CN101323437A - Explosion impact synthetic method of beta-C3N4 - Google Patents
Explosion impact synthetic method of beta-C3N4 Download PDFInfo
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- CN101323437A CN101323437A CNA2008100554971A CN200810055497A CN101323437A CN 101323437 A CN101323437 A CN 101323437A CN A2008100554971 A CNA2008100554971 A CN A2008100554971A CN 200810055497 A CN200810055497 A CN 200810055497A CN 101323437 A CN101323437 A CN 101323437A
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Abstract
The invention relates to a synthetic processing method of ultrahard material, in particular to a Beta-C3N4 ultrahard material explosive shock synthetic method which solves the problem of processing and manufacturing C-N ultrahard material. The invention is characterized in that explosive and reaction precursor are arranged in a sealed container and then the explosive is ignited to cause explosion so as to obtain detonation products; finally, the detonation products is treated with purification processing to obtain the Beta-C3N4 ultrahard material. The invention has the beneficial effects that the method of the invention can prepare a carbonitride compound by synthesis and is practicable; compared with the methods which are listed in the background technology, the method has the advantages of simple operation, short reaction process and convenient purification, etc.
Description
Technical field
The present invention relates to a kind of synthetic working method of superhard material, be specially a kind of β-C
3N
4Explosion impact synthetic method.
Background technology
At (field such as processing and manufacturing) widely used mechanically resistant material titanium nitride, diamond etc. are arranged at present.Diamond has high hardness, diamond derives from natural mineral or artificial the manufacturing, natural diamond is rare precious, thus processing manufacturing industry generally use be man-made diamond, its complicated process of preparation, easy and ferrous alloy reacts, the thermostability extreme difference not only costs an arm and a leg, and can not be used for cutting iron and steel, when diamond temperature in air surpasses 700 ℃, can generate carbonic acid gas.Thereby, at industrial sector, especially aspect the non-heavy cutters of high precision such as the hobcutter of processing automobile tire, pinion cutter, generally adopt rapid steel titanium-nitride technology.Titanium nitride coating technology is simple, and chemical stability and thermostability all surpass diamond, but that its hardness has only is adamantine 1/4th, and wear resistance is relatively poor.
1989, Liu and Cohen were with β-Si
3N
4Structure is a prototype, substitutes β-Si with the C atom
3N
4The position of middle Si has proposed β-C
3N
4Structure is calculated through theory, and the result shows that the bulk modulus of this compound is suitable with diamond.People such as Jennifer L.Corkill have calculated β-C
3N
4The energy band structure of plane wave local density approximation, predict that this compound has high temperature broad-band gap characteristic, can be used as the high temperature wide bandgap semiconductor materials, can be used for making royal purple light, ultra-violet light-emitting device and royal purple optical semiconductor laser.Other Theoretical Calculation shows that also this material also may have special performances such as high insulation, high heat conduction, high refractive index, all has broad application prospects in association areas such as mechanics, calorifics, optics and electricity.
Therefore, the C-N material is the desirable superhard material of all advantages such as a kind of state-of-the art, the chemistry that possesses titanium nitride and thermostability, and its hardness is near diamond, will become to replace diamond and the optimal material of titanium nitride.Can be used as the surface abrasion coating and the high temperature resistance high pressure zone of various Industrial products and extraordinary parts, make product durable in use, increase the service life.Because its thermal conductivity is good, can in making super large-scale integration, bring into play special role, promote microelectronics and development of computer.Carbonitride can also be used to develop various novel high heat conductance devices.In addition, characteristics such as the structural symmetry of carbonitride make it have very big nonlinear optical coefficients, can realize optical frequency translation, therefore, will play crucial effect in the development of laser technology.
The C of C-N series
3N
4, Liu and its hardness of Cohen prophesy may surpass diamond, become the premier superhard material in the world today.Many in the world groups are explored in the research of carrying out this respect at present.The synthetic meaning of the experiment of carboritride with two aspects: the premium properties of hardness and others in the theoretical prediction, indicating that carboritride might all have broad application prospects in every field as a kind of important new function material; On the other hand, as first kind of material that proposes by theoretical prediction fully, the success of macro-scale carbon nitrogen crystal experiment synthetic, indicating that novel material is synthetic explores the leap of carrying out by traditional experience, semiempirical under theory instructs, will become a milestone on the Materials science development history.
Nineteen ninety, people such as Japanese T.Seline adopt and contain N organism Tetracyan-oethylene (C
6N
4) and 1,3,5-triazine (C
3H
3N
3) under 1400 ℃, 5GPa, carry out the High Temperature High Pressure cracking, contain the C of graphite-like structure in the Tetracyano-ethylene split product
4.66The N material, N content is reduced to 17.7at% by 40at%.1996, the J.H.Nguyen of the J.V Badding of pennsylvania, USA and California (California) university adopts the method for diamond opposed anvils respectively, C and N mixture are carried out 2000-2500K, the high temperature and pressure test of 30 ± (5) GPa has obtained a kind of cube of phase carboritride.The Tiers-Rong Lu of Taiwan Chiao Tung university places N with sodium phthalein amine and chloroform
2Carry out photochemical reaction in the gas, subsequently product is heated to 800 ℃ of processing, obtained N/C than the α-C that includes that is 0.23
3N
4The powder of phase.In recent years, the I.Alves of France, people such as H.Montigaud are to trimeric cyanamide (C
3N
6H
6) in N
2Or contain and carry out pyrolysis and 3GPa subsequently in the N organic solvent, the autoclaving about 800 ℃, the product of acquisition mostly is the carbon nitrogen powder of class graphite structure, and the N/C ratio reaches as high as 1.55, but hardness is lower.
1993, the Chunming Niu of university of Harvard (Harvard) adopted pulse laser evaporation C target, and the Nitrogen Atom assistant depositing has obtained carbon-nitrogen film on Si (100) substrate.Subsequently, it is the carbon-nitrogen film of 35～50at% that Z.John Zhang has also obtained N content with ten thousand similar methods, removes α-C in the film
3N
4Phase, β-C
3N
4Mutually, also there is a kind of C
2The N phase, and film has higher resistance and heat conductivity, and thermostability also is better than diamond-film-like ((DLC).Rumanian I.N.Mihailescu replaces N with ammonia
2Gas has been produced and has been contained carbon nitrogen singly-bound, two key and triple-linked hard carbon nitrogen film, and its optical band gap can reach 4.5eV.And R.Alecandrescu is with sensitization laser pyrolysis acetylene, laughing gas (N
2O) and the method for ammonia mixture, make and contain α-C
3N
4Phase, β-C
3N
4The carbon nitrogen fine powder of phase.People such as Z.JohnZhang have introduced low energy N ionic fluid or N plasma body in the pulse laser method of evaporation, the density of intending improving the N content of film and increasing film.
As far back as the beginning of the eighties, Jones and Steward just attempt to adopt the plasma body of N and the multiple H of containing carbide to obtain carbon-nitrogen film, at the end of the eighties, Han and Fledman use the radio frequency plasma method and also attempt preparing carbon-nitrogen film, but the film that they obtain is all non-crystalline state.The Kin Ivtan Yu of California (Califomia) university in 1994 with radio-frequency magnetron sputter method prepared 1 μ m thick contain β-C
3N
4Carbon nitrogen polymer film.After this, magnetron sputtering method and relevant householder method thereof are widely used in the synthetic of carboritride.
King En Ge research group at first adopts heated filament CVD (HFCVD) method to prepare the hard carbon nitrogen film, removes α-C in the film
3N
4, β-C
3N
4Mutually, also find to exist the carboritride phase of some unknown structure.Japan Youji Tani adopts electron cyclotron resonace, and ((ECR) is in N
2Sputter C target in the gas has obtained N/C and is 1.35 carbon-nitrogen film, makes N content reach C
3N
4Stoicheiometry, structural analysis is given in the membrane and is contained α-C
3N
4, β-C
3N
4Mutually with a unknown structure carbon nitrogen mutually.Somnath Bhattacharyya is in methane and N
2Use radio-frequency plasma auxiliary electron cyclotron resonance (ECR-rf) method in the gas mixture and also prepare carbon-nitrogen film, and provided the microtexture of film and the internal relation of electronic structure.Human microwave plasma CVD methods (MPCVD) such as the Gu Yousong of University of Science ﹠ Technology, Beijing have obtained α and β-C that the phantom amount reaches 349GPa on silicon and platinum substrate
3N
4Mix the carbon-nitrogen film that exists.
People such as Montigaud are dissolved in hydrazine (N with melamine
2H
4) among, subsequently at 2.5GPa, to handle under 800～850 ℃ the condition, the carbon nitrogen-atoms that has obtained laminate structure is than the Vandyke brown sample that is about 0.87.People such as Yu-Jun Bai are with CCl
4With NH
4Cl is a raw material, at 400 ℃ of following insulation 20h, then the sample that obtained is washed 5 times, washed with de-ionized water 3 times with acetone, to remove residue and by product wherein; Obtained the powdered sample of brown after the oven dry.Contain class graphite phase C in the analysis revealed product
3N
4, grain-size is about 10nm.
Y.Fahmy and Long-wei Yin utilize the mechanical alloying method to carry out the trial of synthetic carboritride, analyze and find to contain the good β-C of crystallinity in the product
3N
4Around the nano crystal, single crystal particle then is amorphous phase.
The carbon nitrogen precursor of the random graphits structure that the Yu Dongli of University On The Mountain Of Swallows repeatedly obtains trimeric cyanamide after the pyrolysis has carried out impulsive discharge and high speed impact is handled.Thereby its composition of carbon nitrogen precursor powder of having prepared random graphits structure is 33.76at%C, 49.53at%N, 16.71at%H, still keep its random graphits structure after impulsive discharge and shock treatment, but order improves obviously.
People such as N.Tsubouchi adopt high energy C
- 2And N
+Ion radiation beam co-deposition method prepares carbon-nitrogen film.People such as employing organic solution electrodip process, Kazuhiro Yamamoto such as Chuanbo Cao have obtained carbon-nitrogen film respectively in the mode of ion implantation graphite target.Being permitted of University Of Suzhou offered sacriffices to the gods or the spirits of the dead the mixing solutions that peace waits electrolysis methyl alcohol and urea under 60 ℃ and normal pressure, obtained the amorphous carbon nitrogen film on silicon substrate.
Multilayer technique is the effective measure that obtain metastable phase, and a research group of Northwestern Univ USA reports them and adopts magnetron sputtering method successfully to prepare β-C
3N
4The superhard multilayer film of/TiN, the Wu Dawei of Wuhan University etc. adopt double cathode dead front type unbalanced magnetic field direct current reaction magnetron sputtering ion plating method, have prepared C
3N
4The compound alternate films of/TiN, and obtained β-C
3N
4With cube-C
3N
4
One of present adamantine manufacture method is " an explosion method diamond synthesis ", and it is the high voltage transient high temperature that utilizes explosive charge to produce, and graphite is changed into diamond, adopts chemical method to obtain high pure differential diamond product then.About very many of the bibliographical information of this method and patent application.For example described Nano diamond explosion synthesis tank of CN200510048549.9 and Nano diamond explosion synthesis device are improvement of 01125003 the explosive detonation method method for preparing Nano diamond or the like as number of patent application.The energy that produces in view of blast can rearrange the atoms in space structure and produce this characteristic of leap on the performance, thus on synthetic C-N superhard material, also can use for reference this thinking, but concrete raw material selects and then needs really further to probe into consumption.
Summary of the invention
The present invention provides a kind of β-C for the problem that solves processing and manufacturing C-N superhard material
3N
4Explosion impact synthetic method.
The present invention is realized by following technical scheme, a kind of β-C
3N
4Explosion impact synthetic method is that explosive and pre-reaction material are placed in the encloses container, and the blast of then explosive being ignited obtains detonation product, at last detonation product is carried out purification processes and obtains β-C
3N
4Superhard material.
The method of purification processes is, the product after the detonation put into chloroazotic acid soak, and cleaning, drying boils under 180-220 ℃ of condition with the vitriol oil more then, and cleaning, drying is handled with ultrasonic oscillation more again, and calcining at last obtains product.
The preferred RDX of explosive, has certain special unstable group in this explosive molecular structure, these groups make between each element of explosive molecule it is not to carry out combination by the form of maximum bond energy, thereby under suitably external force (heat, impact etc.) acts on, can open chemical bond rapidly, that is to say and carry out violent decomposition reaction, emit heat, regenerate according to big bond energy bonded, chemically stable product.Pre-reaction material, major ingredient is selected C
2H
4N
4, auxiliary CH
3N
5, C.
The consumption of explosive is 3-7 part, and pre-reaction material is the C of 8-14 part
2H
4N
4, 1-4 part CH
3N
5, 1-4 part C.The black powder that blast impulse pressure obtains during for 16Gpa becomes light grey powder through after the purification processes.
Carry out X-ray diffraction (XRD) analysis to carrying product
Adopt Japanese D/MAX-rBX x ray diffractometer x of science to carry out XRD analysis.Test parameter: copper target (wavelength 1.54056
), pipe presses 40KV, pipe stream 100mA, continous way or step scanning mode, scope 10～110 degree, 4 °/min of speed, step-length 0.01 degree, slit width 1 degree.
When Fig. 3,4 lists blast impulse pressure and is 23GPa, the XRD figure spectrum before and after the purification of products.
By Fig. 3,4 as can be known, before detonation product is purified in the XRD figure spectrum peak innumerable and disordered, the multimodal overlapping phenomenon appears between individual regions, the XRD figure spectrum peak after the purification obviously reduces and regular distribution.Because carboritride belongs to more newfound material, do not add in the XRD standard diagram handbook and include, so will react in the table 1 XRD figure of after product compose with people such as Matsumoto to α-, β-, CNx and graphite C mutually
3N
4The strong calculated value in XRD peak analyze comparison.
It can be seen from the table, in the product different ratios ground contain α-, β-C
3N
4, and the CNx that may contain minute quantity and graphite C mutually
3N
4Find contained β-C in the product simultaneously
3N
4Phase, also very approaching with the XRD data of people such as Teter report.
The XRD test result of table 1 reaction product and related data analysis
Infrared absorption spectrum (FTIR) is analyzed
Adopt Japan to lead the 8400S of Tianjin company type infrared absorption spectrometer sample is carried out the FTIR analysis.Grind with the KBr powder mixes behind the sample drying, wait to pulverize the back compressing tablet and test.FTIR test analysis wave-number range is 400～4000cm
-1, resolving power is 0.01cm
-1
When Fig. 5 lists blast impulse pressure and is 23GPa, the FTIR collection of illustrative plates before and after the purification of products.
(a) is C among the figure
2H
4N
4The infrared spectrum of raw material (b) is sample infrared spectrum after the 23GPa shock treatment.By analysis, (a) near the peak that occurs the middle 2218.696cm-1 is a C ≡ N vibration peak in the raw material, and near 1661.201 peaks that occur are C=N stretching vibration peaks in the raw material.(b) peak at 3427.208cm-1 and 1628.407cm-1 place is the N-H formation vibration peak in the sample in; 1085.777cm-1 the strong peak of locating is the stretching vibration peak of C-N; 806.192cm-1 locate and flexural vibration peak that two peaks at 678.896cm-1 place are C-N or N-H.
By analysis, powerful impact energy makes C in the shock treatment process
2H
4N
4In C=N and C ≡ N opened fully, reconfigure and form C-N, with bibliographical information and theoretical prediction basically identical.
The scanning electron microscope (SEM) of material and X-ray energy spectrum (EDS) are analyzed after purifying
The present invention adopts the displaing micro tissue topography and the size of the S-570 of Hitachi type scanning electron microscopic observation sample.Resolving power can reach 3.5nm at high vacuum state, low vacuum state 4.5nm.
Sample SEM photo is seen Fig. 6,7, and sample EDS analytical results is seen Fig. 4 .5.
As can be seen, sample is made up of the small-particle of micron dimension among Fig. 6, and particle size dispersion is even, and Fig. 7 is hexagon β-C
3N
4Individual particle, size is 2-3 μ m, and is consistent with bibliographical information and theoretical prediction shape.Table 2 sample EDS analytical results
| Element Line Weight％ ---------------------------- C Ka 5.53 N Ka 16.49 O Ka 43.28 Al Ka 13.29 Si Ka 15.08 Cr Ka 0.43 Fe Ka 2.02 Sb La 3.86 Total 99.98 |
List the EDS analytical results of product in the table 2, the carbon of sample, nitrogen element ratio are 1: 2.556, with C
3N
4Theoretical chemistry metering comparatively more approaching than (1: 1.333).The beneficial effect of the invention: method of the present invention can be synthesized the preparation carboritride, and this method is practical, compares with method listed in the background technology, simple to operate, advantages such as reaction process is lacked, the convenience of purifying that present method has.
Aspect the application in practice of carbonitride, mainly be to utilize β-C at present
3N
4Piece surface is carried out plated film, so that workpiece is more wear-resisting.The azotized carbon nano particle can strengthen the creep resistance energy of steel simultaneously, so add the performance that the carbonitride particle can improve iron and steel in the process of steel-making.The Another application of carbonitride is the plated film to cutter, will be sharper through the cutter of plated film, has more practicality.This superhard material can become countless Industrial products surface abrasion coatings, thereby prolongs the work-ing life of product greatly, makes product perfect more and durable, has great economic benefit.It is in theory existing that the prophesy of scientist Liu just is based upon condensed state physics, if this prophesy is confirmed that by experiment it just becomes an exemplary using the Condensed Matter Physics theory to come the design exotic materials so.Therefore, the research of C-N series material has become one of research focus of condensed state physics and Materials science aspect.
The synthetic meaning of the experiment of carboritride with two aspects: the premium properties of hardness and others in the theoretical prediction, indicating that carboritride might all have broad application prospects in every field as a kind of important new function material; On the other hand, as first kind of material that proposes by theoretical prediction fully, the success of macro-scale carbon nitrogen crystal experiment synthetic, indicating that novel material is synthetic explores the leap of carrying out by traditional experience, semiempirical under theory instructs, will become a milestone on the Materials science development history.
Description of drawings
Fig. 1 process flow sheet of the present invention
Fig. 2 purification of products process flow sheet
When Fig. 3 is 23GPa for blast impulse pressure, the XRD figure spectrum before the purification of products.
When Fig. 4 is 23GPa for blast impulse pressure, the XRD figure spectrum after the purification of products.
Fig. 5 is a reaction product FTIR collection of illustrative plates
Fig. 6 is a product SEM photo (* 5000)
Fig. 7 is a product SEM photo (* 10000)
Fig. 8 is the apparatus structure synoptic diagram that technology of the present invention is used
Among the figure: 1-electrical detonator, 2-RDX explosive column, 3-presoma powder column, 4-explosive container housing, the organic dividing plate of 5-, 6-steel bushing, 7-explosive container base
Embodiment
Embodiment 1, a kind of β-C
3N
4Explosion impact synthetic method is that explosive and pre-reaction material are placed in the encloses container, and the blast of then explosive being ignited obtains detonation product, at last detonation product is carried out purification processes and obtains β-C
3N
4Superhard material.Explosive is selected RDX, and the consumption of explosive is 4.6 parts, and pre-reaction material is 12 parts C
2H
4N
4, 2 parts CH
3N
5, 2 parts C.
The fundamental characteristics table look-up of table 3RDX explosive
| Character | RDX |
| Formal name used at school | Inferior three basic trintriamines |
| Molecular formula | C 3H 6N 6O 6 |
| Molecular weight | 222 |
| Oxygen balance | -0.216 |
| Pressure (GPa) | 34.7 |
| Temperature (K) | 2590 |
| Detonation velocity (m/s) | 8750 |
| Sudden-heat (KJ/g) | 5.46 |
| Color | White powder |
| Density (g/cm 3) | 1.82 |
| Carbon content (%) | 16.22 |
| Fusing point (K) | 478 |
| Acting ability (KJ/g) is calculated | 1.81 |
| Actual measurement | 1.716 |
| Product volume calculation (cm 3/g) | 980 |
| |
900 |
Table 4
| Raw material | Manufacturer | Content | Molecular weight | Experiment consumption/g |
| C 2H 4N 4 | The Long Huagongshijichang of Chengdu section | ≥98.0％ | 84.08 | 1.2 |
| CH 3N 5 | Tianjin section close europeanized reagent development centre | ≥99％ | 85 | 0.2 |
| C | Tianjin, Tianjin fine chemistry industry institute of section | ≥99％ | 12 | 0.2 |
Experimental installation adopts the research that experimentizes of confined explosion container, this container and test and all adopt 45 with steel bushing
#Steel is processed into and through quench treatment.The experimental installation sketch sees 8.
Because also comprise the impurity such as iron filings, electrical detonator outer cover metal bits, detonator line scrap metal and the outer scurf of detonator line of carbon, machine sheet glass chip, explosive release inwall in the detonation product except that target product, the means that research adopts liquid phase oxidation and vapour phase oxidation process to combine are carried out purification processes to detonation product.
Liquid phase oxidation mainly adopts liquid oxidizers such as the stronger chloroazotic acid of oxidisability, the vitriol oil and concentrated nitric acid at high temperature detonation product to be handled, and is intended to remove metallic impurity and partially carbonized product.Product after vapour phase oxidation process mainly utilizes High Temperature Furnaces Heating Apparatus to liquid-phase oxidation carries out high-temperature calcination, is intended to remove organic impurity and partially carbonized product.The sample purification schemes is seen Fig. 2.
Specifically take following operation measure: the product after the detonation is put into chloroazotic acid soaked 24 hours, cleaning, drying boiled 4 hours under 200 ℃ of conditions with the vitriol oil, cleaning, drying more again then, handled 2 hours with ultrasonic oscillation, calcining obtained product in 2 hours under 500 ℃ of conditions at last again.The vitriol oil conventionally refers generally to concentration more than or equal to 70% sulfuric acid.
In this experiment, two kinds of pre-reaction materials will carry out the control experiment under the different pressures that pressure is 14GPa～34Gpa, and its pressure step-length is that 3GPa has 8 groups, and its pressure is respectively: 14GPa, 17GPa, 20GPa, 23GPa, 26GPa, 29GPa, 32GPa, 34GPa.After determining best pressure, change reactant density, to determine optimum response thing density.After having determined best reactant pressures and density, determine constraint condition preferably by the constraint condition that changes reactant again, and finally draw the technology of the best of the synthetic C-N superhard material of blast impulse.
A kind of β-C
3N
4Explosion impact synthetic method is that explosive and pre-reaction material are placed in the encloses container, and the blast of then explosive being ignited obtains detonation product, at last detonation product is carried out purification processes and obtains β-C
3N
4Superhard material.Explosive is selected RDX, and the consumption of explosive is 3 parts, and pre-reaction material is 14 parts C
2H
4N
4, 1 part CH
3N
5, 4 parts C.Purify and specifically take following operation measure: the product after the detonation is put into chloroazotic acid soaked 15 hours, cleaning, drying boiled 2 hours under 220 ℃ of conditions with the vitriol oil, cleaning, drying more again then, handled 4 hours with ultrasonic oscillation, calcining obtained product in 1 hour under 500 ℃ of conditions at last again.
Claims (6)
1, a kind of β-C
3N
4Explosion impact synthetic method is characterized in that explosive and pre-reaction material are placed in the encloses container, and the blast of then explosive being ignited obtains detonation product, at last detonation product is carried out purification processes and obtains β-C
3N
4Superhard material.
2, β-C according to claim 1
3N
4Explosion impact synthetic method is characterized in that the product after the detonation is put into chloroazotic acid to be soaked, and cleaning, drying boils under 180-220 ℃ of condition with the vitriol oil more then, and cleaning, drying is handled with ultrasonic oscillation more again, and calcining at last obtains product.
3, β-C according to claim 1 and 2
3N
4Explosion impact synthetic method is characterized in that: the consumption of explosive is 3-7 part, and pre-reaction material is the C of 8-14 part
2H
4N
4, 1-4 part CH
3N
5, 1-4 part C.
4, β-C according to claim 1 and 2
3N
4Explosion impact synthetic method is characterized in that: explosive is selected RDX.
5, β-C according to claim 3
3N
4Explosion impact synthetic method, the consumption that it is characterized in that explosive is 4.6 parts, pre-reaction material is 12 parts C
2H
4N
4, 2 parts CH
3N
5, 2 parts C.
6, β-C according to claim 5
3N
4Explosion impact synthetic method is characterized in that: explosive is selected RDX.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232458A (en) * | 2013-04-25 | 2013-08-07 | 大连理工大学 | Method for preparing graphite phase carbon nitride material with monatomic layer structure |
| CN104108687A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Carbon nitride and preparation method thereof |
| CN105883733A (en) * | 2016-04-18 | 2016-08-24 | 扬州大学 | Expandable carbon nitride as well as preparation and expansion methods thereof |
| CN107381520A (en) * | 2017-08-24 | 2017-11-24 | 南昌航空大学 | A kind of band gap is adjustable and the preparation method of the class graphene carbonitride of efficient degradation of organic dye |
| CN109399588A (en) * | 2018-12-20 | 2019-03-01 | 山东大学 | A kind of g-C constructed on substrate3N4Continuous film and preparation method |
-
2008
- 2008-07-25 CN CN2008100554971A patent/CN101323437B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103232458A (en) * | 2013-04-25 | 2013-08-07 | 大连理工大学 | Method for preparing graphite phase carbon nitride material with monatomic layer structure |
| CN104108687A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Carbon nitride and preparation method thereof |
| CN105883733A (en) * | 2016-04-18 | 2016-08-24 | 扬州大学 | Expandable carbon nitride as well as preparation and expansion methods thereof |
| CN107381520A (en) * | 2017-08-24 | 2017-11-24 | 南昌航空大学 | A kind of band gap is adjustable and the preparation method of the class graphene carbonitride of efficient degradation of organic dye |
| CN109399588A (en) * | 2018-12-20 | 2019-03-01 | 山东大学 | A kind of g-C constructed on substrate3N4Continuous film and preparation method |
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|---|---|
| CN101323437B (en) | 2010-09-08 |
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