CN105444502B - The method for preparing transparency aerogel, transparency aerogel glass and refrigerator for refrigerator - Google Patents
The method for preparing transparency aerogel, transparency aerogel glass and refrigerator for refrigerator Download PDFInfo
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- CN105444502B CN105444502B CN201511030604.1A CN201511030604A CN105444502B CN 105444502 B CN105444502 B CN 105444502B CN 201511030604 A CN201511030604 A CN 201511030604A CN 105444502 B CN105444502 B CN 105444502B
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- refrigerator
- glass
- transparency aerogel
- aeroge
- mixed
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D23/00—General constructional features
- F25D23/02—Doors; Covers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2323/00—General constructional features not provided for in other groups of this subclass
- F25D2323/02—Details of doors or covers not otherwise covered
Abstract
The invention discloses prepare transparency aerogel method, transparency aerogel glass and refrigerator for refrigerator, which includes：Upper glass plates, lower glass plate, aeroge component and encapsulating material form placement space between upper glass plates and lower glass plate, at least one of upper glass plates and lower glass plate are upper to have air discharge duct, air discharge duct connection placement space and free surrounding space；Aeroge component is arranged in placement space, and aeroge component is contacted with air discharge duct, encapsulating material cladding upper glass plates, lower glass plate, aeroge component and air discharge duct, and the non-encapsulated material cladding in the lower surface of lower glass plate and the upper surface of upper glass plates.The transparency aerogel glass has relatively low thermal conductivity factor (being not more than 0.01W (mk)) and higher light transmittance, compared with conventional vacuum glass, it is energy-efficient so as to achieve the effect that while refrigerator display type is improved with the characteristics of good heat-insulation effect, low energy consumption.
Description
Technical field
The invention belongs to field of material technology, specifically, the present invention relates to a kind of method for preparing transparency aerogel, using
In the transparency aerogel glass and refrigerator of refrigerator.
Background technology
The babinet and door of domestic refrigerator at present in order to achieve the effect that cold insulation, uses isocyanates and polyether polyols mostly
Alcohol carries out foaming for base stock and forms hard polyaminoester, and the thermal conductivity factor of the polyurethane foam plastics is 0.02-0.03W/
(m·k).However, polyurethane foam has the disadvantages that：1st, the physical blowing agent used in foaming process, such as fluorochlorohydrocarbon chemical combination
Object and pentamethylene etc., the former can destroy ozone layer, and the latter is then inflammable explosive article；2nd, due to the opacity of polyurethane, limitation
Its application in the transparent door body of refrigerator.
Heat insulation is best for vacuum glass in the glass families with transparent display at present, but has the following disadvantages
For：1st, in order to resist atmospheric pressure, supporter is equipped between layer glass, causes vacuum glass overall thermal conductivity is larger (to lead
Hot coefficient is 0.3-0.6W/ (mk)), therefore heat insulation is limited, causes the larger energy consumption of refrigerator；2nd, the heat conduction of vacuum glass
Coefficient is very sensitive to vacuum degree, and internal support structure is unstable, it is made to be acted on easily damaged generation gas leakage by external force,
Thermal and insulating performance is caused to decline to a great extent.
Aerosil is the current minimum solid material with thermal conductivity minimum of density known in the world, in room temperature
Thermal conductivity under normal pressure is generally less than 0.020W/ (mk), under vacuum conditions thermal conductivity can down to 0.004W/ (mk), and
Thermal conductivity of the air under normal-temperature vacuum state is then 0.026W/ (mk).Therefore aeroge glass than present vacuum glass,
The thermal conductivity of Low-e glass, pad pasting glass, heat-reflecting glass etc. will be low.Simultaneously as form the particle ruler of aeroge skeleton
It is very little for 1-20nm, it is smaller than the wavelength of visible ray, therefore aeroge also has a preferable translucency, and it is to infrared and visible ray
Coefficient ratio of burying in oblivion reach more than 100, therefore can be made into visible transparent, infrared dense glass material.On the other hand,
Spread speed is 340m/s to sound in air, and the spread speed in aeroge is only 100-120m/s, therefore aeroge
Glass also has good noise reduction.It is huge latent that these advantages so that application of the aeroge glass on refrigerator door has
Power.
But the aeroge glass prepared at present has following shortcoming：1st, preparation process is complicated and preparation condition is harsh, super to face
Boundary's drying equipment is expensive；2nd, the aeroge glass product prepared can not ensure high light transmittance, be mostly translucent,
Do not have good illustrative.
Therefore, existing related aeroge glass technology is further improved.
Invention content
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, the present invention
One purpose is to propose a kind of method for preparing transparency aerogel, transparency aerogel glass and refrigerator for refrigerator, adopt
There is good translucency, hydrophobicity and air-breathing gas storage performance, and its porosity is not with the transparency aerogel that this method obtains
Less than 85%, it is seen that light transmission rate is not less than 85%, and thermal conductivity factor is not more than 0.010W/ (mk), and heat transfer coefficient is not more than
0.58W/(m2K), bulk density is in 100-180Kg/m3, can during so as to be applied on product such as refrigerator doors glass
It is energy-efficient to achieve the effect that while refrigerator illustrative is improved.
In one aspect of the invention, the present invention proposes a kind of method for preparing transparency aerogel.It is according to the present invention
Embodiment, this method include：
(1) silicon source, organic solvent, surface modifier are mixed with water, to obtain mixed material；
(2) mixed material is mixed with the alcoholic solution containing oxalic acid, to obtain colloidal sol；
(3) gel is mixed with the alcoholic solution containing ammonium hydroxide, to obtain gel；
(4) gel is subjected to burin-in process in alcoholic solution；
(5) gel after the aging for obtaining step (4), which is added in modifying agent, is modified processing；
(6) processing is dried in the modified gel that step (5) obtains under carbon dioxide atmosphere, to obtain
Bright aeroge,
Wherein, in step (1), the silicon source, the organic solvent, the surface modifier and the water according to mole
Than being 1：3~15：1~10：1~10 is mixed.
The transparency aerogel that the method for preparing transparency aerogel according to embodiments of the present invention obtains as a result, has good
Translucency, hydrophobicity and air-breathing gas storage performance, and its porosity is not less than 85%, it is seen that and light transmission rate is not less than 85%, leads
Hot coefficient is not more than 0.010W/ (mk), and heat transfer coefficient is not more than 0.58W/ (m2K), bulk density is in 100-180Kg/m3,
During so as to be applied to product such as refrigerator doors glass, it can reach energy-efficient while refrigerator illustrative is improved
Effect.
In addition, the method according to the above embodiment of the present invention for preparing transparency aerogel can also have following additional skill
Art feature：
In some embodiments of the invention, in step (1), the silicon source is selected from ethyl orthosilicate, positive silicic acid first
At least one of ester and waterglass.Thus, it is possible to significantly improve aeroge translucency.
In some embodiments of the invention, in step (1), the organic solvent is selected from absolute ethyl alcohol, without water beetle
At least one of alcohol and anhydrous propanone.Thus, it is possible to significantly reduce the thermal conductivity factor and heat transfer coefficient of aeroge.
In some embodiments of the invention, in step (1), the surface modifier be selected from trim,ethylchlorosilane,
At least one of hexamethyldisilazane, dimethylformamide, methyltriethoxysilane and methyltrimethoxysilane.By
This, can further reduce the thermal conductivity factor and heat transfer coefficient of aeroge.
In some embodiments of the invention, in step (2), the mixed material is mixed with the alcoholic solution containing oxalic acid
The pH of solution is 1~3 after conjunction.Thus, it is possible to further improve the translucency of aeroge.
In some embodiments of the invention, in step (3), after the gel is mixed with the alcoholic solution containing ammonium hydroxide
The pH of solution is 11~13.Thus, it is possible to further improve the translucency of aeroge.
In some embodiments of the invention, in step (4), the burin-in process is carried out under 50~65 degrees Celsius
36~48 hours.Thus, it is possible to further improve the translucency of aeroge.
In some embodiments of the invention, in step (5), the time of the modification is 24~36 hours.By
This, can further improve the translucency of aeroge.
In some embodiments of the invention, the modifying agent is selected from dimethylformamide, trim,ethylchlorosilane, pregnancy
At least one of base disilazane and n-hexane.Thus, it is possible to further improve the translucency of aeroge.
In some embodiments of the invention, the modifying agent is dimethylformamide and the mixed solution of n-hexane.By
This, can further improve the translucency of aeroge.
In some embodiments of the invention, in step (6), the drying process is to heat up to carry out according to following procedure
's：
65 degrees Celsius are risen to from room temperature and keeps the temperature 1-2 hours under 65 degrees Celsius, are then risen to 80 degrees Celsius and are taken the photograph 80
1-2 hours are kept the temperature under family name's degree, then rise to 120 degrees Celsius and keeps the temperature 3-5 hours at one hundred and twenty degrees centigrade, it is Celsius finally to rise to 150
It spends and keeps the temperature 1-2 hours under 150 degrees Celsius, wherein, the heating rate between each temperature section is separately Celsius for 1-5
Degree/min.Thus, it is possible to further improve the translucency of aeroge.
In the second aspect of the invention, the present invention proposes a kind of transparency aerogel glass for refrigerator.According to this
The embodiment of invention, the transparency aerogel glass for being used for refrigerator include：
Upper glass plates and lower glass plate, form placement space between the upper glass plates and the lower glass plate, it is described on
At least one of glass plate and the lower glass plate be upper to have an air discharge duct, and the air discharge duct connect the placement space and
Free surrounding space；
Aeroge component, the aeroge component are arranged in the placement space, and the aeroge component and institute
Air discharge duct contact is stated, wherein, the aeroge component is to be obtained using the method described above for preparing transparency aerogel；
Encapsulating material, the encapsulating material coat the upper glass plates, the lower glass plate, the aeroge component and
The air discharge duct, and the lower surface of the lower glass plate and the upper surface of the upper glass plates be not by the encapsulating material packet
It covers.
The transparency aerogel glass for refrigerator according to embodiments of the present invention has relatively low thermal conductivity factor (no as a result,
More than 0.01W (mk)) and higher light transmittance, compared with conventional vacuum glass, there is good heat-insulation effect, the spy that low energy consumption
Point, it is energy-efficient so as to achieve the effect that while refrigerator display type is improved.
In addition, the transparency aerogel glass according to the above embodiment of the present invention for refrigerator can also have following add
Technical characteristic：
In some embodiments of the invention, the encapsulating material includes PVB encapsulating materials and sn-bi alloy encapsulating material,
Wherein, the PVB encapsulating materials coat the outer surface of the aeroge component, described in the sn-bi alloy encapsulating material cladding
PVB encapsulating materials, the upper glass plates, the lower glass plate and the air discharge duct.Thus, it is possible to significantly improve the aeroge glass
The service life of glass.
In some embodiments of the invention, the upper glass plates and the lower glass plate are separately selected from tempering
At least one of glass and coated glass.Thus, it is possible to the transparency aerogel glass of different colours and different light transmittances is obtained,
If coated glass selects electropane, glass can also be heated, so as to fulfill defrosting, demisting and as liquid crystal
The effect of display screen.
In some embodiments of the invention, the thickness of the upper glass plates and the lower glass plate is separately 1
~20mm.It can be not only damaged as a result, to avoid glass, but also conducive to installation.
In some embodiments of the invention, the thickness of the aeroge component is 5~20mm.Inventor's discovery, airsetting
The thickness of glue is thicker, and heat-proof quality is better, but can sacrifice certain translucency, thinner on the contrary, then translucency is better, but thermal insulation
It can decline, and select the aeroge component of the application thickness range that both there is higher translucency, have with preferable thermal insulation
Energy.
In the third aspect of the invention, the present invention proposes a kind of refrigerator.According to an embodiment of the invention, the refrigerator
With the transparency aerogel glass for refrigerator described above, such as can be used as refrigerator doors.As a result, by using upper
State the transparency aerogel glass for refrigerator with relatively low thermal conductivity factor (no more than 0.01W (mk)) and higher light transmittance
Glass can achieve the effect that energy-efficient while refrigerator illustrative is improved.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
It obtains significantly or is recognized by the practice of the present invention.
Description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become in the description from combination accompanying drawings below to embodiment
Significantly and it is readily appreciated that, wherein：
Fig. 1 is the method flow schematic diagram according to an embodiment of the invention for preparing transparency aerogel；
Fig. 2 is the cross section structure schematic diagram of the transparency aerogel glass according to an embodiment of the invention for refrigerator；
Fig. 3 is illustrated according to the cross section structure of the transparency aerogel glass for refrigerator of further embodiment of the present invention
Figure.
Specific embodiment
The embodiment of the present invention is described below in detail, the example of the embodiment is shown in the drawings, wherein from beginning to end
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.
In the description of the present invention, it is to be understood that term " " center ", " longitudinal direction ", " transverse direction ", " length ", " width ",
" thickness ", " on ", " under ", "front", "rear", "left", "right", " vertical ", " level ", " top ", " bottom ", " interior ", " outer ", " up time
The orientation or position relationship of the instructions such as needle ", " counterclockwise ", " axial direction ", " radial direction ", " circumferential direction " be based on orientation shown in the drawings or
Position relationship is for only for ease of the description present invention and simplifies description rather than instruction or imply that signified device or element must
There must be specific orientation, with specific azimuth configuration and operation, therefore be not considered as limiting the invention.
In addition, term " first ", " second " are only used for description purpose, and it is not intended that instruction or hint relative importance
Or the implicit quantity for indicating indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.In the description of the present invention, " multiple " are meant that at least two, such as two, three
It is a etc., unless otherwise specifically defined.
In the present invention unless specifically defined or limited otherwise, term " installation ", " connected ", " connection ", " fixation " etc.
Term should be interpreted broadly, for example, it may be being fixedly connected or being detachably connected or integral；Can be that machinery connects
It connects or is electrically connected；It can be directly connected, can also be indirectly connected by intermediary, can be in two elements
The connection in portion or the interaction relationship of two elements, unless otherwise restricted clearly.For those of ordinary skill in the art
For, the concrete meaning of above-mentioned term in the present invention can be understood as the case may be.
In the present invention unless specifically defined or limited otherwise, fisrt feature can be with "above" or "below" second feature
It is that the first and second features are in direct contact or the first and second features pass through intermediary mediate contact.Moreover, fisrt feature exists
Second feature " on ", " top " and " above " but fisrt feature right over second feature or oblique upper or be merely representative of
Fisrt feature level height is higher than second feature.Fisrt feature second feature " under ", " lower section " and " below " can be
One feature is immediately below second feature or obliquely downward or is merely representative of fisrt feature level height less than second feature.
In one aspect of the invention, the present invention proposes a kind of method for preparing transparency aerogel.It is according to the present invention
Embodiment, this method include：(1) silicon source, organic solvent, surface modifier are mixed with water, to obtain mixed material；
(2) mixed material is mixed with the alcoholic solution containing oxalic acid, to obtain colloidal sol；(3) by the gel and the alcohol containing ammonium hydroxide
Solution is mixed, to obtain gel；(4) gel is subjected to burin-in process in alcoholic solution；(5) step (4) is obtained
To aging after gel be added in modifying agent and be modified processing；(6) the modified gel for obtaining step (5) is two
Processing is dried under carbonoxide atmosphere, to obtain transparency aerogel, wherein, in step (1), the silicon source described has
Solvent, the surface modifier and the water are 1 according to molar ratio：3~15：1~10：1~10 is mixed.
Inventor has surprisingly found that, the aeroge with good translucency can be prepared using this method, and
There is apparent reflecting effect to infrared light, so as to which heat radiation can be reduced in the case where not influencing visibility, simultaneously because
Obtained transparency aerogel has good hydrophobicity, is led so as to which obtained aeroge will not influence it due to adsorption moisture
Hot coefficient, secondly obtained transparency aerogel there is good air-breathing gas storage performance, so as to use it for glass when can be grown
Time keeps inside glass vacuum degree, and then prolongs the service life, and its porosity of obtained aeroge is not less than 85%,
Visible light transmittance is not less than 85%, and thermal conductivity factor is not more than 0.010W/ (mk), and heat transfer coefficient is not more than 0.58W/ (m2·
K), bulk density is in 100-180Kg/m3, during so as to be applied to product such as refrigerator doors glass, refrigerator can improved
Achieve the effect that while illustrative energy-efficient.
The method for preparing transparency aerogel of the embodiment of the present invention is described in detail below with reference to Fig. 1.According to this hair
Bright specific embodiment, this method include：
S100：Silicon source, organic solvent, surface modifier are mixed with water
According to an embodiment of the invention, silicon source, organic solvent, surface modifier are mixed with water, so as to
To mixed material.
According to one embodiment of present invention, silicon source, organic solvent, surface modifier and water can be 1 according to molar ratio：
3~15：1~10：1~10 is mixed.Inventor has found that, since silicon source is not soluble in water, organic solvent can be such that silicon source fully divides
Be dispersed in whole system, be conducive to the progress of hydrolysis, if but solvent it is too many, reactant concentration decline, on the one hand reduce
On the other hand reaction rate influences the crosslinking between silicic acid monomer, makes the aerogel structure to be formed loose；Hydrolytie polycondensation mistake simultaneously
The translucency of gained gel can be improved, but the mole of water can excessively slow down polycondensation process by increasing the amount of water in journey, form gas
Gel time declines, and surface modifier is insufficient, then the hydrophilic radical on aeroge surface can not all be taken by hydrophobic group
In generation, causes the reduction of aeroge hydrophobicity, can be generated so as to cause the water not being replaced in gel voids in the drying process huge
Capillary pressure, lead to collapsing for gel network structure, make that porosity reduces or gel crushes, it is uneconomical if too many.
According to still a further embodiment, the concrete type of silicon source is not particularly restricted, those skilled in the art
It can be selected according to actual needs, according to a particular embodiment of the invention, silicon source can be selected from ethyl orthosilicate, positive silicon
At least one of sour methyl esters and waterglass.Inventor has found, using such silicon source as the presoma for preparing transparency aerogel
The translucency that other kinds of silicon source improves gained transparency aerogel can be substantially better than.
According to still another embodiment of the invention, the concrete type of organic solvent is not particularly restricted, art technology
Personnel can be selected according to actual needs, and according to a particular embodiment of the invention, organic solvent is selected from absolute ethyl alcohol, nothing
At least one of water methanol and anhydrous propanone.Inventor has found, using such organic solvent as preparing transparency aerogel
Solvent is substantially better than the translucency that other kinds of organic solvent improves gained transparency aerogel.
According to still another embodiment of the invention, the concrete type of surface modifier is not particularly restricted, this field skill
Art personnel can be selected according to actual needs, and according to a particular embodiment of the invention, surface modifier can be selected from three
In methylchlorosilane, hexamethyldisilazane, dimethylformamide, methyltriethoxysilane and methyltrimethoxysilane
It is at least one.Inventor has found that can be substantially better than other kinds of modifying agent using such surface modifier improves aeroge
Hydrophobicity and porosity.
S200：Mixed material is mixed with the alcoholic solution containing oxalic acid
According to an embodiment of the invention, mixed material obtained above is mixed with the alcoholic solution containing oxalic acid, so as to
So that system hydrolyzes to obtain colloidal sol.It should be noted that unless otherwise specified, " alcoholic solution " herein refers both to " ethanol solution "
Or " methanol solution ".
According to one embodiment of present invention, after mixed material is mixed with the alcoholic solution containing oxalic acid the pH value of solution not by
Especially limitation, those skilled in the art can be selected according to actual needs, according to a particular embodiment of the invention, mixture
The pH value of solution can be 1~3 after material is mixed with the alcoholic solution containing oxalic acid.Inventor has found, can be filled under the pH with guarantee system
Divide hydrolysis, so as to significantly improve the translucency of obtained transparency aerogel.
S300：Colloidal sol is mixed with the alcoholic solution containing ammonium hydroxide
According to an embodiment of the invention, the colloidal sol that above-mentioned hydrolysis obtains is mixed with the alcoholic solution containing ammonium hydroxide, so as to
It can promote colloidal sol polycondensation, treat to stand under 20 degrees centigrades after reaction, you can obtain gel.
According to one embodiment of present invention, the pH value of solution is not by special after colloidal sol is mixed with the alcoholic solution containing ammonium hydroxide
Limitation, those skilled in the art can be selected according to actual needs, and according to a particular embodiment of the invention, colloidal sol is with containing ammonia
The pH of solution can be 11~13 after the alcoholic solution mixing of water.Inventor has found, the polycondensation of colloidal sol can be significantly improved under the pH
Reaction efficiency, so as to further improve the translucency of obtained transparency aerogel.
S400：Gel is subjected to burin-in process in alcoholic solution
According to an embodiment of the invention, the obtained gel of above-mentioned polycondensation is subjected to burin-in process in alcoholic solution, it can be with
So that the crystal gel in gel uniformly increases, so that gel particle particle diameter distribution is uniform in obtained aeroge, into
And ensure it with excellent light transmission.
According to one embodiment of present invention, the condition of burin-in process is not particularly restricted, and those skilled in the art can
To be selected according to actual needs, according to a particular embodiment of the invention, burin-in process can under 50~65 degrees Celsius into
Row 36~48 hours.Inventor has found, the uniformity of gel particle grain size can be significantly improved under the conditions of the burin-in process, so as to
It is further ensured that gained aeroge has excellent light transmission.In the step, specifically, by obtained gel in alcoholic solution
Middle carry out burin-in process every 24 hours, solvent (ethanol solution) is updated primary.
S500：Gel after aging is added in modifying agent and is modified processing
According to an embodiment of the invention, the gel after aging step S400 obtained, which is added in modifying agent, to be modified
Processing.Thus, it is possible to significantly improve translucency, hydrophobicity and the porosity of gained aeroge.
According to one embodiment of present invention, the concrete type of modifying agent is not particularly restricted, those skilled in the art
Can be selected according to actual needs, according to a particular embodiment of the invention, modifying agent can be selected from dimethylformamide,
At least one of trim,ethylchlorosilane, hexamethyldisilazane and n-hexane, it is preferred that modifying agent can be dimethyl methyl acyl
The mixed solution of amine and n-hexane.Inventor has found that the modifying agent of the type can be substantially better than other kinds of modifying agent and carry
Translucency, hydrophobicity and the porosity of high gained aeroge.
In the step, specifically, the gel after aging obtained above is immersed in containing dimethylformamide and just oneself
24~36 hours in the mixed solution of alkane, every 12 hours solvent (mixed solution containing dimethylformamide and n-hexane) more
It is new primary, sample is immersed in 50~65 degrees Celsius of n-hexane 12 hours after to be modified, to exchange in aeroge
Unreacted modifying agent, and do not have 6 hours update hexane solution it is primary.
S600：Processing is dried in obtained modified gel under carbon dioxide atmosphere
According to an embodiment of the invention, modified gel step S500 obtained is done under carbon dioxide atmosphere
Dry processing, so as to obtain transparency aerogel.
According to one embodiment of present invention, the mode modified gel being dried is not particularly restricted, this
Field technology personnel can be selected according to actual needs, according to a particular embodiment of the invention, following procedure may be used
It is dried in the mode of heating：65 degrees Celsius are risen to from room temperature and keeps the temperature 1-2 hours under 65 degrees Celsius, then rise to 80
Degree Celsius and at 80 degrees celsius keep the temperature 1-2 hour, then rise to 120 degrees Celsius and at one hundred and twenty degrees centigrade heat preservation 3-5 hours,
It finally rises to 150 degrees Celsius and keeps the temperature 1-2 hours under 150 degrees Celsius, wherein, the heating rate difference between each temperature section is only
It is on the spot 1-5 degrees celsius/minutes.Inventor has found, by using the heating mode, not into the drying that can significantly improve gel
Efficiency, and can ensure that obtained transparency aerogel has excellent translucency, hydrophobicity and air-breathing gas storage performance.
The method for preparing transparency aerogel according to embodiments of the present invention can be prepared with good translucency
Aeroge, and there is apparent reflecting effect to infrared light, so as to which hot spoke can be reduced in the case where not influencing visibility
It penetrates, simultaneously because obtained transparency aerogel has good hydrophobicity, so as to which obtained aeroge will not be because adsorbing water
Divide and influence its thermal conductivity factor, secondly obtained transparency aerogel has good air-breathing gas storage performance, so as to use it for
Inside glass vacuum degree can be kept during glass for a long time, and then is prolonged the service life, and obtained aeroge its hole
Rate is not less than 85%, it is seen that light transmission rate is not less than 85%, and thermal conductivity factor is not more than 0.010W/ (mk), and heat transfer coefficient is little
In 0.58W/ (m2K), bulk density is in 100-180Kg/m3, can during so as to be applied to product such as refrigerator doors glass
Can be visually seen interior items in the case where not opening refrigerator doors, door opening times are reduced, the same of refrigerator illustrative can improved
When achieve the effect that it is energy-efficient.
In the second aspect of the invention, the present invention proposes a kind of transparency aerogel glass for refrigerator.According to this
The embodiment of invention, the transparency aerogel glass for being used for refrigerator include：Upper glass plates and lower glass plate, the upper glass plates and
Placement space is formed between the lower glass plate, at least one of the upper glass plates and the lower glass plate are upper to have exhaust
Slot, and the air discharge duct connects the placement space and free surrounding space；Aeroge component, the aeroge component are arranged on institute
It states in placement space, and the aeroge component is contacted with the air discharge duct, wherein, the aeroge component is using above-mentioned
What the method for preparing transparency aerogel obtained；Encapsulating material, the encapsulating material coat the upper glass plates, it is described under
Glass plate, the aeroge component and the air discharge duct, and the lower surface of the lower glass plate and the upper glass plates
Upper surface is not coated by the encapsulating material.Inventor has surprisingly found that, passes through the transparent airsetting that the above method is prepared
Glue is as glass aeroge component, since the aeroge component has good translucency, hydrophobicity and air-breathing gas storage performance, from
And the heat insulation of the glass can be significantly improved, it, can during so as to be applied on product for example as refrigerator doors glass
It is energy-efficient to achieve the effect that while refrigerator illustrative is improved, at the same by upper glass plates and lower glass plate at least
One of upper setting air discharge duct so that the air discharge duct can connect aeroge component and free surrounding space in placement space, combine
First the position of air discharge duct exhaust outlet is reserved, then placement space is vacuumized with partial encapsulation material sealing-in in the process, when
After vacuum is extracted into certain amount grade, then from a certain amount of encapsulating material of exhaust ports filling, exhaust outlet filling is got up, only stays one
Point gap, then carries out secondary vacuum pumping at this gap again, and cast encapsulating material carries out on the outside again after vacuumizing
Sealing, so as to by setting air discharge duct that can further be dropped due to having carried out secondary vacuum pumping, the vacuum degree of vacuum glass
It is low, reach more rough vacuum；And after long-time is using process, the vacuum degree of vacuum glass can decline, and can pass through at this time
Outer envelope material is removed, is vacuumized again at exhaust outlet gap, then the means sealed, so as to extend making for the vacuum glass
With the service life, there is excellent heat insulation additionally, due to the transparency aerogel glass, it is solidifying on refrigerator door so as to reduce
Reveal phenomenon.It should be noted that above-mentioned be equally applicable to for the described feature and advantage of method for preparing transparency aerogel
This is used for the transparency aerogel glass of refrigerator, and details are not described herein again.
Below with reference to being described in detail for the transparency aerogel glass of refrigerator for Fig. 2-3 pairs of embodiment of the present invention.Root
According to the embodiment of the present invention, which includes：Upper glass plates 100, lower glass plate 200, airsetting
Glue component 300 and encapsulating material 400.
According to one embodiment of present invention, upper glass plates 100 and lower glass plate 200 correspond to is arranged in parallel up and down, and
Placement space (not shown) is formed between upper glass plates 100 and lower glass plate 200, wherein, upper glass plates 100 and lower glass plate
At least one of 200 is upper with air discharge duct 10, and air discharge duct 10 connects placement space and free surrounding space, as shown in Fig. 2, row
Air drain 10 is arranged in upper glass plates 100.It is vented as a result, by being set at least one of upper glass plates and lower glass plate
Slot so that the air discharge duct can connect aeroge component and free surrounding space in placement space, and part is first used in anabolic process
Encapsulating material sealing-in reserves the position of air discharge duct exhaust outlet, then placement space is vacuumized, when vacuum is extracted into a fixed number
After magnitude, then from a certain amount of encapsulating material of exhaust ports filling, exhaust outlet filling is got up, only stays some gaps, Ran Houzai
Secondary vacuum pumping is carried out at this gap, cast encapsulating material is sealed on the outside again after vacuumizing, so as to pass through
Setting air discharge duct so that, due to having carried out secondary vacuum pumping, the vacuum degree of vacuum glass can be reduced further, reaches lower true
Reciprocal of duty cycle；And after long-time is using process, the vacuum degree of vacuum glass can decline, at this time can be by removing outer envelope material
Material, vacuumizes, then the means sealed at exhaust outlet gap, again so as to extend the service life of the vacuum glass.
According to still a further embodiment, the concrete type of upper glass plates 100 and lower glass plate 200 is not by special
Limitation, those skilled in the art can be selected according to actual needs, according to a particular embodiment of the invention, upper glass plates
100 and lower glass plate 200 can separately be selected from least one of tempered glass and coated glass.Thus, it is possible to
Ensure that gained aeroge glass has higher translucency.
According to still another embodiment of the invention, the thickness of upper glass plates 100 and lower glass plate 200 is not limited especially
System, those skilled in the art can be selected according to actual needs, according to a particular embodiment of the invention, upper glass plates 100
Thickness with lower glass plate 200 is separately 1~20mm.Thus, it is possible to it is further ensured that gained aeroge glass has
Higher translucency.
According to still another embodiment of the invention, aeroge component 300 can be arranged in placement space, and aeroge
Component 300 is contacted with air discharge duct 10.The aeroge component being arranged in placement space can be taken out by air discharge duct as a result,
Vacuum so as to improve the vacuum degree of the aeroge glass, and then further improves the translucency of the aeroge glass.
According to still another embodiment of the invention, the thickness of aeroge component 300 is not particularly restricted, art technology
Personnel can be selected according to actual needs, and according to a particular embodiment of the invention, the thickness of aeroge component 300 can be
5~20mm.Thus, it is possible to the heat-insulated effect of glass is improved while aeroge glass obtained by guarantee has higher translucency
Fruit.
According to still another embodiment of the invention, encapsulating material 400 coats upper glass plates 100, lower glass plate 200, airsetting
Glue component 300 and air discharge duct 10, and the non-encapsulated material in the lower surface of lower glass plate 100 and the upper surface of upper glass plates 200
400 cladding of material.
According to another embodiment of the invention, with reference to figure 3, encapsulating material 400 can include PVB encapsulating materials 41 and tin bismuth
Alloy encapsulating material 42, wherein, PVB encapsulating materials 41 coat the outer surface of aeroge component 300, sn-bi alloy encapsulating material 42
Coat PVB encapsulating materials 41, upper glass plates 100, lower glass plate 200 and air discharge duct 10.Thus, it is possible to ensureing that inside glass is close
The stability of glass is improved while envelope.
In the third aspect of the invention, the present invention proposes a kind of refrigerator.According to an embodiment of the invention, the refrigerator
With the transparency aerogel glass for refrigerator described above, such as can be used as refrigerator doors.As a result, by using upper
State the transparency aerogel glass for refrigerator with relatively low thermal conductivity factor (no more than 0.01W (mk)) and higher light transmittance
Glass, can achieve the effect that while refrigerator display type is improved it is energy-efficient, and compared to commonly using polyurethane foam for guarantor
The refrigerator of adiabator is compared, and glass door for refrigerator of the invention has the characteristics that thickness is thin, light weight, so that identical appearance ruler
The very little lower physical memory space that can increase refrigerator, while the dew condensation phenomenon on the refrigerator door is significantly reduced.It needs to illustrate
, it is above-mentioned for the method for preparing transparency aerogel and for refrigerator transparency aerogel glass distinguish described feature and
Advantage is equally applicable to the refrigerator, and details are not described herein again.
Below with reference to specific embodiment, present invention is described, it should be noted that these embodiments are only to describe
Property, without limiting the invention in any way.
Embodiment
The upper glass plates and lower glass plate of use are respectively tempered glass and coated glass, and thickness is for 5mm；
The aeroge component used is using ethyl orthosilicate (TEOS) as presoma, using absolute methanol as solvent, with three
The mixed solution of methylchlorosilane (TMCS) and dimethylformamide (DMF) (trim,ethylchlorosilane (TMCS) and dimethyl formyl
Amine (DMF) is 5 in molar ratio:1 mixing) as surface modifier, presoma, solvent, surface modifier, deionized water are pressed 1:
5:8:3 molar ratio is added in plastic containers, is stirring evenly and then adding into the methanol solution containing oxalic acid, and it is 1 to adjust pH value, is promoted
System is fully hydrolyzed；The methanol solution containing ammonium hydroxide is added dropwise after lasting stirring a period of time, it is 13 to adjust pH value, accelerates colloidal sol contracting
It is poly-, it is then sealed at 20 DEG C and stands to form gel, after gel-forming, sample is placed in methanol solution and is carried out at aging
Reason, aging temperature are 65 DEG C, ageing time 48h, primary per the update of solvent for 24 hours, and after to be aging, gained sample is submerged
Containing dimethylformamide and n-hexane mixed solution (molar ratio of dimethylformamide and n-hexane be 5:1) in into
Row modification 36h, it is primary per the update of 12h solution, sample is immersed in 12h in 65 DEG C of n-hexane after being modified, is exchanged
Unreacted modifying agent in aeroge, and it is primary per the update of 6h solution, and the modified taking-up sample in surface is placed on intelligent temperature control
Drying box carries out classification drying process according to the temperature program set, and temperature program is：From room temperature rise to 65 degrees Celsius and
1-2 hours are kept the temperature under 65 degrees Celsius, then rise to 80 degrees Celsius and keeps the temperature 1-2 hours at 80 degrees celsius, 120 is then risen to and takes the photograph
Family name's degree simultaneously keeps the temperature 3-5 hours at one hundred and twenty degrees centigrade, finally rises to 150 degrees Celsius and keeps the temperature 1-2 hours under 150 degrees Celsius,
In, the heating rate between each temperature section is separately 1-5 degrees celsius/minutes, finally cools to room temperature with the furnace, obtains
Bright aeroge, thickness 10mm, porosity 90%, it is seen that light transmission rate 87%, thermal conductivity factor are 0.009W/ (m
K), heat transfer coefficient is 0.56W/ (m2K), bulk density is in 150Kg/m3。
Upper glass plates are placed in the upper surface of aeroge component, lower glass plate is placed in the lower surface of aeroge component, wherein
Aeroge size of components is less than upper and lower glass sheet size 2cm, there are air discharge duct on the inside of upper glass plates, in the outer of aeroge component
Surface PVB material sealing-ins, and being vacuumized to placement space, then with sn-bi alloy encapsulating material cladding upper glass plates,
Lower glass plate, PVB outer surfaces and air discharge duct, obtain transparency aerogel glass, and ice is made using the transparency aerogel glass
Chamber door body, the inside refrigerator door are not provided with supporter, other than door body is using aeroge glass, body structure and general refrigerator
It is identical, it is still kept the temperature using polyurethane foam, compared to the refrigerator of conventional vacuum glass, which can be with energy saving 10%-30%.
In the description of this specification, reference term " one embodiment ", " example ", " is specifically shown " some embodiments "
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment of the present invention or example.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It is combined in an appropriate manner in one or more embodiments or example.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the different embodiments or examples described in this specification and the feature of different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (16)
1. a kind of transparency aerogel glass for refrigerator, which is characterized in that including：
Upper glass plates and lower glass plate form placement space, the upper glass between the upper glass plates and the lower glass plate
At least one of plate and the lower glass plate are upper to have air discharge duct, and the air discharge duct connects the placement space and the external world
Space；
Aeroge component, the aeroge component are arranged in the placement space, and the aeroge component and the row
Air drain contacts；
Encapsulating material, the encapsulating material coat the upper glass plates, the lower glass plate, the aeroge component and described
Air discharge duct, and the lower surface of the lower glass plate and the upper surface of the upper glass plates are not coated by the encapsulating material,
In, what the aeroge component was obtained through the following steps：
(1) silicon source, organic solvent, surface modifier are mixed with water, to obtain mixed material；
(2) mixed material is mixed with the alcoholic solution containing oxalic acid, to obtain colloidal sol；
(3) colloidal sol is mixed with the alcoholic solution containing ammonium hydroxide, to obtain gel；
(4) gel is subjected to burin-in process in alcoholic solution；
(5) gel after the aging for obtaining step (4), which is added in modifying agent, is modified processing；
(6) processing is dried in the modified gel that step (5) obtains under carbon dioxide atmosphere, to obtain transparent gas
Gel,
Wherein, in step (1), the silicon source, the organic solvent, the surface modifier and the water are according to molar ratio
1：3~15：1~10：1~10 is mixed.
2. the transparency aerogel glass according to claim 1 for refrigerator, which is characterized in that described in step (1)
Silicon source is selected from least one of ethyl orthosilicate, methyl orthosilicate and waterglass.
3. the transparency aerogel glass according to claim 2 for refrigerator, which is characterized in that described in step (1)
Organic solvent is selected from least one of absolute ethyl alcohol, absolute methanol and anhydrous propanone.
4. the transparency aerogel glass according to claim 3 for refrigerator, which is characterized in that described in step (1)
Surface modifier is selected from trim,ethylchlorosilane, hexamethyldisilazane, dimethylformamide, methyltriethoxysilane and first
At least one of base trimethoxy silane.
5. the transparency aerogel glass of refrigerator to be used for according to claim 1-4 any one of them, which is characterized in that in step
(2) in, the pH of solution is 1~3 after the mixed material is mixed with the alcoholic solution containing oxalic acid.
6. the transparency aerogel glass according to claim 5 for refrigerator, which is characterized in that described in step (3)
The pH of solution is 11~13 after colloidal sol is mixed with the alcoholic solution containing ammonium hydroxide.
7. the transparency aerogel glass according to claim 6 for refrigerator, which is characterized in that described in step (4)
Burin-in process is carried out 36~48 hours under 50~65 degrees Celsius.
8. the transparency aerogel glass according to claim 7 for refrigerator, which is characterized in that described in step (5)
The time of modification is 24~36 hours.
9. the transparency aerogel glass according to claim 8 for refrigerator, which is characterized in that the modifying agent be selected from
At least one of dimethylformamide, trim,ethylchlorosilane, hexamethyldisilazane and n-hexane.
10. the transparency aerogel glass according to claim 9 for refrigerator, which is characterized in that the modifying agent is two
The mixed solution of methylformamide and n-hexane.
11. the transparency aerogel glass of refrigerator to be used for according to claim 6-10 any one of them, which is characterized in that in step
(6) in, the drying process is to heat up to carry out according to following procedure：
65 degrees Celsius are risen to from room temperature and keeps the temperature 1-2 hours under 65 degrees Celsius, then rise to 80 degrees Celsius and at 80 degrees Celsius
Lower heat preservation 1-2 hours then rises to 120 degrees Celsius and keeps the temperature 3-5 hours at one hundred and twenty degrees centigrade, finally rises to 150 degrees Celsius simultaneously
1-2 hours are kept the temperature under 150 degrees Celsius, wherein, the heating rate between each temperature section is separately 1-5 degree mins Celsius
Clock.
12. the transparency aerogel glass according to claim 11 for refrigerator, which is characterized in that the encapsulating material packet
PVB encapsulating materials and sn-bi alloy encapsulating material are included, wherein, the PVB encapsulating materials coat the appearance of the aeroge component
Face, the sn-bi alloy encapsulating material coat the PVB encapsulating materials, the upper glass plates, the lower glass plate and the row
Air drain.
13. the transparency aerogel glass according to claim 12 for refrigerator, which is characterized in that the upper glass plates and
The lower glass plate is separately selected from least one of tempered glass and coated glass.
14. the transparency aerogel glass of refrigerator to be used for according to claim 1,12 or 13 any one of them, which is characterized in that institute
The thickness for stating upper glass plates and the lower glass plate is separately 1~20mm.
15. the transparency aerogel glass according to claim 14 for refrigerator, which is characterized in that the aeroge component
Thickness be 5~20mm.
16. a kind of refrigerator, which is characterized in that the refrigerator has claim 1-15 any one of them for the transparent of refrigerator
Aeroge glass.
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| CN201511030604.1A CN105444502B (en) | 2015-12-30 | 2015-12-30 | The method for preparing transparency aerogel, transparency aerogel glass and refrigerator for refrigerator |
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| CN108059357B (en) * | 2017-12-25 | 2020-09-08 | 乐山职业技术学院 | Normal-pressure preparation method of transparent silicon dioxide aerogel glass |
| JP2020106092A (en) * | 2018-12-27 | 2020-07-09 | アクア株式会社 | Manufacturing method of heat insulation material, and refrigerator including heat insulation material manufactured by using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101774592A (en) * | 2009-10-31 | 2010-07-14 | 华南理工大学 | High heat insulation transparent SiO2 aerogel film material and preparation method thereof |
| CN102180603A (en) * | 2011-02-25 | 2011-09-14 | 东莞市创一新材料科技有限公司 | Integrated transparent thermal insulation SiO2 aerogel composite glass and preparation method thereof |
| CN102836678A (en) * | 2012-08-28 | 2012-12-26 | 青岛科瑞新型环保材料有限公司 | Preparing method of transparent aerogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20060191215A1 (en) * | 2002-03-22 | 2006-08-31 | Stark David H | Insulated glazing units and methods |
| JP2012211721A (en) * | 2011-03-31 | 2012-11-01 | Hitachi Appliances Inc | Refrigerator |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774592A (en) * | 2009-10-31 | 2010-07-14 | 华南理工大学 | High heat insulation transparent SiO2 aerogel film material and preparation method thereof |
| CN102180603A (en) * | 2011-02-25 | 2011-09-14 | 东莞市创一新材料科技有限公司 | Integrated transparent thermal insulation SiO2 aerogel composite glass and preparation method thereof |
| CN102836678A (en) * | 2012-08-28 | 2012-12-26 | 青岛科瑞新型环保材料有限公司 | Preparing method of transparent aerogel |
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