CN104046958B - A kind of apparatus and method modified for micro-nano granules surface - Google Patents
A kind of apparatus and method modified for micro-nano granules surface Download PDFInfo
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- CN104046958B CN104046958B CN201410247956.1A CN201410247956A CN104046958B CN 104046958 B CN104046958 B CN 104046958B CN 201410247956 A CN201410247956 A CN 201410247956A CN 104046958 B CN104046958 B CN 104046958B
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Abstract
The invention discloses a kind of device modified for micro-nano granules surface, including: reaction chamber, its cavity being internally formed is for the reaction compartment as presoma Yu micro-nano granules；Multiple presoma feeding mechanisms, it passes to provide different presomas mutually by pipeline respectively from described reaction chamber；Carrier gas induction system, the carrier gas that presoma is exported by this carrier gas induction system is transported in reaction chamber；And powder granule loading attachment, for carrying micro-nano granules to be finished；Alternately carried presoma respectively to reaction chamber by multiple presoma feeding mechanisms, and enter in the powder granule loading attachment of rotation and carry out ald reaction to contact with micro-nano granules surface, thus cladding thin film is formed on the surface of micro-nano granules, it is achieved surface is modified.The invention also discloses and utilize said apparatus to carry out the method that the surface of micro-nano granules is modified.The present invention can obtain the clad of particle surface high uniformity, and improves integral coating rate and the utilization rate of presoma of powder granule.
Description
Technical field
The invention belongs to powder granule surface coating technology field, be specifically related to a kind of for micro-nano
The apparatus and method that grain surface is modified.
Background technology
Comparing block materials, powder granule material has bigger serface and high surface, has biography
System small-size effect, skin effect and quantum tunneling effect not available for solid material, initiation finishes
Structure and the change of energy state, can produce the things such as much unique light, heat, electricity, magnetic, mechanics, catalysis
Physical chemistry characteristic.
Between the specific surface area that it is huge, modified by suitable surface, can expand further and improve it
Premium properties.The main method that micro-nano granules surface is modified is to be coated with one at particle surface as required
Layer film, forms nucleocapsid structure.Such structure can make nano-particle have more preferable stability,
Weatherability and excellent physicochemical characteristics.Meanwhile, surface is modified and is also contributed to micro-nano meter ruler
The understanding of degree material.
At present, micro-nano powder coating technology can be divided into solid phase method, liquid according to the state of reaction system
Phase method and vapor phase method.Solid phase method mainly by mechanism, high-temperature calcination or high energy ion beam to
Grain surface is activated, and is allowed to adsorb other materials and reach the cladding on surface.But due to mechanical mixture
The adhesion of the nucleocapsid structure realized is not strong, and high energy beam excitation is lower easily forms thickness and uneven components
Cladding, and require that powder granule has the problems such as single dispersibility, the method overall application more has
Limit.Liquid phase method includes heterogeneous flocculence, sol-gal process, polymer encapsulation, the sedimentation method etc., tool
Having that equipment is simple, the advantage of low cost, it is that micro-nano granules surface coating technology is most widely used
Method, but exist course of reaction more complicated, cladding thickness and composition be difficult to accurately control, become
Film purity and the shortcoming such as compactness is the highest.
Vapor phase method mainly includes physical vaporous deposition and chemical vapour deposition technique.The former is by Van der Waals
The effect of power realizes particles coat, and core-shell structure copolymer adhesion is not strong, and chemical vapour deposition technique is then to utilize gas
State material generates solid deposited thing in nano grain surface reaction and reaches the cladding of nano-particle, existing
The most perfect deposition is theoretical, and can be coated with on the surface of any shape, the purity of film layer
High.As a kind of special chemical vapour deposition technique, technique for atomic layer deposition can be at nanoscale chi
Material composition and pattern is accurately controlled, by deposited material with the form of monatomic film in layer on degree
Be plated in body surface, there is high deposition uniformity, by control reaction alternate cycles number of times,
Realize the nanoscale controllable growth of film thickness.Utilize technique for atomic layer deposition on micro-nano granules surface
Carry out the fine and close cladding of nanoscale, can accurately be coated with thickness and component, and there is good conformality.
Current existing powder granule surface modification device or method mainly use the mode of fluidisation, but,
Owing to technique for atomic layer deposition is rooted in traditional flat film growing technology, existing apparatus and method pair
The suitability in micro-nano granules surface deposition need to improve further, major embodiment and planar substrates
Depositing operation has compared marked difference, and in deposition process powder granule due to reunion difficulties in dispersion,
The advantage which results in ald high uniformity can not give full play in particle surface is coated with, bag
Covering that inefficient, presoma utilizes may be the most abundant.
Summary of the invention
Present invention is primarily targeted at and a kind of device modified for micro-nano granules surface and side are provided
Method, it is possible to make full use of the advantage of technique for atomic layer deposition, it is possible to obtain particle surface high uniformity
Clad, and improve integral coating rate and the utilization rate of presoma of powder granule.
In order to solve above-mentioned technical problem, according to one aspect of the present invention, it is provided that a kind of for micro-nano
The device that rice grain surface is modified, carries out ald by the multiple presoma utilizing carrier gas to carry,
Cladding thin film is formed, it is achieved surface is modified, it is characterised in that this device on the surface of micro-nano granules
Including:
Reaction chamber, its cavity being internally formed is for the reaction compartment as presoma Yu micro-nano granules；
Multiple presoma feeding mechanisms, it is communicated with described reaction chamber by pipeline respectively, for respectively
Different presomas is provided in reaction cavity；
Carrier gas induction system, it is arranged on the pipeline of described presoma feeding mechanism, described presoma
It is transported in reaction chamber by the carrier gas of this carrier gas induction system output；And
Powder granule loading attachment, it is contained in described reaction chamber and can rotate axially therein, uses
In carrying micro-nano granules to be finished, this powder granule loading attachment one end be positioned at outside reaction chamber
Rotary drive mechanism connect, the other end with reaction chamber outside vacuum system be connected；
Presoma is alternately carried to described reaction chamber respectively by the plurality of presoma feeding mechanism,
And enter in the powder granule loading attachment of described rotation and carry out atomic layer deposition to contact with micro-nano granules
Long-pending reaction, thus cladding thin film is formed on the surface of micro-nano granules, it is achieved surface is modified.
As the improvement of the present invention, described powder granule loading attachment is that two-layer cylinder set forms, interior
Outer two-layer barrel is the powder of stainless steel sintering filter screen in micron order aperture, and cylinder both ends of the surface are provided with lid
Plate, and be connected with each other to clamp double-layer circular columnar filter screen by stud, it is ensured that powder granule will not be from
Spilling in granule loading attachment, the cover plate at cylinder two ends is respectively by device for sealing magnetic fluid and vacuum system
System and rotary drive mechanism connect.
As the improvement of the present invention, described presoma feeding mechanism includes the presoma storing precursor source
Steel cylinder, the presoma being arranged on the pipeline that presoma steel cylinder is connected with reaction chamber quickly respond valve,
The manual needle valve between valve and steel cylinder is quickly responded, by each presoma feeding mechanism at presoma
Alternately the opening of quickly response valve, it is achieved different presomas alternately enter reaction chamber, manually
The regulation of needle-valve, it is achieved the control of the presoma pulsating pressure size of input.
As the improvement of the present invention, also there is heating and temperature control system, including being arranged in cavity
Heater in the ring heater in portion, presoma supply system and temperature sensor, wherein,
Ring heater and heater are respectively used to heat for reaction chamber and presoma feeding mechanism, described
Temperature sensor is for measuring the temperature of reaction chamber.
As the improvement of the present invention, described vacuum system includes vacuum, choke valve and magnet fluid sealing dress
Putting, wherein said vacuum pump is for reaction chamber evacuation, it is ensured that the clean and removing of reaction environment is anti-
Answering by-product and unnecessary presoma, described device for sealing magnetic fluid is connected with powder granule loading attachment,
For making air-flow in reaction chamber be drawn out of by this powder granule loading attachment, described choke valve is arranged
In device for sealing magnetic fluid downstream, for controlling by powder granule layer in powder granule loading attachment
Air-flow velocity.
As the improvement of the present invention, described rotary drive mechanism includes that motor, shaft coupling, magnetic fluid are close
Seal apparatus, wherein device for sealing magnetic fluid is connected with reaction chamber, and motor is by coupled shaft coupling
Transmission is to the rotating shaft of device for sealing magnetic fluid, thus drives the powder granule being connected with this rotating shaft to load dress
Put rotation.
In the present invention, presoma supply system coupled reaction cavity systems, powder granule loading attachment is put
Inside reaction cavity, powder granule loading attachment one end connects vacuum system, and the other end connects rotation
Motion-promotion force system.Presoma supply system has carrier gas with being connected on the connecting line of reaction cavity system
Induction system, heating system includes the heater being arranged in inside cavity and presoma supply system.
Presoma supply system includes two or more parallel branch, provides different presoma respectively
As reacting gas, its critical piece includes that single-ended or both-end presoma steel cylinder, presoma quickly respond
Valve, quickly responds the manual needle valve between valve and steel cylinder at presoma.The quick responsive valves of presoma
Door is normal closed gate, and the minimum opening time is up to 5ms.In the present invention, reaction cavity is led to by left, center, right
Crossing three part compositions of oxygen-free copper gasket seal, three parts are attached by bolt and nut.Exocoel
Left part is used for taking apart in operation, takes out the powder granule loading attachment of outer chamber.On in the middle part of exocoel
There are two flange-interfaces lower both sides, the piezometer and temp measuring system being respectively used to connect in vacuum system
Temperature sensor, for the pressure and temperature within test chamber.In the middle part of exocoel, the left and right sides is from different
Presoma supply system be connected.About cavity, the inner side of two parts is provided with heater.Reaction
Being uniformly distributed of cavity preferably cylinder design, beneficially internal temperature uniformity and air-flow.
In the present invention, powder granule loading attachment use double-layer circular column structure, inside and outside be micron
The powder of stainless steel sintering filter screen in level aperture, the vacuum of the rustless steel end face at two ends one and cavity side
Device for sealing magnetic fluid in system is connected, another and cavity opposite side rotary motion drive system
Device for sealing magnetic fluid connects.Double-layer circular columnar filter screen is clamped by both ends of the surface by stud, it is ensured that powder body
Granule will not spill from granule loading attachment, and they are pacified by screw thread with device for sealing magnetic fluid
Dress.
It is another aspect of this invention to provide that it is above-mentioned for the modification of micro-nano granules surface to provide one to utilize
The device method that carries out the modification of micro-nano granules surface, its multiple forerunner carried by utilizing carrier gas
Body carries out ald, forms cladding thin film on the surface of micro-nano granules, it is achieved surface is modified,
It is characterized in that, the method includes:
Under certain ald (ALD) reaction temperature, utilize described vacuum system to reaction chamber
Evacuation；
Powder granule loading attachment rotates under the drive of rotary motion drive system, drives powder therein
Body particle rotation is moved；
Multiple presoma alternately enters reaction chamber under carrier gas drives, and loads through described powder granule
There is chemisorbed on powder granule surface after device outer screen；
Carrier gas is utilized to clean unnecessary presoma and reaction by-product under the effect of the vacuum pump of vacuum system
Thing, thus obtain the micro-nano granules that required carrying out surface is modified.
As the improvement of the present invention, the absorption detailed process of each presoma is: precursor pulse
After being passed through reaction cavity, the vacuum pump of vacuum system stops bleeding, and keeps the pressure rings in reaction cavity
Border, the micro-nano granules being rotated with powder granule loading attachment is after rising to certain altitude
Due to the effect freely falling body of gravity, powder granule disperses mutually during falling, its respective table
This presoma of face uniform adsorption,
As the improvement of the present invention, the dwell time is relevant to the size of the specific surface area of powder granule, excellent
Elect 10～120s as, which increase the time of contact of presoma and powder granule surface, promote suction
Attached is fully carried out.
As the improvement of the present invention, the size phase of presoma burst length and the specific surface area of powder granule
Closing, surface area is the biggest, and the burst length is the longest, generally 10～180s/m2, it is ensured that the suction of all surface
Attached fully.
As the improvement of the present invention, the rotating speed of powder granule loading attachment is preferably 30～160rpm, this
Sample adds the time of contact of presoma and powder granule surface, promotes fully carrying out of absorption.
As the improvement of the present invention, the absorption detailed process of each presoma is: with higher rotating speed
Rotating powder granule loading attachment, powder granule carries out circumference fortune the most together due to the biggest centrifugal force
Dynamic, presoma is input in reaction cavity together along with the carrier gas of larger flow, loads from powder granule
The outer screen of device is directed radially through powder granule layer and adsorbs at particle surface, adjusts and passes through powder body
The air-flow velocity of granular layer, utilizes the piezometer inspection being connected respectively with reaction cavity and air vent upstream
Surveying the pressure differential of powder granule layer both sides, when this pressure differential reaches stable, powder granule is produced by it
Barometric gradient power and powder body suffered by centrifugal force balance each other, thus realize the dispersion of powder granule, promote
Enter the uniformity of presoma absorption.
As the improvement of the present invention, the rotating speed of powder granule loading attachment is preferably 160～900rpm.
As the improvement of the present invention, it is preferably 30～500cm/s by the air-flow velocity of powder granule layer.
As the improvement of the present invention, the temperature of reaction cavity system is in the range of room temperature to 550 DEG C.
The surface modification method of the micro-nano granules of the present invention uses pressurize deposition process in actual carrying out
Carry out the modification of powder granule surface.Specifically, after precursor pulse is passed through reaction cavity, close true
The vacuum pump of do-nothing system, stops bleeding, and keeps the pressure environment in reaction cavity, fills with powder granule
Carry put the micro-nano granules being rotated after rising to certain altitude due to gravity effect from
By falling bodies, powder granule disperses mutually during falling, its respective surface uniform adsorption presoma,
Pressure maintaining period terminates final vacuum pump and is taken away with unnecessary presoma by byproduct of reaction, then with same
Mode carries out the absorption of the second presoma；
The surface modification method of the micro-nano granules in the present invention uses balance dispersion heavy in actual carrying out
Long-pending method carries out the modification of powder granule surface, specifically, loads with higher rotational speed powder granule
Device, powder granule carries out circular motion the most together due to the biggest centrifugal force, and presoma is along with relatively
The carrier gas of big flow is input in reaction cavity, together from the outer screen edge of powder granule loading attachment
Radial through powder granule layer and adsorb at particle surface, adjust the air-flow velocity by powder granule layer,
The piezometer being connected with reaction cavity and air vent upstream respectively is utilized to detect powder granule layer both sides
Pressure differential, when this pressure differential reaches stable, its barometric gradient power that powder granule is produced and powder body
Suffered centrifugal force balances each other, thus realizes the dispersion of powder granule, promotes the uniform of presoma absorption
Property.The rotating speed that the method is bigger additionally aids the size reducing the aggregate that powder granule is formed, with
Increase reaction table area further, improve the utilization rate of presoma.
Further, the presoma burst length is relevant to the size of the total surface area of powder granule, surface
Long-pending the biggest, the burst length is the longest, generally 10～180s/m2, it is ensured that the absorption of all surface is abundant.
Further, in pressurize deposition process, the dwell time is big with the specific surface area of powder granule
Little relevant, specific surface area is the biggest, and the dwell time is the longest, and generally 10～120s, before which increasing
Drive the time of contact of body and powder granule surface, promote fully carrying out of absorption.
Further, in pressurize deposition process, the rotating speed of powder granule loading attachment is unsuitable too fast,
Powder granule can be fallen after rotating to certain altitude, and typically choosing rotating speed is 30～160rpm.
Further, in balance dispersed deposition method, the rotating speed of powder granule loading attachment is very fast,
Make powder granule all the time along with loading attachment carries out circular motion without falling, typically choose rotating speed
It is 160～900rpm.
Further, in balance dispersed deposition method, the stream of the carrier gas of presoma is carried by control
The choke valve measuring and utilizing air vent upstream adjusts by the air-flow velocity of powder granule layer to reach
The most stable pressure differential, rotating speed used is the highest, it is achieved the required flow rate of balance is the biggest.Typically use stream
Speed is 30～500cm/s.
Further, the temperature of reaction cavity system is that room temperature is to 550 DEG C.
In general, by the contemplated above technical scheme of the present invention compared with prior art, due to
Use technique for atomic layer deposition, it is ensured that the dispersion that micro-nano powder granule is excellent in deposition process
Property, reduce the size of powder reuniting body, thus increase the surface area participating in reaction, it is achieved particle surface
To presoma uniform, fully adsorb.Specifically, it is possible to obtain following beneficial effect:
(1) in the device that this micro-nano granules surface is modified, the pressurize deposition side under centrifugal action is utilized
Method, it is possible to realize connecing for a long time of presoma and powder granule surface when dispersion powder granule
Touching, presoma absorption is full and uniform, it is ensured that the uniformity of surface deposition thin film, before improve simultaneously
Drive the utilization rate of body.
(2) utilize the balance dispersion under centrifugal action heavy in the device that this micro-nano granules surface is modified
Long-pending method, it is possible to reduce the size of the aggregate that micro-nano granules is formed to a certain extent, protect simultaneously
Card dispersibility, increases the specific surface area participating in reaction, increases the area of institute's modification of surfaces, promotes
The full and uniform absorption of presoma, improves the uniformity of deposition thin film and can increase batch processed
Amount.
(3) in the device that this micro-nano granules surface is modified, presoma and carrier gas stream pass through powder body
The outer screen of grain loading attachment is directed radially through powder granule layer, and is drawn out of from interior side screen,
Under high rotating speed, this air-flow balances with centrifugal force simultaneously, it is to avoid powder body in the design that air-flow flows vertically
Granule is prone to be deposited in the defect of side screen surface of bleeding, it is possible to give full play to centrifugal action for
Grain surface deposition uniformity and the improvement effect of adequacy.
Accompanying drawing explanation
Fig. 1 is a kind of total system for micro-nano granules surface modification apparatus of the embodiment of the present invention
Schematic diagram；
Fig. 2 is the powder granule loading attachment outside drawing of the embodiment of the present invention；
Fig. 3 is the axial sectional view of powder granule loading attachment；
Fig. 4 is powder granule loading attachment radial cross-section；
Fig. 5 is powder granule loading attachment schematic three dimensional views.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with accompanying drawing
And embodiment, the present invention is further elaborated.Should be appreciated that described herein specifically
Embodiment only in order to explain the present invention, is not intended to limit the present invention.Additionally, it is disclosed below
Just may be used as long as technical characteristic involved in each embodiment of the present invention does not constitutes conflict each other
To be mutually combined.
As it is shown in figure 1, the surface modification apparatus of a kind of micro-nano granules, including vacuum system, reaction
Cavity, powder granule loading attachment, presoma supply, heating and temperature control system, carrier gas induction system,
Rotary motion drive system, control system.Presoma supply system coupled reaction cavity, powder granule
Loading attachment is placed in inside reaction cavity, and powder granule loading attachment one end connects vacuum system, another
End connects rotary motion drive system.
It is connected by carrier gas induction system with reaction cavity in presoma supply system, carrier gas transfer pipeline
On mass flow controller 5 is installed.
Presoma supply system includes the presoma branch road of two or more parallel connection, provides respectively not
Same precursor source, its critical piece includes that presoma quickly responds valve 6 and presoma steel cylinder 8,
Presoma quickly responds the manual needle valve 7 between valve and steel cylinder.It is normal that presoma quickly responds valve 6
Valve closing door, the minimum opening time is up to 5ms.Each quickly response valve alternately unlatching, it each props up
Presoma in the steel cylinder on road alternately enters reaction cavity internal system.
Reaction cavity is made up of left, center, right three part, is sealed by oxygen-free copper pad 2.Cavity left part exists
Operation is used for take apart, takes out the powder granule loading attachment 3 of outer chamber.Upper and lower both sides in the middle part of exocoel
There are two flange-interfaces, are respectively used to connect the piezometer 14 in vacuum system and the temperature of temp measuring system
Sensor 4, for the pressure and temperature within test chamber.In the middle part of exocoel the left and right sides from different before
Drive body supply system to be connected.About cavity, the inner side of two parts is provided with ring heater 16.Instead
Answering cavity left part to be connected with the device for sealing magnetic fluid 18 of rotary motion drive system, reaction cavity is right
Portion is connected with the device for sealing magnetic fluid 9 of vacuum system.
Heating and temperature control system includes that the ring heater 16 being arranged on inside cavity and presoma supply
Answer the heater 15 in system and temperature sensor 14.Ring heater 16 and presoma supply
Heater 15 in system respectively reaction cavity 1 and presoma steel cylinder 8, presoma quickly respond
Valve 6 and the pipeline heating of presoma branch road.The temperature within reaction cavity 1 is measured in temperature sensor 14
Degree.
As shown in Fig. 2,3,4,5, powder granule loading attachment uses double-layer circular column structure, inside and outside
Both sides are the powder of stainless steel sintering filter screen 24,26 in micron order aperture, and aperture is preferably 5～10 microns,
Double-layer circular columnar filter screen is clamped by the rustless steel end face 21,25 at two ends by stud 22 and nut 23,
Ensure that powder granule will not spill from granule loading attachment, by removing the two end face and stud
Connect to take out and complete the powder granule that surface is modified.End face 25 is close with the magnetic fluid in vacuum system
Seal apparatus 9 is connected, and end face 21 is connected with the device for sealing magnetic fluid 18 of rotary motion drive system.
Vacuum system includes vacuum pump 12, electromagnetic valve 11, choke 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 completely by powder granule loading attachment 3
It is drawn out of rather than is directly taken away by vacuum pump 12.Choke valve 10 and device for sealing magnetic fluid 9 times
Trip is directly connected to, for controlling by the air-flow velocity of powder granule layer in powder granule loading attachment 3.
After electromagnetic valve 11 is connected on choke valve, determining whether to bleed reaction cavity 1, vacuum pump 12 is responsible for
The pressure of reaction cavity 1 is extracted into the vacuum needed for ALD reaction, it is ensured that the cleaning of reaction environment is also
Cleaning reaction by-product and unnecessary presoma.
Rotary motion drive system include motor 20, shaft coupling 19, device for sealing magnetic fluid 18 and
Bearing 17.Motor 20 provides driving force, and coupled shaft coupling 19 is close to magnetic fluid for transmission
The rotating shaft of seal apparatus 18, device for sealing magnetic fluid 18 is internal and reaction cavity 1 left part is installed
There is bearing 17 to support motion and the stress of rotating shaft.Device for sealing magnetic fluid 18 and reaction cavity 1 phase
Even, ensure the air-tightness of reaction cavity simultaneously.
Control system controls the time that the open and close of vacuum system, presoma pulse and reaction are cleaned
And cycle-index, temperature, the control of powder granule loading attachment 9 and 18 rotating speed.Control system is also
Including two piezometers, piezometer 14 is connected with reaction cavity 1, and piezometer 13 is connected to vacuum
The upstream of choke valve 10 in system.
The embodiment of the present invention utilize the method that the surface of micro-nano granules modified by said apparatus, its tool
Body process is as follows:
Wherein, atom layer deposition process can use pressurize depositing operation or balance dispersed deposition technique.
Below, first introduce use pressurize depositing operation embodiment:
Step S10: pretreatment stage.Powder granule is put in powder granule loading attachment, with necessarily
Rotating speed drive powder body rotate, selection of speed is 30～60rpm.Before fully opening vacuum pump
Electromagnetic valve and choke valve carry out evacuation (vacuum level requirements pressure is less than or equal to 1Pa) to reaction cavity.
Reaction cavity is heated simultaneously, temperature according to selected, reaction controlling be room temperature～550 DEG C.Protect
Hold this process at least 1 hour.Arranging line temperature is 100 DEG C, and presoma quickly responds valve temperature
Degree is 120 DEG C.When the displays temperature of reaction cavity reaches established temperature fluctuation range less than 1 DEG C
Time can carry out subsequent technique.
Step S20: presoma stage pulse.Close the electromagnetic valve before vacuum pump to stop bleeding.Turn on
The manual needle valve that presoma steel cylinder is corresponding reaches certain presoma output.Open presoma quickly to ring
Valve, opening time is answered to be chosen as 60～180s/m2, when it is opened with the quality of carrier gas induction system
The saturated vapor that precursor source is carried in flow controller input carrier gas 20～200sccm is passed through reaction cavity.
After unlatching presoma quickly responds valve closing, stop the input carrier gas of carrier gas induction system.On these rank
The rotary powder that section gives powder granule loading attachment and inside thereof by rotary motion drive system is transported
Dynamic, selection of speed is 30～160rpm.During Gai, precursor A starts absorption on powder granule surface.
Step S30: pressurize absorption phase.Maintain the rotating speed in previous step and pressure 10～120s,
Micro-nano granules after rising to certain altitude due to the effect freely falling body of gravity, powder granule under
Disperseing mutually during falling, precursor A is fully adsorbed on powder granule surface.
Step S40: wash phase.Carrier gas input system to reaction cavity input carrier gas 100～
1000sccm, opens the electromagnetic valve before vacuum pump simultaneously and starts to bleed, and cleaning reaction by-product is with unnecessary
Precursor A, this process maintain 60～180s.
Step S50: carry out the stage pulse of 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: carry out the wash phase of precursor B according to the method for step S40.
Step S80: circulation step S20～S70 as stated above, cycle-index depends on required deposition
Film thickness.Deposition can form the thin film of desired thickness at particle surface after terminating, completes micro-
The surface of nano-particle is modified.
The embodiment using balance dispersed deposition technique is as follows:
Step S10 ': pretreatment stage.Identical with step S10 in deposition process one.
Step S20 ': presoma stage pulse.Selection of speed is 180～900rpm.Keep vacuum pump
The unlatching of front electromagnetic valve.The carrier gas flux adjusting carrier gas process system passes through powder body with throttle valve control
The air-flow velocity of granular layer, utilizes the piezometer inspection being connected respectively with reaction cavity and air vent upstream
Surveying the pressure differential of powder granule layer both sides, flow velocity when reaching stable with pressure differential is carried out powder granule
Dispersed surface deposition, it is general that to use flow velocity be 30～500cm/s.For presoma from steel cylinder
Output, method such as step S20, open presoma and quickly respond valve times 10～100s/m2, carrier gas
The saturated vapor carrying precursor source is passed through reaction cavity.Presoma loads from powder granule along with carrier gas
The outer screen of device is directed radially through powder granule layer and adsorbs at particle surface.
Step S30 ': wash phase.In addition to the conveying stopping presoma all with the condition phase of previous step
With.Cleaning reaction by-product and unnecessary precursor A, this process maintains 60～180s.
Step S40 ': the stage pulse of precursor B is carried out according to the method for step S20.
Step S50 ': the wash phase of precursor B is carried out according to the method for step S30.
Step S60 ': circulation step S20 '～S50 ' as stated above, cycle-index depends on institute
The film thickness that need to deposit.Deposition can form the thin film of desired thickness at particle surface after terminating, complete
The surface of micro-nano granules is modified in pairs.
In order to illustrate further the structure of apparatus and method of the present invention, principle, below in conjunction with specifically
The surface modification process of micro-nano granules, it is described further.
Embodiment one
To the AlH that particle diameter is 50 μm3Particle surface is coated with the Al that one layer of 10nm is thick2O3Thin film is to reduce it
Impact sensitivity, improves safety.Choose trimethyl aluminium (TMA) and water (H2O) it is presoma, itsMain anti- The equation is answered to be:
(A)AlOH*+Al(CH3)3→AlOAl(CH3)2 *+CH4
(B)AlCH3 *+H2O→AlOH*+CH4
Use above-mentioned micro-nano granules surface modification apparatus and corresponding pressurize deposition processing recipe:
By 0.1g AlH3Granule is put in powder granule loading attachment and is installed in reaction cavity,
Connect with device for sealing magnetic fluid.Seal reaction cavity afterwards.
Opening vacuum pump, opens solenoid valve, is incited somebody to action so that reaction cavity is connected with vacuum pump with choke valve
Reaction cavity pressure is evacuated to less than or equal to 1pa.Reacting by heating cavity makes its internal temperature stablize
120 DEG C, heating presoma steel cylinder, presoma bypass line and presoma quickly respond valve and all arrive
80℃.Give powder granule loading attachment rotating speed 60rpm, maintain this state 1 hour.
Close electromagnetic valve, open the manual needle valve after presoma steel cylinder, open the quick responsive valves of presoma
Door, with the carrier gas (N of 100sccm2) carry presoma TMA steam entrance reaction cavity, TMA pulse 60s
Rear closedown presoma quickly responds valve, stops being passed through carrier gas, enters the packing stage of 30s.Rotate
Powder granule freely falling body after reaching a certain height, uniform with presoma TMA in dropping process
Contact absorption.Open electromagnetic valve to bleed, simultaneously to be passed through the carrier gas of 100sccm, clean up
Byproduct of reaction with for presoma TMA.Presoma H2The pulse of O, pressurize are similar with wash phase.
Carry out the circulation 100 times of two kinds of presoma pulses, pressurize and wash phase, deposition terminate after i.e.
Can be at AlH3Particle surface forms the Al that thickness is about 14nm2O3Thin film.
Embodiment two
It is the SiO of 200nm to particle diameter2Particle surface is coated with the Al that one layer of 5nm is thick2O3Thin film is with research
SiO2The surface texture of granule.Choose trimethyl aluminium (TMA) and water (H2 17O) it is presoma.
Use above-mentioned micro-nano granules surface modification apparatus and corresponding balance dispersed deposition technique side
Method:
By SiO2Granule is put in powder granule loading attachment and is installed in reaction cavity, with magnetic
Fluid seal apparatus connects.Seal reaction cavity afterwards.
Opening vacuum pump, opens solenoid valve, is incited somebody to action so that reaction cavity is connected with vacuum pump with choke valve
Reaction cavity pressure is evacuated to less than or equal to 1pa.Reacting by heating cavity makes its internal temperature stablize
200 DEG C, heating presoma steel cylinder, presoma bypass line and presoma quickly respond valve and all arrive
120℃.Give powder granule loading attachment rotating speed 60rpm, maintain this state 2 hours.
Selection of speed is 300rpm.Keep the unlatching of the electromagnetic valve before vacuum pump.Adjust carrier gas (N2) stream
Amount and throttle valve control are 100cm/s by the air-flow velocity of powder granule layer, reach powder granule layer two
The steady statue of lateral pressure difference.Turn on the manual needle valve after presoma TMA steel cylinder, open presoma fast
Speed response valve 60s, carrier gas is carried the saturated vapor of presoma TMA and is passed through reaction cavity.Presoma
TMA is directed radially through powder granule layer along with carrier gas from the outer screen of powder granule loading attachment and inhales
It is attached to particle surface.After the quickly response valve closing of presoma TMA, other conditions are constant, to
Grain surface is carried out, extraction by-product and unnecessary presoma TMA.Presoma H2 17The arteries and veins of O
Punching, pressurize similar with wash phase.
Carry out the circulation 50 times of two kinds of presoma pulses, pressurize and wash phase, after deposition terminates
At SiO2Particle surface forms the Al that thickness is about 5nm2O3Thin film.
As it will be easily appreciated by one skilled in the art that and the foregoing is only presently preferred embodiments of the present invention,
Not in order to limit the present invention, all made within the spirit and principles in the present invention any amendment, etc.
With replacement and improvement etc., should be included within the scope of the present invention.
Claims (22)
1. the device modified for micro-nano granules surface, by utilize that carrier gas carries multiple before
Drive body and carry out ald, thus form cladding thin film on the surface of micro-nano granules, it is achieved surface
Modify, it is characterised in that this device includes:
Reaction chamber, its cavity being internally formed is for the reaction compartment as presoma Yu micro-nano granules；
Multiple presoma feeding mechanisms, it is communicated with described reaction chamber by pipeline respectively, for respectively
Different presomas is provided in reaction cavity；
Carrier gas induction system, it is arranged on the pipeline of described presoma feeding mechanism, described presoma
It is transported in reaction chamber by the carrier gas of this carrier gas induction system output；And
Powder granule loading attachment, it is arranged in described reaction chamber and can rotate axially therein, uses
In carrying micro-nano granules to be finished, this powder granule loading attachment one end be positioned at outside reaction chamber
Rotary drive mechanism connect, the other end with reaction chamber outside vacuum system be connected；
Presoma is alternately carried to described reaction chamber respectively by the plurality of presoma feeding mechanism,
And enter in the powder granule loading attachment of described rotation and carry out atom to contact with micro-nano granules surface
Layer deposition reaction, thus cladding thin film is formed on the surface of micro-nano granules, it is achieved surface is modified.
A kind of device modified for micro-nano granules surface the most according to claim 1, it is special
Levying and be, described powder granule loading attachment is that two-layer cylinder set forms, and inside and outside two-layer barrel is
The powder of stainless steel sintering filter screen in micron order aperture, cylinder both ends of the surface are provided with cover plate, and pass through stud
It is connected with each other to clamp double-layer circular columnar filter screen, it is ensured that powder granule will not be from granule loading attachment
Spilling, the cover plate at cylinder two ends is connected with vacuum system by the first device for sealing magnetic fluid and logical respectively
Second device for sealing magnetic fluid is connected with rotary drive mechanism.
A kind of device modified for micro-nano granules surface the most according to claim 1 and 2,
It is characterized in that, described presoma feeding mechanism includes storing the presoma steel cylinder of precursor source, setting
Presoma on the pipeline that presoma steel cylinder is connected with reaction chamber quickly responds valve, and is positioned at institute
State presoma and quickly respond the manual needle valve between valve and steel cylinder, by each presoma feeding mechanism
Alternately the opening of quickly response valve, it is achieved different presomas alternately enter reaction chamber, and pass through hands
The regulation of dynamic needle-valve, it is achieved the control of the presoma pulsating pressure size of input.
A kind of device modified for micro-nano granules surface the most according to claim 1 and 2,
It is characterized in that also there is heating and temperature control system, add including the annular being arranged on inside cavity
Heater (15) in hot device (16), presoma supply system and temperature sensor (14),
Wherein, ring heater (16) and heater (15) are respectively used to as reaction chamber and presoma
Feeding mechanism heats, and described temperature sensor (14) is used for measuring the temperature of reaction chamber (1).
A kind of device modified for micro-nano granules surface the most according to claim 3, it is special
Levy and be, also there is heating and temperature control system, including the ring heater being arranged on inside cavity
(16) heater (15), in presoma supply system and temperature sensor (14), its
In, ring heater (16) and heater (15) are respectively used to supply for reaction chamber and presoma
Answering device to heat, described temperature sensor (14) is used for measuring the temperature of reaction chamber (1).
6. according to a kind of dress modified for micro-nano granules surface described in claim 1 or 2 or 5
Put, it is characterised in that described vacuum system includes vacuum pump (12), choke valve (10) and first
Device for sealing magnetic fluid (9), wherein said vacuum pump (12) is for reaction chamber evacuation, it is ensured that
Clean and the cleaning reaction by-product of reaction environment and unnecessary presoma, described first magnet fluid sealing
Device (9) is connected with powder granule loading attachment (3), is used for so that air-flow all of in reaction chamber
It is drawn out of after both passing through the powder granule layer in this powder granule loading attachment (3), described choke valve (10)
It is arranged on the first device for sealing magnetic fluid (9) downstream, for controlling by powder granule loading attachment (3)
The air-flow velocity of middle powder granule layer.
A kind of device modified for micro-nano granules surface the most according to claim 3, it is special
Levying and be, described vacuum system includes that vacuum pump (12), choke valve (10) and the first magnetic fluid are close
Seal apparatus (9), wherein said vacuum pump (12) is for reaction chamber evacuation, it is ensured that reaction environment
Clean and cleaning reaction by-product and unnecessary presoma, described first device for sealing magnetic fluid (9)
It is connected with powder granule loading attachment (3), is used for so that air-flow all of in reaction chamber both passes through this powder
Being drawn out of after powder granule layer in body granule loading attachment (3), described choke valve (10) is arranged on
First device for sealing magnetic fluid (9) downstream, for controlling by powder granule loading attachment (3)
The air-flow velocity of powder granule layer.
A kind of device modified for micro-nano granules surface the most according to claim 4, it is special
Levying and be, described vacuum system includes that vacuum pump (12), choke valve (10) and the first magnetic fluid are close
Seal apparatus (9), wherein said vacuum pump (12) is for reaction chamber evacuation, it is ensured that reaction environment
Clean and cleaning reaction by-product and unnecessary presoma, described first device for sealing magnetic fluid (9)
It is connected with powder granule loading attachment (3), is used for so that air-flow all of in reaction chamber both passes through this powder
Being drawn out of after powder granule layer in body granule loading attachment (3), described choke valve (10) is arranged on
First device for sealing magnetic fluid (9) downstream, for controlling by powder granule loading attachment (3)
The air-flow velocity of powder granule layer.
9. according to the one described in claim 1 or 2 or 5 or 7 or 8 for micro-nano granules surface
The device modified, it is characterised in that described rotary drive mechanism includes motor (20), shaft coupling (19)
With the second device for sealing magnetic fluid (18), wherein the second device for sealing magnetic fluid (18) and reaction chamber
(1) being connected, motor (20) gives the second magnetic fluid close by coupled shaft coupling (19) transmission
The rotating shaft of seal apparatus (18), thus drive powder granule loading attachment (3) rotation being connected with this rotating shaft
Turn.
A kind of device modified for micro-nano granules surface the most according to claim 3, its
Being characterised by, described rotary drive mechanism includes motor (20), shaft coupling (19) and the second magnetic current
Body sealing device (18), wherein the second device for sealing magnetic fluid (18) is connected with reaction chamber (1),
Motor (20) gives the second device for sealing magnetic fluid (18) by coupled shaft coupling (19) transmission
Rotating shaft, thus drive be connected with this rotating shaft powder granule loading attachment (3) rotation.
11. a kind of devices modified for micro-nano granules surface according to claim 4, its
Being characterised by, described rotary drive mechanism includes motor (20), shaft coupling (19) and the second magnetic current
Body sealing device (18), wherein the second device for sealing magnetic fluid (18) is connected with reaction chamber (1),
Motor (20) gives the second device for sealing magnetic fluid (18) by coupled shaft coupling (19) transmission
Rotating shaft, thus drive be connected with this rotating shaft powder granule loading attachment (3) rotation.
12. a kind of devices modified for micro-nano granules surface according to claim 6, its
Being characterised by, described rotary drive mechanism includes motor (20), shaft coupling (19) and the second magnetic current
Body sealing device (18), wherein the second device for sealing magnetic fluid (18) is connected with reaction chamber (1),
Motor (20) gives the second device for sealing magnetic fluid (18) by coupled shaft coupling (19) transmission
Rotating shaft, thus drive be connected with this rotating shaft powder granule loading attachment (3) rotation.
13. 1 kinds utilize according to any one of the claims 1-12 for micro-nano granules surface
The method that the device modified carries out the modification of micro-nano granules surface, it is multiple by utilize carrier gas to carry
Presoma carries out ald, forms cladding thin film on the surface of micro-nano granules, it is achieved surface is repaiied
Decorations, it is characterised in that the method includes:
Under certain ald (ALD) reaction temperature, utilize described vacuum system to reaction chamber
Evacuation；
Powder granule loading attachment rotates under the drive of rotary motion drive system, drives powder therein
Body particle rotation is moved；
Multiple presoma alternately enters reaction chamber under carrier gas drives, and loads through described powder granule
There is chemisorbed on powder granule surface after device outer screen；
Carrier gas is utilized to clean unnecessary presoma and reaction by-product under the effect of the vacuum pump of vacuum system
Thing, thus obtain the micro-nano granules that required carrying out surface is modified.
14. according to claim 13 utilize above-mentioned for micro-nano granules surface modify device
The method carrying out the modification of micro-nano granules surface, it is characterised in that the absorption of each presoma is concrete
Process is: after precursor pulse is passed through reaction cavity, and the vacuum pump of vacuum system stops bleeding, and protects
Hold the pressure environment in reaction cavity, micro-nano be rotated with powder granule loading attachment
Grain is due to the effect freely falling body of gravity after rising to certain altitude, and powder granule is in the process fallen
In disperse mutually, its respective this presoma of surface uniform adsorption.
15. according to claim 14 utilize above-mentioned for micro-nano granules surface modify device
The method carrying out the modification of micro-nano granules surface, it is characterised in that dwell time and the ratio of powder granule
The size of surface area is correlated with.
16. modify for micro-nano granules surface according to utilizing described in claims 14 or 15 is above-mentioned
The device method that carries out the modification of micro-nano granules surface, it is characterised in that the presoma burst length with
The size of the total surface area of powder granule is correlated with.
17. modify for micro-nano granules surface according to utilizing described in claims 14 or 15 is above-mentioned
The device method that carries out the modification of micro-nano granules surface, it is characterised in that powder granule loading attachment
Rotating speed be preferably 30～160rpm.
18. according to claim 13 utilize above-mentioned for micro-nano granules surface modify device
The method carrying out the modification of micro-nano granules surface, it is characterised in that the absorption of each presoma is concrete
Process is: with higher rotational speed powder granule loading attachment, powder granule is centrifuged due to the biggest
Power carries out circular motion the most together, and presoma is input to reaction chamber together along with the carrier gas of larger flow
In body, from the outer screen of powder granule loading attachment be directed radially through powder granule layer and adsorb
Grain surface, adjusts by the air-flow velocity of powder granule layer, utilize respectively with reaction cavity and air vent
The pressure differential of the piezometer detection powder granule layer both sides that upstream is connected, when this pressure differential reaches stable
Time, the centrifugal force suffered by its barometric gradient power producing powder granule and powder body balances each other, thus real
The dispersion of existing powder granule, promotes the uniformity of presoma absorption.
19. according to claim 18 utilize above-mentioned for micro-nano granules surface modify device
The method carrying out the modification of micro-nano granules surface, the rotating speed of powder granule loading attachment be preferably 160～
900rpm。
20. modify for micro-nano granules surface according to utilizing described in claim 18 or 19 is above-mentioned
The device method that carries out the modification of micro-nano granules surface, the air-flow velocity by powder granule layer is preferred
It is 30～500cm/s.
21. modify for micro-nano granules surface according to utilizing described in claim 18 or 19 is above-mentioned
The device method that carries out the modification of micro-nano granules surface, the temperature of reaction cavity system is in room temperature extremely
In the range of 550 DEG C.
22. according to claim 20 utilize above-mentioned for micro-nano granules surface modify device
The method carrying out the modification of micro-nano granules surface, the temperature of reaction cavity system is in room temperature to 550 DEG C scope
In.
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| CN104878368B (en) * | 2015-06-09 | 2017-05-10 | 天津巴莫科技股份有限公司 | Powder microwave chemical vapor phase coating equipment capable of realizing continuous production |
| CN105369221B (en) * | 2015-12-17 | 2018-01-30 | 华中科技大学 | The apparatus for atomic layer deposition and its method of a kind of encapsulated nanoparticles |
| CN105386011B (en) * | 2015-12-17 | 2017-09-22 | 华中科技大学 | A kind of powder apparatus for atomic layer deposition fluidized based on planet |
| CN106658934B (en) * | 2017-03-03 | 2023-10-31 | 深圳优普莱等离子体技术有限公司 | Microwave plasma powder treatment device |
| US11174552B2 (en) * | 2018-06-12 | 2021-11-16 | Applied Materials, Inc. | Rotary reactor for uniform particle coating with thin films |
| CN109881180B (en) * | 2019-01-31 | 2020-07-07 | 华中科技大学 | Rapid-circulation atomic layer deposition equipment for micro-nano particles |
| CN109916814B (en) * | 2019-03-18 | 2020-03-13 | 上海交通大学 | Device and method for solid particle thermophysical/chemical visualization and spectral measurement |
| CN109865484A (en) * | 2019-04-01 | 2019-06-11 | 深圳市奥普斯等离子体科技有限公司 | A kind of particle and powder body material plasma surface processor |
| CN110013817A (en) * | 2019-05-21 | 2019-07-16 | 江苏迈纳德微纳技术有限公司 | A kind of atomic level powder modification equipment |
| CN110931713B (en) * | 2019-12-13 | 2020-12-29 | 华中科技大学 | Lithium ion battery anode and preparation method thereof |
| CN212189040U (en) * | 2020-04-08 | 2020-12-22 | 厦门韫茂科技有限公司 | Gas conveying device of powder surface coating machine and powder surface coating machine |
| CN212102999U (en) * | 2020-04-08 | 2020-12-08 | 厦门韫茂科技有限公司 | Wall structure of gas phase reaction powder surface coating machine |
| CN113564564B (en) * | 2021-07-02 | 2022-10-21 | 华中科技大学 | Atomic layer deposition apparatus |
| CN114134483B (en) * | 2021-09-23 | 2023-07-11 | 厦门韫茂科技有限公司 | Atomic layer deposition method and device for coating powder material |
| CN117364063A (en) * | 2023-10-27 | 2024-01-09 | 无锡松煜科技有限公司 | Silver powder and preparation method and application thereof |
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