CN104294366B - Cultivation method of centimeter-level HMX monocrystals - Google Patents
Cultivation method of centimeter-level HMX monocrystals Download PDFInfo
- Publication number
- CN104294366B CN104294366B CN201410535044.4A CN201410535044A CN104294366B CN 104294366 B CN104294366 B CN 104294366B CN 201410535044 A CN201410535044 A CN 201410535044A CN 104294366 B CN104294366 B CN 104294366B
- Authority
- CN
- China
- Prior art keywords
- temperature
- hmx
- crystal
- conical flask
- stage
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
Abstract
The invention belongs to the technical field of cultivating HMX crystals, and particulalry relates to a cultivation method of centimeter-level HMX monocrystals, mainly aiming to solve the problems that crystals in the current HMX monocrystals cultivation are small in size and more in deflects. The cultivation method of centimeter-level HMX monocrystals comprises the following steps: (1) preparing an HMX saturated solution in acetonitrile, filtering and collecting filtrate into a conical flask, and sealing the conical flask into an incubator; (2) cooling, namely in the first-stage, cooling the preparation temperature to 45DEG C at the speed of 1DEG C/30min, in the second stage, cooling to 40DEG C from 45DEG C at the speed of 1DEG C/1h, in the third stage, cooling to 28DEG C from 40DEG C at the speed of 0.1DEG C/5min-0.1DEG C/10min, and in the fourth stage, cooling to room temperature from 28DEG C at the speed of 0.1DEG C/10min-0.1DEG C/30min; and (3) standing for 24-48h after cooling to room temperature.
Description
Technical field
The invention belongs to HMX crystal cultural method technical field is and in particular to a kind of culture of Centimeter Level HMX monocrystalline
Method.
Background technology
RDX (rdx) and HMX (hmx) are most widely used two kinds of explosives at present.Rdx is also known as ring three methylene
Base trintriamine, it is clear crystal, 205～206 DEG C of fusing point, relative density 1.816g/cm3(20.4 DEG C), water insoluble, micro-
It is dissolved in ether and ethanol, slightly higher in acetone and chlorobenzene, more soluble in the ring ethyl ketone heating, nitrobenzene and second triol.Black
The mechanical sensitivity such as the shock of Suo Jin and friction is larger, has been applied to manufacture detonator, booster gains and primacord, and has been widely used as pushing away
Enter agent and the high energy component of propellant powder, be the conventional high explosive using on our times.HMX (hmx) is a kind of violent
Explosive, scientific name cyclotetramethylene-tetranitramine, white granular crystallizes, molecular weight 296.2, and theoretical maximum density is 1.905g/cm3,
Apparent density is 1.89g/cm3, it is homologue with rdx, have tetra- kinds of crystal formations of α, β, γ, δ.Wherein beta-crystalline form is at normal temperatures and pressures
It is stable, α, γ crystal formation is metastable state, and δ crystal formation is unstable.β-hmx is most widely used, becomes more readily available reason
The crystalline form thought, is current using extensively and one of the preferable explosive of combination property.The research of explosive monocrystalline is mainly also concentrated mainly on this
Above two kinds of explosives, monocrystalline research needs monocrystalline to reach more than Centimeter Level, and zero defect.
The method of single crystal cultivation is varied, volatility process as slow in solvent, solvent-thermal method, diffusion method, cocrystallization method etc..Different
The physical and chemical performance of material is different, and the solubility in various solvents is different, so each crystal needs to explore is suitable for itself
The cultural method of big crystal.Inst. of Chemical Material, Chinese Inst. of Engineering Physics Li Hong treasure is using solvent evaporated method research within 2011
The growth of rdx monocrystalline, rdx crystallization solvent used has a great impact to crystal habit, the monocrystalline that the different growth of solvent obtains
Form may be far from it.In rdx single crystal growth process, for controlling crystal defect and solving the problems, such as stress concentration, they
By online concentration determination technology and interference the technical research growth mechanism of rdx crystal, the formation of defect and evolutionary process and
Influence factor, by adjusting and optimizing solution concentration, crystallization temperature, the crystallization condition such as evaporation rate of solvent it is achieved that to crystal
The control of quality.The method can obtain crystal mass preferable Centimeter Level rdx large single crystal under certain crystallization condition.But the party
Method is not suitable for the culture of Centimeter Level hmx crystal, cultivates hmx monocrystalline using solvent evaporation method, hmx monocrystalline and fails to grow up
Situation, maximum culture crystalline size is less than 1cm；Solvent is made respectively using acetonitrile, dimethylformamide and acetone, methyl alcohol and
Ether, as diffusion solvent, cultivates hmx monocrystalline using diffusion method, hmx crystalline size and can only achieve 4mm, and
How the flaw comprising is it is impossible to reach the application study of monocrystalline.
Therefore how to control defect in crystal growing process and stress concentration be single crystal cultivation key technology, existing due to there is polycrystalline
As large single crystal growth more than its monocrystalline particularly Centimeter Level is extremely difficult.
In falling temperature method, in the growth course of crystal, the height of solution temperature decides the speed of growth of crystal, also can change
The properties of crystalline matrix, the such as solvent solubility to solute, and then affect the final shape of crystal.When the temperature is low,
The solubility of solvent is less, and crystal growth is slower, and preferably, and the growth interface of now crystal is smooth to gained crystal homogeneity,
Its growth mechanism is layer growth, and growth rate is also anisotropic, makes gained crystal structure than more complete.When temperature is higher
When, solution viscosity reduces, and mass tranfer coefficient increases, and rate of crystalline growth is accelerated, and gained crystal homogeneity is poor, and now crystal
Growth interface roughening, growth mechanism also transitions into continuous growth, and growth rate is isotropic.So, solution starts
The temperature of cooling also has a significant impact to crystallization process.In addition, during falling temperature method culture monocrystalline, small temperature fluctuation is just
Enough to, in the crystal of growth, cause some non-uniform areas, for improving the integrality of crystal growth it is desirable to temperature-controlled precision to the greatest extent may be used
Can be high.Therefore falling temperature method controls the key of crystal growth is in the growth course of crystal, selects suitable rate of temperature fall, makes molten
Liquid is in all the time in metastable region and maintains suitable degree of supersaturation.
Content of the invention
Present invention is generally directed to there is a problem of in current HMX single crystal cultivation that crystalline size is little, flaw is many, provide a germplasm
Amount is well and size reaches the HMX monocrystal cultivation method of Centimeter Level.
The present invention is that the technical scheme taken that solves the above problems is:
The cultural method of Centimeter Level HMX monocrystalline of the present invention comprises the following steps:
(1) prepare HMX saturated solution first in acetonitrile solution, prepare temperature and be 50 DEG C～60 DEG C, and prepare temperature
The lower constant temperature of degree is stablized 1～2 hour, then temperature filtration at a temperature of preparing again, no more than 5 microns of the filter core aperture filtered,
Collect filtrate in clean conical flask, the filtrate in each conical flask is not less than 300ml, will be equipped with the conical flask sealing of filtrate,
It is put in incubator, setting culture the temperature inside the box is identical with saturated solution preparation temperature, and it is little that here stablizes 0.5～2 at a temperature of preparing
Shi Hou, starts to lower the temperature；
(2) cooling is divided into four-stage: the first stage: drops to 45 DEG C from preparing temperature, rate of temperature fall is 1 DEG C/30min；The
Two-stage: drop to 40 DEG C from 45 DEG C, rate of temperature fall is 1 DEG C/1h；Phase III: drop to 28 DEG C from 40 DEG C, rate of temperature fall is 0.1 DEG C
/ 5min～0.1 DEG C/10min, when filtrate temperature is in the range of 38 DEG C～36 DEG C, begins with crystal and separates out in conical flask；Fourth order
Section: drop to room temperature from 28 DEG C, rate of temperature fall is 0.1 DEG C/10min～0.1 DEG C/30min；
(3) placement 24～48h after filtrate temperature is reduced to room temperature in conical flask, you can obtain the Losec support that size reaches Centimeter Level
Modern monocrystalline.
The present invention adopts gradient cooling method, and whole incubation avoids shaking, and filtrate will stand, and last and about need just can obtain for 5 days
Hmx crystal to Centimeter Level.In order to reach bigger hmx crystal, may be selected when room temperature is relatively low, such as winter is carried out, by
In the volatility of acetonitrile, it is not suitable for improving the preparation temperature of saturated solution.But incubation needs strict control rate of temperature fall, fall
Warm speed is too fast, and nucleus precipitation quantity is more, and limited Dispersion of Solute Matter, in the crystal of too many quantity, is unfavorable for growing up of crystal；
Lowered the temperature slow, time-consuming power consumption, especially lowered the temperature between 40 DEG C～30 DEG C scopes slow, acetonitrile solution volatilizees, and wall built-up phenomenon,
I.e. crystal is not collected on the nucleus of bottom of bottle, but the gas-liquid interface of liquid level upper end separates out, and is attached to above bottle wall, also unfavorable
Growing up in crystal.The HMX monocrystalline of present invention culture, is more than 1 by crystal orientation analysis shows crystal growth largest face
Centimetre, and crystal regularity is good, crystal profile and growth crystal face are clear, and crystal is transparent, inside almost invisible defect.
Brief description
Fig. 1 is the picture of the HMX monocrystalline of the embodiment of the present invention 1 culture；
Fig. 2 is the picture of the HMX monocrystalline of the embodiment of the present invention 2 culture.
Specific embodiment
Embodiment 1
A kind of cultural method of Centimeter Level HMX monocrystalline, step is as follows:
(1) prepare HMX saturated solution first in acetonitrile solution, prepare temperature and be 50～60 DEG C, for ensureing Losec support
The saturation degree of modern saturated solution, at a temperature of preparing, constant temperature is stablized 1 hour, and then at a temperature of preparing, temperature filtration prevents temperature again
Degree reduces, and HMX separates out, and during filtration, filter core aperture is not more than 5 microns, collects filtrate in conical flask, each conical flask
In filtrate be not less than 300ml to ensure to have the solute of abundance to grow up for crystal, will be equipped with the conical flask sealing of filtrate, be put in training
In foster case, setting culture the temperature inside the box is identical with preparing temperature, after stablizing 1 hour, starts to lower the temperature, entirely at a temperature of preparing
Cooling incubation will ensure that incubator stands, it is to avoid shakes；
(2) cooling is divided into four-stage: the first stage: drops to 45 DEG C from preparing temperature, rate of temperature fall is 1 DEG C/30min；The
Two-stage: drop to 40 DEG C from 45 DEG C, rate of temperature fall is 1 DEG C/1h；Phase III: drop to 28 DEG C from 40 DEG C, rate of temperature fall is 0.1 DEG C
/ 5min, when filtrate temperature is in the range of 38 DEG C～36 DEG C, begins with crystal and separates out, the nucleus number of precipitation is at 2～5 in conical flask
When, the crystal mass of culture is optimal；Fourth stage: drop to room temperature from 28 DEG C, rate of temperature fall is 0.1 DEG C/10min；
(3) when in conical flask filtrate temperature be reduced to room temperature after place 24～48h, now HMX crystal substantially no longer grow up,
Maximum HMX crystal has reached the crystal of Centimeter Level, you can takes out, has the indefectible little crystal grain of 2～3mm size in conical flask
Can be as the crystal seed cultivating crystal next time.
The crystal preparing is shown in Fig. 1, is more than 1 centimetre by crystal orientation analysis shows crystal growth largest face, and crystal is regular
Property good, crystal profile and growth crystal face clear, crystal is transparent, inside almost invisible defect.
Embodiment 2
A kind of cultural method of Centimeter Level HMX monocrystalline, step is as follows:
(1) prepare HMX saturated solution first in acetonitrile solution, prepare temperature and be 50～60 DEG C, for ensureing Losec support
The saturation degree of modern saturated solution, at a temperature of preparing, constant temperature is stablized 2 hours, and then at a temperature of preparing, temperature filtration prevents temperature again
Degree reduces, and HMX separates out, and during filtration, filter core aperture is not more than 5 microns, collects filtrate in conical flask, each conical flask
In filtrate be not less than 300ml to ensure to have the solute of abundance to grow up for crystal, will be equipped with the conical flask sealing of filtrate, be put in training
In foster case, setting culture the temperature inside the box is identical with preparing temperature, after stablizing 2 hours, starts to lower the temperature, entirely at a temperature of preparing
Cooling incubation will ensure that incubator stands, it is to avoid shakes；
(2) cooling is divided into four-stage: the first stage: drops to 45 DEG C from preparing temperature, rate of temperature fall is 1 DEG C/30min；The
Two-stage: drop to 40 DEG C from 45 DEG C, rate of temperature fall is 1 DEG C/1h；Phase III: drop to 28 DEG C from 40 DEG C, rate of temperature fall is 0.1 DEG C
/ 10min, when filtrate temperature is in the range of 38 DEG C～36 DEG C, begins with crystal and separates out in conical flask, the nucleus number of precipitation is 2～5
When individual, the crystal mass of culture is optimal；Fourth stage: drop to room temperature from 28 DEG C, rate of temperature fall is 0.1 DEG C/30min；
(3) when in conical flask filtrate temperature be reduced to room temperature after place 24～48h, now HMX crystal substantially no longer grow up,
Maximum HMX crystalline size has reached Centimeter Level, you can take out, the indefectible little crystal grain having 2～3mm size in conical flask can
As the crystal seed cultivating crystal next time.
The crystal preparing is shown in Fig. 2, is more than 1 centimetre by crystal orientation analysis shows crystal growth largest face, and crystal is regular
Property good, crystal profile and growth crystal face clear, crystal is transparent, inside almost invisible defect.
Claims (1)
1. a kind of cultural method of Centimeter Level HMX monocrystalline, is characterized in that comprising the following steps:
(1) prepare HMX saturated solution first in acetonitrile solution, prepare temperature and be 50 DEG C～60 DEG C, and prepare temperature
The lower constant temperature of degree is stablized 1～2 hour, then temperature filtration at a temperature of preparing again, no more than 5 microns of the filter core aperture filtered,
Collect filtrate in clean conical flask, the filtrate in each conical flask is not less than 300ml, will be equipped with the conical flask sealing of filtrate,
It is put in incubator, setting culture the temperature inside the box is identical with saturated solution preparation temperature, and it is little that here stablizes 0.5～2 at a temperature of preparing
Shi Hou, starts to lower the temperature；
(2) cooling is divided into four-stage: the first stage: drops to 45 DEG C from preparing temperature, rate of temperature fall is 1 DEG C/30min；The
Two-stage: drop to 40 DEG C from 45 DEG C, rate of temperature fall is 1 DEG C/1h；Phase III: drop to 28 DEG C from 40 DEG C, rate of temperature fall is 0.1 DEG C
/ 5min～0.1 DEG C/10min, when filtrate temperature is in the range of 38 DEG C～36 DEG C, begins with crystal and separates out in conical flask；Fourth order
Section: drop to room temperature from 28 DEG C, rate of temperature fall is 0.1 DEG C/10min～0.1 DEG C/30min；
(3) placement 24～48h after filtrate temperature is reduced to room temperature in conical flask, that is, obtain the HMX monocrystalline of Centimeter Level.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410535044.4A CN104294366B (en) | 2014-10-11 | 2014-10-11 | Cultivation method of centimeter-level HMX monocrystals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410535044.4A CN104294366B (en) | 2014-10-11 | 2014-10-11 | Cultivation method of centimeter-level HMX monocrystals |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104294366A CN104294366A (en) | 2015-01-21 |
| CN104294366B true CN104294366B (en) | 2017-01-18 |
Family
ID=52314307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410535044.4A Expired - Fee Related CN104294366B (en) | 2014-10-11 | 2014-10-11 | Cultivation method of centimeter-level HMX monocrystals |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104294366B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111498874B (en) * | 2020-02-21 | 2022-10-04 | 天津大学 | Large-particle-size cesium iodide spherical crystal and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE451718B (en) * | 1984-04-04 | 1987-10-26 | Nobel Kemi Ab | SET TO RECRISTALIZE THE EXPLOSIVES OCTOGEN AND HEXOGEN |
| US4785094A (en) * | 1986-09-26 | 1988-11-15 | Morton Thiokol, Inc. | Crystallization of beta HMX |
| US6841016B1 (en) * | 2000-03-02 | 2005-01-11 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Process for the production of crystalline energetic materials |
| CN102320903B (en) * | 2011-06-16 | 2013-11-06 | 中国工程物理研究院化工材料研究所 | Method for preparing high-quality energetic crystal material fine particles |
| CN102887870B (en) * | 2012-09-22 | 2015-07-15 | 山西北化关铝化工有限公司 | Octogen for detonating tube |
| CN102924396B (en) * | 2012-10-25 | 2013-11-27 | 中国工程物理研究院化工材料研究所 | Method for crystal transformation from alpha-HMX to beta-HMX |
-
2014
- 2014-10-11 CN CN201410535044.4A patent/CN104294366B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104294366A (en) | 2015-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109234795A (en) | A kind of crystal growth control method, device, system and computer storage medium | |
| CN105483825A (en) | Preparation method of bromine-lead-cesium single crystals | |
| CN108193271A (en) | Preparation Method is melted in a kind of area that moves horizontally of bromine lead caesium monocrystalline | |
| CN103173850A (en) | Monocrystalline silicon producing process | |
| CN104630878A (en) | Method for preparing large-sized slablike Ce<3+> ion doped rare-earth orthosilicate-series scintillation crystals through horizontal directional solidification | |
| CN104294366B (en) | Cultivation method of centimeter-level HMX monocrystals | |
| CN102691098B (en) | Growing method of sapphire crystal prepared by Kyropoulos method | |
| CN106283178A (en) | A kind of large scale Czochralski crystal growth design and control method | |
| CN110590565A (en) | Method for preparing highly-sphericized 1,1-diamino-2,2-dinitroethylene crystals | |
| CN102703970A (en) | Kyropous method growth of titanium doped sapphire crystals | |
| WO2009140406A3 (en) | Crystal growth apparatus for solar cell manufacturing | |
| CN109326333B (en) | Method for rapidly growing rare earth crystal optical fiber by using micro-pulling-down method | |
| CN102383189B (en) | Preparation method for lead zinc niobate-lead titanate monocrystal | |
| CN105418619A (en) | Special hexanitrohexaazaisowurtzitane preparation method | |
| CN103305911B (en) | Large size Re:YAP series laser crystal horizontal orientation solidifies preparation method | |
| CN110067024A (en) | Photoelectric functional crystal M3RE(PO4)3And preparation method thereof | |
| CN104264213A (en) | EFG (edge-defined film-fed growth) device of large-size doped sapphire crystals and growth process thereof | |
| CN102199160B (en) | A kind of method preparing I type bisulfate clopidogrel | |
| CN102191536A (en) | Method for controlling crystallization and nucleation on crucible bottom when using directional solidification method to grow silicon crystal | |
| CN107488874A (en) | A kind of design method of temperature field structure for rare earth crystal growth technique and the growth technique of low-cost rare earth crystal | |
| CN100422393C (en) | Temperature gradient method rotary multiple crucible crystal growth system | |
| CN102560678B (en) | A kind of method that stray crystal occurs in suppression 4-(4-dimethylaminostyryl) picoline tosilate crystal growing process | |
| CN104630875A (en) | Novel environment-friendly and energy-saving growth method of large-sized blocky information storage ferroelectric single crystals | |
| CN105439980A (en) | Hydrobromide paroxetine-sec-butyl alcohol compound and preparation method thereof | |
| CN104005082A (en) | Growth technology for large-size Ce:YAP scintillation crystals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170118 Termination date: 20181011 |