CN1084489A - A kind ofly prepare adamantine method from graphite or carbonaceous solid matter - Google Patents
A kind ofly prepare adamantine method from graphite or carbonaceous solid matter Download PDFInfo
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- CN1084489A CN1084489A CN93112537A CN93112537A CN1084489A CN 1084489 A CN1084489 A CN 1084489A CN 93112537 A CN93112537 A CN 93112537A CN 93112537 A CN93112537 A CN 93112537A CN 1084489 A CN1084489 A CN 1084489A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/25—Diamond
- C01B32/26—Preparation
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Abstract
A kind ofly prepare adamantine method from graphite or carbonaceous solid matter.Existing preparation man-made diamond method is with high temperature and high pressure method preparation, complex process equipment, or be that raw material production efficient is not high with gas.The present invention constantly stirs the powder of graphite or carbonaceous solid matter in the reactor that is filled with hydrogen or hydrogen mixed gas or floats, gas excitation energy in the reactor is introduced with the form of heating element or plasma body, under 50～106 handkerchief air pressure, under 700～1273K temperature, 0.5～50 hour reaction times got final product.Reaction product is through X-ray diffraction, and Raman spectrum detects and proves diamond crystal.
Description
The present invention a kind ofly prepares adamantine method from graphite or carbonaceous solid matter.
Diamond has the outstanding advantage that surmounts all other materials, and it is not only the hardness champion, and other characteristic such as its thermal conductivity, optical characteristics also is preeminent.The natural diamond source is limited, and therefore updating the man-made diamond preparation method is the target that people pursue for many years.GE has just made man-made diamond with high temperature and high pressure method as far back as nineteen fifty-five.W.G.Eversole under low pressure obtained man-made diamond with vapor growth method and had applied for the U.S. and Canadian Patent (U.S.Patent No.3 030 187 and No.3 030 188, Can Patent No.628 567) with nineteen fifty-nine in 1958.Soviet Union scholar B.V.Deryagin has almost also obtained simultaneously the relevant certificate of the Soviet Union.People such as the nineteen eighty-two Tokyo inorganic N.Setaka of institute have repeated people's such as Deryagin work, have also obtained man-made diamond with the low-pressure vapor phase growth method.To so far, these existing high-pressure processes, equipment complexity, cost costliness; The low-pressure vapor phase method is to be the feedstock production diamond with the gas of various hydrocarbon polymers or steam, is mainly used in growing film, and inefficiency.
The objective of the invention is to overcome present low pressure, to make man-made diamond gas be the inefficient preparation method of raw material, invents a kind of method for preparing the man-made diamond powder from graphite or carbonaceous solid matter.
The present invention prepares diamond from graphite or carbonaceous solid matter under the low-voltage high-temperature condition, the powder of graphite or carbonaceous solid matter is placed in the reactor, be filled with the mixed gas of hydrogen or hydrogen and oxydant gas or hydrogen and hydrocarbon polymer in the reactor, gaseous tension is 50～10
6Handkerchief, temperature of reaction 700～1273K, solid powder/particle is in the state that constantly stirs at reactor, and the gas excitation energy in the reactor is introduced with the form of heating element or plasma body, reacts can obtain diamond fine powder or particle in 0.5～50 hour.
Reaction conditions of the present invention is a gaseous tension 50～10
6Handkerchief, temperature of reaction 700～1273K, reaction pressure is lower, and temperature requirement is very not high, and this all accomplishes in general reaction system easily.Gas can be single hydrogen in the reactor, in order to improve reaction efficiency or to reduce temperature, also can add a small amount of oxydant gas or small amount of carbon hydrogen compound and mix with hydrogen.Raw material and resultant solid powder/particle are in and constantly stir or quick condition in the reaction system.This is because gas phase is excited the particle unstable, they lose activity by collision easily, therefore raw material and resultant fine powder or particle will be excited the high concentration region of particle in gas phase and constantly be stirred or float, make gas be excited particle and constantly stir or there is the chance that fully contacts on the solid material and the resultant powder surface of quick condition with being in, improved reaction efficiency.
In reactor, introduce the mode of excitation energy, can or form plasma body by heating element and realize.The most frequently used heating element be tungsten filament by the electrode connecting line current flow heats, its introducing mode is simple; The producing method of plasma body is to make geseous discharge with radio frequency, microwave, spectrum or combined-voltage.It is consistent substantially that the mode that excitation energy is provided to reactor and existing vapor phase process prepare diamond.
For raw material and resultant powder constantly being stirred and being excited particle and increasing and contact, can make reactor with 4～100 change (inferior)/minute the speed rotation, the reactor center two ends are installed in the arbor wheel of rotation and get final product.
Gas can be single hydrogen in the reactor, also can be the hydrogen gas mixture that contains the oxydant gas of 0.1～10% atomic ratio or contain the hydrocarbon polymer of 0.2～2% volume ratio.The gas of oxydant for example is oxygen, water, carbon monoxide.When directly using the mixed gas of oxygen and hydrogen, oxygen level must be lower than explosivity limits.During the energy, can not use oxygen-containing gas in the reaction system as excitation with heated filament, but and aerobic composition existence during other extrinsic motivated energy.
Hydrogen or hydrogen gas mixture are excited into particle by external energy, and as hydrogen atom, Sauerstoffatom, hydroxy or hydrogen ion, the reaction that participates in carbon generates the gasiform intermediate product, as methane, acetylene, decompose the generation diamond by these gasiform intermediate products again.Hydrogen atom has played energy and has carried, and emits chemical energy when hydrogen atom associates into hydrogen molecule, a similar pump, and the stable state graphite carbon atomic transport low energy forms diamond to the higher metastable state of energy, can be described as the chemical pumping process.Reaction equation: C(graphite)+xH → x/2 H
2+ C(diamond).In order to produce the particle of being excited of enough concentration, must constantly provide excitation energy to system.Diamond fine powder or particle generate and the zone of growing up is that gas phase is excited the high concentration region of particle.Therefore at present generally adopt gaseous compound to prepare the method for man-made diamond, just prepare the part of man-made diamond transition process from graphite or carbonaceous solid matter fine powder.In the presence of this experiment condition hydrogen atom, graphite or carbonaceous solid matter powder can under low pressure be transformed into diamond, and at this moment gaseous compound such as methane, acetylene is the intermediate product of this transition process.
In order to help adamantine nucleation and growth, should be mixed with in the reaction raw materials and be beneficial to the solid fines of bringing out diamond nucleation and growth or particle as substrate material, as silica flour, carborundum powder etc., newly examine in order to bring out a large amount of diamonds of generation, the substrate surface that these powders are big also quickens the diamond fine powder or particulate output improves.It also is effectively directly mixing the diamond fine powder in raw material.It is consistent substantially that nucleation process and existing vapor phase process prepare diamond.
Graphite or carbonaceous solid matter as raw material can be the fine powder or the particle of the allotropic substance of pure or impure carbon such as graphite, decolorizing carbon, coal.The raw material fine silt is more careful better, be good with 10～500 microns among the present invention, and particle carefully helps reaction to carry out, make the raw material fine powder fully be excited the particle effect and generate the diamond fine powder, particle is thinner, the reaction times is weak point more, otherwise then long.
The present invention can even react under normal pressure or a little higher than normal pressure, also be to be not difficult on the processing unit to realize being lower than reaction generation diamond under the normal pressure.Compare with the high-pressure process of prior art, equipment is simple, easy to operate, has reduced cost; Allotropic substance with solid carbon is a raw material, and its density is far longer than gas raw material, and production efficiency is improved greatly, and solid carbon source is higher and reduced because the by product that gas source produces than the density of gaseous carbon sources, as hydrogen.Again because solid material and the resultant powder constantly stirs or the state that floats provides effective gas to be excited particle and solid material and the surperficial chance that contacts of resultant powder, thereby be a kind of processing unit simple, high efficiency manufacturing man-made diamond fine powder or particulate method.
Embodiment one:
Be filled with in 50～250 handkerchief hydrogen quartzy tubular vessel of (containing 0.05～1% volume ratio steam) one, put into the diamond fine powder of decolorizing carbon fine powder and a spot of 1 micron diameter, the temperature of reaction of whole quartz container remains on 800～1223K, makes the hydrogen discharge in the quartz container form plasma body with the 13.56MHz radio-frequency generator with the method for high-frequency induction.Rotate or stir quartzy tubular vessel, per minute 20～60 changes (inferior), the interior solid fines of container is in constantly stirs or quick condition, and through 0.5～5 hour, raw material decolorizing carbon fine powder was transformed into product diamond fine powder.Confirm to obtain the good diamond fine powder of quality with X-ray diffraction and electron microscopic observation, single crystal particle and polycrystalline particle are arranged, the particle dia of the diamond fine powder of generation is at 5～50 micrometer ranges.
Embodiment two:
Be equipped with in the quartzy sealed vessel of energising tungsten filament one, put into diameter less than the silica flour of 500 microns graphite fine powder and 1% weight ratio to promote diamond fine powder nucleation, be filled with hydrogen in the container, the tungsten filament temperature is 2000～2200K, container inner pressure is 5 * 10
3～5 * 10
4Handkerchief, quartz container then remain on 1073～1273K, and with 50～100 rev/mins, constantly rotating quartz container constantly stirs solid-state fine powder, after 2～20 hours, obtain the product bort(z), reaction product detects proof through X-ray diffraction and obtains diamond crystal.Use the Raman spectral detection, at 1333cm
-1There is very precipitous peak at the place, shows to obtain the measured diamond of matter really.
Claims (4)
1, a kind ofly prepares adamantine method from graphite or carbonaceous solid matter, under the low-voltage high-temperature condition, prepare, it is characterized in that the powder of graphite or carbonaceous solid matter is placed in the reactor, be filled with the mixed gas of hydrogen or hydrogen and oxydant gas or hydrogen and hydrocarbon polymer in the reactor, gaseous tension 50～10
6Handkerchief, temperature of reaction 700～1273K, solid powder/particle constantly stir in reactor or float, and the gas excitation energy in the reactor is introduced 0.5～50 hour reaction times with the form of heating element or plasma body.
2, prepare adamantine method according to claim 1 is described from graphite or carbonaceous solid matter, it is characterized in that can the rotational response device, speed be 4～100 change (inferior)/minute.
3, prepare adamantine method according to claim 1 is described from graphite or carbonaceous solid matter, it is characterized in that gas can be single hydrogen in the reactor, also can be the hydrogen gas mixture that contains the oxydant gas of 0.1～10% atomic ratio or contain the hydrocarbon polymer of 0.2～2% volume ratio.
4, prepare adamantine method according to claim 1 is described from graphite or carbonaceous solid matter, the powder size that it is characterized in that graphite or carbonaceous solid matter is 10～500 micrometer ranges.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93112537A CN1036061C (en) | 1993-08-23 | 1993-08-23 | Preparation of diamond from graphite or carbonaceous solid matter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93112537A CN1036061C (en) | 1993-08-23 | 1993-08-23 | Preparation of diamond from graphite or carbonaceous solid matter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1084489A true CN1084489A (en) | 1994-03-30 |
| CN1036061C CN1036061C (en) | 1997-10-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93112537A Expired - Fee Related CN1036061C (en) | 1993-08-23 | 1993-08-23 | Preparation of diamond from graphite or carbonaceous solid matter |
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| CN (1) | CN1036061C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093084C (en) * | 1999-11-11 | 2002-10-23 | 袁德祎 | Method for regenerating diamond with waste material |
| CN103482623A (en) * | 2013-09-05 | 2014-01-01 | 大连理工大学 | Method for preparing nano diamonds by using direct-current arc process |
| CN101679041B (en) * | 2008-02-06 | 2014-01-29 | 住友电气工业株式会社 | Polycrystalline diamond |
| CN104884385A (en) * | 2012-12-05 | 2015-09-02 | 剑桥企业有限公司 | Method for producing synthetic diamonds |
| CN106744931A (en) * | 2016-12-09 | 2017-05-31 | 哈尔滨工业大学 | A kind of method that plasma etching graphite prepares diamond particles |
| WO2019085558A1 (en) * | 2017-11-02 | 2019-05-09 | 长沙新材料产业研究院有限公司 | Method for treating gemstone, and modified gemstone |
| CN112877773A (en) * | 2021-01-13 | 2021-06-01 | 哈尔滨工业大学 | Non-air-flow MPCVD single crystal diamond growth method using solid carbon source |
-
1993
- 1993-08-23 CN CN93112537A patent/CN1036061C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093084C (en) * | 1999-11-11 | 2002-10-23 | 袁德祎 | Method for regenerating diamond with waste material |
| CN101679041B (en) * | 2008-02-06 | 2014-01-29 | 住友电气工业株式会社 | Polycrystalline diamond |
| CN104884385A (en) * | 2012-12-05 | 2015-09-02 | 剑桥企业有限公司 | Method for producing synthetic diamonds |
| CN103482623A (en) * | 2013-09-05 | 2014-01-01 | 大连理工大学 | Method for preparing nano diamonds by using direct-current arc process |
| CN103482623B (en) * | 2013-09-05 | 2015-06-24 | 大连理工大学 | Method for preparing nano diamonds by using direct-current arc process |
| CN106744931A (en) * | 2016-12-09 | 2017-05-31 | 哈尔滨工业大学 | A kind of method that plasma etching graphite prepares diamond particles |
| CN106744931B (en) * | 2016-12-09 | 2018-11-02 | 哈尔滨工业大学 | A kind of method that plasma etching graphite prepares diamond particles |
| WO2019085558A1 (en) * | 2017-11-02 | 2019-05-09 | 长沙新材料产业研究院有限公司 | Method for treating gemstone, and modified gemstone |
| CN112877773A (en) * | 2021-01-13 | 2021-06-01 | 哈尔滨工业大学 | Non-air-flow MPCVD single crystal diamond growth method using solid carbon source |
| CN112877773B (en) * | 2021-01-13 | 2022-05-24 | 哈尔滨工业大学 | Non-air-flow MPCVD single crystal diamond growth method using solid carbon source |
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| Publication number | Publication date |
|---|---|
| CN1036061C (en) | 1997-10-08 |
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