CN100336583C - Assembled mould for liquid phase reaction, phase conversion and preparation of porous solidified body - Google Patents
Assembled mould for liquid phase reaction, phase conversion and preparation of porous solidified body Download PDFInfo
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- CN100336583C CN100336583C CNB2005100443231A CN200510044323A CN100336583C CN 100336583 C CN100336583 C CN 100336583C CN B2005100443231 A CNB2005100443231 A CN B2005100443231A CN 200510044323 A CN200510044323 A CN 200510044323A CN 100336583 C CN100336583 C CN 100336583C
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Abstract
The present invention relates to an assembled mould for liquid phase reaction, phase conversion and the preparation of a porous solidification body. The assembled mould comprises an external cylinder of the mould, an internal cylinder of the mould, sealing plugs of the internal cylinder, a sealing ring of the internal cylinder, a pressure ring of the sealing plugs, an internal pressure transmission piston, a sealing ring of the external cylinder, and an external pressure transmission piston, wherein the middle part of the internal cylinder is provided with the two sealing plugs of the internal cylinder which are correspondingly installed; a space which is used for storing liquid is formed between the two sealing plugs of the internal cylinder; the external sides of the sealing plugs of the internal cylinder are respectively provided with the sealing ring of the internal cylinder and the pressure ring of the sealing plugs; the internal cylinder which is provided with the sealing plugs of the internal cylinder, the sealing ring of the internal cylinder, and the pressure ring of the sealing plugs is sheathed in the external cylinder of the mould; both ends in the external cylinder are respectively provided with the internal pressure transmission piston and the external pressure transmission piston; the sealing ring of the external cylinder is arranged between the internal pressure transmission piston and the external pressure transmission piston, and the external surface of the external cylinder of the mould is provided with a heating pipe. By the mould, new substances and new phases which can not be prepared under the usual conditions can be obtained, and the mould can also be used for preparing the porous solidification body. The present invention has wide application in the fields of the preparation of new materials, chemical industry production, the development of novel functional materials and devices, etc.
Description
(1) technical field:
The present invention relates to a kind of mould, particularly a kind of assembling die that is used for liquid phase reactor, phase transition and preparation porous firming body.
(2) background technology:
HTHP phase transition method plays considerable effect in preparation new material process, obtained at present using widely.Except cubic boron nitride and diamond that people know, also have considerable unique construction and functional material all to obtain by this method.Up to the present, people drop into lot of manpower and material resources aspect the synthetic new material of HTHP, and make this method obtain considerable progress.But, the distinct disadvantage that this method exists is to need to use large-scale high-tension apparatus, experiment condition is very harsh, has therefore also just caused the inherent defect of the low output of high investment, and feasible 26S Proteasome Structure and Function material as excellent performances such as cubic boron nitride and diamonds is difficult to be used widely.If above-mentioned phase transition process is transferred in the liquid phase environment, utilize liquid system to have isotropic nature, help stablizing the characteristics of high symmetry thing phase, be hopeful to reduce significantly phase transition temperature and pressure fully.In addition, by the choose reasonable liquid component, make solid matter at first dissolve and enter liquid phase, make it to separate out again applying under certain temperature and pressure condition, promptly experience the transition process of solid-state → liquid (dissolving) → solid-state (heavily separating out), the phase transition process that originally need could realize under HTHP is finished under quite gentle condition, thus the reduce superhard material significantly preparation cost of (for example diamond and cubic boron nitride etc.).Simultaneously, because liquid phase environment provides an extremely beneficial place for the growth of superhard material, therefore use this method also can access large-sized superhard material crystal, and can't accomplish with solid-state high temperature and high pressure method.
In order to obtain having the material of special construction and character, in people explore the process of new material, use various extreme conditions morely, wherein hydro-thermal and solvent process for thermosynthesizing use exactly two kinds of means more widely.Utilize hydrothermal synthesis method, prepared a large amount of 26S Proteasome Structure and Function materials now, wherein the most representative with synthesizing of quartz crystal and micropore/mesoporous material.Solvent thermal process is the new method that grew up in recent years, it is bringing into play important effect aspect the preparation of non-oxidized substance nano material, utilize this method successfully to synthesize multiple nano powder, line, tube materials such as comprising gallium nitride, cubic boron nitride, boride, carbide, and its range of application is also in rapid expansion.
For the liquid phase reaction course under the researching high-temperature high pressure extreme condition, prepare difficult to obtain material under the serial usual conditions, people update at the material and the design aspect of reactor, make the limiting temperature of hydro-thermal and solvent thermal reaction and pressure improve constantly.But, up to the present, still there is the more shortcoming that is difficult to overcome in autoclave, comprise: have fixing contact between the temperature and pressure that limiting temperature that can reach when utilizing reactor to react and pressure still dislike lower, reactor is interior, can't independent modulation, and in reactor, can only carry out a kind of liquid reaction of form, can't realize the former bit combination of multiple reaction formation.
But the porous firming body is owing to have suitable mechanical strength, big specific area, high surface-active and the aperture of modulation in quite on a large scale, be worth having important use aspect the development of absorption, catalysis, chemical industry, environmental protection, medical treatment, composite functional material and sensitive material, porous nano solid wherein is the outstanding person in this class material especially.The porous nano solid also has some unique advantages except the advantage with general porous material, for example, surface-active is higher, has the dual quantum limitation effect in nano particle inside and the duct, makes the adjustable relict ground of material property bigger etc.In environmental protection and Chemical Manufacture, the porous nano solid is desirable adsorbent and catalyst, and it not only is easy to reclaim, and has eliminated the secondary pollution problem; Aspect the Sensitive Apparatus development, the porous nano solid is owing to have high surface-active and big specific area, and the variation of environment is very responsive to external world, can make high performance sensor with it; In the development of photoelectricity composite functional material, the dual quantum limitation effect of porous nano solid and high surface make it easier and form strong chemical bond with second phase material, and to the very strong quantum limitation effect of second phase material generation, thereby produce new character and function, lay the foundation for developing diversified composite function nano material.
Have purposes extremely widely just because of the porous firming body, people have been developed multiple preparation method having carried out a large amount of system explorations aspect this class preparation methods.These preparation methods can be divided into three big classes: the one, and high temperature pore forming method, the 2nd, the template assemble method in the solution, the 3rd, hydro-thermal hot-press method.Though wherein the high temperature pore forming method can obtain the sintered body of certain intensity, in sintering process, be difficult to growing up of control nano particle, and the stability as the nano particle of raw material is had higher requirements; The advantage of the template assemble method in the solution is to obtain the porous material that the aperture is even, the duct is regularly arranged (for example molecular sieve), but the adjustable sex change of the aperture of porous material that this method obtains is very poor, and is difficult to obtain the porous material of macropore and ultra-large aperture.This method another one shortcoming is can only obtain pulverous material at present; The hydro-thermal hot-press method then is a kind of low-temperature sintering forming method, and it has the advantage that the sample preparation temperature is low, condition is easy to control, and can obtain having the solid of higher mechanical strength.But the material system that this method is suitable for is less, and for the addition of liquid pore creating material strict restriction is arranged, for practical application brings a lot of inconvenience.For overcoming these shortcomings, we had once developed a kind of controlled gasifying solvent hot-press method, had successfully prepared multiple porous nano solid.
Realize the liquid phase reactor and the preparation porous firming body of solid matter, most critical be exactly special container---Mould design.Also do not have at present to find and the similar mould of the present invention, do not see similar research paper and patented technology yet.
(3) summary of the invention:
For overcoming the defective of prior art, the invention provides a kind of assembling die that is used for liquid phase reactor, phase transition and preparation porous firming body.Utilize this assembling die, can realize the phase transition process in the HTHP liquid phase environment, realize the preparation low-cost in enormous quantities of superhard material such as cubic boron nitride and diamond and body piece crystal thereof; When being applied to liquid phase reactor, fluid pressure can reach thousands of even up to ten thousand atmospheric pressure at an easy rate, temperature then from room temperature until thousands of degrees centigrade, and liquid reactive temperature and pressure can regulate independently of each other, and can finish high pressure liquid phase reaction and solid-state hot pressing simultaneously; In addition, this assembling die can also be applied to prepare porous firming body (comprising the porous nano solid), not only make the addition of liquid pore creating material not be subjected to any restriction, and can be combined into one the template-mediated pore forming process of mesoporous material and controlled gasifying solvent hot pressing, once finish.
A kind of liquid phase reactor that is used for, the assembling die of phase transition and preparation porous firming body, comprise the mould urceolus, the mould inner core, the inner core sealing-plug, the inner core sealing ring, the sealing-plug pressure ring, interior pressure transmission piston, urceolus sealing ring and outer pressure transmission piston, in the middle of the mould inner core two inner core sealing-plugs of installing relatively, it between two inner core sealing-plugs a space that is used to hold liquid sample, the inner core sealing-plug outside is provided with inner core sealing ring and sealing-plug pressure ring successively, and the inner core sealing-plug is housed, the mould inner core of inner core sealing ring and sealing-plug pressure ring is sleeved in the mould urceolus; Pressure transmission piston and outer pressure transmission piston in two ends are respectively equipped with in the mould urceolus, be provided with the urceolus sealing ring between interior pressure transmission piston and the outer pressure transmission piston, interior pressure transmission piston outside between pressure transmission piston and sealing-plug pressure ring, the inner core sealing-plug, pressure transmission piston in the pressure that press produces is passed to by outer pressure transmission piston, and be delivered on sealing-plug pressure ring and the inner core sealing-plug by interior pressure transmission piston, fluid sample is exerted pressure, and simultaneously interior pressure transmission piston pushes the sealing that the urceolus sealing ring is realized urceolus with outer pressure transmission piston; The outer tube outer surface of mould is provided with heating tube.
According to the requirement of operating pressure, the mould urceolus can be a single layer structure, also can be bilayer or sandwich construction.
Inner core sealing ring and urceolus sealing ring can be the single layer structures that is made of softer material, also can be by two kinds of soft, that hardness is different two-layer composites that material constitutes.
The inner core sealing-plug that is made of the heat resisting corrosion-proof corrosion material is provided with screw rod, and this screw rod passes the sealing-plug pressure ring, inner core sealing-plug, inner core sealing ring is fixedlyed connected with sealing-plug pressure ring three on screw rod with the pretension nut driving to be integral.
Part central authorities near interior pressure transmission piston on the outer pressure transmission piston that is made of the withstand voltage material of high strength are provided with a circular holes.
On the interior pressure transmission piston that constitutes by the withstand voltage material of high strength near the part central authorities of sealing-plug pressure ring, inner core sealing-plug and be provided with the space that is used for storaging liquid on every side, part central authorities near outer pressure transmission piston on the interior pressure transmission piston are provided with one and interior pressure transmission piston all-in-one-piece cylinder, after the installation, this cylinder is positioned at the part central, circular hole of close pressure transmission piston on the outer pressure transmission piston.
The major function of each parts of the present invention is as follows:
1, the mould urceolus of sandwich construction comprises skin and internal layer, and is outer to power that compresses in advance of internal layer generation, so that strengthen the anti-pressure ability of internal layer.Ectonexine can be processed with identical materials, also can be with different materials processing.Ordinary circumstance is the internal layer high material of hardness, and the strong materials processing of outer use resistance to tension.Superficies are set up heating tube, are used to mold heated.The main effect of urceolus is for inner core provides support, and makes it to be unlikely to when bearing high pressure distortion.
2, the effect of mould inner core is under the support of urceolus, constitutes an airtight space with the sealing-plug at two ends, is liquid reactive main container.The general use of inner core is heat-resisting, corrosion-resistant material processing.
3, inner core sealing-plug, inner core sealing ring and sealing-plug pressure ring form a combination sealing system by the fixedlying connected of screw rod on the inner core sealing-plug and pretension nut.A same cover combination sealing system is placed on the other end symmetry ground of mould inner core, and combination sealing system that two covers are staggered relatively and mould inner core are formed an airtight reaction vessel jointly.
When carrying out liquid reaction under high pressure, the inner core sealing ring need use the materials processing of higher-strength, so that effectively liquid is sealed; On the contrary, when needs prepared the block materials of porous, the inner core sealing ring needed the lower materials processing of working strength, so that solvent can be extruded from inner core smoothly in the later stage of experimentation.
4, interior pressure transmission piston generally is to process with the higher pressure-resistant material of intensity, its effect has two: the one, and the pressure that press is produced is delivered on sealing-plug pressure ring and the inner core sealing-plug, fluid sample is exerted pressure, the 2nd, push the urceolus sealing ring with outer pressure transmission piston, realize the sealing of urceolus.In addition, part central authorities and the space on every side thereof near sealing-plug pressure ring, inner core sealing-plug is used for storing the liquid that is extruded from inner core on interior pressure transmission piston.
5, outer pressure transmission piston also is to be processed by the higher pressure-resistant material of intensity, main effect is: one, the pressure that press is produced passes to urceolus sealing ring and interior pressure transmission piston in mould, the 2nd, push the urceolus sealing ring with interior pressure transmission piston, make it to realize sealing all around to urceolus to expanding.
Assembling die of the present invention before use, at first the inner core sealing ring is enclosed within on the inner core sealing-plug, make the screw rod at inner core sealing-plug middle part pass circular hole on the sealing-plug pressure ring then, then be screwed into the pretension nut on the screw rod at inner core sealing-plug middle part and tighten slightly, again pack into an end of mould inner core of the inner core sealing-plug that combines, inner core sealing ring and sealing-plug pressure ring, tighten pretension nut 12 once more and inner core sealing ring 11 is outwards expanded and the end envelope of mould inner core is tight; After in inner core, adding sample, again according to the aforesaid operations process the other end good seal of mould inner core.
The cylinder of pressure transmission piston passes the middle circular hole of urceolus sealing ring in making, pierce into the middle circular holes of outer pressure transmission piston again, an end of this combiner being put into the mould urceolus fixes, then the inner core of good seal is put into urceolus from the other end of urceolus, again the combiner of being made up of interior pressure transmission piston, urceolus sealing ring and outer pressure transmission piston is put into the other end of mould urceolus and fix, being available forcing press applies the temperature of suitable pressure, control mould to mould, begins experiment.
The present invention has following feature:
The mould urceolus adopts individual layer or sandwich construction, can use single layer structure when operating pressure is relatively lower, and when mould need be worked, needs to use the multiple layer combination structure under higher pressure.Urceolus generally uses high-strength material processing.In addition,, make mould go for chemical reaction and material preparation process under the multiple extreme condition, and change and clean very convenient at the urceolus of mould the inside lining inner core.Inner core uses the materials processing of heat-and corrosion-resistant, and requires to have suitable intensity.
Mould uses the combination sealing mode, and the material preparation process is carried out under solid conditions, also can prepare material under liquid-phase condition.Simultaneously, can also when preparation porous firming body, solvent be discharged with controlled manner, obtain the better porous firming body of performance by changing the kind of inner/outer tube sealing ring.
After the inner core sealing-plug of mould passes the sealing-plug pressure ring, with the tension of pretension nut, the inner core sealing ring is expanded in advance and be adjacent to the inner core inwall, thereby fluid sample is implemented effective seal.
When mould is used for liquid phase phase transformation under the high-temperature and high-pressure conditions and liquid phase compound experiment, the inner/outer tube sealing ring need use material (for example plastics, graphite and the mild alloy etc.) processing with higher melt and intensity, makes liquid non-leakage so that can bear harsh experiment condition; When being used for the experiment of original position liquid reaction and curing molding, the intensity of inner core sealing ring should be lower than the urceolus sealing ring.At this moment, under low slightly pressure, carry out liquid phase reactor and liquid phase phase transition process in advance, treat that this process is finished after, liquid is discharged after improving pressure from sample, then carry out solid-phase sintering and crystallisation procedure does.When mould was used to prepare the porous firming body, the inner core sealing ring used elasticity flexible material manufacturing preferably, and urceolus then can be used the higher material manufacturing of intensity.Like this, can in inner core, finish controlled pore-creating process, and then after suitably improving pressure liquid be extruded from inner core, finish solidification process.
Utilize assembling die of the present invention, the aperture uniformity and the porosity of sample have not only obviously been improved, and can regulate and control the arrangement mode of duct in sample artificially, make the range of application of porous firming body expand to many frontiers such as development of microcavity opto-electronic device array.
(4) description of drawings:
Fig. 1 is the assembling effect figure of novel assembling die of the present invention.
Fig. 2 is the sectional side view of mould urceolus among the present invention.
Fig. 3 is the sectional side view of mould inner core among the present invention.
Fig. 4 is the profilograph of the pressure ring of inner core sealing usefulness among the present invention.
Fig. 5 (a) is the structural representation of single layer structure inner core sealing ring among the present invention.
Fig. 5 (b) is the structural representation of double-decker inner core sealing ring among the present invention.
Fig. 6 is the profilograph of inner core sealing-plug among the present invention.
Fig. 7 is the profilograph of the present invention's China and foreign countries' pressure transmission piston.
Fig. 8 (a) is the structural representation of single layer structure urceolus sealing ring among the present invention.
Fig. 8 (b) is the structural representation of double-decker urceolus sealing ring among the present invention.
Fig. 9 is the profilograph of interior pressure transmission piston among the present invention.
Wherein, 1, the urceolus sealing ring, 2, the internal layer of mould urceolus, 3, the skin of mould urceolus, 4, the mould inner core, 5, the inner core sealing-plug, 6, sealing-plug pressure ring, 7, outer pressure transmission piston, 8, interior pressure transmission piston, 9, be used for the space of storaging liquid, 10, hold the space of liquid sample, 11, inner core sealing ring, 12, the pretension nut, 13, heating tube.
(5) specific embodiment:
Below in conjunction with specific embodiment the structure of mould of the present invention and using method thereof and purposes are further described:
Embodiment 1: structure of the present invention such as Fig. 1 are to shown in Figure 9, comprise mould urceolus 2 and 3, mould inner core 4, inner core sealing-plug 5, inner core sealing ring 11, sealing-plug pressure ring 6, interior pressure transmission piston 8, urceolus sealing ring 1 and outer pressure transmission piston 7, in the middle of the mould inner core 4 two inner core sealing-plugs of installing relatively 5, it between two inner core sealing-plugs 5 space 9 that is used for storaging liquid, the outside of inner core sealing-plug 5 is provided with inner core sealing ring 11 and sealing-plug pressure ring 6 successively, and inner core sealing-plug 5 is housed, the mould inner core 4 of inner core sealing ring 11 and sealing-plug pressure ring 6 is sleeved in mould urceolus 2 and 3; Pressure transmission piston 8 and outer pressure transmission piston 7 in two ends are respectively equipped with in the mould urceolus are provided with urceolus sealing ring 1 between interior pressure transmission piston 8 and the outer pressure transmission piston 7, and the outer tube outer surface of mould is provided with heating tube 13.
The inner core sealing-plug 5 that is made of the heat resisting corrosion-proof corrosion material is provided with screw rod, and this screw rod passes sealing-plug pressure ring 6, is screwed on the screw rod inner core sealing-plug 5, inner core sealing ring 11 fixedlyed connected with sealing-plug pressure ring 6 threes with pretension nut 12 to be integral.Outer pressure transmission lower part of piston central authorities are provided with a circular holes, be provided with the space that is used for storaging liquid around interior pressure transmission piston lower central and the bottom, center upper portion is provided with one and interior pressure transmission piston all-in-one-piece cylinder, and after the installation, this cylinder is positioned at the circular holes of outer pressure transmission piston lower central.
The mould urceolus adopts single layer structure, and inner core sealing ring and urceolus sealing ring all use softer material polytetrafluoroethylene (PTFE) processing, and the liquid phase reactor of utilizing this mould to carry out under pressure＜200MPa condition is tested.At this moment the inner core sealing ring is as the primary seal circle, and liquid reaction carries out in inner core fully; The urceolus sealing ring is then made auxiliary seal usefulness, so that prevent that liquid sample is under pressure to external leakage.
Embodiment 2: with embodiment 1, difference is that the mould urceolus adopts single layer structure, low-intensity material silicon rubber processing during the inner core sealing ring uses, the urceolus sealing ring uses the material polytetrafluoroethylene (PTFE) processing of higher-strength, and this moment, mould was used to prepare the porous nano firming body.During experiment, at first packing in the inner core with the nano particle of solvent mixing, assemble mould after, pressure is set in lower numerical value, simultaneously sample is heated.Temperature and pressure improved pressure the inner core sealing ring was lost efficacy after constant a period of time, and solvent is extruded out, and solid particle under pressure 60～200MPa condition, forms the aperture at mesoporous porous firming body in the macropore scope 180～250 ℃ of temperature.
Embodiment 3: with embodiment 1, difference is that the mould urceolus adopts single layer structure, the processing of inner core sealing ring use soft graphite, the processing of urceolus sealing ring use mild alloy.This moment, mould was used for liquid phase phase transformation and the in-situ sintering experiment under the mesolow power.During experiment, at first even solid particle and solvent, place inner core then, after sealing and assembling mould, pressure is set in 90～150MPa, simultaneously sample is heated.Temperature and pressure improved temperature and pressure the inner core sealing ring was lost efficacy after constant a period of time, and solvent is extruded out, and solid particle becomes fine and close ceramic body at high temperature with in-situ sintering under the pressure acting in conjunction.
Embodiment 4: with embodiment 1, different is that the mould urceolus adopts double-decker, at this moment utilizes this mould can carry out the liquid phase high pressure compound experiment of pressure under 400～600MPa condition.
Embodiment 5: with embodiment 2, different is that the mould urceolus adopts double-decker, can utilize this mould to prepare the porous firming body of micropore in this case under pressure 360～500MPa condition.
Embodiment 6: with embodiment 1, different is that the mould urceolus adopts four-layer structure, and at this moment mould can be used for carrying out the liquid phase high pressure compound experiment of pressure under 600～1200MPa condition.
Embodiment 7: with embodiment 1, different is that the mould urceolus adopts four-layer structure, inner core and urceolus sealing ring all use composite sealing ring (Fig. 5 (b) and Fig. 8 (b)), and the mould of this structure can be used for the liquid phase super-pressure compound experiment under pressure＞1200MPa condition.
Embodiment 8: with embodiment 1, different is that the mould urceolus adopts four-layer structure, low-intensity material polytetrafluoroethylene (PTFE) processing during the inner core sealing ring uses, and composite sealing ring (Fig. 8 (b)) is used in the urceolus sealing.Utilize this mould can be under the high pressure of pressure＞500MPa and ultra-high pressure condition the porous firming body of preparation micropore.
Embodiment 9: with embodiment 8, urceolus sealing that different is is adopted is the single sealing ring of tube with high-strength material processing.
Embodiment 10: with embodiment 6, different is that urceolus adopts eight layers of structure, and the mould of this structure can use under the condition of operating pressure＞1500MPa.
Embodiment 11: with embodiment 7, different is that urceolus adopts eight layers of structure, and the mould of this structure can use under the condition of operating pressure＞1800MPa.
Embodiment 12: as the concrete application of mould of the present invention, we utilize this mould hydro-thermal reaction under high-temperature and high-pressure conditions to synthesize a cube BN.The concrete structure of mould therefor is in the experiment: the mould urceolus adopts two-layer composite, and the inner/outer tube sealing ring of mould is all processed with polytetrafluoroethylene (PTFE).The experiment detailed process is: the H of stoichiometric proportion
3BO
3, N
2H
4H
2O and NaN
3Dissolve in the water and after stirring, mixed solution is sealed in the mould inner core.After installing inner core sealing and with set of molds, mould is applied the pressure of 120MPa, simultaneously temperature was elevated to 300 ℃ of constant temperature after 8～10 hours, make mould naturally cool to room temperature and just can obtain the cubic boron nitride crystallite with forcing press.
Embodiment 13: as the concrete application example of another one of mould of the present invention, we utilize this mould hydro-thermal reaction under high-temperature and high-pressure conditions to synthesize a cube carbonitride.The concrete structure of mould therefor is in the experiment: the mould urceolus adopts three-layer composite structure, and the inner core sealing ring of mould is processed with polytetrafluoroethylene (PTFE), urceolus sealing ring polytetrafluoroethylene (PTFE) and soft graphite composite sealing ring.The experiment detailed process is: the CBr of stoichiometric proportion
4And NaN
3Dissolve in the water, stir fast after 20～30 minutes mixed solution is packed in the inner core, sealing.After entire die is assembled, on mould, apply the pressure of 250MPa, after 12～20 hours, make mould naturally cool to room temperature mold heated to 280～340 ℃ constant temperature simultaneously, so just can obtain a cube carbonitride crystallite.
Embodiment 14: utilize mould of the present invention hydro-thermal diamond synthesis under high-temperature and high-pressure conditions.The concrete structure of mould therefor is in the experiment: the mould urceolus adopts three-layer composite structure, and the inner core of mould and urceolus sealing ring all adopt polytetrafluoroethylene (PTFE) and mild alloy composite sealing ring.The experiment detailed process is: the K of stoichiometric proportion
2CO
3Dissolve in the water with laminar white phosphorus, stir fast after 20～30 minutes mixed solution is packed in the inner core, sealing.After entire die is assembled, on mould, apply the pressure of 250～400MPa, after 16～20 hours, make mould naturally cool to room temperature mold heated to 350～400 ℃ constant temperature simultaneously, so just can obtain diamond crystallites.
Embodiment 15: with embodiment 12, different is to have replaced water with benzene, uses BCl simultaneously
3And NaNH
2Replaced H
3BO
3, N
2H
4H
2O and NaN
3, so just can obtain a cube BN nanocrystal.
Embodiment 16: utilize mould of the present invention synthesis of cubic carbonitride under HTHP solvent heat condition.The concrete structure of mould is: urceolus adopts three-layer composite structure, and the inner core of mould and urceolus sealing ring all adopt polytetrafluoroethylene (PTFE) and soft graphite composite sealing ring.During experiment, at first with the CCl of stoichiometric proportion
4With NaN
3And Li
3The mixture of N mixes, and adds excessive 5～10 times CCl again
4Said mixture is packed into behind mould and the good seal, mould is applied the pressure of 350～450MPa, simultaneously with mold heated to 400 ℃ constant temperature 8 hours.Treat mold cools down after room temperature, just can obtain a cube NANO CRYSTALLINE CARBON NITRIDES.
Embodiment 17: with embodiment 16, difference is Li
3N is replaced by the metallic potassium with mole, can obtain the composite Nano crystal of diamond and cube carbonitride like this.
Embodiment 18: utilize mould of the present invention diamond synthesis under HTHP solvent heat condition.The concrete structure of mould is: urceolus adopts three-layer composite structure, and the inner core of mould and urceolus sealing ring all adopt polytetrafluoroethylene (PTFE) and mild alloy composite sealing ring.During experiment, at first with the Na of stoichiometric proportion
2C
2O
4Powder mixes in benzene with laminar white phosphorus, then this mixture is packed into behind mould and the good seal, and mould is applied the pressure of 450MPa, simultaneously with mold heated to 360 ℃ constant temperature 12 hours.Treat mold cools down after room temperature, just can obtain the diamond nano crystalline substance.
Embodiment 19: utilize mould of the present invention to realize the phase transition of boron nitride under the HTHP hydrothermal condition.The concrete structure of mould is: urceolus adopts four layers of composite construction, and the inner core of mould and urceolus sealing ring all adopt polytetrafluoroethylene (PTFE) and mild alloy composite sealing ring.In the experiment, after the hexagonal boron nitride crystallite fully ground, the saturated aqueous solution with ammonium borate mixed again, then sample was packed into behind mould and the good seal, mould is applied the pressure of 800～1200MPa, simultaneously with mold heated to 380～450 ℃ and constant temperature 20 hours.Treat mold cools down after room temperature, just can obtain the cubic boron nitride crystallite.
Embodiment 20: utilize mould of the present invention to realize the phase transition of graphite under the HTHP hydrothermal condition.The concrete structure of mould is: urceolus adopts five layers of composite construction, and the inner core of mould and urceolus sealing ring all adopt soft graphite and mild alloy composite sealing ring.In the experiment, after non-crystalline graphite fully ground, mix with deionized water again, then sample is packed into behind mould and the good seal, mould is applied the pressure of 1800～2500MPa, simultaneously with mold heated to 780～900 ℃ and constant temperature 6 hours.Treat mold cools down after room temperature, just can obtain diamond crystallites.
Embodiment 21: with embodiment 20, different is to have replaced amorphous graphite with the amorphous state carbonitride.
Embodiment 22: with embodiment 19, different is: replaced the saturated aqueous solution of ammonium borate with benzene, replaced the hexagonal boron nitride crystallite with nm-class boron nitride.
Embodiment 23: with embodiment 19, different is: use CCl
4The saturated aqueous solution that has replaced ammonium borate has replaced the hexagonal boron nitride crystallite with nano silicon nitride carbon.
Embodiment 24: utilize mould of the present invention can realize all the elements among the patent of invention ZL03111872.0 easily, prepare diversified porous nano firming body.
Embodiment 25: utilize mould of the present invention to prepare the duct and arrange orderly porous nano firming body.Because mould of the present invention can combine liquid reaction process and in-situ pore-formed and solidification process, once finishes, therefore amount of solvent is not subjected to any restriction when preparing the porous firming body.Utilize this advantage, we are incorporated into the pore forming process of mesoporous material in the preparation of porous firming body, obtain the porous nano firming body that arrange in order in the duct in conjunction with in-situ solidifying again.
The concrete structure of mould is: urceolus adopts double-decker, inner core sealing ring fluorubber and polytetrafluoroethylene (PTFE) composite sealing ring, and the urceolus sealing ring is then processed with polytetrafluoroethylene (PTFE).Experimentation is: at first alumina nano powder and water mixed, and the rare colloidal sol of furnishing, and then add surfactant (for example, CTAB etc.) according to the amount of 100 times of critical concentrations.Fully stir and, in the mould inner core of packing into, seal and entire die is assembled through after the ultrasonic dispersion.On mould, at first apply the pressure of 40～60MPa, make the temperature of mould slowly be elevated to 180～200 ℃ and constant temperature 24～36 hours then.Then pressure is brought up to 80～120MPa lentamente, temperature is elevated to 220～250 ℃.In this process, water and surfactant are come out by extruding from inner core, in the space of pressure transmission piston, then stay size even and regularly arranged aluminum oxide porous nanometer firming body in duct in the mould inner core in entering.
Embodiment 26: with embodiment 25, different is: replaced alumina nano powder with the silica nanometer powder, what obtain at last is the even and regularly arranged porous silica nanometer firming body of duct size.
Embodiment 27: with embodiment 25, different is: no longer add any surfactant in the liquid, and aluminium oxide nano pruinescence titanic oxide nano replaces.Can obtain pore size unanimity, spatial distribution so evenly and have a TiO 2 porous nanometer firming body of high porosity.
Embodiment 28: with embodiment 25, different is: no longer add any surfactant in the liquid, and aluminium oxide nano pruinescence zirconium dioxide nanometer powder replaces.Can obtain pore size unanimity, spatial distribution so evenly and have a zirconium dioxide porous nano firming body of high porosity.
Embodiment 29: with embodiment 25, different is: no longer add any surfactant in the liquid, and the oxidized zinc nano powder of alumina nano powder replaces.Can obtain pore size unanimity, spatial distribution so evenly and have a zinc oxide porous nano firming body of high porosity.
Embodiment 30: with embodiment 25, different is: no longer add any surfactant in the liquid, and aluminium oxide nano pruinescence hydroxyapatite nano powder replaces.Can obtain pore size unanimity, spatial distribution so evenly and have a hydroxyapatite porous nano firming body of high porosity.
Embodiment 31: utilize mould of the present invention to carry out the high-pressure liquid phase transformation and the in-situ sintering process study of boron nitride nanometer material.The mould urceolus adopts three-decker, and the inner core sealing ring is processed with soft graphite, and the urceolus sealing ring is processed with mild alloy.In the experimentation, at first boron nitride nanometer powder and CCl
4Mix and handle with ultrasonic wave, in the mould inner core of packing into then, sealing.After treating mould assembled, mould is applied the pressure of 160～220MPa, then the temperature of mould slowly is heated to 280 ℃ of also constant temperature 8～12 hours with forcing press.After this process is finished, again pressure is brought up to 650～800MPa gradually, simultaneously temperature is brought up to 1000～1200 ℃ of constant temperature 6～8 hours.
In said process, CCl
4Come out by extruding from inner core gradually, enter the gap of interior pressure transmission piston and decompose charing, the nanocrystalline crystalline quality of the cubic boron nitride in the inner core constantly improves, and is sintered into fine and close hard ceramic body.
Embodiment 32 is with embodiment 31, and different is: boron nitride nanometer pruinescence non-crystalline graphite replaces, and what obtain at last is fine and close hard Nano diamond sintered body.
Claims (6)
1, a kind of liquid phase reactor that is used for, the assembling die of phase transition and preparation porous firming body, it is characterized in that, comprise the mould urceolus, the mould inner core, the inner core sealing-plug, the inner core sealing ring, the sealing-plug pressure ring, interior pressure transmission piston, urceolus sealing ring and outer pressure transmission piston, in the middle of the mould inner core two inner core sealing-plugs of installing relatively, it between two inner core sealing-plugs a space that is used to hold liquid sample, the inner core sealing-plug outside is provided with inner core sealing ring and sealing-plug pressure ring successively, and the inner core sealing-plug is housed, the mould inner core of inner core sealing ring and sealing-plug pressure ring is sleeved in the mould urceolus; Pressure transmission piston and outer pressure transmission piston in two ends are respectively equipped with in the mould urceolus, be provided with the urceolus sealing ring between interior pressure transmission piston and the outer pressure transmission piston, interior pressure transmission piston outside between pressure transmission piston and sealing-plug pressure ring, the inner core sealing-plug, pressure transmission piston in the pressure that press produces is passed to by outer pressure transmission piston, and be delivered on sealing-plug pressure ring and the inner core sealing-plug by interior pressure transmission piston, fluid sample is exerted pressure, and simultaneously interior pressure transmission piston pushes the sealing that the urceolus sealing ring is realized urceolus with outer pressure transmission piston; The outer tube outer surface of mould is provided with heating tube.
2, a kind of assembling die that is used for liquid phase reactor, phase transition and preparation porous firming body as claimed in claim 1 is characterized in that according to the requirement of operating pressure, the mould urceolus can be a single layer structure, also can be bilayer or sandwich construction.
3, a kind of assembling die that is used for liquid phase reactor, phase transition and preparation porous firming body as claimed in claim 1, it is characterized in that, inner core sealing ring and urceolus sealing ring can be the single layer structures that is made of softer material, also can be the two layer composite structure up and down that is made of two kinds of soft, that hardness is different materials.
4, a kind of assembling die that is used for liquid phase reactor, phase transition and preparation porous firming body as claimed in claim 1, it is characterized in that, the inner core sealing-plug that is made of the heat resisting corrosion-proof corrosion material is provided with screw rod, this screw rod passes the sealing-plug pressure ring, inner core sealing-plug, inner core sealing ring is fixedlyed connected with sealing-plug pressure ring three on screw rod with the pretension nut driving to be integral.
5, a kind of assembling die that is used for liquid phase reactor, phase transition and preparation porous firming body as claimed in claim 1 is characterized in that, the part central authorities near interior pressure transmission piston on the outer pressure transmission piston that is made of the withstand voltage material of high strength are provided with a circular holes.
6, a kind of assembling die that is used for liquid phase reactor, phase transition and preparation porous firming body as claimed in claim 1, it is characterized in that, on the interior pressure transmission piston that constitutes by the withstand voltage material of high strength near the part central authorities of sealing-plug pressure ring, inner core sealing-plug and be provided with the space that is used for storaging liquid on every side, part central authorities near outer pressure transmission piston on the interior pressure transmission piston are provided with one and interior pressure transmission piston all-in-one-piece cylinder, after the installation, this cylinder is positioned at the part central, circular hole of close pressure transmission piston on the outer pressure transmission piston.
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| CNB2005100443231A CN100336583C (en) | 2005-07-29 | 2005-07-29 | Assembled mould for liquid phase reaction, phase conversion and preparation of porous solidified body |
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| CNB2005100443231A CN100336583C (en) | 2005-07-29 | 2005-07-29 | Assembled mould for liquid phase reaction, phase conversion and preparation of porous solidified body |
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| CN100336583C true CN100336583C (en) | 2007-09-12 |
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| CN102848578B (en) * | 2012-07-28 | 2014-06-25 | 大连理工大学 | Method for preparing oleophobic pore-forming microsphere template |
| CN112048771A (en) * | 2020-08-04 | 2020-12-08 | 上海玺唐半导体科技有限公司 | Reaction kettle, device and method for growing gallium nitride crystal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051317A (en) * | 1989-10-31 | 1991-05-15 | 西北有色金属研究院 | The forming method of reducing guide pipe |
| CN1273153A (en) * | 1999-05-11 | 2000-11-15 | 住友特殊金属株式会社 | Device and method for processing rare earth alloy powder |
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2005
- 2005-07-29 CN CNB2005100443231A patent/CN100336583C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051317A (en) * | 1989-10-31 | 1991-05-15 | 西北有色金属研究院 | The forming method of reducing guide pipe |
| CN1273153A (en) * | 1999-05-11 | 2000-11-15 | 住友特殊金属株式会社 | Device and method for processing rare earth alloy powder |
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