CN108126532A - A kind of preparation method of hydrophobic ceramic film - Google Patents
A kind of preparation method of hydrophobic ceramic film Download PDFInfo
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- CN108126532A CN108126532A CN201711315998.4A CN201711315998A CN108126532A CN 108126532 A CN108126532 A CN 108126532A CN 201711315998 A CN201711315998 A CN 201711315998A CN 108126532 A CN108126532 A CN 108126532A
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- 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
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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
- B01D67/0039—Inorganic membrane manufacture
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
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Abstract
The present invention relates in the technical field of membrane separation of environmental protection, and in particular to a kind of preparation method of hydrophobic ceramic film.Ceramic powder slurry obtained handles slurry to obtain aluminium oxide ceramics plate membrane by the present invention.It is dipped in zinc oxide precursor and obtains plating seed layer ceramic membrane, finally obtain hydrophobic ceramic film.One layer of zinc oxide colloidal sol is plated in aluminium oxide ceramics tablet film surface, zinc oxide seed crystal is obtained after heat treatment, zinc-oxide nano column is grown into after hydro-thermal method, obtains micrometer/nanometer composite construction.Raising of the zinc-oxide nano column to ceramic membrane surface roughness, increases contact angle, so as to increase the hydrophobicity of ceramic membrane.There are the CF of low-surface-energy in silicon fluoride molecule3And CF2Groups are waited, silicon fluoride molecular layer is shown as hydrophobic property, promotes silicon fluoride and ceramic surface hydroxyl reaction with microwave treatment.Ceramic membrane hydrophobic performance is improved, has widened the application field of ceramic membrane.
Description
Technical field
The present invention relates to environmental protection technical field of membrane separation, and in particular to a kind of preparation method of hydrophobic ceramic film.
Background technology
Ceramic membrane is also known as inorganic ceramic membrane, is prepared and the anisotropic membrane of formation through special process with inorganic ceramic material.Ceramics
Film is divided into two kinds of tubular ceramic membrane and ceramic membrane.Ceramic membrane is one kind in inoranic membrane, belongs to consolidating in membrane separation technique
Body membrane material, mainly using inorganic ceramic materials such as the aluminium oxide of different size, zirconium oxide, titanium oxide and silica as support
Body is formed through surface coating, high-temperature firing.Mainly there are four perforated membrane, filter membrane, packaging film, battery membranes, thermal isolation film types.
China's inorganic ceramic membrane passes through the development of more than ten years, obtains in various fields such as medicine, chemical industry, food, environmental protection and widely should
With becoming that China's high performance membrane Material Field is with the fastest developing speed, is also one of most promising kind.
Inorganic ceramic membrane is the important component of high performance membrane material, and it is emerging to belong to the strategy that state key is greatly developed
Industry is the important component of field of new materials.Inorganic ceramic membrane be it is a kind of there is the thin-film material efficiently separated, tool
There are good separative efficiency height, effect stability, chemical stability, acid and alkali-resistance, organic solvent-resistant, resistance to bacterium, high temperature resistant, antipollution, machinery
Numerous advantages such as intensity is high, regenerability is good, separation process is simple, low energy consumption, simple and convenient operation and maintenance, service life length.Due to
The superperformance of ceramic membrane so that its development is very rapid, and sales volume has accounted for 20% or so of entire film market, and is increased with year
35% development speed develops, the application to have succeeded in many fields.
As the strategic new industry that state key is greatly developed, outside the superperformance that ceramic membrane possesses, currently on the market
Ceramic membrane also exist and desalinize seawater and surface hydrophobic is poor, itself brittleness height is broken, raw material during water-oil separating for distilling
Expensive, the defects of production cost is high, development is limited.
Therefore, the developmental research in following ceramic membrane field is also very important.
Invention content
Present invention mainly solves the technical issues of, desalinize seawater for ceramic membrane in distillation and surface hydrophobic be poor during water-oil separating
The defects of, provide a kind of preparation method of hydrophobic ceramic film.
In order to solve the above-mentioned technical problem, the technical solution adopted in the present invention is：
A kind of preparation method of hydrophobic ceramic film, it is characterised in that specifically preparation process is：
（1）Polyether sulfone, polyvinylpyrrolidone and 1-Methyl-2-Pyrrolidone are mixed, ball milling in planetary ball mill is placed in and obtains
To mixed with polymers liquid, alumina powder is added in mixed with polymers liquid and continues ball milling, obtains ceramic powder slurry；
（2）Ceramic powder slurry is vacuumized after removing air entrapment, poured into the material fluid bath of casting mold, control scraper traction
Rate is that ceramic powder slurry is made in slot to be laid in carrier band surface, keeps knife away from after treating ceramic powder slurry curtain coating, obtaining
To casting films band, casting films band is placed in tap water at normal temperature and is impregnated, taken out casting films band and spontaneously dry, obtain green, it will
Green cuts into tablet green compact, tablet green compact is placed in the heating of resistance furnace Program, sintering obtains aluminium oxide ceramics tablet
Film；
（3）30~35g acetic acid dihydrate zinc is dissolved in 100~120mL ethylene glycol monomethyl ethers, obtains mixed solution, to mixing
It is added in solution and obtains zinc oxide precursor with the equimolar ethanol amine of acetic acid dihydrate zinc, heat temperature raising stirring；
（4）It after aluminium oxide ceramics plate membrane is immersed in zinc oxide precursor, lifts upwards, obtains plating glue earthenware slab film, treat
It after plating the natural drying of glue earthenware slab film, is placed in tube furnace and is heated to, preheat, then be warming up to, after heat preservation, natural cooling
Plating seed layer ceramic membrane is obtained to room temperature；
（5）Acetic acid dihydrate zinc, hexa, water are mixed to get solution in beaker, plating seed layer ceramic membrane is used
Polytetrafluoroethylene (PTFE) pedestal is fixed on beaker bottom, and beaker is covered with surface plate, and to beaker heat temperature raising, heat preservation obtains plating nanometer
Zinc ceramic membrane；
（6）Plating Nano-Zinc ceramic membrane is cleaned by ultrasonic successively with acetone, absolute ethyl alcohol, water in advance, by ten trifluoro octyl groups three
Ethoxysilane is mixed with ethyl alcohol, makes silicon fluoride ethanol solution, and the plating Nano-Zinc ceramic membrane after cleaning is placed in silicon fluoride
It is impregnated in ethanol solution, takes out the plating Nano-Zinc ceramic membrane after dipping, be placed in baking oven, heat temperature raising, it is dry, obtain hydrophobic pottery
Porcelain film.
Step（1）Polyether sulfone, polyvinylpyrrolidone and the mass ratio of 1-Methyl-2-Pyrrolidone mixing is 3 ︰
1 ︰ 5,2~3h of Ball-milling Time, the grain size of alumina powder is 0.70~0.75 μm, and the addition of alumina powder is mixed with polymers liquid
The 20~25% of quality, continuation Ball-milling Time are 18~20h.
Step（2）The pumpdown time is 3~4min, and scraper pulling speed is 18~20cm/min, and knife is away from being 0.8
~1.2mm, soaking time for 22~for 24 hours, it is 2~3 days to spontaneously dry the time, and the sizes of tablet green compact is 70mm × 80mm, journey
Sequence warming temperature is 1500~1550 DEG C, and sintering time is 10~12h.
Step（3）Temperature is 55~60 DEG C after the heat temperature raising, and mixing time is 25~30min.
Step（4）The pull rate is 3.0~5.0cm/min, and the naturals drying time is 7~8h, after heat temperature raising
Temperature is 300~350 DEG C, and preheating time is 10~15min, and heating rate is 2 DEG C/min again, and soaking time is 1~2h.
Step（5）The acetic acid dihydrate zinc, hexa, water mixing mass ratio be 3 ︰, 1 ︰ 50, heating rises
Temperature is 90~95 DEG C after temperature, and soaking time is 55~60min.
Step（6）Ultrasonic frequency is 25~30KHz during described ultrasonic cleaning, the mass fraction of silicon fluoride ethanol solution
It is 3%, dip time is 20~22h, and temperature is 100~110 DEG C after heat temperature raising, and drying time is
5~6h.
The beneficial effects of the invention are as follows：
（1）Alumina powder and mixed with polymers ball milling are obtained ceramic powder slurry by the present invention, and slurry is cast, is done
Dry, sintering obtains aluminium oxide ceramics plate membrane, then aluminium oxide ceramics plate membrane is immersed zinc oxide precursor, through drying, preheating,
Heat preservation obtains plating seed layer ceramic membrane, finally carries out siloxanes and modifies to obtain hydrophobic ceramic film, aluminium oxide ceramics tablet film surface
For porous structure, it is made of many micron-sized alumina particle accumulations, plating last layer on surface by dip-coating method aoxidizes
Zinc colloidal sol obtains zinc oxide seed crystal after heat treatment, be evenly distributed on each Membranes On Alumina Particles Surface, is grown after hydro-thermal method is handled
Into zinc-oxide nano column, so as to obtain micrometer/nanometer composite construction, zinc-oxide nano column puies forward ceramic membrane surface roughness
Height increases the contact angle of ceramic membrane surface, so as to improve the hydrophobicity of ceramic membrane；
（2）Due to the presence of surface hydroxyl, general oxide material manifests themselves as hydrophily, i.e. liquid water is contacted in film surface
Angle is less than 90 °, and there are-the CF of low-surface-energy in silicon fluoride molecule3With-CF2Groups are waited, silicon fluoride molecular layer is shown as hydrophobic spy
Property, promote silicon fluoride and ceramic surface hydroxyl reaction with microwave treatment, accelerate the time of reaction modification, also increase water and making pottery
The contact angle of porcelain film surface so as to improve ceramic membrane hydrophobic performance, has widened the application field of ceramic membrane.
Specific embodiment
1 ︰ 5 of polyether sulfone, polyvinylpyrrolidone and 1-Methyl-2-Pyrrolidone 3 ︰ in mass ratio are mixed, are placed in planet
2~3h of ball milling obtains mixed with polymers liquid in ball mill, is 0.70~0.75 by the grain size of mixed with polymers liquid quality 20~25%
μm alumina powder add in mixed with polymers liquid in continue 18~20h of ball milling, obtain ceramic powder slurry；To ceramic powder slurry
Vacuumize after 3~4min removes air entrapment, pour into the material fluid bath of casting mold, control scraper pulling speed for 18~
20cm/min makes in slot ceramic powder slurry be laid in carrier band surface, and knife is kept to treat ceramic powder slurry away from for 0.8~1.2mm
After curtain coating, obtain casting films band, casting films band is placed in tap water at normal temperature impregnate 22~for 24 hours, take out casting films bands from
It is so 2~3 days dry, green is obtained, green is cut into the tablet green compact that size is 70mm × 80mm, tablet green compact are put
1500~1550 DEG C are warming up in resistance furnace Program, 10~12h is sintered, obtains aluminium oxide ceramics plate membrane；By 30~35g bis-
Acetate hydrate zinc is dissolved in 100~120mL ethylene glycol monomethyl ethers, obtains mixed solution, is added into mixed solution and two water
The equimolar ethanol amine of zinc acetate is closed, 55~60 DEG C of 25~30min of stirring is heated to, obtains zinc oxide precursor；By oxygen
After changing in aluminium earthenware slab film immersion zinc oxide precursor, lifted, plated upwards with the pull rate of 3.0~5.0cm/min
Glue earthenware slab film after glue earthenware slab film to be plated spontaneously dries 7~8h, is placed in tube furnace and is heated to 300~350
DEG C, 10~15min is preheated, then 500~520 DEG C are risen to the heating rate of 2 DEG C/min, after keeping the temperature 1~2h, naturally cool to room
Temperature obtains plating seed layer ceramic membrane；1 ︰ 50 of acetic acid dihydrate zinc, hexa, water 3 ︰ in mass ratio are mixed in beaker
Solution is obtained, plating seed layer ceramic membrane is fixed on beaker bottom with polytetrafluoroethylene (PTFE) pedestal, beaker is covered with surface plate, to burning
90~95 DEG C of heat temperature raising of cup, keeps the temperature 55~60min, obtains plating Nano-Zinc ceramic membrane；Nano-Zinc ceramic membrane will be plated in advance with third
Ketone, absolute ethyl alcohol, water are cleaned by ultrasonic successively, and control ultrasonic frequency is 25~30KHz, by ten trifluoro octyl group triethoxies
Silane is mixed with ethyl alcohol, makes the silicon fluoride ethanol solution that mass fraction is 3%, the plating Nano-Zinc ceramic membrane after cleaning is put
20~22h is impregnated in silicon fluoride ethanol solution, the plating Nano-Zinc ceramic membrane after dipping is taken out, is placed in baking oven, heat temperature raising
To 100~110 DEG C, dry 5~6h obtains hydrophobic ceramic film.
Example 1
1 ︰ 5 of polyether sulfone, polyvinylpyrrolidone and 1-Methyl-2-Pyrrolidone 3 ︰ in mass ratio are mixed, are placed in planetary ball mill
Ball milling 2h obtains mixed with polymers liquid in machine, and the alumina powder that the grain size of mixed with polymers liquid quality 20% is 0.70 μm is added in
Continue ball milling 18h in mixed with polymers liquid, obtain ceramic powder slurry；3min is vacuumized to ceramic powder slurry and removes internal gas
It after bubble, pours into the material fluid bath of casting mold, control scraper pulling speed is 18cm/min, and ceramic powder slurry in slot is made to tile
In carrier band surface, after keeping knife away from ceramic powder slurry curtain coating for 0.8mm, is treated, casting films band is obtained, casting films band is put
22h is impregnated in tap water at normal temperature, casting films band is taken out and spontaneously dries 2 days, obtain green, green is cut into size is
Tablet green compact are placed in resistance furnace Program and are warming up to 1500 DEG C, are sintered 10h, aoxidized by the tablet green compact of 70mm × 80mm
Aluminium earthenware slab film；30g acetic acid dihydrate zinc is dissolved in 100mL ethylene glycol monomethyl ethers, obtains mixed solution, to mixed solution
In add with the equimolar ethanol amine of acetic acid dihydrate zinc, be heated to 55 DEG C stirring 25min, obtain zinc oxide precursor
Body；After aluminium oxide ceramics plate membrane is immersed in zinc oxide precursor, lifted, obtained upwards with the pull rate of 3.0cm/min
Glue earthenware slab film is plated, after glue earthenware slab film to be plated spontaneously dries 7h, is placed in tube furnace and is heated to 300 DEG C, preheating
10min, then 500 DEG C are risen to the heating rate of 2 DEG C/min, after keeping the temperature 1h, cooled to room temperature obtains plating seed layer ceramics
Film；1 ︰ 50 of acetic acid dihydrate zinc, hexa, water 3 ︰ in mass ratio are mixed to get solution in beaker, seed crystal will be plated
Layer ceramic membrane is fixed on beaker bottom with polytetrafluoroethylene (PTFE) pedestal, and beaker is covered with surface plate, to 90 DEG C of beaker heat temperature raising, protects
Warm 55min obtains plating Nano-Zinc ceramic membrane；Plating Nano-Zinc ceramic membrane is subjected to ultrasound successively with acetone, absolute ethyl alcohol, water in advance
Cleaning, control ultrasonic frequency are 25KHz, and tridecafluoro-n-octyltriethoxysilane with ethyl alcohol is mixed, makes mass fraction
For 3% silicon fluoride ethanol solution, the plating Nano-Zinc ceramic membrane after cleaning is placed in silicon fluoride ethanol solution and impregnates 20h, taken out
Plating Nano-Zinc ceramic membrane after dipping, is placed in baking oven, is heated to 100 DEG C, and dry 5h obtains hydrophobic ceramic film.
Example 2
1 ︰ 5 of polyether sulfone, polyvinylpyrrolidone and 1-Methyl-2-Pyrrolidone 3 ︰ in mass ratio are mixed, are placed in planetary ball mill
Ball milling 2.5h obtains mixed with polymers liquid in machine, and the alumina powder that the grain size of mixed with polymers liquid quality 27% is 0.73 μm is added
Enter continuation ball milling 19h in mixed with polymers liquid, obtain ceramic powder slurry；Ceramic powder slurry is vacuumized in 3.5min removings
It after portion's bubble, pours into the material fluid bath of casting mold, control scraper pulling speed is 19cm/min, makes ceramic powder slurry in slot
Carrier band surface is laid in, after keeping knife away from ceramic powder slurry curtain coating for 1.0mm, is treated, casting films band is obtained, by casting films
Band, which is placed in tap water at normal temperature, impregnates 23h, takes out casting films band and spontaneously dries 2 days, obtains green, green is cut into ruler
Tablet green compact are placed in resistance furnace Program and are warming up to 1525 DEG C, are sintered 11h, obtain by the very little tablet green compact for 70mm × 80mm
Aluminium oxide ceramics plate membrane；33g acetic acid dihydrate zinc is dissolved in 110mL ethylene glycol monomethyl ethers, obtains mixed solution, to mixing
Added in solution with the equimolar ethanol amine of acetic acid dihydrate zinc, be heated to 57 DEG C stirring 27min, before obtaining zinc oxide
Drive body；After aluminium oxide ceramics plate membrane is immersed in zinc oxide precursor, lifted, obtained upwards with the pull rate of 4.0cm/min
To plating glue earthenware slab film, after glue earthenware slab film to be plated spontaneously dries 7.5h, it is placed in tube furnace and is heated to 325 DEG C,
13min is preheated, then 510 DEG C are risen to the heating rate of 2 DEG C/min, after keeping the temperature 1.5h, cooled to room temperature obtains plating seed crystal
Layer ceramic membrane；1 ︰ 50 of acetic acid dihydrate zinc, hexa, water 3 ︰ in mass ratio are mixed to get solution in beaker, it will
Plating seed layer ceramic membrane is fixed on beaker bottom with polytetrafluoroethylene (PTFE) pedestal, beaker is covered with surface plate, to beaker heat temperature raising
93 DEG C, 57min is kept the temperature, obtains plating Nano-Zinc ceramic membrane；Plating Nano-Zinc ceramic membrane is used into acetone, absolute ethyl alcohol, water successively in advance
It is cleaned by ultrasonic, control ultrasonic frequency is 27KHz, and tridecafluoro-n-octyltriethoxysilane with ethyl alcohol is mixed, is made
Mass fraction is 3% silicon fluoride ethanol solution, and the plating Nano-Zinc ceramic membrane after cleaning is placed in silicon fluoride ethanol solution and is impregnated
21h takes out the plating Nano-Zinc ceramic membrane after dipping, is placed in baking oven, is heated to 105 DEG C, and dry 5.5h obtains hydrophobic pottery
Porcelain film.
Example 3
1 ︰ 5 of polyether sulfone, polyvinylpyrrolidone and 1-Methyl-2-Pyrrolidone 3 ︰ in mass ratio are mixed, are placed in planetary ball mill
Ball milling 3h obtains mixed with polymers liquid in machine, and the alumina powder that the grain size of mixed with polymers liquid quality 25% is 0.75 μm is added in
Continue ball milling 20h in mixed with polymers liquid, obtain ceramic powder slurry；4min is vacuumized to ceramic powder slurry and removes internal gas
It after bubble, pours into the material fluid bath of casting mold, control scraper pulling speed is 20cm/min, and ceramic powder slurry in slot is made to tile
In carrier band surface, after keeping knife away from ceramic powder slurry curtain coating for 1.2mm, is treated, casting films band is obtained, casting films band is put
It is impregnated in tap water at normal temperature for 24 hours, takes out casting films band and spontaneously dry 3 days, obtain green, green is cut into size is
Tablet green compact are placed in resistance furnace Program and are warming up to 1550 DEG C, are sintered 12h, aoxidized by the tablet green compact of 70mm × 80mm
Aluminium earthenware slab film；35g acetic acid dihydrate zinc is dissolved in 120mL ethylene glycol monomethyl ethers, obtains mixed solution, to mixed solution
In add with the equimolar ethanol amine of acetic acid dihydrate zinc, be heated to 60 DEG C stirring 30min, obtain zinc oxide precursor
Body；After aluminium oxide ceramics plate membrane is immersed in zinc oxide precursor, lifted, obtained upwards with the pull rate of 5.0cm/min
Glue earthenware slab film is plated, after glue earthenware slab film to be plated spontaneously dries 8h, is placed in tube furnace and is heated to 350 DEG C, preheating
15min, then 520 DEG C are risen to the heating rate of 2 DEG C/min, after keeping the temperature 2h, cooled to room temperature obtains plating seed layer ceramics
Film；1 ︰ 50 of acetic acid dihydrate zinc, hexa, water 3 ︰ in mass ratio are mixed to get solution in beaker, seed crystal will be plated
Layer ceramic membrane is fixed on beaker bottom with polytetrafluoroethylene (PTFE) pedestal, and beaker is covered with surface plate, to 95 DEG C of beaker heat temperature raising, protects
Warm 60min obtains plating Nano-Zinc ceramic membrane；Plating Nano-Zinc ceramic membrane is subjected to ultrasound successively with acetone, absolute ethyl alcohol, water in advance
Cleaning, control ultrasonic frequency are 30KHz, and tridecafluoro-n-octyltriethoxysilane with ethyl alcohol is mixed, makes mass fraction
For 3% silicon fluoride ethanol solution, the plating Nano-Zinc ceramic membrane after cleaning is placed in silicon fluoride ethanol solution and impregnates 22h, taken out
Plating Nano-Zinc ceramic membrane after dipping, is placed in baking oven, is heated to 110 DEG C, and dry 6h obtains hydrophobic ceramic film.
Comparative example
With the ceramic membrane of company of Hefei City production as a comparison case in hydrophobic ceramic film produced by the present invention and comparative example
Ceramic membrane is detected, and testing result is as shown in table 1：1st, test method
Surface water contact angle is tested with contact angle tester.
Example 1~3 and the ceramic membrane of comparative example prepared by the present invention carries out acidproof, alkaline resistance properties test：At 100 DEG C,
It is impregnated in a concentration of 40% concentrated sulfuric acid for 24 hours, the sodium hydroxide solution a concentration of 20% impregnates for 24 hours, tests the power of ceramic membrane
Learn intensity.Mechanical strength loss late, mass loss rate calculation are according to standard GB/T/T1970《Porous ceramics acid and alkali resistance
Method for testing performance》It is measured.
Pure water flux refers under certain temperature and operating pressure, the spring that the film of unit area is penetrated within the unit interval
Water.Pure water flux is directly proportional to filter efficiency.
Before test, the both ends of preparating example 1~3 of the present invention and the ceramic membrane of comparative example are sealed respectively, ceramic membrane is made
Component, then respectively to one end of membrane module under conditions of meter pressure is 0.1MPa（Water inlet）Pure water is passed through, measures 30min
The inner membrane member other end（Water outlet）The volume V of the pure water of transmission（L）, calculate the pure water flux of ceramic membrane（PWF）.
Pure water flux=through pure water volume/(ceramic-film tube external surface area × permeation ceramic membrane required time × operation pressure
Power）
Table 1
According to data in table 1 it is found that ceramic membrane resistance to chemical corrosion produced by the present invention is strong, there is higher acid and alkali resistance
Can, hydrophobicity is good, and filter efficiency is high, has wide prospect of the application.
Claims (7)
1. a kind of preparation method of hydrophobic ceramic film, it is characterised in that specifically preparation process is：
（1）Polyether sulfone, polyvinylpyrrolidone and 1-Methyl-2-Pyrrolidone are mixed, ball milling in planetary ball mill is placed in and obtains
To mixed with polymers liquid, alumina powder is added in mixed with polymers liquid and continues ball milling, obtains ceramic powder slurry；
（2）Ceramic powder slurry is vacuumized after removing air entrapment, poured into the material fluid bath of casting mold, control scraper traction
Rate is that ceramic powder slurry is made in slot to be laid in carrier band surface, keeps knife away from after treating ceramic powder slurry curtain coating, obtaining
To casting films band, casting films band is placed in tap water at normal temperature and is impregnated, taken out casting films band and spontaneously dry, obtain green, it will
Green cuts into tablet green compact, tablet green compact is placed in the heating of resistance furnace Program, sintering obtains aluminium oxide ceramics tablet
Film；
（3）30~35g acetic acid dihydrate zinc is dissolved in 100~120mL ethylene glycol monomethyl ethers, obtains mixed solution, to mixing
It is added in solution and obtains zinc oxide precursor with the equimolar ethanol amine of acetic acid dihydrate zinc, heat temperature raising stirring；
（4）It after aluminium oxide ceramics plate membrane is immersed in zinc oxide precursor, lifts upwards, obtains plating glue earthenware slab film, treat
After plating the natural drying of glue earthenware slab film, heat temperature raising in tube furnace is placed in, preheats, then be warming up to, after heat preservation, naturally cools to
Room temperature obtains plating seed layer ceramic membrane；
（5）Acetic acid dihydrate zinc, hexa, water are mixed to get solution in beaker, plating seed layer ceramic membrane is used
Polytetrafluoroethylene (PTFE) pedestal is fixed on beaker bottom, and beaker is covered with surface plate, and to beaker heat temperature raising, heat preservation obtains plating nanometer
Zinc ceramic membrane；
（6）Plating Nano-Zinc ceramic membrane is cleaned by ultrasonic successively with acetone, absolute ethyl alcohol, water in advance, by ten trifluoro octyl groups three
Ethoxysilane is mixed with ethyl alcohol, makes silicon fluoride ethanol solution, and the plating Nano-Zinc ceramic membrane after cleaning is placed in silicon fluoride
It is impregnated in ethanol solution, takes out the plating Nano-Zinc ceramic membrane after dipping, be placed in baking oven, heat temperature raising, it is dry, obtain hydrophobic pottery
Porcelain film.
2. a kind of preparation method of hydrophobic ceramic film according to claim 1, it is characterised in that：Step（1）Described is poly-
The mass ratio of ether sulfone, polyvinylpyrrolidone and 1-Methyl-2-Pyrrolidone mixing is 3 ︰ 1 ︰ 5,2~3h of Ball-milling Time, is aoxidized
The grain size of aluminium powder is 0.70~0.75 μm, and the addition of alumina powder is the 20~25% of mixed with polymers liquid quality, continues ball milling
Time is 18~20h.
3. a kind of preparation method of hydrophobic ceramic film according to claim 1, it is characterised in that：Step（2）The pumping
Vacuum time is 3~4min, and scraper pulling speed is 18~20cm/min, knife away from for 0.8~1.2mm, soaking time for 22~
For 24 hours, it is 2~3 days to spontaneously dry the time, and the size of tablet green compact is 70mm × 80mm, and temperature programming temperature is 1500~1550
DEG C, sintering time is 10~12h.
4. a kind of preparation method of hydrophobic ceramic film according to claim 1, it is characterised in that：Step（3）Described adds
Temperature is 55~60 DEG C after heat heating, and mixing time is to 25~30min.
5. a kind of preparation method of hydrophobic ceramic film according to claim 1, it is characterised in that：Step（4）Described carries
Pulling rate degree is 3.0~5.0cm/min, and the naturals drying time is 7~8h, and temperature is 300~350 DEG C after heat temperature raising, during preheating
Between for 10~15min, heating rate is 2 DEG C/min again, and soaking time is 1~2h.
6. a kind of preparation method of hydrophobic ceramic film according to claim 1, it is characterised in that：Step（5）Described two
Acetate hydrate zinc, hexa, water mixing mass ratio for 3 ︰, 1 ︰ 50, temperature is 90~95 DEG C after heat temperature raising, heat preservation
Time is 55~60min.
7. a kind of preparation method of hydrophobic ceramic film according to claim 1, it is characterised in that：Step（6）Described is super
Ultrasonic frequency is 25~30KHz when sound cleans, and the mass fraction of silicon fluoride ethanol solution is 3%, and dip time is 20~22h,
Temperature is 100~110 DEG C after heat temperature raising, and drying time is
5~6h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109481989A (en) * | 2018-09-10 | 2019-03-19 | 张国隆 | A kind of high temperature resistant dehumidifying ceramic element and preparation method thereof |
| CN109694257A (en) * | 2018-12-12 | 2019-04-30 | 合肥信达膜科技有限公司 | A kind of factory formula and preparation process of porous ceramic film |
| CN109761639A (en) * | 2019-03-05 | 2019-05-17 | 南京理工大学 | Nano-structure porous silicon aluminate films material and preparation method thereof |
| CN111228896A (en) * | 2020-01-21 | 2020-06-05 | 江苏扬农化工集团有限公司 | Filter, preparation method thereof and application thereof in treatment of dichlorobenzene rectification residues |
| CN111871228A (en) * | 2020-07-22 | 2020-11-03 | 浙江工业大学 | ZnO micro-nano composite structure ceramic membrane and preparation method and application thereof |
| CN113173805A (en) * | 2021-04-30 | 2021-07-27 | 萍乡学院 | Method for constructing ceramic-based lotus leaf bionic hydrophobic micro-nano mastoid structure on glaze |
| CN113230906A (en) * | 2021-03-26 | 2021-08-10 | 华北电力大学 | Preparation method of self-made coal ash hydrophobic ceramic composite membrane |
| CN113292354A (en) * | 2021-06-10 | 2021-08-24 | 深圳陶陶科技有限公司 | Porous ceramic atomizing core and preparation method thereof |
| CN113370603A (en) * | 2021-04-25 | 2021-09-10 | 青岛农业大学 | Super-hydrophobic biological composite membrane and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406029A (en) * | 2013-07-25 | 2013-11-27 | 大连理工大学 | Preparation method for ZIFs membrane containing zinc adopting sandwich structure and supported by high temperature resistant zinc oxide nanorod |
| CN105396570A (en) * | 2015-11-09 | 2016-03-16 | 南京工业大学 | Preparation method of ceramic membrane loaded zinc oxide photocatalyst |
| WO2016114625A1 (en) * | 2015-01-16 | 2016-07-21 | 고려대학교 산학협력단 | Nanoporous polymer membrane and method for preparing same |
| CN106582330A (en) * | 2016-12-12 | 2017-04-26 | 四川煜天石油机械设备有限公司 | Heavy metal-containing floating oil filter membrane |
| CN106746725A (en) * | 2017-03-21 | 2017-05-31 | 天津城建大学 | A kind of preparation method of new ZnO nano laminated structure coating |
| US9682346B1 (en) * | 2016-10-20 | 2017-06-20 | Sultan Qaboos University | Nanostructured zinc oxide membrane for separating oil from water |
| CN107352980A (en) * | 2017-07-11 | 2017-11-17 | 芜湖市宝艺游乐科技设备有限公司 | A kind of aluminum oxide ceramic membrane with super hydrophobic surface and preparation method thereof |
| CN107413204A (en) * | 2017-07-17 | 2017-12-01 | 大连理工大学 | The method for preparing highly oriented two-dimensional metallic organic backbone nanometer chip film using the inducing zinc growth of graphene oxide confinement |
-
2017
- 2017-12-12 CN CN201711315998.4A patent/CN108126532A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406029A (en) * | 2013-07-25 | 2013-11-27 | 大连理工大学 | Preparation method for ZIFs membrane containing zinc adopting sandwich structure and supported by high temperature resistant zinc oxide nanorod |
| WO2016114625A1 (en) * | 2015-01-16 | 2016-07-21 | 고려대학교 산학협력단 | Nanoporous polymer membrane and method for preparing same |
| CN105396570A (en) * | 2015-11-09 | 2016-03-16 | 南京工业大学 | Preparation method of ceramic membrane loaded zinc oxide photocatalyst |
| US9682346B1 (en) * | 2016-10-20 | 2017-06-20 | Sultan Qaboos University | Nanostructured zinc oxide membrane for separating oil from water |
| CN106582330A (en) * | 2016-12-12 | 2017-04-26 | 四川煜天石油机械设备有限公司 | Heavy metal-containing floating oil filter membrane |
| CN106746725A (en) * | 2017-03-21 | 2017-05-31 | 天津城建大学 | A kind of preparation method of new ZnO nano laminated structure coating |
| CN107352980A (en) * | 2017-07-11 | 2017-11-17 | 芜湖市宝艺游乐科技设备有限公司 | A kind of aluminum oxide ceramic membrane with super hydrophobic surface and preparation method thereof |
| CN107413204A (en) * | 2017-07-17 | 2017-12-01 | 大连理工大学 | The method for preparing highly oriented two-dimensional metallic organic backbone nanometer chip film using the inducing zinc growth of graphene oxide confinement |
Non-Patent Citations (1)
| Title |
|---|
| 马正先等编著: "《纳米氧化锌制备原理与技术》", 30 June 2009, 中国轻工业出版社 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109481989A (en) * | 2018-09-10 | 2019-03-19 | 张国隆 | A kind of high temperature resistant dehumidifying ceramic element and preparation method thereof |
| CN109481989B (en) * | 2018-09-10 | 2021-02-26 | 景应政 | High-temperature-resistant dehumidifying ceramic filter element and preparation method thereof |
| CN109694257A (en) * | 2018-12-12 | 2019-04-30 | 合肥信达膜科技有限公司 | A kind of factory formula and preparation process of porous ceramic film |
| CN109761639A (en) * | 2019-03-05 | 2019-05-17 | 南京理工大学 | Nano-structure porous silicon aluminate films material and preparation method thereof |
| CN109761639B (en) * | 2019-03-05 | 2021-10-08 | 南京理工大学 | Nano porous aluminosilicate film material and preparation method thereof |
| CN111228896A (en) * | 2020-01-21 | 2020-06-05 | 江苏扬农化工集团有限公司 | Filter, preparation method thereof and application thereof in treatment of dichlorobenzene rectification residues |
| CN111871228A (en) * | 2020-07-22 | 2020-11-03 | 浙江工业大学 | ZnO micro-nano composite structure ceramic membrane and preparation method and application thereof |
| CN113230906A (en) * | 2021-03-26 | 2021-08-10 | 华北电力大学 | Preparation method of self-made coal ash hydrophobic ceramic composite membrane |
| CN113370603A (en) * | 2021-04-25 | 2021-09-10 | 青岛农业大学 | Super-hydrophobic biological composite membrane and preparation method and application thereof |
| CN113370603B (en) * | 2021-04-25 | 2022-05-31 | 青岛农业大学 | Super-hydrophobic biological composite membrane and preparation method and application thereof |
| CN113173805A (en) * | 2021-04-30 | 2021-07-27 | 萍乡学院 | Method for constructing ceramic-based lotus leaf bionic hydrophobic micro-nano mastoid structure on glaze |
| CN113292354A (en) * | 2021-06-10 | 2021-08-24 | 深圳陶陶科技有限公司 | Porous ceramic atomizing core and preparation method thereof |
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