CN109384216A - The manufacturing method of carbon nano structure growth CVD device and carbon nano structure - Google Patents
The manufacturing method of carbon nano structure growth CVD device and carbon nano structure Download PDFInfo
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- CN109384216A CN109384216A CN201810707847.1A CN201810707847A CN109384216A CN 109384216 A CN109384216 A CN 109384216A CN 201810707847 A CN201810707847 A CN 201810707847A CN 109384216 A CN109384216 A CN 109384216A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
Abstract
The present invention provides a kind of manufacturing method of carbon nano structure growth CVD device and carbon nano structure for growing carbon nano structure in object to be processed whole surface, which includes treatment furnace (1) with CVD device (M)；Conveyer (15), to transport object to be processed (Fm) by the mode in treatment furnace；Gas leading-in device (11,12), carbon containing unstrpped gas is imported into treatment furnace；And heating device (13), heat unstrpped gas；The CVD device grows carbon nano structure on the surface by handling indoor object to be processed；Conveyer, which has, places object to be processed and the shoestring (Vm) mobile with fixing speed, forms the multiple openings for allowing carbon nano structure to grow to the placement surface side (Fm1) of object to be processed on the shoestring；In the CVD device, mesh (Bm) is between shoestring and object to be processed.
Description
Technical field
The carbon nano structure that the present invention relates to a kind of for growing the carbon nano structures such as carbon nanotube and graphene is raw
The manufacturing method of long CVD device and carbon nano structure.
Background technique
The CVD device of this carbon nano structure growth is for example known in patent document 1.Wherein there is treatment furnace；
Conveyer, transporting object to be processed makes it by treatment furnace；Gas leading-in device imports carbon containing into treatment furnace
Unstrpped gas；And heating device, heat unstrpped gas.Conveyer has multiple rollers of interval configuration and wound on this
Cricoid mesh band (shoestring) around a little rollers transports the mesh band part for being located at upside by carrying out rotation driving to roller
The object to be processed of upper placement, passes through it in treatment furnace.Also, by period in treatment furnace, after making heating
Unstrpped gas contact treatment object surface, making carbon nano structure is including the process object of the placement surface side of object to be processed
Object is grown on surface.
Herein, in such as conveyer of above patent document 1, due to usually having defined tension, institute on mesh band
To need to use outer diameter (line footpath) biggish wire rod as composition mesh band to persistently steadily transport object to be processed
Wire rod, or increase used wire rod and reduce aperture opening ratio, so that mesh belt be made to have mechanical strength.At this point, known handled
The part opposite with each wire rod of the placement surface side of object does not grow carbon nano structure (generating so-called band trace).This quilt
Be considered for example due to when line footpath is big unstrpped gas can not reach the perspective plane of the wire rod of the placement surface side of object to be processed and draw
It rises.To there are problems that the electrode material in substrate two sides growth carbon nanotube as battery can not be used to.
[existing technical literature]
[patent document]
No. 4581146 bulletins of [patent document 1] Japanese Patent No.
Summary of the invention
Technical problems to be solved by the inivention
In view of the foregoing, the subject of the invention is to provide one kind, and carbon nano structure can be made in object to be processed whole table
The manufacturing method of the carbon nano structure growth CVD device and carbon nano structure of looking unfamiliar long.
Solve the means of technical problem
To solve the above subject, carbon nano structure growth CVD device of the invention is comprising: processing
Furnace；Conveyer, to transport object to be processed by the mode in treatment furnace；Gas leading-in device imports into treatment furnace and contains
The unstrpped gas of carbon；And heating device, heat unstrpped gas；The carbon nano structure growth CVD device makes carbon nanometer
Structural body is grown on the surface by handling indoor object to be processed；Conveyer, which has, places object to be processed and with rule
The mobile shoestring of constant speed degree, being formed on the shoestring allows carbon nano structure to place what surface side was grown to object to be processed
Multiple openings；In the carbon nano structure growth CVD device, mesh is between shoestring and object to be processed.
Using the present invention, since the mesh between shoestring and object to be processed is not usually with defined
The mesh of tension, so without considering mechanical strength.Therefore, the line of the wire rod of mesh is constituted for example, by minimizing
Diameter, or increase the aperture opening ratio of mesh as far as possible, the unstrpped gas after can making heating reaches the placement surface side of object to be processed
Whole surface.So as to grow carbon nano structure in object to be processed whole surface.
However, in order to make the unstrpped gas after heating reach the whole surface for placing surface side of object to be processed, Ke Yikao
Considering is suspended at object to be processed on shoestring using fixture, but when installs fixture needs to take time and energy colored in object to be processed
Between, such productivity can decline.In the present invention, it is preferred to constituted the shoestring with mesh band, the mesh be set as by
The outer diameter wire rod smaller than the wire rod for constituting the mesh band forms and is formed as band-like, moves with the movement of the mesh band
It is dynamic.Using which, it is not required to installs fixture, therefore not will lead to productivity decline.
Further more, in the present invention, the aperture opening ratio of the mesh is preferably provided at 50~99.8% range.If opening
Rate is less than 50%, then the unstrpped gas provided sometimes is insufficient, and the growth of carbon nano structure can be deteriorated, or take mesh
The trace of shape, on the other hand, if aperture opening ratio is more than 99.8%, the mechanical strength of mesh can decline sometimes.
Further more, in the present invention, when keeping the net with the state rolled using the mesh of sheet as the mesh
Eye body, and with the outlet roller for sending out the mesh and when rolling the take-up roll for the mesh sent out by outlet roller,
The conveyer can also be made of multiple rollers and driving portion, and the multiple roller configures between these outlet rollers and take-up roll simultaneously
It is wrapped around the mesh band, the driving portion rotation drives the driving roller in these multiple rollers.At this point, if by mesh with
The overlapping of mesh band is placed, when carrying out rotation driving with roller to driving keeps mesh band mobile with fixing speed, can mesh it is adjoint
The movement of the mesh band of the movement and move.No setting is required as a result, to outlet roller and take-up roll carry out rotation driving driving portion,
The cost of CVD device can be reduced.
Further more, the manufacturer of the carbon nano structure of the invention using above-mentioned carbon nano structure growth CVD device
Method characterized by comprising object to be processed is placed into mesh after by shoestring and mesh overlapping by preparatory process
On；And growth process, move shoestring and mesh in treatment furnace, after heating is made during in through treatment furnace
Unstrpped gas is contacted with object to be processed surface, grows carbon nano structure on the object to be processed surface；In the growth
In process, carbon nano structure is grown by following stages, it may be assumed that in the carbon nano junction for placing surface side growth of object to be processed
Structure body respectively with constitute first stage for contacting of each wire rod of mesh, and the carbon nano structure contacted with each wire rod is into one
One-step growth carries the second stage of object to be processed by the carbon nano structure of these growths.
Using the present invention, in second stage, between the object to be processed and mesh that carbon nano structure is carried
Gap is formed, the unstrpped gas after heating can reach the whole surface of the placement surface side of object to be processed by the gap.As a result,
Carbon nano structure can be grown in the whole surface of the placement surface side of object to be processed.
Detailed description of the invention
Whether Fig. 1 shows the schematic cross sectional views of the CVD device of embodiments of the present invention.
Fig. 2 (a)~(c) is the schematic diagram for illustrating the manufacturing method of carbon nano structure of embodiments of the present invention.
Specific embodiment
With reference to the accompanying drawings, the metal foil Fm of catalyst (illustration omitted) is formed with using on surface as object to be processed,
In case where to grow carbon nanotube Ct on the surface of the metal foil Fm passed through in treatment furnace 1, to CVD device of the invention
Embodiment be illustrated.
Referring to Fig.1, M is the CVD device of embodiments of the present invention.CVD device M, which has, makes carbon nanotube in metal foil Fm
The columnar treatment furnace 1 of upper growth.Following settings is using carriage direction of the metal foil Fm in treatment furnace 1 as X-direction (Fig. 1
In left and right directions) right side, using the width direction of metal foil Fm as Y direction (direction orthogonal with the paper of Fig. 1), with
The orthogonal direction of plane including these X-directions and Y direction is Z-direction (up and down direction in Fig. 1), is illustrated.
In the X-direction two sides for the treatment of furnace 1, it is continuously provided with the ancillary chamber 2 of upstream side and the ancillary chamber in downstream side respectively
3.It is connected and is inserted with the front-end configuration of the tracheae 12 of mass flow controller 11 with gas source (not shown) in treatment furnace 1,
It can be to provide that flow imports carbon containing unstrpped gas into treatment furnace 1.At this point, mass flow controller 11 and tracheae 12 constitute power
Gas leading-in device in sharp claim.
The outside for the treatment of furnace 1 is provided with heating device 13, the unstrpped gas imported in treatment furnace 1 is heated, by
The unstrpped gas of heating, is supplied to the surface of metal foil Fm by this.Since device conduct well known to lamp and heating wire etc. can be used
Heating device 13, so detailed description will be omitted herein.The outside of heating device 13 be provided with above and below heat-insulating material 14a,
14b。
There is above-mentioned CVD device M transport metal foil Fm to manage the conveyer 15 passed through in furnace 1 at which.Conveyer 15
With Vm and the multiple (present embodiments that are spaced configuration of the mesh with Vm are wound with the cricoid mesh as shoestring
In be 4) roller 15a, 15b, 15c, 15d.The rotary shaft (illustration omitted) of motor DM is connected on roller 15a, when roller 15a is by electricity
When motivation DM driving rotation, keep mesh band Vm mobile with fixing speed.In order to make mesh band Vm with defined tension (such as 20
~80N), by the assembling biggish wire rod of outer diameter (line footpath) d1 as wires W 1 of the mesh with Vm is constituted, have mesh band Vm
There is mechanical strength.Further more, being formed with multiple openings on mesh band Vm, the opening allows carbon nanotube Ct putting to metal foil Fm
Set the growth of the face side Fm1.
There is outlet roller 21 and outlet roller 22 in the ancillary chamber 2 of upstream side, the outlet roller 21 is protected with the state of winding
Metal foil Fm is held, and sends out metal foil Fm, the outlet roller 22 keeps band-like mesh Bm with the state of winding, and is sending out
Send out mesh Bm in the downstream side of roller 21.The mesh being assembled into using the outer diameter wires W 2 smaller than constituting wires W 1 of the mesh with Vm
Body (such as mesh band) is used as mesh Bm.The outside diameter d 2 of the wires W 2 of mesh Bm is preferably provided at the model of 0.01~0.1mm
In enclosing.If outside diameter d 2, less than 0.01mm, sometimes due to temperature rises, wires W 2 extends, use sagging to the mesh band side Vm
The effect of mesh Bm can reduce, on the other hand, if outside diameter d 2 more than 0.1mm, can not make sometimes metal foil Fm sufficiently from
Float in wires W 2, to take the trace of mesh Bm shape.Further more, the aperture opening ratio of mesh Bm be preferably provided at 50~
99.8% range.If the unstrpped gas that aperture opening ratio less than 50%, provides sometimes is insufficient, the growth meeting of carbon nano structure
It is deteriorated, or takes the trace of the shape of mesh, on the other hand, if aperture opening ratio is more than 99.8%, mesh Bm sometimes
Mechanical strength can decline.
Take-up roll 31 and take-up roll 32 are provided in the ancillary chamber 3 in downstream side, the winding of take-up roll 31 recycling passes through
The metal foil Fm that treatment furnace 1 and carbon nanotube Ct have been grown, the take-up roll 32 wind recycling in the upstream side of take-up roll 31
Mesh Bm.Herein, it is also contemplated that will temporarily have the state of the metal foil Fm and mesh Bm of carbon nanotube Ct to be overlapped
It winds up, but if mesh Bm compression is contacted with carbon nanotube Ct, carbon nanotube Ct will take the trace of mesh Bm,
Therefore preferably mesh Bm and metal foil Fm are separated, is wound recycling respectively.
Conveyer 15 is constituted by like this, when carrying out rotation driving to roller 15a by motor DM, mesh band Vm
It is mobile with fixing speed.It is overlapped mesh Bm on mobile mesh band Vm, metal foil Fm is placed on mesh Bm.Therefore,
Keep the mesh Bm sent out with movement of the mesh with Vm mobile, and then with fixing speed (such as 0.01~1.0m/min) fortune
The metal foil Fm for sending the movement with mesh Bm and sending out passes through in treatment furnace 1.By to the gold passed through in treatment furnace 1
The surface for belonging to foil Fm provides the unstrpped gas heated by heating device 13, and carbon nanotube Ct is grown on a surface.
Above-mentioned CVD device M has control device known in band microcomputer or sequencer etc., manages by the way that control device is unified
Manage the operating of above-mentioned mass flow controller 11, the operating of heating device 13 and operating of motor DM etc..
Then, Fig. 2 is referred again to, using above-mentioned CVD device M, the substance of catalyst film is formd with the surface of metal foil Fm
As object to be processed, so that the manufacture for carbon nanotube Ct is grown on the surface of metal foil Fm, to carbon nano structure
The embodiment of method is illustrated.It can be used Ni foil as metal foil Fm, can be used Fe film as catalyst film.
Firstly, will pacify as the mesh of shoestring with mode of the Vm around roller 15a, 15b, 15c, 15d
Mesh band Vm is filled, metal foil Fm is mounted on outlet roller 21, mesh Bm is mounted on outlet roller 22.Mesh as a result,
Bm is overlapped on mesh band Vm, and metal foil Fm is placed on mesh Bm (preparatory process).
Herein, it is open as long as shoestring has and mesh Bm can be supported, therefore be not limited in above-mentioned mesh band
Mesh-shape product as Vm, such as shape as step chains (Ladder chain) or step line (roller chain) can be used,
Or the product of the crawler belt shape of the connected cyclic track of thin pallet.It can provide following unstrpped gas as long as can guarantee
Aperture opening ratio, and do not interfere carbon nanotube Ct's on the surface of the object to be processed (metal foil Fm) placed on mesh Bm
Growth, then the shape of shoestring is unrestricted.
Then, by rotating driven roller 15a with motor DM, mesh band Vm is mobile with fixing speed.Due to mobile net
Mesh Bm is overlapped on eye band Vm, so mesh Bm is sent out by the outlet roller being arranged in the ancillary chamber 2 of upstream side, submitting
To moving on the right side of X-direction in treatment furnace 1 together with mesh Bm and mesh band Vm, later, by the ancillary chamber 3 in downstream side
The take-up roll 32 of setting is rolled.Further more, due to being placed with metal foil Fm on mesh Bm, so being sent by what is be arranged in ancillary chamber 2
Roller 21 sends out metal foil Fm out, the metal foil Fm of submitting together with mesh Bm in treatment furnace 1 to moving on the right side of X-direction,
After by treatment furnace 1, rolled by the take-up roll 31 being arranged in the ancillary chamber 3 in downstream side.According to raw from the surface metal foil Fm
It grows the length (such as 125 μm) of the carbon nanotube Ct to get up and is appropriately arranged with the time that metal foil Fm passes through in treatment furnace 1.
In this way, controlling mass flow controller 11 during metal foil Fm passes through in treatment furnace 1 to provide flow (example
As importing carbon containing unstrpped gas into treatment furnace 1, (pressure in treatment furnace 1 is 1kPa~atmosphere to 100~2000sccm) at this time
Pressure).It can be used the alcohols such as hydrocarbons or ethyl alcohol such as ethylene gas, acetylene gas and methane gas as carbon containing original
Expect gas.Diluent gas can be imported in treatment furnace 1 together with such unstrpped gas, hydrogen, nitrogen or argon gas etc. can be used
Rare gas is as diluent gas.Under this state, if unstrpped gas is heated to predetermined temperature by starting heating device 13,
Unstrpped gas after heating is supplied to the surface metal foil Fm, carbon nanotube gets up (to grow work from the growth of the surface metal foil Fm
Sequence).Heating temperature can be appropriately positioned in the range of 400~1050 DEG C according to the type of unstrpped gas.Such as using ethylene
It may be configured as 750 DEG C when gas, may be configured as 720 DEG C when using acetylene gas, may be configured as 800 when using methane gas
℃。
It with the mesh Bm between Vm and metal foil Fm is not usually with regulation between mesh using present embodiment
Tension mesh, so without considering mechanical strength.Thus, for example constituting the wires W 2 of mesh Bm by minimizing
Line footpath d2, can make heating after unstrpped gas reach metal foil Fm the placed side side Fm1 whole surface.As a result, can make
Carbon nanotube Ct is grown in the whole surface of metal foil Fm.
In above-mentioned growth process, carbon nanotube Ct is grown by following stages, it may be assumed that in the placed side of metal foil Fm
The first stage that the carbon nanotube Ct of the side Fm1 growth is contacted with each wires W 2 for constituting mesh Bm respectively (referring to Fig. 2 (a))；
And the carbon nanotube Ct further growth contacted with each wires W 2, the carbon nanotube Ct bearing metal foil Fm grown by these
Second stage.When second stage is by carbon nanotube Ct bearing metal foil Fm, the shape between mesh Bm and metal foil Fm
At gap S, the unstrpped gas after heating can reliably reach the wires W 2 of the placed side side Fm1 of metal foil Fm by gap S
Perspective plane.Carbon nanotube Ct can be grown in the whole surface of the placement surface side of metal foil as a result,.
However, the whole surface of the placed side side Fm1 in order to make the unstrpped gas arrival metal foil Fm after heating, in order to
Form above-mentioned gap S, it may be considered that suspend metal foil Fm using fixture, but installs fixture needs are taken time and energy on metal foil Fm
With take time, such productivity can decline.In the present embodiment, shoestring is constituted with mesh band Vm, mesh Bm is set as
Be made of the wires W 2 smaller than constituting wires W 1 of the mesh with Vm of outside diameter d 2 and be formed as band-like, the movement with mesh with Vm and
Movement is not required to installs fixture, therefore not will lead to productivity decline.
More than, embodiments of the present invention are illustrated, but present invention is not limited to the embodiments described above, it can be not
Beyond suitably being deformed in the range of the scope of the invention.In the above-described embodiment, to use metal foil Fm as processing pair
As the case where object in order to be illustrated, it is not limited to this, can be used others substrate.
In the above-described embodiment, in case where heating the unstrpped gas imported in treatment furnace 1 by heating device 13
Be illustrated, but as long as the unstrpped gas after heating is supplied to object to be processed surface, such as be also possible to by
Unstrpped gas after 1 external heat for the treatment of furnace is imported into treatment furnace 1.
In the above-described embodiment, so that carbon nanotube Ct is illustrated in case where generating, but other carbon is made to receive
The case where rice growth such as structural body such as graphene the also applicable present invention.
In the above-described embodiment, to use the metal foil Fm of sheet as object to be processed, mesh Bm is formed as sheet
In case where be illustrated, but the shape of mesh Bm is not limited to this, such as when object to be processed is the substrate of rectangle
When, mesh Bm may be alternatively formed to profile rectangular shape corresponding with the profile of the substrate.At this point, by the way that mesh Bm is placed
On supporting substrate, mobile mesh band Vm, substrate can be made to pass through in process chamber 1.
Further more, other motor of driving outlet roller 21,22 and take-up roll 31,32 can also be also set up.But such as above-mentioned implementation
Shown in mode, if be configured to when keeping mesh band Vm mobile with fixing speed, mesh Bm is with the mesh of the movement with Vm
Movement and move, and then metal foil Fm mobile, then no setting is required other motor can reduce the cost of CVD device.
In the above-described embodiment, it is illustrated in case where the section of the wires W 2 of mesh Bm is positive round,
But the section of wires W 2 is not limited to this, and the wire rod for having ellipse, triangle, diamond-shaped cross-section can be used, but it is preferable to use sections
The wires W 2 contacted with the placed side Fm1 line of metal foil Fm.
Description of symbols
Bm ... mesh, Fm ... metal foil (object to be processed), the placed side Fm1 ..., M ... carbon nano structure growth
CVD device, Vm ... mesh band (shoestring), W1 ... constitute wire rod of the mesh with Vm, the wire rod of W2 ... mesh Bm, 1 ... processing
Furnace, 11 ... mass flow controllers (gas leading-in device), 12 ... tracheaes (gas leading-in device), 13 ... heating devices.
Claims (4)
1. a kind of carbon nano structure growth CVD device comprising:
Treatment furnace；
Conveyer, to transport object to be processed by the mode in treatment furnace；
Gas leading-in device imports carbon containing unstrpped gas into treatment furnace；And
Heating device heats unstrpped gas；
The carbon nano structure growth CVD device makes carbon nano structure in the table by handling indoor object to be processed
It is grown on face；
Conveyer, which has, places object to be processed and the shoestring mobile with fixing speed, and being formed on the shoestring allows carbon
The multiple openings placing surface side grow of the nanostructure to object to be processed；
In the carbon nano structure growth CVD device, mesh is between shoestring and object to be processed.
2. carbon nano structure growth CVD device according to claim 1, it is characterised in that:
The shoestring is made of mesh band；
The band-like mesh that the mesh is made of the outer diameter wire rod smaller than the wire rod for constituting the mesh band, with institute
It states the movement of mesh band and moves.
3. carbon nano structure growth CVD device according to claim 1 or 2, it is characterised in that:
The aperture opening ratio of the mesh is arranged in the range of 50~99.8%.
4. a kind of manufacturing method of carbon nano structure, raw using carbon nano structure described in any one of any one of claims 1 to 33
Long CVD device, which is characterized in that the manufacturing method of the carbon nano structure includes:
Object to be processed is placed into mesh by preparatory process after by shoestring and mesh overlapping；And
Process is grown, moves shoestring and mesh in treatment furnace, the original after heating is made during in through treatment furnace
Material gas is contacted with object to be processed surface, grows carbon nano structure on the object to be processed surface；
In the growth process, carbon nano structure is grown by following stages, it may be assumed that in the placement surface side of object to be processed
The first stage that the carbon nano structure of growth is contacted with each wire rod for constituting mesh respectively；And the carbon contacted with each wire rod
Nanostructure further growth carries the second stage of object to be processed by the carbon nano structure of these growths.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017152995A JP6476245B2 (en) | 2017-08-08 | 2017-08-08 | CVD apparatus for carbon nanostructure growth and method for producing carbon nanostructure |
| JP2017-152995 | 2017-08-08 |
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| Publication Number | Publication Date |
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| CN109384216A true CN109384216A (en) | 2019-02-26 |
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| CN201810707847.1A Pending CN109384216A (en) | 2017-08-08 | 2018-07-02 | The manufacturing method of carbon nano structure growth CVD device and carbon nano structure |
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| Country | Link |
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| JP (1) | JP6476245B2 (en) |
| KR (1) | KR20190016451A (en) |
| CN (1) | CN109384216A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109775690A (en) * | 2019-03-25 | 2019-05-21 | 杭州英希捷科技有限责任公司 | A kind of method of continuous producing carbon nano-tube array |
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|---|---|
| JP6476245B2 (en) | 2019-02-27 |
| KR20190016451A (en) | 2019-02-18 |
| JP2019031706A (en) | 2019-02-28 |
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