CN107445452A - A kind of process units and production method that graphene film is prepared in glass surface - Google Patents
A kind of process units and production method that graphene film is prepared in glass surface Download PDFInfo
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- CN107445452A CN107445452A CN201710800954.4A CN201710800954A CN107445452A CN 107445452 A CN107445452 A CN 107445452A CN 201710800954 A CN201710800954 A CN 201710800954A CN 107445452 A CN107445452 A CN 107445452A
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- melting furnaces
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B13/00—Rolling molten glass, i.e. where the molten glass is shaped by rolling
- C03B13/01—Rolling profiled glass articles, e.g. with I, L, T cross-sectional profiles
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B15/00—Drawing glass upwardly from the melt
- C03B15/02—Drawing glass sheets
- C03B15/04—Drawing glass sheets from the free surface of the melt
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- Engineering & Computer Science (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The present invention relates to a kind of process units that graphene film is prepared in glass surface, including melting furnaces and the holding vessel equipped with graphene dispersing solution, holding vessel connects nozzle by spray pipe, and nozzle is arranged in melting furnaces；The first feeder channel is connected on melting furnaces and the second feed is logical；First feeder channel connects the first flow-guiding channel, and the first flow-guiding channel connects the first forming room, and the first forming room connects the first annealing kiln, and the first annealing kiln connects the first cold end cutter device；Second feeder channel connects the second flow-guiding channel, and the second flow-guiding channel connects the second forming room, and the second forming room connects the second annealing kiln, and the second annealing kiln connects the second cold end cutter device.Advantages of the present invention：The method that the present invention uses the line of a kiln two, ordinary plate glass is produced while graphene film glass is produced, can high efficiency, low cost prepare individual layer in continuous ribbon surfaces or few layer, continuous uniform thin film of graphite, its electric conductivity and light transmission are all protected.
Description
Technical field
It is more particularly to a kind of to prepare graphene film in glass surface the present invention relates to plate glass production technical field
Process units and production method.
Background technology
Existing flat glass production line includes " line of a kiln one " and " kiln is multi-thread " two kinds of forms, and the former is a melting furnaces
Glass metal be only supplied a kind of former, produce the glass of single variety, the latter is the glass metal of a melting furnaces while supplies
A variety of formers while the plate glass for producing different cultivars, such as：Float glass floats with being produced while float glass
Method glass while horizontal drawing glass, rolled glass with producing, horizontal drawing glass and production etc. while rolled glass.
Coated glass is produced on existing flat glass production line, it is main using using chemical vapor deposition or thermal spraying
Method, i.e., a plated film area is set on the molten tin bath or annealing kiln of float glass line or horizontal drawing line, Coating Materials is applied and is plated to motion
Ribbon surfaces, it can be prepared in glass surface thin including metal film, metal-oxide film, silicon fiml, nonmetal oxide
A variety of films such as film, but graphene film is not prepared on existing flat glass production line using the above method at this stage.
Research shows, glass surface direct growth graphene film need higher temperature, longer time, compared with harsh environment,
Equipment costly, current method and equipment can not meet the requirement of online production.
Graphene film is prepared mainly using the method for liquid phase film in glass surface at present, that is, utilizes reduction-oxidation graphite
It is raw material that alkene or liquid phase, which peel off graphene, and monolithic glass plate surface after dicing coats a layer graphene film, though this method
It is so simple to operate, but have the following disadvantages：Although redox graphene is easily prepared, cost is low, due to that can not recover completely
Caused structure is destroyed in oxidizing process so that film performance is greatly reduced, it is difficult to prepares the graphene film of high quality；Liquid phase
It is a kind of graphene of high quality to peel off graphene, can obtain the few individual layer of defect or few Rotating fields, have scale system
Standby, raw material extensively, technique and equipment it is simple, unique advantage such as cost is cheap, easy functionalization, but applied using liquid phase method
When film, it is difficult to control the continuity, uniformity and quality of film, reason is：Graphene dispersing solution concentration is very low, graphite
Alkene lamella size is too small, when coating is too thin, the graphene film skewness of glass surface, and discontinuously, though translucency is good,
Electric conductivity is poor；When coating is too thick, the glass surface graphene film number of plies is too many, and lamella superposition is serious, though electric conductivity is good,
Light transmission is very poor；The problems such as dispersant in graphene dispersing solution is difficult to remove, high boiling organic solvent is difficult to volatilization,
So that liquid phase peels off graphene and is difficult to apply under normal temperature plating conditions；Further, since being operated on monolithic glass plate, exist
The problem of efficiency is low, and cost is higher.
The content of the invention
The invention aims to solve to have shortcoming in background technology, and the one kind proposed prepares stone in glass surface
The process units and production method of black alkene film.
To achieve these goals, present invention employs following technical scheme：
A kind of process units that graphene film is prepared in glass surface, including melting furnaces, it is characterised in that：Two are provided with melting furnaces
Individual discharging opening, two discharging openings connect the first feeder channel and the second feeder channel, are externally provided with melting furnaces equipped with graphene respectively
The holding vessel of dispersion liquid, holding vessel connection spray pipe, spray pipe connection nozzle, nozzle are arranged in melting furnaces；
First feeder channel connects the first production line, and the first water conservancy diversion that the first production line includes the first feeder channel of connection leads to
Road, the first flow-guiding channel connect the first forming room, and the first forming room connects the first annealing kiln, and the first annealing kiln connects the first cold end
Cutter device；
Second feeder channel connects the second production line, and the second water conservancy diversion that the second production line includes the second feeder channel of connection leads to
Road, the second flow-guiding channel connect the second forming room, and the second forming room connects the second annealing kiln, and the second annealing kiln connects the second cold end
Cutter device.
Described device can have technical scheme further below on the basis of above-mentioned technical proposal：
Two discharging openings are arranged on the wall of the melting furnaces end, and are arranged on the vertical centerline of melting furnaces end wall
On, the nozzle is arranged on the longitudinally central line of melting furnaces.
First feeder channel is arranged on the top of second feeder channel, and the first feeder channel is that overflow-type supplies
Material road, the liquid level of glass metal is arranged on the middle part of the first feeder channel feeding mouth in the melting furnaces, and the second feeder channel is flow liquid
Hole formula supply channel, the feeding mouth of the second feeder channel are being immersed in below liquid level completely.
A bending is provided with first feeder channel, the angle of bending is 80-100 degree.
The angle of the bending is 90 degree, and the longitudinally perpendicular arrangement of first production line and the melting furnaces is set.
Second production line is linearly arranged setting along the longitudinally central line of the melting furnaces.
The melting furnaces are made up of melting end, diversion division and cooling end, two barricades are additionally provided with the upside of cooling end, each
Barricade and the discharging opening corresponding matching on the upside of melting furnaces, two barricades form splayed guiding gutter, and the osculum of splayed guiding gutter is set
Put in the side of discharging opening.
One group of first air inlet for being used to be passed through inert protective gas is provided with the top of the melting furnaces, in the side wall of melting furnaces
One group of exhaust outlet is provided with, one group of second air inlet is equipped with first flow-guiding channel and first forming room.
A kind of production method that graphene film is prepared in glass surface, it is characterised in that comprise the following steps：
Step 1: melten glass liquid is processed in melting furnaces；
Step 2: by nozzle into melting furnaces glass metal surface spraying graphene dispersing solution, glass metal surface formed graphene
Lamella；
Step 3: the floating glass metal for having graphene sheet layer in upper strata is processed to obtain the glass with graphene film by the first production line
Glass plate；
Step 4: the pure glass metal of lower floor is processed to obtain plate glass by the second production line.
The production method can have technical scheme further below on the basis of above-mentioned technical proposal：
In first production line, obtained in the first forming room by horizontal drawing forming process or calendaring molding method, processing even
Continuous ribbon surfaces form graphene film, then process to obtain by the first annealing kiln and the first cold end cutter device and have stone
The glass plate of black alkene film.
The advantage of the invention is that：It is small that the present invention is effectively prepared for low concentration, lamella size using liquid phase stripping method
Graphene dispersing solution, and solvent is thoroughly removed using the high temperature of glass metal, obtain individual layer in glass surface or lack layer, company
Continuing the uniform thin film of graphite, its electric conductivity and light transmission is all protected, the method that the present invention uses the line of a kiln two,
Can high efficiency, low cost prepare graphene film in continuous ribbon surfaces, while graphene film glass is produced
Produce ordinary plate glass.
Brief description of the drawings
Fig. 1 is the basic structure schematic diagram of the present invention；
Fig. 2 is Fig. 1 A-A views；
Fig. 3 is Fig. 1 B-B views；
Fig. 4 is horizontal sheet process process principle schematic diagram；
Fig. 5 is rolling process process principle schematic diagram.
Embodiment
In order that the present invention is more clearly understood, the present apparatus is described in detail below in conjunction with accompanying drawing, tool described herein
Body embodiment only to explain the present invention, is not intended to limit the present invention.
As shown in Figure 1, Figure 2 and Figure 3, a kind of production dress that graphene film is prepared in glass surface provided by the invention
Put, including melting furnaces 1,1 prior art of melting furnaces, the glass metal 7 of melting is provided with melting furnaces 1, in vertical on the end wall of melting furnaces 1
Two discharging openings are set on heart line, and the discharging opening of upside connects the first feeder channel 2, and the discharging opening connection second of the side of downside supplies
Expect passage 3.
The melting furnaces 1 are made up of melting end 1a, diversion division 1b and cooling end 1c, and two are additionally provided with the upside of cooling end 1c
Barricade 11, each barricade 11 and the discharging opening corresponding matching of the upside of melting furnaces 1, two barricades 11 form splayed guiding gutter, eight words
The osculum of shape guiding gutter is arranged on the side of discharging opening.The holding vessel 8 equipped with graphene dispersing solution is externally provided with melting furnaces 1, is stored
Tank 8 connects spray pipe 9, and spray pipe 9 connects nozzle 10, and nozzle 10 is arranged in cooling end 1c.It is provided with cooling end 1c top
One group of first air inlet 15 for being used to be passed through inert protective gas, is provided with two row's exhaust outlets 16 in the side wall of melting furnaces 1.
First feeder channel 2 is overflow-type supply channel, and the liquid level 4 in the melting furnaces 1 is arranged on the first feeder channel 2
The middle part of feeding mouth, a bending 2a is provided with the first feeder channel 2, bending 2a angle is 80-100 degree, and this programme is excellent
Elect 90 degree as.First feeder channel 2 connects the first production line 5, and the first production line 5 and melting furnaces 1 is vertical in the presence of bending 2a
Set to vertical arrangement, the first production line 5 includes the first flow-guiding channel 21 of the first feeder channel 2 of connection, the first flow-guiding channel
21 the first forming room 22 of connection, the first forming room 22 connect the first annealing kiln 23, and the first annealing kiln 23 connects the cutting of the first cold end
Device 24, the first flow-guiding channel 21, the first forming room 22, the structure of the first annealing kiln 23 and the first cold end cutter device 24 are
Prior art.One group of second air inlet for being passed through inert protective gas is equipped with the first flow-guiding channel 21 and the first forming room 22
Mouth 17.
Second feeder channel 3 is dog-hole formula supply channel, and the feeding mouth of the second feeder channel 3 is being immersed in glass completely
The lower section of liquid level 4 of glass liquid 7, the second feeder channel 3 connect the second production line 6, and the second production line 6 is along the longitudinal direction of melting furnaces 1
Heart line is linearly arranged setting, and the second production line 6 includes the second flow-guiding channel 31 of the second feeder channel 3 of connection, the second water conservancy diversion
Passage 31 connects the second forming room 32, and the second forming room 32 connects the second annealing kiln 33, and the second annealing kiln 33 connects the second cold end
Cutter device 34, the second flow-guiding channel 31, the second forming room 32, the structure of the second annealing kiln 33 and the second cold end cutter device 34
It is prior art.
The process units be the line of a kiln two double feed duct devices, it by glass melting, clarification, cooling, spraying, divide
The processes such as stream, shaping, annealing, cold end cutting process graphene film glass and ordinary plate glass,
On the basis of above-mentioned process units, prepare graphene film in glass surface and use following production method, specifically include with
Lower step：
Step 1: process melten glass liquid 7 in melting furnaces 1, frit after the melting end 1a fusings and clarification of melting furnaces 1,
The glass metal 7 of melting is obtained, glass metal 7 enters cooling end 1c by diversion division 1b.
Step 2: divided by nozzle 10 to the graphite spraying alkene dispersion liquid of liquid level 4 of the glass metal 7 of cooling end 1c leading portion
Solvent in dispersion liquid is then swum on liquid level 4 by thermal evaporation volatilization, graphene sheet layer in dispersity, as glass metal 7 is to cold
But portion 1c Outlet-side flows, the graphene sheet layer of scattered floating state is stopped and water conservancy diversion by barricade 11, to the longitudinal centre line of kiln 1
In set of regions, it is covered with the liquid level 4 of central area glass metal 7 and contacts with each other, connects from beginning to end, the graphene sheet layer of continuous uniform,
Bilevel glass metal is shunted by double supply channels, respectively enters the first production line 5 and the second production line 6.
Step 3: the floating glass metal for having graphene sheet layer in upper strata obtained by the processing of the first production line 5 it is thin with graphene
The glass plate of film, in the first production line 5, by horizontal drawing forming process or calendaring molding method in the first forming room 22, process
Graphene film is formed in continuous ribbon surfaces, is then processed by the first annealing kiln 23 and the first cold end cutter device 24
Obtain the glass plate with graphene film.
Step 4: the pure glass metal of lower floor obtains plate glass by the processing of the second production line 6, in order to pursue the more of product
Sample, the method for the second production line 6 shaping can use the shaping of existing float tin groove, horizontal drawing shaping or calendaring molding, obtain
The plate glass of multi items.
The concrete operations of the horizontal sheet process are as shown in figure 4, glass metal 7 enters for horizontal drawing through the first flow-guiding channel 21
One forming room 22, the glass metal 7 in the first forming room 22 are divided into skin glass liquid 71, middle level glass metal 73 and bottom in depth
Glass metal 72, skin glass liquid 71 due to liquid level radiate, bottom glass liquid 72 due to bottom of pond radiate, both temperature are relatively low, by
It is higher in the temperature of middle level glass metal 73, when on drawing, along the first forming room 22 from the upward drawing glassribbons of the Free Surface of glass metal 7
74, width keeps stable, and the skin glass liquid 71 that surface is covered with continuous graphite alkene lamella is directly becoming the inboard cortex of plate root, bottom
Layer glass metal 72 turns into outside cortex to plate root outside, and middle level glass metal 73 arrives the lower section of plate root, is formed after drawing in plate root
Layer, glass tape 74 are turned along air cushion slewing rollers 12, moved in the horizontal direction by after vertical drawing certain altitude, are cooled and solidified,
The glass raw sheet 75 that surface has graphene film is formed, glass raw sheet 75 is through the first annealing kiln 23 and the first cold end cutter device
24 obtain the glass plate that surface has graphene film.
The concrete operations of the rolling process are as shown in figure 5, glass metal 7 overflows from the tail end of the first flow-guiding channel 21, into use
In the first forming room 22 of calendering, glass metal 7 is flowed between the upper pressure roller 14 being mutually correspondingly arranged of calender and lower compression roller 13,
Water flowing cools down among two pressure rollers, and the glass metal 7 flowed through between up-down rollers cools down rapidly, the continuous glass of thickness needed for formation
Band, while roll-in, graphene sheet layer is also cured to glass pane surface, forms the continuous glass that surface has graphene film
Glass raw sheet 75, then obtain the glass plate for having graphene film in surface through the first annealing kiln 23 and the first cold end cutter device 24.
Claims (10)
1. a kind of process units that graphene film is prepared in glass surface, including melting furnaces（1）, it is characterised in that：In melting furnaces（1）
Two discharging openings are provided with, two discharging openings connect the first feeder channel respectively（2）With the second feeder channel（3）, in melting furnaces（1）
It is externally provided with the holding vessel equipped with graphene dispersing solution（8）, holding vessel（8）Connect spray pipe（9）, spray pipe（9）Connect nozzle
（10）, nozzle（10）It is arranged on melting furnaces（1）It is interior；
First feeder channel（2）Connect the first production line（5）, the first production line（5）Including connecting the first feeder channel（2）
The first flow-guiding channel（21）, the first flow-guiding channel（21）Connect the first forming room（22）, the first forming room（22）Connection first
Annealing kiln（23）, the first annealing kiln（23）Connect the first cold end cutter device（24）；
Second feeder channel（3）Connect the second production line（6）, the second production line（6）Including connecting the second feeder channel（3）
The second flow-guiding channel（31）, the second flow-guiding channel（31）Connect the second forming room（32）, the second forming room（32）Connection second
Annealing kiln（33）, the second annealing kiln（33）Connect the second cold end cutter device（34）.
A kind of 2. process units that graphene film is prepared in glass surface according to claim 1, it is characterised in that：Two
The individual discharging opening is arranged at the melting furnaces（1）On the wall of end, and it is arranged on melting furnaces（1）The vertical centerline of end wall
On, the nozzle（10）It is arranged on melting furnaces（1）On longitudinally central line.
A kind of 3. process units that graphene film is prepared in glass surface according to claim 1, it is characterised in that：Institute
State the first feeder channel（2）It is arranged on second feeder channel（3）Top, and the first feeder channel（2）It is that overflow-type supplies
Material road, the melting furnaces（1）Interior glass metal（7）Liquid level（4）It is arranged on the first feeder channel（2）The middle part of feeding mouth, second supplies
Expect passage（3）It is dog-hole formula supply channel, the second feeder channel（3）Feeding mouth be immersed in liquid level completely（4）Lower section.
A kind of 4. process units that graphene film is prepared in glass surface according to claim 1, it is characterised in that：
First feeder channel（2）It is provided with a bending（2a）, bending（2a）Angle be 80-100 degree.
A kind of 5. process units that graphene film is prepared in glass surface according to claim 4, it is characterised in that：Institute
State bending（2a）Angle be 90 degree, first production line（5）With the melting furnaces（1）Longitudinally perpendicular arrangement set.
A kind of 6. process units that graphene film is prepared in glass surface according to claim 1, it is characterised in that：Institute
State the second production line（6）Along the melting furnaces（1）Longitudinally central line is linearly arranged setting.
A kind of 7. process units that graphene film is prepared in glass surface according to claim 1, it is characterised in that：Institute
State melting furnaces（1）By melting end（1a）, diversion division（1b）And cooling end（1c）Composition, in cooling end（1c）Upside be additionally provided with two
Barricade（11）, each barricade（11）With melting furnaces（1）The discharging opening corresponding matching of upside, two barricades（11）Form splayed water conservancy diversion
Groove, the osculum of splayed guiding gutter are arranged on the side of discharging opening.
A kind of 8. process units that graphene film is prepared in glass surface according to claim 1, it is characterised in that：
The melting furnaces（1）Top be provided with one group and be used to be passed through the first air inlet of inert protective gas（15）, in melting furnaces（1）Side wall
It is provided with one group of exhaust outlet（16）, in first flow-guiding channel（21）With first forming room（22）On be equipped with one group
Two air inlets（17）.
9. a kind of production method that graphene film is prepared in glass surface, it is characterised in that comprise the following steps：
Step 1: in melting furnaces（1）Inside process melten glass liquid；
Step 2: pass through nozzle（10）To melting furnaces（1）Interior glass metal surface spraying graphene dispersing solution, is formed on glass metal surface
Graphene sheet layer；
Step 3: the floating glass metal for having graphene sheet layer in upper strata passes through the first production line（5）Processing obtains having graphene film
Glass plate；
Step 4: the pure glass metal of lower floor passes through the second production line（6）Processing obtains plate glass.
10. production method according to claim 1, it is characterised in that：In first production line（5）In, at the first one-tenth
Type room（22）It is interior that processing obtains forming graphene film in continuous ribbon surfaces by horizontal drawing forming process or calendaring molding method,
Then the first annealing kiln is passed through（23）With the first cold end cutter device（24）Processing obtains the glass plate with graphene film.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710800954.4A CN107445452A (en) | 2017-09-07 | 2017-09-07 | A kind of process units and production method that graphene film is prepared in glass surface |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710800954.4A CN107445452A (en) | 2017-09-07 | 2017-09-07 | A kind of process units and production method that graphene film is prepared in glass surface |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115849861A (en) * | 2022-11-22 | 2023-03-28 | 安徽宇航派蒙健康科技股份有限公司 | Composite graphene heat-conducting film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043654A (en) * | 2011-10-12 | 2013-04-17 | 国家纳米科学中心 | Film containing graphene and/or graphene oxide, and preparation method thereof |
| CN204174061U (en) * | 2014-09-28 | 2015-02-25 | 长兴旗滨玻璃有限公司 | A kind of melting furnaces of three floatation glass production lines |
-
2017
- 2017-09-07 CN CN201710800954.4A patent/CN107445452A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043654A (en) * | 2011-10-12 | 2013-04-17 | 国家纳米科学中心 | Film containing graphene and/or graphene oxide, and preparation method thereof |
| CN204174061U (en) * | 2014-09-28 | 2015-02-25 | 长兴旗滨玻璃有限公司 | A kind of melting furnaces of three floatation glass production lines |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115849861A (en) * | 2022-11-22 | 2023-03-28 | 安徽宇航派蒙健康科技股份有限公司 | Composite graphene heat-conducting film and preparation method thereof |
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Application publication date: 20171208 |
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