CN106517111A - High-temperature and high-pressure preparation method of chromium nitride - Google Patents
High-temperature and high-pressure preparation method of chromium nitride Download PDFInfo
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- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 84
- 239000011780 sodium chloride Substances 0.000 claims abstract description 42
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 28
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims abstract description 25
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000000227 grinding Methods 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- 229960000359 chromic chloride Drugs 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 18
- 238000009413 insulation Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 238000010298 pulverizing process Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 20
- 229910052582 BN Inorganic materials 0.000 description 12
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical group [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/062—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with chromium, molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Ceramic Products (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a high-temperature and high-pressure preparation method of chromium nitride, and belongs to the technical field of preparation of the semiconductor material chromium nitride. The method includes the steps that chromium trichloride, sodium azide and sodium chloride used for reducing the reaction rate serve as raw materials and are fully mixed, and the mixture is made into a cylinder shape through cold pressing and then put into a synthesis cavity of a press; heat preservation and pressure maintaining are conducted for 15-60 minutes under the conditions that the pressure is 5 GPa and the temperature ranges from 1700 DEG C to 2000 DEG C, and a CrN and NaCl mixed blocky product is obtained; after grinding, washing and drying, high-purity CrN powder is obtained. According to the method, it is unnecessary to monitor the oxygen and nitrogen concentration in the reaction cavity all the time, and it is unnecessary to use circulating ammonia reactants at a high temperature. Compared with a traditional preparation method, the preparation time is greatly shortened, the cost is low, the reaction is controllable, and high-purity CrN can be obtained by simply cleaning the reaction product; besides, a new reaction mechanism is adopted.
Description
Technical field
The invention belongs to technical field prepared by semi-conducting material chromium nitride, is related to the High Temperature High Pressure of chromium nitride (CrN)
Preparation method.
Background technology
Nitride is gathered around in modern society and is had a wide range of applications, invariably as they are uncommon or even unique property
Matter.For example, c-BN, Si3N4Possess ultrahigh hardness as cutting material, GaN is most widely used semi-conducting material, corrosion-resistant
Low transition metal nitride TiN, hydrogen storage material Li3N, the MoN with superconducting property etc.. CrN is a kind of non-oxidizability, resistance to
Burn into high rigidity (HV1750), high temperature resistant (700 DEG C) and there is the dilute magnetic semiconductor material of preferable thermal conductivity.Made using it
Make cutter, punching press and be drawn mould, powder moulding mold, folding part, die casting etc., possess outstanding resistance to compression, anti scuffing with
And specularity.It is widely used in modern industry, technique productions as coating, additive, membrane material.It is that modern technologies production can not
Or the material for lacking.
Traditional mode of production CrN powder crystal synthesizes often through ammonolysis process.Typically will be through batch mixing, the mistake of reacting furnace sintering
Journey.Reacting furnace sintering needs to be synthesized under the hot environment of the ammonia of flowing, also need strictly to control oxygen in reacting furnace,
The pressure of nitrogen.Length reaction time (2-20h is up to during insulation), production cost is high, and it is high to react the CrN oxygen content for generating.Cause
This invents a kind of CrN methods of cheap, efficient, safe preparation and is promoted tool and is of great significance.It is high
The synthetic method of warm high pressure can typically significantly reduce reaction time, be obviously improved production efficiency.Professor He Duanwei carries within 2012
Ion exchange reaction under the high pressure for going out is obtained chromium nitride (CrN).Its reactant is sodium chromate (Na2CrO4) and hexagonal boron nitride
(h-BN), reaction temperature 800-1400 DEG C, reaction pressure are 0-5GPa.But hexagonal boron nitride (h-BN) commercial synthesis cost compared with
It is high.Therefore find new reactant and response mechanism is advantageous to the high High Temperature High Pressure technology of preparing of this highly effective and safe
Promote.
The content of the invention
The technical problem to be solved in the present invention is to prepare highly purified CrN using the synthetic method of High Temperature High Pressure.
The high temperature and high pressure preparation process of the chromium nitride of the present invention is with CrCl3And NaN3For raw material, reduce anti-by adding NaCl
Answer the safety of rate guarantee experiment and stablizing for cavity.The present invention may gas release and synthesize safety consideration addition
NaCl and NaN3Mol ratio is at least 2 times or so to reduce reaction rate, i.e., may abundant release gas N2With rubbing for NaCl
At least 1 times or so of ratio of that.The present invention synthesizes initial mass sample, reaction product by adjusting reaction temperature and response time
For CrN and NaCl, and high-purity C rN is obtained by washing.
Reactive chemistry formula：
CrCl3+NaN3→CrN+NaCl
The concrete technical scheme of the present invention is as described below
A kind of preparation method of the High Temperature High Pressure of chromium nitride, is synthesized using press；Technical process have raw material mixing, it is cold
Molded, assembling, High Temperature High Pressure synthesis, cooling release are obtained block product；The cold moudling is that pressing machine synthetic cavity is big
It is little mixed material is pressed into it is cylindric；Described assembling, is that the raw material of mixing is loaded container, places into heating container,
And load thermal-insulating sealing container, place in synthetic cavity；Described cooling release, after being High Temperature High Pressure synthetic product, stops
Only electrified regulation makes assembling block naturally cool to room temperature, then release；Characterized in that, described raw material mixing, is by trichlorine
Change chromium (CrCl3), Hydrazoic acid,sodium salt (NaN3) and Sodium Chloride (NaCl) in molar ratio 1:2:4～5 are mixed；Described high temperature is high
Be pressed into, be pressure be 5GPa, temperature be 1700～2000 DEG C at 15～60min of heat-insulation pressure keeping；Last block product is passed through
Grinding, washing are pulverized, after being dried, highly purified CrN powder is obtained.
Described block product, is the mixture of CrN and NaCl.Block product can be obtained through pulverizing grinding, washing
Highly purified CrN.
High Temperature High Pressure building-up process add Sodium Chloride (NaCl) be mainly used in reduce reaction rate, it is ensured that the safety of experiment with
Stablizing for cavity, is conducive to CrN to generate.
The experiment of the present invention can be completed on domestic 6 × 600T of SPD type cubic hinge press.Test result indicate that temperature,
The proportioning of raw material is the key factor of the CrN for affecting synthesis.Can be seen that under synthesis condition of the present invention by embodiment 1～6,
That is chromium trichloride, Hydrazoic acid,sodium salt and Sodium Chloride in molar ratio 1: 2: 4～5, synthesis pressure is 5.0GPa, and synthesis temperature scope is
1700～2000 DEG C, heat-insulation pressure keeping 15～60 minutes, product can be obtained high-purity under conditions of pulverizing grinding, washing
The CrN of degree.Preferred raw material mixing is that chromium trichloride, Hydrazoic acid,sodium salt and Sodium Chloride are mixed in molar ratio at 1: 2: 5；Preferably
High Temperature High Pressure synthesize, be pressure 5GPa, temperature be 1700 DEG C～2000 DEG C at heat-insulation pressure keeping 15min.
Preferably, synthetic product pulverize grinding after, can be washed away with dilute hydrochloric acid be likely to occur in product due to taking
The hydroxide of the Na that the sample after going out is generated with air contact, the NaCl for being gone in product with 70 DEG C of washing again afterwards.
In order to ensure the uniformity of the synthetic cavity temperature during being synthesized, the heating source that this method is adopted is switched on
Graphite-pipe heater-type is heated；In order to ensure that raw material is not reacted with the graphite-pipe for producing heat, the cavity of synthetic sample is adopted
Hexagonal boron nitride (h-BN) is protected；It is in order to ensure the safety and stablization of the synthetic cavity during being synthesized and unnecessary
Gas N2Do not leak, this method adopt pressure be always high pressure 5GPa.
Present invention process flow process is simple；The oxygen and nitrogen gas concn of reaction chamber need not be monitored the moment；Need not be in high temperature
The lower ammonia using circulation；Product is obtained by the proportioning of regulation simple substance raw material, temperature and time, and passes through water-washing method
Obtain highly purified chromium nitride CrN.The inventive method substantially reduces manufacturing cycle compared with traditional preparation methods, cost compared with
It is low.It is compared with forefathers' high pressure method for preparing, all wide with reaction interval, react controllable；Product cleaning is simple.The side of the present invention
It is owned by France in new response mechanism.
Description of the drawings
Fig. 1 be embodiment 1 be Jing washing obtained in chromium nitride X-ray diffraction pattern.
It is X-ray diffraction pattern that the product for preparing is not washed with water that Fig. 2 is embodiment 1.
Fig. 3 be embodiment 2 be the chromium nitride for preparing X-ray diffraction pattern.
Fig. 4 be embodiment 3 be the chromium nitride for preparing X-ray diffraction pattern.
Fig. 5 be embodiment 4 be the chromium nitride for preparing X-ray diffraction pattern.
Fig. 6 be embodiment 5 be the chromium nitride for preparing X-ray diffraction pattern.
Fig. 7 be embodiment 6 be the chromium nitride for preparing X-ray diffraction pattern.
Fig. 8 be comparative example 1 be the chromium nitride for preparing X-ray diffraction pattern.
Fig. 9 be comparative example 2 be the chromium nitride for preparing X-ray diffraction pattern.
Figure 10 be comparative example 3 be the chromium nitride for preparing X-ray diffraction pattern.
Specific embodiment
Embodiment 1
By analytically pure chromium trichloride (CrCl3), Hydrazoic acid,sodium salt (NaN3) and Sodium Chloride (NaCl) fill at 1: 2: 5 in molar ratio
Point mixing, using hydraulic press powder it is molded after, by sample load synthetic cavity in the middle of.Energization Graphite thermal tube is adopted in assembling cavity
Heating, is incubated with pyrophillite and pressure transmission material, and using the sample in hexagonal boron nitride protection synthetic cavity, synthesis pressure is
5.0GPa, synthesis temperature are 1800 DEG C, and the heat-insulation pressure keeping time is 30min, and after stopping heating, sample is unloaded after naturally cooling to room temperature
Pressure, products therefrom is the mixture of CrN and NaCl.Jing after pulverizing grinding, washing and drying, high-purity chromium nitride powder is obtained.
Sample specific X-ray diffraction patterns of the product mixtures Jing after pulverizing grinding, washing are shown in Fig. 1.
The product mixtures that this condition is prepared pulverize grinding, see Fig. 2 without the specific X-ray diffraction patterns of washing sample.
Embodiment 2
By analytically pure chromium trichloride (CrCl3), Hydrazoic acid,sodium salt (NaN3) and Sodium Chloride (NaCl) fill at 1: 2: 5 in molar ratio
Point mixing, using hydraulic press powder it is molded after, by sample load synthetic cavity in the middle of.Energization Graphite thermal tube is adopted in assembling cavity
Heating, is incubated with pyrophillite and pressure transmission material, and using the sample in hexagonal boron nitride protection synthetic cavity, synthesis pressure is
5.0GPa, synthesis temperature are 1800 DEG C, and the heat-insulation pressure keeping time is 15min, and after stopping heating, sample is unloaded after naturally cooling to room temperature
Pressure, products therefrom is the mixture of CrN and NaCl, and the specific X-ray diffraction patterns of chromium nitride Jing after pulverizing grinding, washing are shown in figure
3。
Embodiment 3
By analytically pure chromium trichloride (CrCl3), Hydrazoic acid,sodium salt (NaN3) and Sodium Chloride (NaCl) fill at 1: 2: 5 in molar ratio
Point mixing, using hydraulic press powder it is molded after, by sample load synthetic cavity in the middle of.Energization Graphite thermal tube is adopted in assembling cavity
Heating, is incubated with pyrophillite and pressure transmission material, and using the sample in hexagonal boron nitride protection synthetic cavity, synthesis pressure is
5.0GPa, synthesis temperature are 1800 DEG C, and the heat-insulation pressure keeping time is 60 minutes, and after stopping heating, sample is unloaded after naturally cooling to room temperature
Pressure, products therefrom is the mixture of CrN and NaCl, and the specific X-ray diffraction patterns of chromium nitride Jing after pulverizing grinding, washing are shown in figure
4。
Embodiment 4
By analytically pure chromium trichloride (CrCl3), Hydrazoic acid,sodium salt (NaN3) and Sodium Chloride (NaCl) fill at 1: 2: 5 in molar ratio
Point mixing, using hydraulic press powder it is molded after, by sample load synthetic cavity in the middle of.Energization Graphite thermal tube is adopted in assembling cavity
Heating, is incubated with pyrophillite and pressure transmission material, and using the sample in hexagonal boron nitride protection synthetic cavity, synthesis pressure is
5.0GPa, synthesis temperature are 1700 DEG C, and the heat-insulation pressure keeping time is 15min, and after stopping heating, sample is unloaded after naturally cooling to room temperature
Pressure, products therefrom is the mixture of CrN and NaCl, and the specific X-ray diffraction patterns of chromium nitride Jing after pulverizing grinding, washing are shown in figure
5。
Embodiment 5
By analytically pure chromium trichloride (CrCl3), Hydrazoic acid,sodium salt (NaN3) and Sodium Chloride (NaCl) fill at 1: 2: 5 in molar ratio
Point mixing, using hydraulic press powder it is molded after, by sample load synthetic cavity in the middle of.Energization Graphite thermal tube is adopted in assembling cavity
Heating, is incubated with pyrophillite and pressure transmission material, and using the sample in hexagonal boron nitride protection synthetic cavity, synthesis pressure is
5.0GPa, synthesis temperature are 1900 DEG C, and the heat-insulation pressure keeping time is 15min, and after stopping heating, sample is unloaded after naturally cooling to room temperature
Pressure, products therefrom is the mixture of CrN and NaCl, and the specific X-ray diffraction patterns of chromium nitride Jing after pulverizing grinding, washing are shown in figure
6。
Embodiment 6
By analytically pure chromium trichloride (CrCl3), Hydrazoic acid,sodium salt (NaN3) and Sodium Chloride (NaCl) fill at 1: 2: 5 in molar ratio
Point mixing, using hydraulic press powder it is molded after, by sample load synthetic cavity in the middle of.Energization Graphite thermal tube is adopted in assembling cavity
Heating, is incubated with pyrophillite and pressure transmission material, and using the sample in hexagonal boron nitride protection synthetic cavity, synthesis pressure is
5.0GPa, synthesis temperature are 2000 DEG C, and the heat-insulation pressure keeping time is 15min, and after stopping heating, sample is unloaded after naturally cooling to room temperature
Pressure, products therefrom is the mixture of CrN and NaCl, and the specific X-ray diffraction patterns of chromium nitride Jing after pulverizing grinding, washing are shown in figure
7。
Comparative example 1
By analytically pure chromium trichloride (CrCl3), Hydrazoic acid,sodium salt (NaN3) and Sodium Chloride (NaCl) fill at 1: 1: 5 in molar ratio
Point mixing, using hydraulic press powder it is molded after, by sample load synthetic cavity in the middle of.Energization Graphite thermal tube is adopted in assembling cavity
Heating, is incubated with pyrophillite and pressure transmission material, and using the sample in hexagonal boron nitride protection synthetic cavity, synthesis pressure is
5.0GPa, synthesis temperature are 1800 DEG C, and the heat-insulation pressure keeping time is 15min, and after stopping heating, sample is unloaded after naturally cooling to room temperature
Pressure, products therefrom Jing pulverize grinding, washing, and specific X-ray diffraction patterns are shown in Fig. 8.
Comparative example 1 is due to NaN in reacting substance3Ratio it is too low, after product cleaning almost without CrN presence, yield
Lowly, it is unfavorable for high-purity CrN synthesis.
Comparative example 2
By analytically pure chromium trichloride (CrCl3), Hydrazoic acid,sodium salt (NaN3) and Sodium Chloride (NaCl) fill at 1: 2: 5 in molar ratio
Point mixing, using hydraulic press powder it is molded after, by sample load synthetic cavity in the middle of.Energization Graphite thermal tube is adopted in assembling cavity
Heating, is incubated with pyrophillite and pressure transmission material, and using the sample in hexagonal boron nitride protection synthetic cavity, synthesis pressure is
5.0GPa, synthesis temperature are 1600 DEG C, and the heat-insulation pressure keeping time is 15min, and after stopping heating, sample is unloaded after naturally cooling to room temperature
Pressure, products therefrom Jing pulverize grinding, washing, and specific X-ray diffraction patterns are shown in Fig. 9.
Comparative example 2 is low due to reaction temperature, after product cleaning almost without CrN presence low yield, and other impurities
Peak is more, is unfavorable for high-purity CrN synthesis.
Comparative example 3
By analytically pure chromium trichloride (CrCl3), Hydrazoic acid,sodium salt (NaN3) and Sodium Chloride (NaCl) fill at 1: 2: 5 in molar ratio
Point mixing, using hydraulic press powder it is molded after, by sample load synthetic cavity in the middle of.Energization Graphite thermal tube is adopted in assembling cavity
Heating, is incubated with pyrophillite and pressure transmission material, and using the sample in hexagonal boron nitride protection synthetic cavity, synthesis pressure is
5.0GPa, synthesis temperature are 1800 DEG C, and the heat-insulation pressure keeping time is 5min, and after stopping heating, sample is unloaded after naturally cooling to room temperature
Pressure, products therefrom Jing pulverize grinding, washing, and specific X-ray diffraction patterns are shown in Figure 10.
Comparative example 3 due in reacting substance the response time it is too short, reaction generates product and deposits entirely without the sign peak of crystal CrN
.
Claims (4)
1. a kind of preparation method of the High Temperature High Pressure of chromium nitride, is synthesized using press；Technical process has raw material mixing, colds pressing
Molding, assembling, High Temperature High Pressure synthesis, cooling release, are obtained block product；The cold moudling is pressing machine synthetic cavity size
Mixed material is pressed into cylindric；Described assembling, is that the raw material of mixing is loaded container, places into heating container, and
Load thermal-insulating sealing container, place in synthetic cavity；Described cooling release, after being High Temperature High Pressure synthetic product, stops
Electrified regulation makes assembling block naturally cool to room temperature, then release；Characterized in that, described raw material mixing, is by tri-chlorination
Chromium, Hydrazoic acid,sodium salt and Sodium Chloride in molar ratio 1:2:4～5 are mixed；Described High Temperature High Pressure synthesis, is to be in pressure
5GPa, temperature are 15～60min of heat-insulation pressure keeping at 1700～2000 DEG C；Last block product is dried through pulverizing grinding, washing
After obtain highly purified CrN powder.
2. the preparation method of the High Temperature High Pressure of chromium nitride according to claim 1, it is characterised in that described raw material mixing
It is chromium trichloride, Hydrazoic acid,sodium salt and Sodium Chloride in molar ratio 1:2:5 are mixed.
3. the preparation method of the High Temperature High Pressure of chromium nitride according to claim 1 and 2, it is characterised in that in synthetic product
After pulverizing grinding, the hydroxide of the Na generated with air contact due to the sample for taking out in product is washed away with dilute hydrochloric acid, it
Washed again afterwards.
4. the preparation method of the High Temperature High Pressure of chromium nitride according to claim 1 and 2, it is characterised in that described washing,
It is the NaCl gone in product with 70 DEG C of washing.
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| CN201610963363.4A CN106517111B (en) | 2016-11-04 | 2016-11-04 | The high temperature and high pressure preparation process of chromium nitride |
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| CN201610963363.4A CN106517111B (en) | 2016-11-04 | 2016-11-04 | The high temperature and high pressure preparation process of chromium nitride |
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| CN106517111B CN106517111B (en) | 2019-01-29 |
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| CN108640684A (en) * | 2018-05-25 | 2018-10-12 | 北京中材人工晶体研究院有限公司 | A kind of preparation method of mid-infrared laser doped transition metal ions zinc selenide ceramics |
| CN109399582A (en) * | 2019-01-02 | 2019-03-01 | 吉林化工学院 | It is prepared by the high temperature and pressure of block materials molybdenum nitride |
| CN111170287A (en) * | 2020-02-07 | 2020-05-19 | 吉林大学 | High-temperature high-pressure preparation method of tetragonal strontium diazenium |
| CN111170288A (en) * | 2020-02-07 | 2020-05-19 | 吉林大学 | High-temperature high-pressure preparation method of monoclinic phase barium diazenium |
| CN115321495A (en) * | 2022-07-28 | 2022-11-11 | 东北石油大学 | Metal nitrogen-rich compound FeN 8 Method of synthesis of |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108640684A (en) * | 2018-05-25 | 2018-10-12 | 北京中材人工晶体研究院有限公司 | A kind of preparation method of mid-infrared laser doped transition metal ions zinc selenide ceramics |
| CN109399582A (en) * | 2019-01-02 | 2019-03-01 | 吉林化工学院 | It is prepared by the high temperature and pressure of block materials molybdenum nitride |
| CN109399582B (en) * | 2019-01-02 | 2022-05-31 | 吉林化工学院 | High-temperature high-pressure preparation of block material molybdenum nitride |
| CN111170287A (en) * | 2020-02-07 | 2020-05-19 | 吉林大学 | High-temperature high-pressure preparation method of tetragonal strontium diazenium |
| CN111170288A (en) * | 2020-02-07 | 2020-05-19 | 吉林大学 | High-temperature high-pressure preparation method of monoclinic phase barium diazenium |
| CN115321495A (en) * | 2022-07-28 | 2022-11-11 | 东北石油大学 | Metal nitrogen-rich compound FeN 8 Method of synthesis of |
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| CN106517111B (en) | 2019-01-29 |
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