CN105879706A - Graphene oxide-polymer hybridized all-heat exchange membrane and preparation method and application thereof - Google Patents
Graphene oxide-polymer hybridized all-heat exchange membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN105879706A CN105879706A CN201610361406.1A CN201610361406A CN105879706A CN 105879706 A CN105879706 A CN 105879706A CN 201610361406 A CN201610361406 A CN 201610361406A CN 105879706 A CN105879706 A CN 105879706A
- Authority
- CN
- China
- Prior art keywords
- heat exchange
- graphene oxide
- total heat
- polymer
- supporting layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Carbon And Carbon Compounds (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a graphene oxide-polymer hybridized all-heat exchange membrane and a preparation method and application thereof. The all-heat exchange membrane comprises a graphene oxide/polymer dense layer with the thickness of 200-500 microns and a porous supporting layer, wherein the dense layer is compounded on the supporting layer. The preparation method comprises the steps that graphene oxide dispersion liquid is added to a polymer solution, heating is performed to reach the temperature of 40-120 DEG C, stirring is performed for 6-12 hours, and then filtering and vacuum defoamation are performed to obtain a membrane casting solution; the pretreated supporting layer is coated with the membrane casting solution, vacuum drying is performed for 1-5 hours, washing is performed with deionized water to make the solution neutral, and drying is performed at room temperature to prepare the graphene oxide-polymer hybridized all-heat exchange membrane. The all-heat exchange membrane can effectively block harmful gases, has high energy exchange efficiency, mechanical properties, thermal stability and antimicrobial properties, can be assembled into an all-heat exchange component by adopting an existing known method and is used in an all-heat exchanger.
Description
Technical field
The invention belongs to air-conditioning total heat recovery technical field, relate to a kind of Total heat exchange film and preparation method thereof
And application, it is specifically related to Total heat exchange film of a kind of graphene oxide-polymer hybrid and preparation method thereof
With the total-heat exchanger using this film to carry out energy exchange.
Background technology
Along with the rapid growth of building energy consumption, building energy conservation becomes the grand strategy of China's energy development, and
Having about 55% in building energy consumption is heating and air conditioning energy consumption, is the key factor of restriction building energy conservation.With
Gradually stepping up of people's living standard, people are more and more higher to the requirement of indoor air quality, cause
Novel wind energy consumption becomes the important component part of air conditioning energy consumption.Therefore, how IAQ (indoor air quality) is being ensured
Under premise, reduce air conditioning energy consumption and become the developing of paramount importance problem of air-Conditioning Research.Research
Show: new for outdoor wind can be sent after filtration, purification, hot and humid area process by air conditioner heat recovery system
Enter indoor, the most again by the air draft of foul indoor through filtering, purifying, after hot wet recovery outside discharge chamber,
And indoor air temperature is not entered to be affected by the most distinguished and the most admirable, it is effectively improved building energy consumption ratio, can reduce
The new wind load of air conditioning system 50%～80%, can efficiently solve raising air quality and reduce air-conditioning
Contradiction between energy consumption.
Although standard GB/T/T21087-2007 requires that air-to-air energy recovery equipment is at winter or summer
Enthalpy exchange efficiency under operating mode respectively reaches 55%, more than 50%, but up to the present, due to technology
Immature, the heat recovery efficiency of most domestic total-heat exchanger product, only about 50%, far lags behind
International most advanced level, and generally there is the shortcomings such as the moisture absorption high, easy of waste gas leak rate is mouldy, have a strong impact on
The effects of energy conservation and environmental protection of total-heat exchanger and service life.
Therefore obtain high-performance Total heat exchange film, be suitable for the fresh air optimized system of series of varying environment, greatly
Reduce greatly the gap of China's new wind air optimizing system auxiliary products quality and international most advanced level, break and send out
Reach National Technical barrier, drive the fast development of related industry, the most effectively country will be promoted " energy-conservation
Reduce discharging " process, there is far-reaching strategic importance and good social benefit.
Summary of the invention
It is an object of the invention to provide a kind of graphene oxide-polymer miscellaneous for above-mentioned technical problem
The Total heat exchange film changed, this film can be while keeping high harmful gas barrier, and Total heat exchange is imitated
Rate increases considerably, and the addition of graphene oxide effectively improves the mechanical performance of film, heat stability
And antibiotic property.
Total heat exchange film of the present invention, including graphene oxide/polymer compacted zone, open support
Layer, described compacted zone is compounded on described supporting layer；Wherein the thickness of compacted zone be 200 μm～
500μm。
Described graphene oxide/polymer compacted zone is graphene oxide with polymer according to 0.1～1:
100 mass ratioes are polymerized；
Further, described Total heat exchange film is for can be made into tubular membrane, hollow-fibre membrane or Flat Membrane.
It is a further object to provide the Total heat exchange film of above-mentioned graphene oxide-polymer hybrid
Preparation method, the method comprises the following steps:
Step (1), polymeric film material is added in solvent orange 2 A, be configured to the solution of 5～20wt%；
It is subsequently placed in heated and stirred 6～10h at 40～120 DEG C, obtains polymer solution；
Described polymeric film material is hydrophilic polymer, for starch based polymers, polyvinyl alcohol, vinegar
Appointing in acid cellulose, polrvinyl chloride, polyacrylamide, chitosan, sodium alginate, aqueous polyurethane
Anticipate one or more mixture；
Step (2), add graphene oxide into ultrasonic disperse in solvent B, ultrasonic disperse power be 100W～
1000W, ultrasonic disperse time 0.1h～5h, be configured to the graphene oxide dispersion of 0.01～0.2wt%；
Described solvent orange 2 A, B each stand alone as deionized water, acetic acid, acetone, normal heptane, dimethyl
Any one or two kinds in Methanamide, methyl pyrrolidone；
Step (3), the polymer that the graphene oxide dispersion of step (2) adds step (1) are molten
In liquid, it is heated to 40～120 DEG C and stirs 6～12h, then obtaining casting solution after filtration, vacuum defoamation；
During wherein in graphene oxide dispersion, graphene oxide is polymer solution polymer quality 0.1～
1wt%；
Step (4), supporting layer is carried out surface clean pretreatment；
Described supporting layer is organic supporting layer or inorganic supporting layer, and the most organic supporting layer is polysulfones, polyethers
Any one in sulfone, polyethylene, polypropylene, Kynoar, politef or cellulose acetate
Supporting layer；Inorganic supporting layer is a kind of material or several in aluminium oxide, zirconium oxide, silicon oxide or titanium oxide
Plant composite material support layer.
Step (5), by step (3) prepare Casting solution be coated in pretreated of step (4)
On support layer, thickness is 200 μm～500 μm, is vacuum dried 1-5h, is washed with deionized water to neutrality,
It is dried under room temperature and prepares graphene oxide-polymer hybrid Total heat exchange film.
Described step (5) uses the tape casting, rolling process, knifing, spraying, spin coating or immersion-lifting
Method.
A further object of the present invention is that the Total heat exchange film of above-mentioned graphene oxide-polymer hybrid can group
Dress up full heat exchanging element application in total-heat exchanger.
The Total heat exchange film of the present invention, can effectively intercept harmful gas, have high energy exchange efficiency,
Mechanical performance, heat stability and antibiotic property, can be assembled into Total heat exchange unit according to existing known method
Part, is used in total-heat exchanger.
The Total heat exchange film of the present invention is the casting film that graphene oxide is dispersed in high molecular polymer
In liquid, utilize rapid water channel characteristic and the high-termal conductivity of layered graphite oxide alkene, thus realize aoxidizing stone
Ink alkene modifying polymer film has efficient Exchange of apparent heat efficiency and latent heat exchange efficiency；Graphene oxide/
Polymer film surface is fine and close, effectively intercepts harmful gas, and additionally the addition of graphene oxide, adds
The mechanical performance of film, heat stability and antibiotic property.The preparation condition of film is gentle, and operating process is simple, easily
Produce in lot-size metaplasia, there is the application prospect that preferable industrialized production is basic and wide.
The invention have benefit that:
(1) the Total heat exchange film that a kind of brand-new cost performance is high is provided.
(2) the Total heat exchange membrane preparation method of the present invention is simple, and cost of material is low, it is easy to popularization and application.
(3) what the present invention provided can effectively intercept harmful gas, has high energy exchange efficiency, machinery
The Total heat exchange film of performance, heat stability and antibiotic property can be used for whole hot-air exchanger, for indoor offer
The dirty noxious air of fresh air, effectively eliminating, recovery air-conditioning HVAC energy (reclaim in air draft aobvious simultaneously
Heat and latent heat).
Detailed description of the invention
Below by embodiment, invention is expanded on further, but is not limiting as the present invention.
The Total heat exchange film of graphene oxide-polymer hybrid of the present invention, uses following methods to be prepared from:
Step (1), polymeric film material is added in solvent orange 2 A, be configured to the solution of 5～20wt%；
It is subsequently placed in heated and stirred 6～10h at 40～120 DEG C, obtains polymer solution；
Described polymeric film material is hydrophilic polymer, for starch based polymers, polyvinyl alcohol, vinegar
Appointing in acid cellulose, polrvinyl chloride, polyacrylamide, chitosan, sodium alginate, aqueous polyurethane
Anticipate one or more mixture；
Step (2), add graphene oxide into ultrasonic disperse in solvent B, ultrasonic disperse power be 100W～
1000W, ultrasonic disperse time 0.1h～5h, be configured to the graphene oxide dispersion of 0.01～0.2wt%；
Described solvent orange 2 A, B each stand alone as deionized water, acetic acid, acetone, normal heptane, dimethyl
Any one or two kinds in Methanamide, methyl pyrrolidone；
Step (3), the polymer that the graphene oxide dispersion of step (2) adds step (1) are molten
In liquid, it is heated to 40～120 DEG C and stirs 6～12h, then obtaining casting solution after filtration, vacuum defoamation；
During wherein in graphene oxide dispersion, graphene oxide is polymer solution polymer quality 0.1～
1wt%；
Step (4), supporting layer is carried out surface clean pretreatment；
Described supporting layer is organic supporting layer or inorganic supporting layer, and the most organic supporting layer is polysulfones, polyethers
Any one in sulfone, polyethylene, polypropylene, Kynoar, politef or cellulose acetate
Supporting layer；Inorganic supporting layer is a kind of material or several in aluminium oxide, zirconium oxide, silicon oxide or titanium oxide
Plant composite material support layer.
Step (5), by step (3) prepare Casting solution use the tape casting, rolling process, knifing,
Spraying, spin coating or immersion-czochralski method are coated on step (4) pretreated supporting layer, and thickness is
200 μm～500 μm, be vacuum dried 1-5h, be washed with deionized water to neutrality, is dried and prepares under room temperature
Graphene oxide-polymer hybrid Total heat exchange film.
The above-mentioned Total heat exchange film prepared, props up including graphene oxide/polymer compacted zone, porous
Support layer, described compacted zone is compounded on described supporting layer；Wherein the thickness of compacted zone be 200 μm～
500μm.Described graphene oxide/polymer compacted zone be graphene oxide with polymer according to
0.1～1:100 mass ratio is polymerized.
Described Total heat exchange film is for can be made into tubular membrane, hollow-fibre membrane or Flat Membrane.
Temperature exchange efficiency that following example are used and enthalpy exchange efficiency method of testing are all with reference to country
Cooling in summer operating mode in standard GB/T21087-2007 " air-to-air energy recovery equipment ", newly
Wind side dry-bulb temperature 35 DEG C, wet bulb temperature 28 DEG C；Air draft side dry-bulb temperature 27 DEG C, wet bulb temperature 19.5 DEG C；
Manufactured Total heat exchange movement exchange area about 10m2.Anti-microbial property test is with reference to country's light industry mark
Quasi-QB/T2591-2003 " antibiotic plastic Anti-microbial Performance Tests method and antibacterial effect ".
Embodiment 1
(1) 15g cellulose acetate is joined in 85g acetic acid, heated and stirred 10h at 50 DEG C,
Solution left standstill is stand-by.
(2) being dissolved in 50mL deionized water by the graphene oxide of 0.1g, ultrasonic disperse power is 100W,
Ultrasonic time is 5h, and ultrasonic disperse forms graphene oxide water solution.
(3) aqueous dispersions of the graphene oxide in step (2) is added the acetic acid in step (1)
In cellulose solution, 50 DEG C of heated and stirred 10h, then obtain casting solution after filtration, vacuum defoamation.
(4) to 80g/m2, thickness be that the polysulfones supporter of 100 microns carries out surface clean pretreatment；
(5) solvent evaporated method is used to be coated in step (4) warp the Casting solution that step (3) prepares
On the supporting layer of pretreatment, thickness is 200 μm～500 μm, is vacuum dried 1h, is washed with deionized water
To neutral, it be dried under room temperature and prepare graphene oxide-cellulose acetate hydridization Total heat exchange film.This is the hottest
Exchange membrane can be fabricated to flat membrane component.
After testing, Total heat exchange thin film prepared by the present embodiment, carbon dioxide transit dose is
1.6*104cm3/m2·day·0.1MPa；Make Total heat exchange film movement, equal at new wind and air draft air quantity
For 200m3Under/h, temperature exchange efficiency is 68.0%, enthalpy exchange efficiency 73.8%.Anti-microbial property:
To colon bacillus and the antibiotic rate of staphylococcus aureus > 99%.
Comparative example 1
(1) 15g cellulose acetate is joined in 85g acetic acid, heated and stirred 10h at 50 DEG C,
Solution obtains casting solution after filtration, vacuum defoamation.
(2) to 80g/m2, thickness be that the polysulfones supporter of 100 microns carries out surface clean pretreatment；
(3) solvent evaporated method is used to be coated in step (3) warp the Casting solution that step (1) prepares
On the supporting layer of pretreatment, thickness is 200 μm～500 μm, is vacuum dried 1h, is washed with deionized water
To neutral, it be dried under room temperature and prepare cellulose acetate Total heat exchange film.This Total heat exchange film can be fabricated to put down
Plate membrane component.
After testing, Total heat exchange thin film prepared by this comparative example, carbon dioxide transit dose is
0.5*104cm3/m2·day·0.1MPa；Make Total heat exchange film movement, equal at new wind and air draft air quantity
For 200m3Under/h, temperature exchange efficiency is 50.1%, enthalpy exchange efficiency 54.6%.Anti-microbial property:
Antibiotic rate < 10% to colon bacillus and staphylococcus aureus.
Embodiment 2
(1) joining in 90g water by 10g polyvinyl alcohol, heated and stirred 8h at 90 DEG C, solution is quiet
Put stand-by.
(2) being dissolved in 50mL deionized water by the graphene oxide of 0.08g, ultrasonic disperse forms oxidation
Graphene aqueous solution.
(3) aqueous dispersions of the graphene oxide in step (2) is added the poly-second in step (1)
In enolate solution, 60 DEG C of heated and stirred 10h, then obtain casting solution after filtration, vacuum defoamation.
(4) to 80g/m2, thickness be that the polyether sulfone supporter of 90 microns carries out surface clean pretreatment；
(5) Casting solution that step (3) prepares is coated in step (4) pretreated supporting layer
On, thickness is 200 μm～500 μm, 60 DEG C of dry 5h, prepares graphene oxide-polyvinyl alcohol miscellaneous
Change Total heat exchange film.This Total heat exchange film can be fabricated to flat membrane component.
After testing, Total heat exchange thin film prepared by the present embodiment, carbon dioxide transit dose is 3.4*102
cm3/m2·day·0.1MPa；Make Total heat exchange film movement, be 200m at new wind and air draft air quantity3/h
Under the conditions of, temperature exchange efficiency is 64.5%, enthalpy exchange efficiency 70.4%.Anti-microbial property: to large intestine angstrom
Uncommon Salmonella and the antibiotic rate of staphylococcus aureus > 99%.
Comparative example 2
(1) 10g polyvinyl alcohol is joined in 90g water, heated and stirred 12h at 90 DEG C, pass through
Casting solution is obtained after filtration, vacuum defoamation.
(2) to 80g/m2, thickness be that the polyether sulfone supporter of 90 microns carries out surface clean pretreatment；
(3) Casting solution that step (1) prepares is coated in step (3) pretreated supporting layer
On, thickness is 200 μm～500 μm, and 60 DEG C of dry 5h prepare polyvinyl alcohol Total heat exchange film.Should
Total heat exchange film can be fabricated to flat membrane component.
After testing, Total heat exchange thin film prepared by this comparative example, carbon dioxide transit dose is
1.5*103cm3/m2·day·0.1MPa；Make Total heat exchange film movement, equal at new wind and air draft air quantity
For 200m3Under/h, temperature exchange efficiency is 48.6%, enthalpy exchange efficiency 52.2%.Anti-microbial property:
Antibiotic rate < 15% to colon bacillus and staphylococcus aureus.
Embodiment 3
(1) joining in 95g water by 5g sodium alginate, heated and stirred 12h at 60 DEG C, solution is quiet
Put stand-by.
(2) being dissolved in 50mL deionized water by the graphene oxide of 0.05g, ultrasonic disperse forms oxidation
Graphene aqueous solution.
(3) aqueous dispersions of the graphene oxide in step (2) is added the Sargassum in step (1)
In acid sodium solution, 60 DEG C of heated and stirred 10h, then obtain casting solution after filtration, vacuum defoamation.
(4) polyvinylidene fluoride hollow fiber supporter is carried out surface clean pretreatment；
(5) the Casting solution dip-coating method that step (3) prepares is coated in step (4) through pre-place
On the supporting layer of reason, thickness is 200 μm～500 μm, 50 DEG C of dry 5h, prepared graphene oxide-
Sodium alginate hydridization Total heat exchange film.This Total heat exchange film can be fabricated to hollow fibre membrane component.
After testing, Total heat exchange thin film prepared by the present embodiment, carbon dioxide transit dose is 3.4*103
cm3/m2·day·0.1MPa；Make Total heat exchange film movement, be 200m at new wind and air draft air quantity3/h
Under the conditions of, temperature exchange efficiency is 69.5%, enthalpy exchange efficiency 75.0%.Anti-microbial property: to large intestine angstrom
Uncommon Salmonella and the antibiotic rate of staphylococcus aureus > 99%
Comparative example 3
(1) 5g sodium alginate is joined in 95g water, heated and stirred 12h at 60 DEG C, passed through
Casting solution is obtained after filter, vacuum defoamation.
(2) polyvinylidene fluoride hollow fiber supporter is carried out surface clean pretreatment；
(3) Casting solution that step (1) prepares is coated in step (3) pretreated supporting layer
On, thickness is 200 μm～500 μm, and 50 DEG C of dry 5h prepare sodium alginate Total heat exchange film.Should
Total heat exchange film can be fabricated to hollow fibre membrane component.
After testing, Total heat exchange thin film prepared by this comparative example, carbon dioxide transit dose is
4.5*102cm3/m2·day·0.1MPa；Make Total heat exchange film movement, equal at new wind and air draft air quantity
For 200m3Under/h, temperature exchange efficiency is 46.1%, enthalpy exchange efficiency 56.8%.Anti-microbial property:
Antibiotic rate < 10% to colon bacillus and staphylococcus aureus.
Embodiment 4
(1) 10g acrylamide is joined in 85g deionized water, and adds appropriate initiator,
Under nitrogen protective condition, heat at 120 DEG C, standing, deaeration after reaction 6h, i.e. make all
Even polyacrylamide solution.
(2) being dissolved in 50mL deionized water by the graphene oxide of 0.1g, ultrasonic disperse power is 100W,
Ultrasonic time is 5h, and ultrasonic disperse forms graphene oxide water solution.
(3) aqueous dispersions of the graphene oxide in step (2) is added poly-third in step (1)
In acrylamide solution, 50 DEG C of heated and stirred 6h, then obtain casting solution after filtration, vacuum defoamation.
(4) to 80g/m2, that thickness is that the politef supporter of 100 microns carries out surface clean is pre-
Process；
(5) Casting solution that step (3) prepares is coated in step (4) pretreated supporting layer
On, thickness is 200 μm～500 μm, and vacuum drying 12h prepares graphene oxide-polyacrylamide
Hydridization Total heat exchange film.This Total heat exchange film can be fabricated to flat membrane component.
After testing, Total heat exchange thin film prepared by the present embodiment, carbon dioxide transit dose is
0.6*104cm3/m2·day·0.1MPa；Make Total heat exchange film movement, equal at new wind and air draft air quantity
For 200m3Under/h, temperature exchange efficiency is 67.0%, enthalpy exchange efficiency 72.9%.Anti-microbial property:
To colon bacillus and the antibiotic rate of staphylococcus aureus > 99%.
Comparative example 4
(1) 10g acrylamide is joined in 85g deionized water, and adds appropriate initiator,
Under nitrogen protective condition, heat at 150 DEG C, standing, deaeration after reaction 40min, i.e. make
Uniform polyacrylamide solution.
(2) to 80g/m2, that thickness is that the politef supporter of 100 microns carries out surface clean is pre-
Process；
(3) Casting solution that step (1) prepares is coated in step (3) pretreated supporting layer
On, thickness is 200 μm～500 μm, and vacuum drying 12h prepares polyacrylamide Total heat exchange film.
This Total heat exchange film can be fabricated to flat membrane component.
After testing, Total heat exchange thin film prepared by this comparative example, carbon dioxide transit dose is
0.1*104cm3/m2·day·0.1MPa；Make Total heat exchange film movement, equal at new wind and air draft air quantity
For 200m3Under/h, temperature exchange efficiency is 49.2%, enthalpy exchange efficiency 53.5%.Anti-microbial property:
Antibiotic rate < 10% to colon bacillus and staphylococcus aureus.
Embodiment 5
(1) joining in 90g water by 10g chitosan, heated and stirred 10h at 40 DEG C, solution is quiet
Put stand-by.
(2) being dissolved in 50mL deionized water by the graphene oxide of 0.1g, ultrasonic disperse forms oxidation
Graphene aqueous solution.
(3) aqueous dispersions of the graphene oxide in step (2) is added the shell in step (1) to gather
In sugar juice, 50 DEG C of heated and stirred 10h, then obtain casting solution after filtration, vacuum defoamation.
(4) to TiO2Ceramic supporting body carries out surface clean pretreatment；
(5) the Casting solution dip-coating method that step (3) prepares is coated in step (4) through pre-place
On the supporting layer of reason, thickness is 200 μm～500 μm, 50 DEG C of vacuum drying 1.5h, prepares oxidation stone
Ink alkene-chitosan hybrid Total heat exchange film.This Total heat exchange film can be fabricated to tubular membrane element.
After testing, Total heat exchange thin film prepared by the present embodiment, carbon dioxide transit dose is 1.2*104
cm3/m2·day·0.1·MPa；Make Total heat exchange film movement, be at new wind and air draft air quantity
200m3Under/h, temperature exchange efficiency is 65.5%, enthalpy exchange efficiency 72.3%.Anti-microbial property: right
Colon bacillus and the antibiotic rate of staphylococcus aureus > 99%.
Comparative example 5
(1) 10g chitosan is joined in 90g acetic acid, heated and stirred 12h at 25 DEG C, pass through
Casting solution is obtained after filtration, vacuum defoamation.
(2) to TiO2Ceramic supporting body carries out surface clean pretreatment；
(3) Casting solution that step (1) prepares is coated in step (3) pretreated supporting layer
On, thickness is 200 μm～500 μm, and 50 DEG C of vacuum drying 1.5h prepare chitosan Total heat exchange film.
This Total heat exchange film can be fabricated to tubular membrane element.
After testing, Total heat exchange thin film prepared by this comparative example, carbon dioxide transit dose is
0.5*104cm3/m2·day·0.1MPa；Make Total heat exchange film movement, equal at new wind and air draft air quantity
For 200m3Under/h, temperature exchange efficiency is 45.6%, enthalpy exchange efficiency 50.8%.Anti-microbial property:
Antibiotic rate < 20% to colon bacillus and staphylococcus aureus.
Embodiment 6
(1) 8g polyurethane and 10g hydroxyalkyl starch are joined in 82g water, heat at 50 DEG C
Stirring 12h forms polyurethane/hydroxyalkyl starch mixed solution, and solution left standstill is stand-by.
(2) being dissolved in 50mL deionized water by the graphene oxide of 0.05g, ultrasonic disperse forms oxidation
Graphene aqueous solution.
(3) aqueous dispersions of the graphene oxide in step (2) is added the poly-ammonia in step (1)
In ester/hydroxyalkyl starch mixed solution, 50 DEG C of heated and stirred 10h, then obtain after filtration, vacuum defoamation
To casting solution.
(4) alumina-zirconia doughnut supporter is carried out surface clean pretreatment；
(5) the Casting solution dip-coating method that step (3) prepares is coated in step (4) through pre-place
On the supporting layer of reason, thickness is 200 μm～500 μm, 50 DEG C of dry 5h, prepared graphene oxide-
Polyurethane/hydroxyalkyl starch hydridization Total heat exchange film.This Total heat exchange film can be fabricated to doughnut membrane element
Part.
After testing, Total heat exchange thin film prepared by the present embodiment, carbon dioxide transit dose is 6.9*103
cm3/m2·day·0.1MPa；Make Total heat exchange film movement, be 200m at new wind and air draft air quantity3/h
Under the conditions of, temperature exchange efficiency is 68.8%, enthalpy exchange efficiency 76.0%.Anti-microbial property: to large intestine angstrom
Uncommon Salmonella and the antibiotic rate of staphylococcus aureus > 99%
Comparative example 6
(1) 8g polyurethane and 10g hydroxyalkyl starch are joined in 82g water, heat at 50 DEG C
Stirring 12h forms polyurethane/hydroxyalkyl starch mixed solution, and solution left standstill is stand-by.
(2) alumina-zirconia doughnut supporter is carried out surface clean pretreatment；
(3) Casting solution that step (1) prepares is coated in step (3) pretreated supporting layer
On, thickness is 200 μm～500 μm, 50 DEG C of dry 5h polyurethane/hydroxyalkyl starch Total heat exchange
Film.This Total heat exchange film can be fabricated to hollow fibre membrane component.
After testing, Total heat exchange thin film prepared by this comparative example, carbon dioxide transit dose is
6.3*102cm3/m2·day·0.1MPa；Make Total heat exchange film movement, equal at new wind and air draft air quantity
For 200m3Under/h, temperature exchange efficiency is 44.6%, enthalpy exchange efficiency 58.9%.Anti-microbial property:
Antibiotic rate < 10% to colon bacillus and staphylococcus aureus.
Embodiment 7
(1) joining in 80g acetone by 20g polrvinyl chloride, at 120 DEG C, heated and stirred 6h is formed
Polyvinyl chloride solution, solution left standstill is stand-by.
(2) being dissolved in 50mL deionized water by the graphene oxide of 0.005g, ultrasonic disperse forms oxygen
Functionalized graphene aqueous solution.
(3) aqueous dispersions of the graphene oxide in step (2) is added the polychlorostyrene in step (1)
In vinyl solution, 50 DEG C of heated and stirred 10h, then obtain casting solution after filtration, vacuum defoamation.
(4) polyethylene support body is carried out surface clean pretreatment；
(5) Casting solution dipping the tape casting step (3) prepared is coated in step (4) through pre-place
On the supporting layer of reason, thickness is 200 μm～500 μm, 50 DEG C of dry 5h, prepared graphene oxide-
Polrvinyl chloride hydridization Total heat exchange film.This Total heat exchange film can be fabricated to flat membrane component.
After testing, Total heat exchange thin film prepared by the present embodiment, carbon dioxide transit dose is 6.9*103
cm3/m2·day·0.1MPa；Make Total heat exchange film movement, be 200m at new wind and air draft air quantity3/h
Under the conditions of, temperature exchange efficiency is 65.4%, enthalpy exchange efficiency 70.8%.Anti-microbial property: to large intestine angstrom
Uncommon Salmonella and the antibiotic rate of staphylococcus aureus > 99%
Comparative example 7
(1) joining in 80g acetone by 20g polrvinyl chloride, at 120 DEG C, heated and stirred 6h is formed
Polyvinyl chloride solution, solution left standstill is stand-by.
(2) polyethylene support body is carried out surface clean pretreatment；
(3) Casting solution that step (1) prepares is coated in step (3) pretreated supporting layer
On, thickness is 200 μm～500 μm, 50 DEG C of dry 5h polrvinyl chloride Total heat exchange films.This is complete
Heat exchange membranes can be fabricated to flat membrane component.
After testing, Total heat exchange thin film prepared by this comparative example, carbon dioxide transit dose is
0.9*103cm3/m2·day·0.1MPa；Make Total heat exchange film movement, equal at new wind and air draft air quantity
For 200m3Under/h, temperature exchange efficiency is 43.6%, enthalpy exchange efficiency 56.9%.Anti-microbial property:
Antibiotic rate < 10% to colon bacillus and staphylococcus aureus.
Embodiment 8
By aluminium foil, domestic and international commercial membranes and make exchange area 10m from masking2Same film assembly.
Carry out temperature exchange efficiency and enthalpy exchange efficiency performance test, be 200m at new wind and air draft air quantity3/h
Under the conditions of, result is as shown in the table:
Result shows, the graphene oxide modification Total heat exchange film of the present invention and aluminium foil, domestic and international commercial membranes
Comparing, temperature exchange efficiency and enthalpy exchange efficiency have obvious advantage, and have preferably harmful gas
Barrier.
Above-described embodiment is not the restriction for the present invention, and the present invention is not limited only to above-described embodiment,
As long as meeting application claims, belong to protection scope of the present invention.
Claims (9)
1. the Total heat exchange film of graphene oxide-polymer hybrid, it is characterised in that include oxidation
Graphene/polymer compacted zone, porous support layer, described compacted zone is compounded on described supporting layer；
Described graphene oxide/polymer compacted zone is graphene oxide with polymer according to 0.1～1:
100 mass ratioes are polymerized.
The Total heat exchange film of a kind of graphene oxide-polymer hybrid the most as claimed in claim 1,
The thickness that it is characterized in that compacted zone is 200 μm～500 μm.
The Total heat exchange film of a kind of graphene oxide-polymer hybrid the most as claimed in claim 1,
It is characterized in that described Total heat exchange film is for can be made into tubular membrane, hollow-fibre membrane or Flat Membrane.
4. a preparation method for the Total heat exchange film of graphene oxide-polymer hybrid, its feature exists
Comprise the following steps in the method:
Step (1), polymeric film material is added in solvent orange 2 A, be configured to the solution of 5～20wt%；
It is subsequently placed in heated and stirred 6～10h at 40～120 DEG C, obtains polymer solution；
Step (2), adding graphene oxide into ultrasonic disperse in solvent B, ultrasonic disperse power is
100W～1000W, ultrasonic disperse time 0.1h～5h, be configured to the graphite oxide of 0.01～0.2wt%
Alkene dispersion liquid；
Step (3), the graphene oxide dispersion of step (2) is added the polymer of step (1)
In solution, it is heated to 40～120 DEG C and stirs 6～12h, then being cast after filtration, vacuum defoamation
Film liquid；Polymer quality during wherein graphene oxide is polymer solution in graphene oxide dispersion
0.1～1wt%；
Step (4), supporting layer is carried out surface clean pretreatment；
Step (5), to be coated in step (4) pretreated for Casting solution step (3) prepared
On supporting layer, thickness is 200 μm～500 μm, is vacuum dried 1-5h, is washed with deionized water to neutrality,
It is dried under room temperature and prepares graphene oxide-polymer hybrid Total heat exchange film.
The Total heat exchange film of a kind of graphene oxide-polymer hybrid the most as claimed in claim 1 or
Preparation method described in claim 4, it is characterised in that described polymeric film material is that hydrophilic gathers
Compound, for starch based polymers, polyvinyl alcohol, cellulose acetate, polrvinyl chloride, polyacrylamide,
Any one or a few mixture in chitosan, sodium alginate, aqueous polyurethane.
The Total heat exchange film of a kind of graphene oxide-polymer hybrid the most as claimed in claim 1 or
Preparation method described in claim 4, it is characterised in that described supporting layer is organic supporting layer or inorganic
Supporting layer, the most organic supporting layer be polysulfones, polyether sulfone, polyethylene, polypropylene, polyacrylonitrile,
Any one supporting layer in politef or cellulose acetate；Inorganic supporting layer is aluminium oxide, oxygen
Change a kind of material in zirconium, silicon oxide or titanium oxide or several composite material support layer.
The Total heat exchange film of a kind of graphene oxide-polymer hybrid the most as claimed in claim 4
Preparation method, it is characterised in that described solvent orange 2 A, B each stand alone as deionized water, acetic acid, acetone,
Any one or two kinds in normal heptane, dimethylformamide, methyl pyrrolidone.
The Total heat exchange film of a kind of graphene oxide-polymer hybrid the most as claimed in claim 4
Preparation method, it is characterised in that described step (5) use the tape casting, rolling process, knifing, spraying,
Spin coating or immersion-czochralski method.
The Total heat exchange film of a kind of graphene oxide-polymer hybrid the most as claimed in claim 1 can
It is assembled into full heat exchanging element application in total-heat exchanger.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610361406.1A CN105879706A (en) | 2016-05-26 | 2016-05-26 | Graphene oxide-polymer hybridized all-heat exchange membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610361406.1A CN105879706A (en) | 2016-05-26 | 2016-05-26 | Graphene oxide-polymer hybridized all-heat exchange membrane and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105879706A true CN105879706A (en) | 2016-08-24 |
Family
ID=56717947
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610361406.1A Pending CN105879706A (en) | 2016-05-26 | 2016-05-26 | Graphene oxide-polymer hybridized all-heat exchange membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105879706A (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106310978A (en) * | 2016-10-17 | 2017-01-11 | 江苏新风环保科技有限公司 | Compound air filter membrane based on chitosan and graphene oxide and preparation method of compound air filter membrane |
| CN106474939A (en) * | 2016-12-08 | 2017-03-08 | 河海大学 | A kind of modified carbon nano-tube/graphene oxide shitosan is combined poly (ether-sulfone) ultrafiltration membrane and its preparation method and application |
| CN106492647A (en) * | 2016-12-31 | 2017-03-15 | 青岛翰兴知识产权运营管理有限公司 | A kind of preparation method of the modified sodium alginate polyacrylonitrile hollow fiber membrane of Graphene |
| CN106582327A (en) * | 2016-12-21 | 2017-04-26 | 华南理工大学 | Silver-carrying graphene oxide-polyvinyl alcohol ultrafiltration membrane and preparation and application thereof |
| CN106582311A (en) * | 2016-12-31 | 2017-04-26 | 青岛翰兴知识产权运营管理有限公司 | Preparation method of graphene-modifying sodium alginate-polyacrylonitrile neterogeny reinforced type hollow fiber membrane |
| CN106582310A (en) * | 2016-12-31 | 2017-04-26 | 青岛翰兴知识产权运营管理有限公司 | Preparation method of graphene-modified and homogeneously-enhanced sodium alginate-polyvinyl chloride hollow fiber membrane |
| CN106669435A (en) * | 2016-12-31 | 2017-05-17 | 青岛翰兴知识产权运营管理有限公司 | Graphene modified sodium alginate-polyacrylonitrile heterogeneous enhanced type hollow fiber membrane |
| CN106669434A (en) * | 2016-12-31 | 2017-05-17 | 青岛翰兴知识产权运营管理有限公司 | Graphene modified sodium alginate-polyacrylonitrile hollow-fiber membrane |
| CN106669469A (en) * | 2016-12-31 | 2017-05-17 | 青岛翰兴知识产权运营管理有限公司 | Graphene-modified sodium alginate-polyvinyl chloride homogenously-enhanced hollow fiber membrane |
| CN108031310A (en) * | 2017-12-13 | 2018-05-15 | 四川银趣环保科技有限公司 | A kind of preparation method of the filtering net film based on graphene and high molecular material |
| CN109019745A (en) * | 2018-08-20 | 2018-12-18 | 南京大学 | A kind of preparation method improving multi-functional hybridized film particulate load amount |
| CN109304100A (en) * | 2017-07-28 | 2019-02-05 | 中国科学院宁波材料技术与工程研究所 | A kind of charged ultra-thin sea water desalination membrane and the preparation method and application thereof based on graphene |
| CN109650779A (en) * | 2019-01-18 | 2019-04-19 | 四川大学 | A kind of preparation method of graphene aerogel/polyurethane foaming conductive composites |
| WO2019132467A1 (en) * | 2017-12-26 | 2019-07-04 | Korea Atomic Energy Research Institute | Reduced graphene oxide, reduced graphene oxide-functional material complex, and manufacturing method thereof |
| CN110325264A (en) * | 2016-09-08 | 2019-10-11 | 日东电工株式会社 | The antimicrobial element of graphene oxide |
| CN110743378A (en) * | 2019-10-29 | 2020-02-04 | 吉金学 | Modified wet film, preparation method thereof and application of modified wet film in manufacturing of heat exchange device of air conditioner external unit |
| CN110964280A (en) * | 2019-12-12 | 2020-04-07 | 江苏大翔科技有限公司 | Moisture-permeable and bacteriostatic composite film for total heat exchanger and preparation method thereof |
| CN111363341A (en) * | 2020-04-01 | 2020-07-03 | 青岛华世洁环保科技有限公司 | Heat exchange base material, rotary wheel heat exchanger rotary core carrier, rotary wheel heat exchanger rotary core and preparation method thereof, and rotary wheel heat exchanger |
| CN114130207A (en) * | 2021-11-19 | 2022-03-04 | 中科朗劢技术有限公司 | Multifunctional total heat exchange membrane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600734A (en) * | 2012-03-27 | 2012-07-25 | 南京工业大学 | Enhanced graphene oxide hollow fiber composite membrane and preparation method thereof |
| CN105073235A (en) * | 2013-04-12 | 2015-11-18 | 通用电气公司 | Membranes comprising graphene |
-
2016
- 2016-05-26 CN CN201610361406.1A patent/CN105879706A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102600734A (en) * | 2012-03-27 | 2012-07-25 | 南京工业大学 | Enhanced graphene oxide hollow fiber composite membrane and preparation method thereof |
| CN105073235A (en) * | 2013-04-12 | 2015-11-18 | 通用电气公司 | Membranes comprising graphene |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110325264A (en) * | 2016-09-08 | 2019-10-11 | 日东电工株式会社 | The antimicrobial element of graphene oxide |
| CN106310978A (en) * | 2016-10-17 | 2017-01-11 | 江苏新风环保科技有限公司 | Compound air filter membrane based on chitosan and graphene oxide and preparation method of compound air filter membrane |
| CN106310978B (en) * | 2016-10-17 | 2020-03-31 | 江苏新风环保科技有限公司 | Composite air filter membrane based on chitosan and graphene oxide and preparation method thereof |
| CN106474939A (en) * | 2016-12-08 | 2017-03-08 | 河海大学 | A kind of modified carbon nano-tube/graphene oxide shitosan is combined poly (ether-sulfone) ultrafiltration membrane and its preparation method and application |
| CN106582327A (en) * | 2016-12-21 | 2017-04-26 | 华南理工大学 | Silver-carrying graphene oxide-polyvinyl alcohol ultrafiltration membrane and preparation and application thereof |
| CN106582327B (en) * | 2016-12-21 | 2019-08-20 | 华南理工大学 | A kind of silver-colored graphene oxide-polyvinyl alcohol ultrafiltration membrane of load and its preparation and application |
| CN106582311A (en) * | 2016-12-31 | 2017-04-26 | 青岛翰兴知识产权运营管理有限公司 | Preparation method of graphene-modifying sodium alginate-polyacrylonitrile neterogeny reinforced type hollow fiber membrane |
| CN106669434A (en) * | 2016-12-31 | 2017-05-17 | 青岛翰兴知识产权运营管理有限公司 | Graphene modified sodium alginate-polyacrylonitrile hollow-fiber membrane |
| CN106669469A (en) * | 2016-12-31 | 2017-05-17 | 青岛翰兴知识产权运营管理有限公司 | Graphene-modified sodium alginate-polyvinyl chloride homogenously-enhanced hollow fiber membrane |
| CN106669435A (en) * | 2016-12-31 | 2017-05-17 | 青岛翰兴知识产权运营管理有限公司 | Graphene modified sodium alginate-polyacrylonitrile heterogeneous enhanced type hollow fiber membrane |
| CN106582310A (en) * | 2016-12-31 | 2017-04-26 | 青岛翰兴知识产权运营管理有限公司 | Preparation method of graphene-modified and homogeneously-enhanced sodium alginate-polyvinyl chloride hollow fiber membrane |
| CN106492647A (en) * | 2016-12-31 | 2017-03-15 | 青岛翰兴知识产权运营管理有限公司 | A kind of preparation method of the modified sodium alginate polyacrylonitrile hollow fiber membrane of Graphene |
| CN109304100A (en) * | 2017-07-28 | 2019-02-05 | 中国科学院宁波材料技术与工程研究所 | A kind of charged ultra-thin sea water desalination membrane and the preparation method and application thereof based on graphene |
| CN108031310A (en) * | 2017-12-13 | 2018-05-15 | 四川银趣环保科技有限公司 | A kind of preparation method of the filtering net film based on graphene and high molecular material |
| WO2019132467A1 (en) * | 2017-12-26 | 2019-07-04 | Korea Atomic Energy Research Institute | Reduced graphene oxide, reduced graphene oxide-functional material complex, and manufacturing method thereof |
| CN109019745A (en) * | 2018-08-20 | 2018-12-18 | 南京大学 | A kind of preparation method improving multi-functional hybridized film particulate load amount |
| CN109019745B (en) * | 2018-08-20 | 2021-06-22 | 南京大学 | Preparation method for improving particle loading capacity of multifunctional hybrid membrane |
| CN109650779A (en) * | 2019-01-18 | 2019-04-19 | 四川大学 | A kind of preparation method of graphene aerogel/polyurethane foaming conductive composites |
| CN110743378A (en) * | 2019-10-29 | 2020-02-04 | 吉金学 | Modified wet film, preparation method thereof and application of modified wet film in manufacturing of heat exchange device of air conditioner external unit |
| CN110964280A (en) * | 2019-12-12 | 2020-04-07 | 江苏大翔科技有限公司 | Moisture-permeable and bacteriostatic composite film for total heat exchanger and preparation method thereof |
| CN111363341A (en) * | 2020-04-01 | 2020-07-03 | 青岛华世洁环保科技有限公司 | Heat exchange base material, rotary wheel heat exchanger rotary core carrier, rotary wheel heat exchanger rotary core and preparation method thereof, and rotary wheel heat exchanger |
| CN111363341B (en) * | 2020-04-01 | 2022-03-08 | 青岛华世洁环保科技有限公司 | Heat exchange base material, rotary wheel heat exchanger rotary core carrier, rotary wheel heat exchanger rotary core and preparation method thereof, and rotary wheel heat exchanger |
| CN114130207A (en) * | 2021-11-19 | 2022-03-04 | 中科朗劢技术有限公司 | Multifunctional total heat exchange membrane and preparation method thereof |
| CN114130207B (en) * | 2021-11-19 | 2024-01-09 | 中科朗劢技术有限公司 | Multifunctional total heat exchange membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105879706A (en) | Graphene oxide-polymer hybridized all-heat exchange membrane and preparation method and application thereof | |
| CN103877870B (en) | There is Total heat exchange film and the total-heat exchanger of antibacterial and antimildew function | |
| CN101947416B (en) | High-selectivity asymmetric moisture-permeable film as well as preparation method and application thereof | |
| CN100395008C (en) | A hydrophilic-hydrophobic bipolar composite membrane and method for preparing same | |
| US11285442B2 (en) | Self-supporting highly moisture-permeable heat-insulating aerogel film and preparation method thereof | |
| ES2924560T3 (en) | heat and moisture exchanger | |
| EP2652191B1 (en) | Polymer composite materials for building air conditioning or dehumidification and preparation method thereof | |
| CN105597566A (en) | Preparation method and application of novel total heat exchange film | |
| CN110016814B (en) | Antibacterial asymmetric total heat exchange membrane, total heat exchange core and total heat exchanger | |
| CN106521975B (en) | A kind of Total heat exchange film and preparation method thereof | |
| CN103877864B (en) | A kind of new and effective Total heat exchange film and total-heat exchanger | |
| CN103194058A (en) | High-thermal-conductive moisture permeable film and preparation method thereof | |
| CN102061026A (en) | Diathermanous and moisture permeable composite film and preparation method thereof | |
| CN105833736A (en) | High-selectivity low-thermal conductivity asymmetric permeable membrane as well as preparation method and application thereof | |
| CN102888062B (en) | Heat exchange heterogeneous composite film and preparation method thereof | |
| CN103342828A (en) | Efficient moisture-permeable film prepared by a one-step process and application thereof | |
| CN103879034B (en) | A kind of high-air-tightness Total heat exchange film and total-heat exchanger | |
| CN113402767A (en) | Polyamide total heat exchange membrane based on interfacial polymerization and preparation method thereof | |
| KR101237285B1 (en) | Polymer composite materials for building air conditioning or dehumidification and preparation method thereof | |
| CN110964280A (en) | Moisture-permeable and bacteriostatic composite film for total heat exchanger and preparation method thereof | |
| CN109012591A (en) | A kind of expanded graphite/carbonization poly-dopamine composite material and preparation method and the application as benzene gas adsorbent | |
| CN110305362A (en) | It is a kind of intelligently to control dampness barrier composite film and its preparation method and application | |
| CN105921036A (en) | Washable heat exchange membrane, core with washable heat exchange membrane and preparation method for washable heat exchange membrane | |
| CN100348304C (en) | Composite support liquid film and its preparing method | |
| CN105709617B (en) | A method of preparing hybrid inorganic-organic Total heat exchange film with sol-gal process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160824 |