, mica, Al
2O
3, ZrO
2Deng stupalith, electro-conductive material etc.
It is presoma that the present invention adopts the mixture of liquid phase carboritride or carbon containing, nitrogenous compound, produces gaseous steam with heating zone heating work liquid, owing to do not adopt the gas phase presoma, thereby avoided using expensive utility appliance, simplified reaction process.Simultaneously, used working fluid itself contains C--N key, has improved chemical reactivity; The elementary composition of working fluid is C, N, H, can prepare the higher film of purity.
Concrete, the step of the nanocrystalline carboritride film preparation of the present invention is as follows:
(1) substrate is carried out pre-treatment: in the preprocessing process of substrate, substrate need be through polishing and matting.Matting is ultrasonic 20min, ultrasonic 20min in dehydrated alcohol again in acetone soln earlier.In addition, at the platinum substrate can also be in inert protective gas anneal, 800～1000 ℃ of annealing temperatures, time 10～30min, anneal can make the grain growth of platinum substrate, improve the degree of crystallinity of sedimentary crystalline phase carbon-nitrogen film.
(2) substrate of handling well is placed quartz glass tube, put into the central position in high temperature process furnances constant temperature zone.Feed carrier gas, get rid of the air in the reactive system, the carbon-nitrogen film of oxide deposition when preventing the working fluid high temperature pyrolysis, flow is not higher than 1000 standard cm
3/ min(SCCM).
(3) with peristaltic pump working fluid is pumped in the pre-mixing pipe, opens the heating zone switch, when the temperature in the pre-mixing pipe reaches the boiling temperature of working fluid, enter tube furnace behind working fluid steam and the carrier gas process flow control meter; Substrate temperature in the quartz glass tube is measured by the temperature controller of high temperature process furnances.Substrate temperature remains on 700～1100 ℃; Under this temperature, working fluid steam begins deposition.In deposition process, the flow control of mixing steam is at 5～300 standard cm
3/ min(SCCM).By regulating the flow of mixing steam, can obtain the carbon-nitrogen film of different thickness.General, the flow of gas is big more, and the film that makes is thick more.
It is presoma that the present invention adopts the mixture of liquid phase carboritride or nitrogenous, carbonaceous component and carboritride, by the mol ratio of nitrogen carbon component in pilot-gas flow velocity and the presoma, regulates the carbon-nitrogen ratio example in the carbon-nitrogen film in the final product.In addition, the pyrolysis temperature of presoma also is the important parameter of carboritride crystallization and size of particles.Working fluid of the present invention is steam heated under 700～1100 ℃ and reacts, this pyrolytic reaction is to carry out under higher temperature, hot conditions helps obtaining the better carbon-nitrogen film of crystal property, but along with the rising of temperature, different material base and the film substrate bond strengths between the carbon-nitrogen film have certain variation.The nanocrystalline carbon-nitrogen film of the present invention's preparation has showed excellent tribological property as the antifriction antiwear material, little frictional experiment test shows, the nanocrystalline carbon-nitrogen film and the stainless steel steel ball of preparation are joined pair, load is under the condition of 1 N, frictional coefficient still was stabilized near 0.14 in 50 hours, and wear rate is 8.9 * 10
-16m
3/ (Nm), film substrate bond strength reaches 1520 mN, has anti-wear and wear-resistant performance preferably, good stability, and long service life has a wide range of applications in tribological field.
Method of the present invention is raw materials used cheap and easy to get, and is simple to operate, good reproducibility, easy realization of large-scale production.
The present invention also provides a kind of device of described nanocrystalline carboritride film preparation, comprises the airing system, working fluid pre-hybrid system and the high temperature pyrolysis system that connect successively; Described working fluid pre-hybrid system comprises the heating unit of pre-mixing pipe, pre-mixing pipe outer wall and the liquid feed device that supplies working fluid to the pre-mixing pipe.
Described working fluid pre-hybrid system is made up of peristaltic pump, pre-mixing working cavity, the quality control meter of connection successively and heating zone four parts that are wrapped in outside the pre-mixing working cavity;
Described airing system is made up of gas cylinder, steam line and the under meter that is connected on the pipeline;
The quartz glass tube that described high temperature pyrolysis system comprises high temperature process furnances and places high temperature process furnances, the quartz glass tube front end has acceptance from the working fluid steam of working fluid pre-hybrid system and the inlet mouth of carrier gas; The end of quartz glass tube is connected with the device that absorption reaction generates tail gas.
Substrate is positioned in the silica tube.
Wherein, the working fluid pre-hybrid system provides and regulates and control reaction precursor body required in the deposition process of carbon-nitrogen film.
Airing system provides the carrier gas of delivery working steam in the carbon-nitrogen film process of growth, and plays the effect of inertia protection gas, prevents carboritride oxidation in the thin film growth process, controls and measure its flow simultaneously.
The high temperature pyrolysis system provides the hot environment of carbon-nitrogen film growth.
Employing apparatus of the present invention have been simplified preparation technology, have been improved preparation method's repeatability, for the crystalline phase carbon-nitrogen film material that obtains even compact is laid a good foundation.
This contrive equipment also can prepare the compound of other types by the composition that changes presoma.As to select toluene be presoma, and high temperature pyrolysis toluene prepares the high graphite film of degree of crystallinity.Preparation condition is the same.
The present invention has following advantage with respect to prior art:
The nanocrystalline carbon-nitrogen film of the inventive method synthetic is even, fine and close, inclusion-free, good crystallinity, tribological property excellence.Experimental installation is simple, process stabilizing, reliable, and good reproducibility is easy to suitability for industrialized production.
Description of drawings
Fig. 1 prepares the setting drawing of nanocrystalline carbon-nitrogen film for the present invention, 1-Ar gas cylinder wherein, 2-needle-valve, the 3-under meter, 4-working liquid, 5-peristaltic pump, 6-pre-mixing pipe, the 7-heating zone, 8-quartz glass tube, 9-substrate, the 10-high temperature process furnances, the 11-surge flask, 12-liquid-absorbent bottle, 13 are the quality control meter.
Fig. 2 is the atomic power shape appearance figure of the nanocrystalline carbon-nitrogen film of embodiment 1 acquisition;
Fig. 3 is the atomic power shape appearance figure of the nanocrystalline carbon-nitrogen film of embodiment 2 acquisitions;
Fig. 4 is the X-ray diffractogram of the nanocrystalline carbon-nitrogen film of embodiment 2 acquisitions;
Fig. 5 is the laser raman figure of the nanocrystalline carbon-nitrogen film of embodiment 3 acquisitions;
Fig. 6 joins secondary frictional coefficient figure for nanocrystalline carbon-nitrogen film and stainless steel steel ball that embodiment 2 obtains;
Fig. 7 is the nanocrystalline carbon-nitrogen film delineation test curve figure that embodiment 2 obtains;
Fig. 8 is the frictional coefficient figure of different thickness carbon-nitrogen films.
Embodiment
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Used instrument is as follows in following examples:
AFM analyzes the SPA400 type atomic force microscope that used instrument is NSK (SII) company, and sedimentary nanocrystalline carbon-nitrogen film surface topography is also estimated its surfaceness simultaneously on the observation silicon substrate.AFM analyzes to adopt and raps pattern, tests under the environment of room temperature (24 ± 2 ℃), and the radius at tooth tip of probe and elastic constant are no more than 20nm and 2.0N/m respectively.
The used instrument of XRD analysis is X ' pert pro type x-ray diffractometer (XRD, Dutch Philips company), adopts Cu K α line excitaton source, λ=0.1542 nm, and voltage 40 kV, electric current 40 mA, film sample directly detects.
The Raman spectrographic is measured and is carried out on the RM-1000 of Britain Renishaw company type micro-Raman spectroscopy.Excitation wavelength is 457.5 nm, and slit width 50 μ m adopt the back scattering device to collect scattered light.100% power is 10 mW on the arrival sample.Measurement is finished under the envrionment temperature of 296 K.
Estimating the tribology experiments of the friction and wear behavior of film carries out on the product UMT-2 of U.S. CE TR company type friction wear testing machine.Test conditions is: 1 N loads, sliding velocity 300 mm/min, room temperature (relative humidity RH=50%), stroke 6 mm, the idol part is the stainless steel steel ball of＜4 mm, frictional coefficient is by the automatic record of registering instrument, and the slip cycle index when increasing suddenly with frictional coefficient is as the friction durability of film, and every kind of sample test is got its mean value 3 times.
The device for preparing nanocrystalline carbon-nitrogen film as shown in Figure 1, comprises the airing system, working fluid pre-hybrid system and the high temperature pyrolysis system that connect successively; Described airing system is made up of Ar gas cylinder 1, steam line and the needle-valve 2, the under meter 3 that are connected on the pipeline; Described working fluid pre-hybrid system comprises the heating zone 7 of pre-mixing pipe 6, pre-mixing pipe outer wall and to the liquid feed device peristaltic pump 5 of pre-mixing pipe for working fluid 4, enters the high temperature pyrolysis system behind working fluid steam that pre-mixing pipe 6 comes out and the carrier gas process quality control meter 13.The quartz glass tube 8 that the high temperature pyrolysis system comprises high temperature process furnances 10 and places high temperature process furnances 10, quartz glass tube 8 front ends have acceptance from the working fluid steam of working fluid pre-hybrid system and the inlet mouth of carrier gas; The end of quartz glass tube is connected with the device 11,12 that absorption reaction generates tail gas; Substrate 9 places quartz glass tube 8.
With the silicon chip is substrate, quadrol is a presoma, behind the air in the Ar air-flow feeding reactor removal system, peristaltic pump is pumped into quadrol in the pre-mixing pipe with the speed of 0.5ml/min, heating pre-mixing pipe is to the boiling temperature of quadrol, the temperature of control tube furnace is 700 ℃, the mixed gas of quadrol and Ar gas enters in the high temperature process furnances with the flow of 80ml/min, behind the pyrolytic decomposition 30min, close the peristaltic pump switch and stop sample introduction, continue to feed Ar gas subsequently and calcine 30min down for 700 ℃, close heating unit at preset temp, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.Its pattern as shown in Figure 2, the rootmean-square surfaceness of nanocrystalline carbon-nitrogen film is 2.05nm, average particle size particle size is 82nm.
With the silicon chip is substrate, quadrol is a presoma, behind the air in the Ar air-flow feeding reactor removal system, peristaltic pump is pumped into quadrol in the pre-mixing pipe with the speed of 0.5ml/min, heating pre-mixing pipe is to the boiling temperature of quadrol, the temperature of control tube furnace is 900 ℃, the mixed gas of quadrol and Ar gas enters in the high temperature process furnances behind the pyrolytic decomposition 30min with the flow of 80ml/min, close the peristaltic pump switch and stop sample introduction, continue to feed the Ar rare gas element subsequently and calcine 30min down for 900 ℃ at preset temp, close heating unit, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.Its pattern as shown in Figure 3, the rootmean-square surfaceness of nanocrystalline carbon-nitrogen film is 4.81nm, average particle size particle size is 210nm; Crystalline structure as shown in Figure 4,2 θ angles are 25.6
oCorrespond to the crystalline carboritride.
Embodiment 3
With the silicon chip is substrate, quadrol is a presoma, behind the air in the Ar air-flow feeding reactor removal system, peristaltic pump is pumped into quadrol in the pre-mixing pipe with the speed of 2.0ml/min, heating pre-mixing pipe is to the boiling temperature of quadrol, the temperature of control tube furnace is 950 ℃, the mixed gas of quadrol and Ar gas enters in the high temperature process furnances behind the pyrolytic decomposition 30min with the flow of 80ml/min, close the peristaltic pump switch and stop sample introduction, continuing to feed the Ar rare gas element subsequently calcined 1 hour down for 950 ℃ at preset temp, close heating unit, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.Its Raman spectrum as seen from the figure, exists ring-type and catenate sp as shown in Figure 5
2The graphite carbon atom of hydridization.
Embodiment 4
With the alumina ceramic plate is substrate, quadrol is a presoma, nitrogen gas stream feeds the air in the reactor removal system, peristaltic pump is pumped into quadrol in the pre-mixing pipe with the speed of 0.5ml/min, heating pre-mixing pipe is to the boiling temperature of quadrol, the temperature of control tube furnace is 900 ℃, quadrol and N
2The mixed gas of gas enters in the high temperature process furnances behind the pyrolytic decomposition 30min, closes the peristaltic pump switch and stops sample introduction, continues to feed N subsequently
2Calcine 30min down for 900 ℃ at preset temp, close heating unit, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.
Embodiment 5
With the quartz plate is substrate, and propylamine is a presoma, N
2Air-flow feeds the air in the reactor removal system, and peristaltic pump is pumped into propylamine in the pre-mixing pipe with the speed of 1.0ml/min, and heating pre-mixing pipe is to the boiling temperature of working fluid, and the temperature of control tube furnace is 950 ℃, working fluid steam and N
2The mixed gas of gas enters in the high temperature process furnances pyrolytic decomposition and closes heating unit after 4 hours, naturally cools to room temperature, obtains nanocrystalline carbon-nitrogen film.
Embodiment 6
With the quartz plate is substrate, aniline is presoma, feeding Ar gas is removed the air in the reactor assembly, peristaltic pump is pumped into aniline in the pre-mixing pipe with the speed of 5ml/min, heating pre-mixing pipe is to the boiling temperature of aniline, the temperature of control tube furnace is 900 ℃, the mixed gas of aniline and Ar gas enters in the high temperature process furnances behind the pyrolytic decomposition 30min with the flow of 100ml/min, close the peristaltic pump switch and stop sample introduction, continuing to feed the Ar rare gas element subsequently calcined 2 hours down for 900 ℃ at preset temp, close heating unit, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.
Embodiment 7
With the good zirconia ceramics sheet of pre-treatment is substrate, with the triethylene tetramine is presoma, behind the air in the He air-flow feeding reactor removal system, peristaltic pump is pumped into working fluid in the pre-mixing pipe with the speed of 5ml/min, heating pre-mixing pipe is to the boiling temperature of working fluid, the temperature of control tube furnace is 1000 ℃, the mixed gas of working fluid steam and He gas entered in the high temperature process furnances pyrolytic decomposition after 1 hour, close the peristaltic pump switch and stop sample introduction, continue to feed the He rare gas element subsequently and calcine 30min down for 1000 ℃ at preset temp, close heating unit, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.
Embodiment 8
With the silicon chip is substrate, the mixed solution of quadrol and ammoniacal liquor (mol ratio is 1:2) is a presoma, the Ar air-flow feeds the air in the reactor removal system, peristaltic pump is pumped in the pre-mixing pipe with the speed of the 2.0ml/min mixed solution with quadrol and ammoniacal liquor, heating pre-mixing pipe is to the boiling temperature of working fluid, the temperature of control tube furnace is 900 ℃, the mixed gas of working fluid steam and Ar gas enters in the high temperature process furnances high temperature pyrolysis after 3 hours with the flow of 50ml/min, close heating unit, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.
Embodiment 9
With the good Pt sheet of pre-treatment is substrate, the mixed solution of methylamine and quadrol (mol ratio is 1:0.5) is a presoma, the He air-flow feeds the air in the reactor removal system, peristaltic pump is pumped into working fluid in the pre-mixing pipe with the speed of 1.0ml/min, heating pre-mixing pipe is to the boiling temperature of working fluid, the temperature of control tube furnace is 1000 ℃, the mixed gas of working fluid steam and He gas entered in the high temperature process furnances pyrolytic decomposition after 1 hour, close the peristaltic pump switch and stop sample introduction, continue to feed the He rare gas element subsequently and calcine 15min down for 1000 ℃ at preset temp, close heating unit, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.
With the silicon chip is substrate, the mixed solution of toluene and quadrol (mol ratio is 1:5) is a presoma, the Ar air-flow feeds the air in the reactor removal system, peristaltic pump is pumped in the pre-mixing pipe with the speed of the 2.0ml/min mixed solution with toluene and quadrol, heating pre-mixing pipe is to the boiling temperature of working fluid, the temperature of control tube furnace is 950 ℃, the mixed gas of working fluid steam and Ar gas entered in the high temperature process furnances pyrolytic decomposition after 1 hour, close the peristaltic pump switch and stop sample introduction, continue to feed the Ar rare gas element subsequently and calcine 30min down for 950 ℃ at preset temp, close heating unit, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.
Embodiment 11
With the alumina ceramic plate is substrate, with pyridine, the mixed solution of trimeric cyanamide and ammoniacal liquor (mol ratio is 3:2:1) is a presoma, the He air-flow feeds the air in the reactor removal system, peristaltic pump with the speed of 3.0ml/min with pyridine, the mixed solution of trimeric cyanamide and ammoniacal liquor is pumped in the pre-mixing pipe, heating pre-mixing pipe is to the boiling temperature of working fluid, the temperature of control high temperature process furnances is 1000 ℃, the mixed gas of working fluid steam and He gas entered in the tube furnace pyrolytic decomposition after 1 hour, close the peristaltic pump switch and stop sample introduction, continuing to feed the He rare gas element subsequently calcined 1 hour down for 1000 ℃ at preset temp, close heating unit, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.
Tribological property---friction and wear test
Test one
The nanocrystalline carbon-nitrogen film and the stainless steel steel ball of embodiment 2 preparations are joined the secondary tribological property test of carrying out on little frictional testing machines.Frictional coefficient is by the automatic record of registering instrument, and the slip cycle index when increasing suddenly with frictional coefficient is as the friction durability of film.The mensuration of wear rate is to measure the mill spot cross-sectional area of carbon-nitrogen film with surface profiler, then calculates wear volume and wear rate with applied load and sliding distance.The delineation experiment is that load is linear increasing from 30mN to 3000mN at its film substrate bond strength of UMT-2 experiment aircraft measurements, and needle type radius is the little section of the composite diamond of 0.4mm moves forward 3.0mm with the speed of 0.6mm/s a distance.The position of critical load is frictional coefficient and raises rapidly or the detected position of acoustic emission signal.As can be seen from Figure 6 load is under the condition of 1 N, and frictional coefficient still was stabilized near 0.14 in 50 hours.Wear rate is calculated as 8.9 * 10
-16m
3/ (Nm), can find out among Fig. 7 that film substrate bond strength reaches 1520 mN, the nanocrystalline carbon-nitrogen film of preparation has anti-wear and wear-resistant performance preferably.
Test two
According to the preparation method of embodiment 2,, obtain the carbon nitrogen film of different thicknesses of layers by changing the flow of quadrol and Ar oxygen mixture.By above-mentioned friction and wear test method, record under 900 ℃ of same temperature, the frictional coefficient of different thickness carbon-nitrogen films is as shown in Figure 8.As can be seen from Figure 8, the frictional coefficient of the carbon-nitrogen film of same temperature preparation is close, all is about 0.2.Yet the film thickness difference has directly influenced frictional wear life-span of carbon-nitrogen film.Along with the increase of film thickness, wear-out life increases afterwards earlier and reduces.When the thickness of carbon-nitrogen film was about 1.3 microns, wear-out life was the longest, and frictional coefficient still was stabilized in below 0.2 in 50 hours.This application example explanation: the present invention can prepare the carbon-nitrogen film of different thickness, and under uniform temp, the frictional coefficient of film changes little, but the thickness of film is the key factor that influences wear-out life.
Claims (10)
1. the preparation method of a nanocrystalline carbon-nitrogen film, it is characterized in that, the substrate that pre-treatment is good is put into high temperature process furnances, feed after carrier gas drains air in the reactive system, the working fluid of the carbon containing nitrogen component of liquid state is pumped into pre-mixing Guan Zhongyu carrier gas to be mixed, after treating that pre-mixing pipe temperature surpasses the boiling temperature of working fluid, working fluid steam and carrier gas enter in the high temperature process furnances high temperature pyrolysis and deposit and obtain nanocrystalline carbon-nitrogen film.
2. the preparation method of nanocrystalline carbon-nitrogen film as claimed in claim 1, it is characterized in that, the working fluid of the carbon containing nitrogen component of described liquid state is the liquid phase carboritride or is the mixed solution of carbon containing and/or nitrogenous compound and carboritride that the volume ratio of carbon containing and/or nitrogen component and carboritride is 1:0.05-20.
3. the preparation method of nanocrystalline carbon-nitrogen film as claimed in claim 2, it is characterized in that described liquid phase carboritride is a methylamine, ethamine, thyl methyl amine, dimethylamine, quadrol, diethylamine, propylamine, propylene diamine, butylamine, butanediamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, polyethylene polyamine, the first Isopropylamine, aniline, N-methyl-N-ethylaniline, pyridine, acetonitrile, cyanobenzene, adjacent toluic nitrile, hydrazine, between tolylhydrazine, tryptamines, pentanoic, vulkacit H, trimeric cyanamide, polyamines, alkaloid, aliphatic amide, the water of aromatic amine or one or more the mixture in the organic solution; Carbon compound is one or more in benzene, toluene, ethylbenzene, dimethylbenzene, diethylbenzene or first and second benzene, and nitrogenous compound is an ammoniacal liquor.
4. as the preparation method of one of claim 1-3 described nanocrystalline carbon-nitrogen film, it is characterized in that, working fluid steam and carrier gas enter in the high temperature process furnances back 700～1100 ℃ of following pyrolytic reaction 15min～10 hour, naturally cool to room temperature, obtain nanocrystalline carbon-nitrogen film.
5. the preparation method of nanocrystalline carbon-nitrogen film as claimed in claim 4, it is characterized in that, behind 700～1100 ℃ of following high temperature pyrolysis reaction 15min～5 hour, close the working fluid sampling device, continue to feed carrier gas in the reactive system, the carboritride that obtains again same roasting temperature 15min～5 hours, is naturally cooled to room temperature, obtain nanocrystalline carbon-nitrogen film.
6. the preparation method of nanocrystalline carbon-nitrogen film as claimed in claim 5 is characterized in that, enters the pre-mixing pipe by the peristaltic pump pumps working fluid, and extraction speed is 0.05～10ml/min.
7. the preparation method of nanocrystalline carbon-nitrogen film as claimed in claim 6 is characterized in that, the carrier gas that feeds system is Ar, He, N
2Or H
2, its flow is not more than 1000 standard cm
3/ min.
8. the preparation method of nanocrystalline carbon-nitrogen film as claimed in claim 7 is characterized in that, substrate is Pt, and pre-treatment comprises matting, polishing and annealing, and described annealing conditions is: protection of inert gas, 800～1000 ℃ of temperature, time 10～30min.
9. the preparation facilities of nanocrystalline carbon-nitrogen film is characterized in that, comprises the airing system, working fluid pre-hybrid system and the high temperature pyrolysis system that connect successively; Described working fluid pre-hybrid system comprises the heating unit of pre-mixing pipe, pre-mixing pipe outer wall and the liquid feed device that supplies working fluid to the pre-mixing pipe.
10. the preparation facilities of nanocrystalline carbon-nitrogen film as claimed in claim 9 is characterized in that,
Described working fluid pre-hybrid system is made up of peristaltic pump, pre-mixing working cavity, the quality control meter of connection successively and heating zone four parts that are wrapped in outside the pre-mixing working cavity;
Described airing system is made up of gas cylinder, steam line and the under meter that is connected on the pipeline;
The quartz glass tube that described high temperature pyrolysis system comprises high temperature process furnances and places high temperature process furnances, the quartz glass tube front end has acceptance from the working fluid steam of working fluid pre-hybrid system and the inlet mouth of carrier gas; The end of silica tube is connected with the device that absorption reaction generates tail gas.
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| US20100015030A1 (en) * | 2006-07-13 | 2010-01-21 | Mohammad Aref Hasan Mamakhel | Carbon nitride preparation method |
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| CN105925954A (en) * | 2016-05-27 | 2016-09-07 | 清华大学 | Preparation method of semiconductor carbon nitride films |
| CN105925954B (en) * | 2016-05-27 | 2020-04-14 | 清华大学 | Preparation method of semiconductor carbon nitride film |
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