CN104046958A - Device and method for surface modification of micro-nano particles - Google Patents
Device and method for surface modification of micro-nano particles Download PDFInfo
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- CN104046958A CN104046958A CN201410247956.1A CN201410247956A CN104046958A CN 104046958 A CN104046958 A CN 104046958A CN 201410247956 A CN201410247956 A CN 201410247956A CN 104046958 A CN104046958 A CN 104046958A
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Abstract
The invention discloses a device for surface modification of micro-nano particles. The device comprises a reaction cavity, a plurality of precursor supply devices, a carrier gas conveying system and a powder particle loading device, wherein a cavity formed inside the reaction cavity is used as a reaction space of precursors and the micro-nano particles; the plurality of precursor supply devices are respectively communicated with the reaction cavity by virtue of pipelines to provide different precursors; the precursors are conveyed to the reaction cavity by virtue of carrier gas output by the carrier gas conveying system; the powder particle loading device is used for loading the micro-nano particles to be modified; the precursors are alternately conveyed to the reaction cavity by virtue of the plurality of precursor supply devices respectively, and enter the rotary powder particle loading device so as to be in contact with the surfaces of the micro-nano particles to perform an atomic layer deposition reaction, thus forming a coating thin film on the surfaces of the micro-nano particles and realizing surface modification. The invention also discloses a method for performing surface modification on the micro-nano particles by using the device. The device and method disclosed by the invention can be used for obtaining a coating layer with high particle surface uniformity and improving the overall coating rate of the powder particles and the utilization rate of the precursors.
Description
Technical field
The invention belongs to powder granule surface coating technology field, be specifically related to a kind of apparatus and method for micro-nano granules finishing.
Background technology
Compare block materials, powder granule material has bigger serface and high surface, there is the not available small-size effect of conventional solid material, surface effects and quantum tunneling effect, cause the variation of structure and energy state, can produce the physics-chem characteristics such as the light, heat, electricity, magnetic, mechanics, catalysis of many uniquenesses.
Between its huge specific surface area, by suitable finishing, can further expand and improve its premium properties.The main method of micro-nano granules finishing is as required at the coated thin film of particle surface, formation nucleocapsid structure.Such structure can make nano particle have better stability, weathering resistance and good physics-chem characteristic.Meanwhile, finishing also contributes to the understanding to micro-nano-scale material.
At present, micro-nano powder coating technology can be divided into solid phase method, liquid phase method and vapor phase process according to the state of reaction system.Solid phase method is mainly by mechanical effect, high-temperature calcination or high energy ion beam, particle surface to be activated, and makes it to adsorb other materials and reaches the coated of surface.But the bonding force of nucleocapsid structure realizing due to mechanically mixing is not strong, high energy beam excitation is lower easily forms the coated of thickness and uneven components, and requires powder granule to have the problems such as single dispersiveness, and the method overall application is comparatively limited.Liquid phase method comprises heterogeneous flocculence, sol-gel method, polymer overmold method, the precipitator method etc., there is the advantage that equipment is simple, cost is low, it is the method that micro-nano granules surface coating technology is most widely used, the shortcomings such as reaction process more complicated, coated thickness and composition are difficult for accurately controlling but exist, and film forming purity and compactness are high not.
Vapor phase process mainly comprises physical vaporous deposition and chemical Vapor deposition process.It is coated that the former realizes particle by the effect of Van der Waals force, core-shell bonding force is not strong, chemical Vapor deposition process is to utilize gaseous substance to generate solid deposited thing and reach the coated of nano particle in nano grain surface reaction, existing comparatively perfect deposition theory, and can be coated on the surface of any shape, the purity of rete is high.As a kind of special chemical vapour deposition technique, technique for atomic layer deposition can accurately be controlled material composition and pattern on nano level yardstick, by be deposited material with the form of monatomic film in layer be plated in body surface, there is high deposition uniformity, react the number of times of alternate cycles by control, realize the nano level controllable growth of film thickness.The densification that utilizes technique for atomic layer deposition to carry out nanoscale on micro-nano granules surface is coated, and can accurately be coated thickness and component, and have good conformality.
Current existing powder granule finishing equipment or method mainly adopt the mode of fluidisation, but, because technique for atomic layer deposition is rooted in traditional flat film growing technology, existing apparatus and method need further raising for the suitability of micro-nano granules surface deposition, major embodiment has marked difference compared with planar substrates depositing operation, and in deposition process powder granule due to reunion difficulties in dispersion, this has caused the advantage of ald high uniformity can not give full play in particle surface is coated, coating efficiency is lower, presoma utilization may be abundant not.
Summary of the invention
Main purpose of the present invention is to provide a kind of apparatus and method for micro-nano granules finishing, can make full use of the advantage of technique for atomic layer deposition, the coating layer of particle surface high uniformity be can obtain, and the integral coating rate of powder granule and the utilization ratio of presoma improved.
In order to solve the problems of the technologies described above, according to one aspect of the present invention, a kind of device for micro-nano granules finishing is provided, carry out ald by the multiple presoma that utilizes carrier gas to carry, form coated film on the surface of micro-nano granules, realize finishing, it is characterized in that, this device comprises:
Reaction chamber, its inner cavity forming is for the reaction compartment as presoma and micro-nano granules;
Multiple presoma feeding mechanisms, it communicates with described reaction chamber by pipeline respectively, for providing different presomas to reaction cavity respectively;
Carrier gas delivery system, it is arranged on the pipeline of described presoma feeding mechanism, and described presoma is transported in reaction chamber by the carrier gas of this carrier gas delivery system output; And
Powder granule stowage unit, it is contained in described reaction chamber and axial-rotation therein, for carrying micro-nano granules to be finished, this powder granule stowage unit one end is connected with the rotary drive mechanism being positioned at outside reaction chamber, and the other end is connected with the vacuum system outside reaction chamber;
Alternately carry presoma to described reaction chamber respectively by described multiple presoma feeding mechanisms, and enter in the powder granule stowage unit of described rotation and carry out ald reaction to contact with micro-nano granules, thereby form coated film on the surface of micro-nano granules, realize finishing.
As improvement of the present invention, described powder granule stowage unit is that two-layer cylinder set forms, inside and outside two-layer barrel is the powder of stainless steel sintering filter screen in micron order aperture, cylindrical shell both ends of the surface are provided with cover plate, and interconnect that by double-screw bolt double-layer circular columnar filter screen is clamped, ensure that powder granule can not spill from particle stowage unit, the cover plate at cylindrical shell two ends is connected with vacuum system and rotary drive mechanism by device for sealing magnetic fluid respectively.
As improvement of the present invention, described presoma feeding mechanism comprise store the presoma steel cylinder of precursor source, the presoma being arranged on the pipeline that presoma steel cylinder is connected with reaction chamber responds valve fast, respond fast the manual needle-valve between valve and steel cylinder at presoma, by alternately opening of the quick response valve on each presoma feeding mechanism, realize different presomas and alternately enter reaction chamber, by the adjusting of manual needle-valve, realize the control of the presoma pulsating pressure size of input.
As improvement of the present invention, also there is heating and temperature controlling system, comprise heating unit and temperature sensor in ring heater, the presoma supply system that is arranged on inside cavity, wherein, ring heater and heating unit are respectively used to as reaction chamber and the heating of presoma feeding mechanism, and described temperature sensor is for measuring the temperature of reaction chamber.
As improvement of the present invention, described vacuum system comprises vacuum, throttling valve and device for sealing magnetic fluid, wherein said vacuum pump is for vacuumizing reaction chamber, ensure the clean and cleaning reaction by product of reaction environment and unnecessary presoma, described device for sealing magnetic fluid is connected with powder granule stowage unit, be used for making reaction chamber air-flow to be drawn out of by this powder granule stowage unit, described throttling valve is arranged on device for sealing magnetic fluid downstream, for controlling by the air-flow velocity of powder granule stowage unit powder granule layer.
As improvement of the present invention, described rotary drive mechanism comprises motor, shaft coupling, device for sealing magnetic fluid, wherein device for sealing magnetic fluid is connected with reaction chamber, motor is the rotating shaft to device for sealing magnetic fluid by coupled shaft coupling transmission, thereby drives the powder granule stowage unit rotation being connected with this rotating shaft.
In the present invention, presoma supply system ligation cavity system, powder granule stowage unit is placed in reaction cavity inside, and powder granule stowage unit one end connects vacuum system, and the other end connects the power system that rotatablely moves.On the connecting pipeline of presoma supply system and reaction cavity system, be connected with carrier gas delivery system, heating system comprises the heating unit being arranged in inside cavity and presoma supply system.
Presoma supply system comprises two or more parallel branch, provide respectively different presomas as reactant gases, its major parts comprises that single-ended or both-end presoma steel cylinder, presoma respond valve fast, respond the manual needle-valve between valve and steel cylinder fast at presoma.It is normal closed gate that presoma responds valve fast, and the minimum opening time can reach 5ms.In the present invention, reaction cavity consists of three parts of oxygen free copper gasket seal left, center, right, and three parts connect by bolt and nut.Exocoel left part, in operation for taking apart, takes out the powder granule stowage unit of exocoel inside.There are two flange-interfaces upper and lower both sides, exocoel middle part, are respectively used to connect pressure warning unit in vacuum system and the temperature sensor of temp measuring system, for detection of the pressure and temperature of inside cavity.The left and right sides, exocoel middle part is connected from different presoma supply systems.The inner side of two parts in cavity left and right is provided with well heater.Preferably right cylinder design of reaction cavity, is conducive to being uniformly distributed of internal temperature homogeneity and air-flow.
In the present invention, powder granule stowage unit adopts double-layer circular columnar structure, inside and outside both sides are the powder of stainless steel sintering filter screen in micron order aperture, one of the stainless steel end face at two ends is connected with the device for sealing magnetic fluid in the vacuum system of cavity one side, and another is connected with the rotatablely move device for sealing magnetic fluid of transmission system of cavity opposite side.Both ends of the surface clamp double-layer circular columnar filter screen by double-screw bolt, ensure that powder granule can not spill from particle stowage unit, and they and device for sealing magnetic fluid are installed by screw thread.
According to another aspect of the present invention, a kind of method of utilizing the above-mentioned device for micro-nano granules finishing to carry out micro-nano granules finishing is provided, it carries out ald by the multiple presoma that utilizes carrier gas to carry, form coated film on the surface of micro-nano granules, realize finishing, it is characterized in that, the method comprises:
Under certain ald (ALD) temperature of reaction, utilize described vacuum system to vacuumize reaction chamber;
Powder granule stowage unit rotates under the drive of the transmission system that rotatablely moves, and drives powder granule wherein to rotatablely move;
Multiple presoma alternately enters reaction chamber under carrier gas drives, and through on powder granule surface, chemisorption occurring after described powder granule stowage unit outer screen;
Under the effect of the vacuum pump of vacuum system, utilize carrier gas to clean unnecessary presoma and byproduct of reaction, thus the micro-nano granules of finishing that obtained required carrying out.
As improvement of the present invention, the absorption detailed process of each presoma is: when presoma pulse passes into after reaction cavity, the vacuum pump of vacuum system stops bleeding, keep the pressure environment in reaction cavity, the micro-nano granules being rotated with powder granule stowage unit is rising to the effect freely falling body due to gravity after certain altitude, powder granule fall process in mutually disperse, its separately surface uniform adsorb this presoma
As improvement of the present invention, the dwell time is relevant to the size of the specific surface area of powder granule, is preferably 10～120s, has increased like this duration of contact on presoma and powder granule surface, has promoted fully carrying out of absorption.
As improvement of the present invention, the presoma burst length is relevant to the size of the specific surface area of powder granule, and surface-area is larger, and the burst length is longer, is generally 10～180s/m
2, ensure that the absorption of all surface is abundant.
As improvement of the present invention, the rotating speed of powder granule stowage unit is preferably 30～160rpm, has increased like this duration of contact on presoma and powder granule surface, has promoted fully carrying out of absorption.
As improvement of the present invention, the absorption detailed process of each presoma is: with higher rotational speed powder granule stowage unit, powder granule is because very large centrifugal force carries out circumferential motion together thereupon, presoma is along with the carrier gas of larger flow is input in reaction cavity together, from the outer screen of powder granule stowage unit radially by powder granule layer and be adsorbed on particle surface, adjust by the air-flow velocity of powder granule layer, utilize the pressure warning unit being connected with venting port upstream with reaction cavity respectively to detect the pressure difference of powder granule layer both sides, when this pressure difference reaches while stablizing, its pressure gradient power and suffered centrifugal force of powder that powder granule is produced balances each other, thereby realize the dispersion of powder granule, promote the homogeneity of presoma absorption.
As improvement of the present invention, the rotating speed of powder granule stowage unit is preferably 160～900rpm.
As improvement of the present invention, be preferably 30～500cm/s by the air-flow velocity of powder granule layer.
As improvement of the present invention, the temperature of reaction cavity system is within the scope of room temperature to 550 DEG C.
The surface modification method of micro-nano granules of the present invention carries out middle employing pressurize deposition method and carries out powder granule finishing actual.Specifically, when presoma pulse passes into after reaction cavity, close the vacuum pump of vacuum system, stop bleeding, keep the pressure environment in reaction cavity, the micro-nano granules being rotated with powder granule stowage unit is rising to the effect freely falling body due to gravity after certain altitude, powder granule disperses mutually in the process falling, it is surface uniform absorption presoma separately, pressure maintaining period finishes final vacuum pump takes byproduct of reaction and unnecessary presoma away, then carries out in the same way the absorption of the second presoma;
The surface modification method of the micro-nano granules in the present invention carries out middle employing balance dispersed deposition method and carries out powder granule finishing actual, specifically, with higher rotational speed powder granule stowage unit, powder granule is because very large centrifugal force carries out circumferential motion together thereupon, presoma is along with the carrier gas of larger flow is input in reaction cavity together, from the outer screen of powder granule stowage unit radially by powder granule layer and be adsorbed on particle surface, adjust by the air-flow velocity of powder granule layer, utilize the pressure warning unit being connected with venting port upstream with reaction cavity respectively to detect the pressure difference of powder granule layer both sides, when this pressure difference reaches while stablizing, its pressure gradient power and suffered centrifugal force of powder that powder granule is produced balances each other, thereby realize the dispersion of powder granule, promote the homogeneity of presoma absorption.The rotating speed that the method is larger also contributes to reduce the size of the coacervate that powder granule forms, and with further augmenting response surface-area, improves the utilization ratio of presoma.
Further, the presoma burst length is relevant to the size of the total surface area of powder granule, and surface-area is larger, and the burst length is longer, is generally 10～180s/m
2, ensure that the absorption of all surface is abundant.
Further, in pressurize deposition method, the dwell time is relevant to the size of the specific surface area of powder granule, specific surface area is larger, and the dwell time is longer, is generally 10～120s, increase like this duration of contact on presoma and powder granule surface, promoted fully carrying out of absorption.
Further, in pressurize deposition method, the rotating speed of powder granule stowage unit is unsuitable too fast, makes powder granule rotating to after certain altitude, and generally choosing rotating speed is 30～160rpm.
Further, in balance dispersed deposition method, the rotating speed of powder granule stowage unit is very fast, makes powder granule all the time along with stowage unit carries out circumferential motion and can not fall, and generally choosing rotating speed is 160～900rpm.
Further, in balance dispersed deposition method, carry the flow of carrier gas of presoma and the throttling valve adjustment that the utilizes venting port upstream air-flow velocity by powder granule layer by control to reach final stable pressure difference, rotating speed used is higher, and the required flow rate of realizing balance is larger.General employing flow velocity is 30～500cm/s.
Further, the temperature of reaction cavity system is room temperature to 550 DEG C.
In general, the above technical scheme of conceiving by the present invention compared with prior art, owing to adopting technique for atomic layer deposition, can ensure micro-nano powder particle good dispersiveness in deposition process, reduce the size of powder reuniting body, thereby increase participate in reaction surface-area, realize particle surface to presoma evenly, fully absorption.Particularly, can obtain following beneficial effect:
(1) in the device of this micro-nano granules finishing, utilize the pressurize deposition method under centrifugation, can under the state of dispersion powder particle, realize the Long contact time on presoma and powder granule surface, presoma absorption is full and uniform, ensure the homogeneity of surface deposition film, improved the utilization ratio of presoma simultaneously.
(2) in the device of this micro-nano granules finishing, utilize the balance dispersed deposition method under centrifugation, can reduce to a certain extent the size of the coacervate that micro-nano granules forms, ensure dispersed simultaneously, increase the specific surface area that participates in reaction, increase the area of institute's modification of surfaces, promote the full and uniform absorption of presoma, improved the homogeneity of deposit film and can increase batch processed amount.
(3) in the device of this micro-nano granules finishing, presoma and carrier gas air-flow radially pass through powder granule layer by the outer screen of powder granule stowage unit, and be drawn out of from interior side screen, this air-flow while and centrifugal force balance under high rotating speed, avoid powder granule in design that air-flow flows to be vertically easy to be deposited in bleeding the defect on a side screen surface, can give full play to the improve effect of centrifugation for particle surface deposition uniformity and adequacy.
Brief description of the drawings
Fig. 1 is a kind of total system schematic diagram for micro-nano granules finishing device of the embodiment of the present invention;
Fig. 2 is the powder granule stowage unit outside drawing of the embodiment of the present invention;
Fig. 3 is the axial sectional view of powder granule stowage unit;
Fig. 4 is powder granule stowage unit radial cross-section;
Fig. 5 is powder granule stowage unit schematic three dimensional views.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.In addition,, in each embodiment of described the present invention, involved technical characterictic just can combine mutually as long as do not form each other conflict.
As shown in Figure 1, a kind of finishing device of micro-nano granules, comprises vacuum system, reaction cavity, powder granule stowage unit, presoma supply, heating and temperature control system, carrier gas delivery system, the transmission system that rotatablely moves, Controlling System.Presoma supply system ligation cavity, powder granule stowage unit is placed in reaction cavity inside, and powder granule stowage unit one end connects vacuum system, and the other end connects the transmission system that rotatablely moves.
Be connected by carrier gas delivery system with reaction cavity in presoma supply system, mass flow controller 5 is installed on carrier gas transfer line.
Presoma supply system comprises the presoma branch road that two or more is in parallel, different precursor source is provided respectively, its major parts comprises that presoma responds valve 6 and presoma steel cylinder 8 fast, responds the manual needle-valve 7 between valve and steel cylinder fast at presoma.Presoma responds valve 6 fast for normal closed gate, and the minimum opening time can reach 5ms.Each fast response valve alternately open, its separately the presoma in the steel cylinder of branch road alternately enter reaction cavity internal system.
Reaction cavity is made up of left, center, right three parts, seals by oxygen free copper pad 2.Cavity left part, in operation for taking apart, takes out the powder granule stowage unit 3 of exocoel inside.There are two flange-interfaces upper and lower both sides, exocoel middle part, are respectively used to connect pressure warning unit 14 in vacuum system and the temperature sensor 4 of temp measuring system, for detection of the pressure and temperature of inside cavity.The left and right sides, exocoel middle part is connected from different presoma supply systems.The inner side of two parts in cavity left and right is provided with ring heater 16.Reaction cavity left part is connected with the device for sealing magnetic fluid 18 of the transmission system that rotatablely moves, and reaction cavity right part is connected with the device for sealing magnetic fluid 9 of vacuum system.
Heating comprises heating unit 15 and the temperature sensor 14 in ring heater 16 and the presoma supply system that is arranged on inside cavity with temperature controlling system.Heating unit 15 in ring heater 16 and presoma supply system is respectively reaction cavity 1 and presoma steel cylinder 8, presoma and responds fast the pipeline heating of valve 6 and presoma branch road.Temperature sensor 14 is measured the temperature of reaction cavity 1 inside.
As shown in Fig. 2,3,4,5, powder granule stowage unit adopts double-layer circular columnar structure, inside and outside both sides are the powder of stainless steel sintering filter screen 24,26 in micron order aperture, aperture is preferably 5～10 microns, the stainless steel end face 21,25 at two ends clamps double-layer circular columnar filter screen by double-screw bolt 22 and nut 23, ensure that powder granule can not spill from particle stowage unit, by removing the powder granule that is connected to have taken out finishing of these two end faces and double-screw bolt.End face 25 is connected with the device for sealing magnetic fluid 9 in vacuum system, and end face 21 is connected with the device for sealing magnetic fluid 18 of the transmission system that rotatablely moves.
Vacuum system comprises vacuum pump 12, magnetic valve 11, throttling valve 10 and device for sealing magnetic fluid 9.Device for sealing magnetic fluid 9 ensures that the air-flow in reaction cavity 1 is drawn out of by powder granule stowage unit 3 completely, instead of is directly taken away by vacuum pump 12.Throttling valve 10 is directly connected with device for sealing magnetic fluid 9 downstreams, for controlling by the air-flow velocity of powder granule stowage unit 3 powder granule layers.After magnetic valve 11 is connected on throttling valve, determine reaction cavity 1 whether to bleed, vacuum pump 12 is responsible for that the pressure of reaction cavity 1 is extracted into ALD and is reacted required vacuum tightness, ensures the clean and cleaning reaction by product of reaction environment and unnecessary presoma.
The transmission system that rotatablely moves comprises motor 20, shaft coupling 19, device for sealing magnetic fluid 18 and bearing 17.Motor 20 provides motivating force, the rotating shaft to device for sealing magnetic fluid 18 for transmission of coupled shaft coupling 19, and device for sealing magnetic fluid 18 inside and reaction cavity 1 left part are provided with bearing 17 and carry out the motion of supporting revolving shaft and stressed.Device for sealing magnetic fluid 18 is connected with reaction cavity 1, ensures the resistance to air loss of reaction cavity simultaneously.
The control of the time that open and close, presoma pulse and the reaction of Controlling System control vacuum system cleaned and cycle index, temperature, powder granule stowage unit 9 and 18 rotating speeds.Controlling System also comprises two pressure warning units, and pressure warning unit 14 is connected with reaction cavity 1, and pressure warning unit 13 is connected to the upstream of throttling valve 10 in vacuum system.
The method of utilizing the finishing of said apparatus to micro-nano granules of the embodiment of the present invention, its detailed process is as follows:
Wherein, atom layer deposition process can adopt pressurize depositing operation or balance dispersed deposition technique.
Below, paper adopts the embodiment of pressurize depositing operation:
Step S10: pretreatment stage.Powder granule is put into powder granule stowage unit, drive powder to rotate with certain rotating speed, selection of speed is at 30～60rpm.Magnetic valve and the throttling valve opened completely before vacuum pump vacuumize (vacuum tightness requires pressure to be less than or equal to 1Pa) to reaction cavity.Reaction cavity is heated, temperature is room temperature～550 DEG C according to selected reaction control simultaneously.Keep this process at least 1 hour.It is 100 DEG C that pipeline temperature is set, and it is 120 DEG C that presoma responds valve temperature fast.When reaching when established temperature fluctuation range are no more than 1 DEG C, the displays temperature of reaction cavity can carry out subsequent technique.
Step S20: presoma stage pulse.Closing magnetic valve before vacuum pump bleeds stopping.Turn on the manual needle-valve that presoma steel cylinder is corresponding and reach certain presoma work output.Open presoma and respond fast valve, the opening time is chosen as 60～180s/m
2, the saturation steam that carries precursor source with the mass flow controller input carrier gas 20～200sccm of carrier gas delivery system in the time that it is opened passes into reaction cavity.Respond fast after valve closes when opening presoma, stop carrier gas delivery system input carrier gas.Give powder granule stowage unit and inner rotary powder motion thereof in this stage by the transmission system that rotatablely moves, selection of speed is 30～160rpm.In this process, precursor A starts to be adsorbed on powder granule surface.
Step S30: pressurize absorption phase.Maintain rotating speed and pressure 10～120s in previous step, micro-nano granules is rising to the effect freely falling body due to gravity after certain altitude, and powder granule disperses mutually in the process falling, and precursor A is fully adsorbed on powder granule surface.
Step S40: wash phase.Carrier gas input system is to reaction cavity input carrier gas 100～1000sccm, and the magnetic valve of simultaneously opening before vacuum pump starts to bleed, cleaning reaction by product and unnecessary precursor A, and this process maintains 60～180s.
Step S50: the stage pulse that carries out precursor B according to the method for step S20.
Step S60: carry out the pressurize absorption of precursor B according to the method for step S30.
Step S70: the wash phase that carries out precursor B according to the method for step S40.
Step S80: circulation step S20～S70 as stated above, cycle index depends on the film thickness of required deposition.The film that can form at particle surface desired thickness after deposition finishes, completes the finishing to micro-nano granules.
Adopt the embodiment of balance dispersed deposition technique as follows:
Step S10 ': pretreatment stage.Identical with the step S10 in deposition method one.
Step S20 ': presoma stage pulse.Selection of speed is 180～900rpm.Keep the unlatching of the magnetic valve before vacuum pump.Adjust carrier gas flux and the throttle valve control of carrier gas process system and pass through the air-flow velocity of powder granule layer, utilize the pressure warning unit being connected with venting port upstream with reaction cavity respectively to detect the pressure difference of powder granule layer both sides, the flow velocity reaching while stablizing with pressure difference carries out the dispersed surface deposition to powder granule, and generally adopting flow velocity is 30～500cm/s.Output for presoma from steel cylinder, method, as step S20, is opened presoma and is responded fast valve time 10～100s/m
2, the saturation steam that precursor source is carried in carrier gas passes into reaction cavity.Presoma along with carrier gas from the outer screen of powder granule stowage unit radially by powder granule layer and be adsorbed on particle surface.
Step S30 ': wash phase.All identical with the condition of previous step except stopping the conveying of presoma.Cleaning reaction by product and unnecessary precursor A, this process maintains 60～180s.
Step S40 ': the stage pulse that carries out precursor B according to the method for step S20.
Step S50 ': the wash phase that carries out precursor B according to the method for step S30.
Step S60 ': circulation step S20 '～S50 ' as stated above, cycle index depends on the film thickness of required deposition.The film that can form at particle surface desired thickness after deposition finishes, completes the finishing to micro-nano granules.
In order to illustrate further structure, the principle of apparatus and method of the present invention, below in conjunction with the finishing process of concrete micro-nano granules, it is described further.
Embodiment mono-
Be the AlH of 50 μ m to particle diameter
3particle surface is coated the thick Al of one deck 10nm
2o
3film, to reduce its impact sensitivity, improves security.Choose trimethyl aluminium (TMA) and water (H
2o) be presoma, its
main anti- answer equation to be:
(A)AlOH
*+Al(CH
3)
3→AlOAl(CH
3)
2 *+CH
4
(B)AlCH
3 *+H
2O→AlOH
*+CH
4
Adopt above-mentioned micro-nano granules finishing device and corresponding pressurize depositing operation method:
By 0.1g AlH
3particle is put into powder granule stowage unit and is arranged on reaction cavity, connects with device for sealing magnetic fluid.Sealed reaction cavity afterwards.
Open vacuum pump, opens solenoid valve and throttling valve, so that reaction cavity is connected with vacuum pump, is evacuated to reaction cavity pressure to be less than or equal to 1pa.Reacting by heating cavity makes its internal temperature be stabilized in 120 DEG C, and heating presoma steel cylinder, presoma branch road pipeline and presoma respond valve fast all to 80 DEG C.Give powder granule stowage unit rotating speed 60rpm, maintain this state 1 hour.
Shut electromagnetic valve, opens the manual needle-valve after presoma steel cylinder, opens presoma and responds fast valve, with the carrier gas (N of 100sccm
2) carry presoma TMA steam and enter reaction cavity, after TMA pulse 60s, close presoma and respond fast valve, stop passing into carrier gas, enter the packing stage of 30s.Powder granule freely falling body after reaching a certain height of rotation completes absorption with presoma TMA uniform contact in dropping process.Open magnetic valve and bleed, simultaneously to pass into the carrier gas of 100sccm, clean up byproduct of reaction with for presoma TMA.Presoma H
2pulse, pressurize and the wash phase of O are similar.
Carry out the circulation 100 times of two kinds of presoma pulses, pressurize and wash phases, can be at AlH after deposition finishes
3particle surface forms the Al that thickness is about 14nm
2o
3film.
Embodiment bis-
The SiO that is 200nm to particle diameter
2particle surface is coated the thick Al of one deck 5nm
2o
3film is with research SiO
2the surface tissue of particle.Choose trimethyl aluminium (TMA) and water (H
2 17o) be presoma.
Adopt above-mentioned micro-nano granules finishing device and corresponding balance dispersed deposition processing method:
By SiO
2particle is put into powder granule stowage unit and is arranged on reaction cavity, connects with device for sealing magnetic fluid.Sealed reaction cavity afterwards.
Open vacuum pump, opens solenoid valve and throttling valve, so that reaction cavity is connected with vacuum pump, is evacuated to reaction cavity pressure to be less than or equal to 1pa.Reacting by heating cavity makes its internal temperature be stabilized in 200 DEG C, and heating presoma steel cylinder, presoma branch road pipeline and presoma respond valve fast all to 120 DEG C.Give powder granule stowage unit rotating speed 60rpm, maintain this state 2 hours.
Selection of speed is 300rpm.Keep the unlatching of the magnetic valve before vacuum pump.Adjust carrier gas (N
2) flow and throttle valve control be 100cm/s by the air-flow velocity of powder granule layer, reaches the poor steady state of powder granule layer pressure at both sides.Turn on the manual needle-valve after presoma TMA steel cylinder, open presoma and respond fast valve 60s, the saturation steam that presoma TMA is carried in carrier gas passes into reaction cavity.Presoma TMA along with carrier gas from the outer screen of powder granule stowage unit radially by powder granule layer and be adsorbed on particle surface.After the quick response valve closes of presoma TMA, other conditions are constant, particle surface cleaned to extraction by product and unnecessary presoma TMA.Presoma H
2 17pulse, pressurize and the wash phase of O are similar.
Carry out the circulation 50 times of two kinds of presoma pulses, pressurize and wash phases, can be at SiO after deposition finishes
2particle surface forms the Al that thickness is about 5nm
2o
3film.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (15)
1. for a device for micro-nano granules finishing, carry out ald, thereby form coated film on the surface of micro-nano granules by the multiple presoma that utilizes carrier gas to carry, realize finishing, it is characterized in that, this device comprises:
Reaction chamber, its inner cavity forming is for the reaction compartment as presoma and micro-nano granules;
Multiple presoma feeding mechanisms, it communicates with described reaction chamber by pipeline respectively, for providing different presomas to reaction cavity respectively;
Carrier gas delivery system, it is arranged on the pipeline of described presoma feeding mechanism, and described presoma is transported in reaction chamber by the carrier gas of this carrier gas delivery system output; And
Powder granule stowage unit, it is arranged in described reaction chamber and axial-rotation therein, for carrying micro-nano granules to be finished, this powder granule stowage unit one end is connected with the rotary drive mechanism being positioned at outside reaction chamber, and the other end is connected with the vacuum system outside reaction chamber;
Alternately carry presoma to described reaction chamber respectively by described multiple presoma feeding mechanisms, and enter in the powder granule stowage unit of described rotation and react to carry out ald with micro-nano granules Surface Contact, thereby form coated film on the surface of micro-nano granules, realize finishing.
2. a kind of device for micro-nano granules finishing according to claim 1, it is characterized in that, described powder granule stowage unit is that two-layer cylinder set forms, inside and outside two-layer barrel is the powder of stainless steel sintering filter screen in micron order aperture, cylindrical shell both ends of the surface are provided with cover plate, and interconnect that by double-screw bolt double-layer circular columnar filter screen is clamped, ensure that powder granule can not spill from particle stowage unit, the cover plate at cylindrical shell two ends is connected with vacuum system and rotary drive mechanism by device for sealing magnetic fluid respectively.
3. a kind of device for micro-nano granules finishing according to claim 1 and 2, it is characterized in that, described presoma feeding mechanism comprises the presoma steel cylinder of storing precursor source, the presoma being arranged on the pipeline that presoma steel cylinder is connected with reaction chamber responds valve fast, and respond fast the manual needle-valve between valve and steel cylinder at described presoma, by alternately opening of the quick response valve on each presoma feeding mechanism, realize different presomas and alternately enter reaction chamber, and by the adjusting of manual needle-valve, realize the control of the presoma pulsating pressure size of input.
4. according to a kind of device for micro-nano granules finishing described in any one in claim 1-3, it is characterized in that, also there is heating and temperature controlling system, comprise heating unit (15) and temperature sensor (14) in ring heater (16), the presoma supply system that is arranged on inside cavity, wherein, ring heater (16) and heating unit (15) are respectively used to as reaction chamber and the heating of presoma feeding mechanism, and described temperature sensor (14) is for measuring the temperature of reaction chamber (1).
5. according to a kind of device for micro-nano granules finishing described in any one in claim 1-4, it is characterized in that, described vacuum system comprises vacuum pump (12), throttling valve (10) and device for sealing magnetic fluid (9), wherein said vacuum pump (12) is for vacuumizing reaction chamber, ensure the clean and cleaning reaction by product of reaction environment and unnecessary presoma, described device for sealing magnetic fluid (9) is connected with powder granule stowage unit (3), for making all air-flows of reaction chamber all through being drawn out of after the powder granule layer in this powder granule stowage unit (3), described throttling valve (10) is arranged on device for sealing magnetic fluid (9) downstream, for controlling by the air-flow velocity of powder granule stowage unit (3) powder granule layer.
6. according to a kind of device for micro-nano granules finishing described in any one in claim 1-5, it is characterized in that, described rotary drive mechanism comprises motor (20), shaft coupling (19) and device for sealing magnetic fluid (18), wherein device for sealing magnetic fluid (18) is connected with reaction chamber (1), motor (20) is the rotating shaft to device for sealing magnetic fluid (18) by coupled shaft coupling (19) transmission, thereby drives powder granule stowage unit (3) rotation being connected with this rotating shaft.
7. one kind is utilized the method that in the claims 1-6, the device for micro-nano granules finishing described in any one carries out micro-nano granules finishing, it carries out ald by the multiple presoma that utilizes carrier gas to carry, form coated film on the surface of micro-nano granules, realize finishing, it is characterized in that, the method comprises:
Under certain ald (ALD) temperature of reaction, utilize described vacuum system to vacuumize reaction chamber;
Powder granule stowage unit rotates under the drive of the transmission system that rotatablely moves, and drives powder granule wherein to rotatablely move;
Multiple presoma alternately enters reaction chamber under carrier gas drives, and through on powder granule surface, chemisorption occurring after described powder granule stowage unit outer screen;
Under the effect of the vacuum pump of vacuum system, utilize carrier gas to clean unnecessary presoma and byproduct of reaction, thus the micro-nano granules of finishing that obtained required carrying out.
8. the method for utilizing the above-mentioned device for micro-nano granules finishing to carry out micro-nano granules finishing according to claim 7, it is characterized in that, the absorption detailed process of each presoma is: when presoma pulse passes into after reaction cavity, the vacuum pump of vacuum system stops bleeding, keep the pressure environment in reaction cavity, the micro-nano granules being rotated with powder granule stowage unit is rising to the effect freely falling body due to gravity after certain altitude, powder granule disperses mutually in the process falling, its separately surface uniform adsorb this presoma.
9. the method for utilizing the above-mentioned device for micro-nano granules finishing to carry out micro-nano granules finishing according to claim 8, is characterized in that, the dwell time is relevant to the size of the specific surface area of powder granule, is preferably 10～120s.
10. the above-mentioned device for micro-nano granules finishing that utilizes according to claim 8 or claim 9 carries out the method for micro-nano granules finishing, it is characterized in that, the presoma burst length is relevant to the size of the total surface area of powder granule, is preferably 10～180s/m
2.
The above-mentioned device for micro-nano granules finishing that utilizes in 11. according to Claim 8-10 described in any one carries out the method for micro-nano granules finishing, it is characterized in that, the rotating speed of powder granule stowage unit is preferably 30～160rpm.
12. methods of utilizing the above-mentioned device for micro-nano granules finishing to carry out micro-nano granules finishing according to claim 7, it is characterized in that, the absorption detailed process of each presoma is: with higher rotational speed powder granule stowage unit, powder granule is because very large centrifugal force carries out circumferential motion together thereupon, presoma is along with the carrier gas of larger flow is input in reaction cavity together, from the outer screen of powder granule stowage unit radially by powder granule layer and be adsorbed on particle surface, adjust by the air-flow velocity of powder granule layer, utilize the pressure warning unit being connected with venting port upstream with reaction cavity respectively to detect the pressure difference of powder granule layer both sides, when this pressure difference reaches while stablizing, its pressure gradient power and suffered centrifugal force of powder that powder granule is produced balances each other, thereby realize the dispersion of powder granule, promote the homogeneity of presoma absorption.
13. methods of utilizing the above-mentioned device for micro-nano granules finishing to carry out micro-nano granules finishing according to claim 12, the rotating speed of powder granule stowage unit is preferably 160～900rpm.
14. carry out the method for micro-nano granules finishing according to the above-mentioned device for micro-nano granules finishing that utilizes described in claim 12 or 13, are preferably 30～500cm/s by the air-flow velocity of powder granule layer.
15. according to the method for utilizing the above-mentioned device for micro-nano granules finishing to carry out micro-nano granules finishing described in any one in claim 12-14, and the temperature of reaction cavity system is within the scope of room temperature to 550 DEG C.
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|---|---|---|---|---|
| CN104878368A (en) * | 2015-06-09 | 2015-09-02 | 天津巴莫科技股份有限公司 | Powder microwave chemical vapor phase coating equipment capable of realizing continuous production |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030194493A1 (en) * | 2002-04-16 | 2003-10-16 | Applied Materials, Inc. | Multi-station deposition apparatus and method |
| CN102534556A (en) * | 2012-02-20 | 2012-07-04 | 姜谦 | Normal-pressure multi-cavity atomic layer deposition equipment |
| CN103443325A (en) * | 2011-03-01 | 2013-12-11 | 应用材料公司 | Apparatus and process for atomic layer deposition |
-
2014
- 2014-06-06 CN CN201410247956.1A patent/CN104046958B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030194493A1 (en) * | 2002-04-16 | 2003-10-16 | Applied Materials, Inc. | Multi-station deposition apparatus and method |
| CN103443325A (en) * | 2011-03-01 | 2013-12-11 | 应用材料公司 | Apparatus and process for atomic layer deposition |
| CN102534556A (en) * | 2012-02-20 | 2012-07-04 | 姜谦 | Normal-pressure multi-cavity atomic layer deposition equipment |
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