CN109433018A - A kind of thickness is less than the preparation method of the ultra-thin silicon substrate alcohol-water separation film of 50nm - Google Patents
A kind of thickness is less than the preparation method of the ultra-thin silicon substrate alcohol-water separation film of 50nm Download PDFInfo
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- CN109433018A CN109433018A CN201811431858.8A CN201811431858A CN109433018A CN 109433018 A CN109433018 A CN 109433018A CN 201811431858 A CN201811431858 A CN 201811431858A CN 109433018 A CN109433018 A CN 109433018A
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- 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
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- 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
- B01D69/10—Supported membranes; Membrane supports
Abstract
The invention belongs to membrane material preparation field, in particular to a kind of thickness is less than the preparation method of the ultra-thin silicon substrate alcohol-water separation film of 50nm.Common dip-coating method in current film-forming process, there are separating layer thickness big (> 300nm), flux it is smaller, can not accuracy controlling preparation process the problems such as, be difficult to reach 200nm or less using separating layer thickness prepared by the methods of spin-coating method, swabbing process.In view of the above problems, the organic silicon sol of low concentration is atomized by the present invention using ultrasonic wave, make the countless fine droplets of colloidal dispersion, then by carrier gas purge by the sol deposition of atomization on porous polymer support body, it is finally dried, prepares the ultra-thin silicon substrate alcohol-water separation film of separating layer thickness < 50nm.
Description
Technical field
The invention belongs to separate field of membrane preparation, in particular to a kind of thickness is less than the ultra-thin silicon substrate alcohol-water separation film of 50nm
Preparation method.
Background technique
Sol-gel method accurately controls aperture and pore structure, can directly be prepared on supporter (or transition zone)
To porous coated implants.As the inorganic silicon fiml of tradition, organosilicon membrane generally uses sol-gel method to prepare, and coating method is usual
There are dip-coating method, spin-coating method and swabbing process etc..
Common dip-coating method is exactly to immerse the one side of support body among colloidal sol well prepared in advance, time of infusion
Supporter is smoothly lifted from colloidal sol with certain speed later and is come out, then through calcining removing solvent and carries out dehydrating condensation
Reaction is to form porous separating layer.Spin-coating method is that support body is fixed on turntable, and during support body rotation, colloidal sol is dripped
Spin coating operation, drying are carried out on support body, repeats this process for several times, and finally carrying out calcining can be obtained film.Swabbing process is with de-
Rouge cotton dips colloidal sol, quickly rubs on support body in a direction, and organosilicon membrane is obtained after calcining.
Dip-coating method is there are separating layer thickness big (> 300nm), flux is smaller, can not accuracy controlling preparation process etc. ask
Topic, is difficult to reach 200nm or less using separating layer thickness prepared by the methods of spin-coating method, swabbing process.How to guarantee
Film it is complete fine and close it is flawless under the premise of thickness is reduced be current masking technique difficult point.
Summary of the invention
In view of the above technical problems, the present invention uses ultrasonic atomizatio physical deposition methods preparative separation film, will using ultrasonic wave
The organic silicon sol of low concentration is atomized, and is subsequently deposited upon on porous polymer support body, is finally dried, prepares separation thickness
The ultra-thin silicon substrate alcohol-water separation film of degree < 50nm.
It is specific the preparation method is as follows:
Isopropanol (IPA) is added in beaker, compound silicon source presoma is then added and stirs to abundant dissolution, stirring is simultaneously
Water (H is added dropwise2O), nitric acid (HNO is added dropwise after continuing 1~2min of stirring3), beaker is transferred in water bath with thermostatic control immediately, is persistently stirred
It mixes and obtains within 1~3 hour silica solution and with IPA by its concentration dilution to 0.1~0.5wt%；Colloidal sol after dilution is poured into ultrasound
Atomizer, colloidal sol are dispersed into small drop by ultrasonic wave, then enter settling chamber with argon gas, drop from atomizing nozzle vertically upward
Ejection is subsequently deposited upon on PA/PS composite membrane support body, and support body is placed horizontally at the surface of atomizing nozzle and is fixed on plate glass
On plate, so that the temperature of polymer support body is maintained at 80~100 DEG C by heating device, after completing primary depositing, solvent is made to evaporate 2
~3min is deposited next time again, and seperation film can be obtained in dry 15~20min at 80~200 DEG C after deposition 3~5 times.
Wherein the molar ratio of each component is compound silicon source presoma: H2O:HNO3=1:120:0.1, bath temperature be 50~
60 DEG C, argon gas flow velocity is 150~400mL/min, and logical 30~60s of argon gas completes primary depositing every time.
The compound silicon source presoma is BTESM and AEAPS, their molar ratio is 1:0.1~0.4.Bridging silicon source
Precursor B TESM or BTESE (1,2- bis- (triethoxy silicon substrate) ethane), BTESEthy (1,2- bis- (triethoxy silicon substrate) second
Alkene) etc. its structure itself there is very strong rigidity, with they prepare silica solution be deposited on polymer support body, evaporation solvent
Unbalanced stress can be generated in interface of the separating layer in conjunction with support body during (solvent is isopropyl alcohol and water), to make film table
Face is also easy to produce the defects of crackle.In order to guarantee that the integrality of film needs to greatly increase frequency of depositing, cause separating layer thickness without
Method further decreases.It is copolymerized by a kind of AEAPS with flexible structure and BTESM, in the silicon network structure of BTESM
The long side-chain radical for introducing AEAPS, enhances the flexibility of separating layer structure, it is possible to prevente effectively from generation the defects of crackle, only
Needing to deposit 3~5 times just can form perfect sunken separating layer.On the contrary, if single use Long carbon chain side flexible silicon
Presoma such as AEAPS in source is as separation layer materials, and long Side Chain Flexibility structure is during drying due to lacking rigid support
It is easy to cause silicon network tunnel collapse and forms dead hole and blind hole, be unfavorable for being applicable in the microcellular structure of the separation of small molecuies such as alcohol water
Construct.
The polymer support body is placed horizontally at the surface of atomizing nozzle, is 4~6cm at a distance from atomizing nozzle, if spray
Mist mouth and support body hypotelorism will lead to local droplet aggregation, can not be in support body surface uniform deposition.The temperature of polymer support body
Control evaporates solvent rapidly by the high temperature using support body surface, to quickly form gel layer at 80~100 DEG C.Deposition
Drying is silanol group further occurrence in order to allow residual solvent further to evaporate, in silicon network at 80~200 DEG C after the completion
Dehydration condensation forms finer and close silicon network structure.The present invention passes through weight by the way of sprayed deposit straight up
Power factor excludes bulky grain droplet, and narrow size droplet diameter, while when avoiding sprayed deposit straight down, upper cold and lower heat, causes
Convection current in caloic conduction, reduces the droplet quantity for reaching support body surface, to be conducive to improve the uniformity and deposition speed of film
Rate.
Detailed description of the invention
Fig. 1 is that compound silicon source precursor B TESM and AEAPS is copolymerized hydrolysis-condensation reaction mechanism figure.
Fig. 2 is that the surface (a) of seperation film prepared by embodiment 1 and section (b) SEM scheme.
Fig. 3 is the surface SEM figure of film prepared by comparative example 1.
Fig. 4 is the section SEM figure of seperation film prepared by comparative example 2.
Fig. 5 is the section SEM figure of seperation film prepared by comparative example 3.
Specific embodiment
The technical characteristic that the present invention is further illustrated by the following examples, but protection scope of the present invention is not
It is limited to the following example.
Embodiment 1
(1) it prepares BTESM/AEAPS colloidal sol: 24.494gIPA being added in 100mL beaker, is then added
0.500gBTESM and 0.078gAEAPS stir 2min, and 3.808g water is added dropwise in stirring while, continue to stir be added dropwise 1 after 2min~
2 drop 68wt% concentrated nitric acids, beaker is transferred in 50 DEG C of waters bath with thermostatic control, silica solution and with IPA that its is dense is persistently stirred 2 hours to obtain
Degree is diluted to 0.2wt%；
(2) colloidal sol prepared by step (1) is poured into ultrasonic atomizer, colloidal sol is dispersed into diameter by the ultrasonic wave of 2.4MHz and is
Then 1~2 μm of drop enters settling chamber with the argon gas that flow velocity is 300mL/min, drop sprays so vertically upward from atomizing nozzle
After be deposited on PA/PS composite membrane support body, support body is placed horizontally at the surface of atomizing nozzle and is fixed on plate glass plate, lead to
Crossing heating device makes the temperature of support body be maintained at 80 DEG C, is deposited next time after solvent evaporation 2min, every time logical argon gas when
Between be 45s, seperation film can be obtained in dry 15min at 120 DEG C after deposition 5 times.
(3) 90wt% isopropanol/water solution is separated using seperation film, flux is 3.1kg/ (m2H), separation factor
It is 400.
Fig. 2 is that the surface (a) of seperation film prepared by embodiment 1 and section (b) SEM scheme, and is as can be seen from the figure separated
Thickness degree is about 50nm, and film surface is perfect to be fallen into.
Comparative example 1
(1) it prepares BTESM colloidal sol: 21.309gIPA being added in 100mL beaker, 0.500gBTESM stirring is then added
3.171g water is added dropwise while stirring by 2min, continues that 1~2 drop 68wt% concentrated nitric acid is added dropwise after stirring 2min, beaker is transferred to
In 50 DEG C of waters bath with thermostatic control, persistently stirs and obtain within 2 hours silica solution and be 0.2wt% by its concentration dilution with IPA；
(2) colloidal sol prepared by step (1) is poured into ultrasonic atomizer, colloidal sol is dispersed into diameter by the ultrasonic wave of 2.4MHz and is
Then 1~2 μm of drop enters settling chamber with the argon gas that flow velocity is 300mL/min, drop sprays so vertically upward from atomizing nozzle
After be deposited on PA/PS composite membrane support body, support body is placed horizontally at the surface of atomizing nozzle and is fixed on plate glass plate, lead to
Crossing heating device makes the temperature of support body be maintained at 80 DEG C, is deposited next time after solvent evaporation 2min, every time logical argon gas when
Between be 45s, film can be obtained in dry 15min at 120 DEG C after deposition 5 times.
(3) 90wt% isopropanol/water solution is separated using the film, as shown in figure 3, because film surface has crackle,
So without separating property.
Comparative example 2
(1) it prepares BTESM/AEAPS colloidal sol: 24.494gIPA being added in 100mL beaker, is then added
0.500gBTESM and 0.078gAEAPS stir 2min, and 3.808g water is added dropwise in stirring while, continue to stir be added dropwise 1 after 2min~
2 drop 68wt% concentrated nitric acids, beaker is transferred in 50 DEG C of waters bath with thermostatic control, silica solution and with IPA that its is dense is persistently stirred 2 hours to obtain
Degree is diluted to 0.2wt%；
(2) colloidal sol prepared by step (1) is poured into ultrasonic atomizer, colloidal sol is dispersed into diameter by the ultrasonic wave of 2.4MHz and is
Then 1~2 μm of drop enters settling chamber with the argon gas that flow velocity is 300mL/min, drop sprays so vertically upward from atomizing nozzle
After be deposited on PA/PS composite membrane support body, support body is placed horizontally at the surface of atomizing nozzle and is fixed on plate glass plate,
It is deposited next time after so that solvent is evaporated 2min under room temperature, the time of logical argon gas is 45s every time, after depositing 5 times at 120 DEG C
Seperation film can be obtained in dry 15min.
(3) 90wt% isopropanol/water solution is separated using seperation film, flux is 2.5kg/ (m2H), separation factor
It is 380.
Fig. 4 is the section SEM figure of seperation film prepared by comparative example 2, and as can be seen from the figure separating layer thickness is big
About 100nm.
Comparative example 3
(1) it prepares BTESM/AEAPS colloidal sol: 24.494gIPA being added in 100mL beaker, is then added
0.500gBTESM and 0.078gAEAPS stir 2min, and 3.808g water is added dropwise in stirring while, continue to stir be added dropwise 1 after 2min~
2 drop 68wt% concentrated nitric acids, beaker is transferred in 50 DEG C of waters bath with thermostatic control, silica solution and with IPA that its is dense is persistently stirred 2 hours to obtain
Degree is diluted to 0.2wt%；
(2) colloidal sol prepared by step (1) is poured into ultrasonic atomizer, colloidal sol is dispersed into diameter by the ultrasonic wave of 2.4MHz and is
Then 1~2 μm of drop enters settling chamber with the argon gas that flow velocity is 300mL/min, drop sprays so vertically downward from atomizing nozzle
After be deposited on PA/PS composite membrane support body, support body is placed horizontally at the underface of atomizing nozzle and is fixed on plate glass plate, lead to
Crossing heating device makes the temperature of support body be maintained at 80 DEG C, is deposited next time after solvent evaporation 2min, every time logical argon gas when
Between be 45s, seperation film can be obtained in dry 15min at 120 DEG C after deposition 5 times.
(3) 90wt% isopropanol/water solution is separated using seperation film, flux is 2.0kg/ (m2H), separation factor
It is 405.
Fig. 5 is the section SEM figure of seperation film prepared by comparative example 3, and as can be seen from the figure separating layer thickness is big
About 150nm.
Claims (8)
1. the preparation method that a kind of thickness is less than the ultra-thin silicon substrate alcohol-water separation film of 50nm, which is characterized in that it is specific the preparation method comprises the following steps:
(1) isopropanol (IPA) is added in beaker, compound silicon source presoma stirring is then added, stirs while water (H is added dropwise2O),
Nitric acid (HNO is added dropwise after continuing stirring3), beaker is transferred in water bath with thermostatic control immediately after, persistently stirs to get silica solution simultaneously
With IPA by its concentration dilution；
(2) colloidal sol after dilution is poured into ultrasonic atomizer, colloidal sol is dispersed into small drop by ultrasonic wave, then with argon gas into
Enter settling chamber, drop is deposited on polymer support body after spraying vertically upward from atomizing nozzle, and polymer support body is placed horizontally at spray
The surface of mist mouth is simultaneously fixed on plate glass plate, so that the temperature of polymer support body is maintained at 80~100 by heating device
DEG C, it after completing primary depositing, is deposited next time again after evaporating solvent, drying is at 80~200 DEG C after depositing for several times
Seperation film can be obtained.
2. the preparation method that thickness as described in claim 1 is less than the ultra-thin silicon substrate alcohol-water separation film of 50nm, it is characterised in that: each
The molar ratio of component is compound silicon source presoma: H2O:HNO3=1:120:0.1.
3. the preparation method that thickness as described in claim 1 is less than the ultra-thin silicon substrate alcohol-water separation film of 50nm, it is characterised in that: multiple
Silicon source presoma is closed using bis- (triethoxy silicon substrate) methane (BTESM) and N- (2- aminoethyl) -3- aminopropyl-triethoxy silicon
Alkane (AEAPS) copolymerization, the molar ratio of BTESM and AEAPS are 1:0.1~0.4, the concentration after silica solution dilution is 0.1~
0.5wt%.
4. the preparation method that thickness as described in claim 1 is less than the ultra-thin silicon substrate alcohol-water separation film of 50nm, it is characterised in that: water
Bath temperature is 50~60 DEG C, is persistently stirred under bath temperature 1~3 hour.
5. the preparation method that thickness as described in claim 1 is less than the ultra-thin silicon substrate alcohol-water separation film of 50nm, it is characterised in that: super
The ultrasonic frequency that sound atomizer uses is 1.5~3MHz, and polymer support body is 4~6cm at a distance from atomizing nozzle.
6. the thickness of benefit is less than the preparation method of the ultra-thin silicon substrate alcohol-water separation film of 50nm as described in claim 1, it is characterised in that:
The flow velocity of argon gas is 150~400mL/min, and logical 30~60s of argon gas completes primary depositing every time, and frequency of depositing is 3~5 times.
7. the preparation method that thickness as described in claim 1 is less than the ultra-thin silicon substrate alcohol-water separation film of 50nm, it is characterised in that: dry
The dry time is 15~20min.
8. the preparation method that thickness as described in claim 1 is less than the ultra-thin silicon substrate alcohol-water separation film of 50nm, it is characterised in that: poly-
Close the composite membrane that object support body is polyamide (PA) and polystyrene (PS), membrane aperture is 1~2nm, molecular cut off for 600~
1000。
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| CN115025635A (en) * | 2022-06-30 | 2022-09-09 | 常州大学 | Preparation method of bridge organic silicon/GO composite nanofiltration membrane |
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