CN110449035A - A kind of water-oil separationg film and preparation method thereof - Google Patents
A kind of water-oil separationg film and preparation method thereof Download PDFInfo
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- CN110449035A CN110449035A CN201910770122.1A CN201910770122A CN110449035A CN 110449035 A CN110449035 A CN 110449035A CN 201910770122 A CN201910770122 A CN 201910770122A CN 110449035 A CN110449035 A CN 110449035A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/08—Thickening liquid suspensions by filtration
- B01D17/085—Thickening liquid suspensions by filtration with membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
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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
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
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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
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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
- B01D2325/24—Mechanical properties, e.g. strength
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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
Abstract
The invention belongs to technical field of inorganic nonmetallic materials more particularly to a kind of water-oil separationg film and preparation method thereof.This application provides a kind of preparation methods of water-oil separationg film, comprising the following steps: step 1 mixes ceramic powder, solvent and acid-base modifier, obtains ceramic powder slurry；Step 2, by the ceramic powder slurry and organic acid hybrid reaction, obtain the first reactant；Step 3 emulsifies the mixing of first reactant, surfactant and organic solvent, obtains the second reactant；Second reactant is successively formed and is dried by step 4, obtains ceramic membrane biscuit；The ceramic membrane biscuit is sintered by step 5, obtains porous ceramic film；Hydrophobic layer is arranged in the surface of the water-oil separating ceramic membrane by step 6, obtains water-oil separationg film.Invention provides a kind of micro-nano compound structure intensity height, and micro-/ nano particle is not easy to wear and falls off, reusable, free of contamination water-oil separationg film.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials more particularly to a kind of water-oil separationg film and preparation method thereof.
Background technique
In recent years, as China is to the attention of environmental protection and the yearning of beautiful homeland, the environmental consciousness of people is generally mentioned
Height, corresponding environmental protection Industry Policy are put into effect in succession.Wherein, the application demand of water-oil separating seems especially urgent, and such as ocean is far taken turns
Oil spills accident caused by water-oil separating problem, oiliness/aqueous two-phase mixture separation of Organic Chemistry Laboratory,
And trench oil recycling of kitchen industry etc..In general, current separation method mainly include physical method, bioanalysis,
Chemical method and electrochemical process etc., wherein physical method separation includes gravitational method separation, centrifugal process separation, filtration method separation etc. again.This
A little traditional oily water separation techniques generally have the advantages such as equipment is simple, single treatment is at low cost, and operating method is simple, but another
The disadvantages of aspect, the generally existing separative efficiency of these methods is lower, occupied area is larger, and greasy dirt recovery efficiency is low, it is difficult to it is full
The more and more harsh environmental requirement of foot.
In recent years, the progress of material science has greatly pushed the technology of water-oil separating field to develop.For example, utilizing material
Novel water-oil separating membrane material, has become the research hotspot of surface and interface Material Field at present constructed by the special wellability on surface
One of, and it is increasingly becoming the important method of cleaning oil slick and water-oil separating, it is expected to solution the problems such as solving water pollution
It will certainly play a crucial role.In general, water-oil separating and traditional point are carried out using the special wellability of material
It is compared from method, has the advantages that material properties stabilization, good separating effect, separative efficiency are high.
In general, water-oil separating material can be divided into two kinds according to material properties: 1) super-hydrophobic-super oleophylic seperation film,
Be otherwise known as the seperation film " except oil type "；2) super hydrophilic-superoleophobic seperation film, be otherwise known as the seperation film " except water type ".Wherein " oil removing
Type " seperation film is because the advantages of its oil-water selectivity is strong, good separating effect, is widely used, but the essence of its oleophylic makes this material
Material has the following problems during use: being easily polluted by the oil, throwing aside after use or the processing modes such as burns often
Cause the secondary pollution to environment.Therefore, how to develop environmentally protective, reusable, and preparation process is simple, is convenient for work
The water-oil separating membrane material for super-hydrophobic-super oleophylic seperation film " removing oil type " that industry metaplasia produces just seems particularly important.
With the development of industry with ecological environmental protection increasingly urgent, Ecological Civilization Construction has become State-level
Strategic task, the oil mixing with water body of industrial discharge are the number one killers of ecological disruption ecological environment.Therefore, how purified industrial
Waste water, oil mixing with water body are always the research hot topic project of academia and industry.
The technical disadvantages of current " removing oil type (super-hydrophobic-super oleophylic) " water-oil separationg film mainly have:
1) process flow is complicated, industrial controllability is not strong, as patent CN201810742339.7 uses Static Spinning
The complicated technology of silk plus LBL self-assembly prepares water-oil separationg film, process-intensive, process complexity；2) current technology,
Such as coating, crystalline growth, electro-deposition, prepared micro-nano compound structure is generally unstable, and micro-/particle of receiving is easy to wear and de-
It falls；3) material of main part is used as using polymer, the problems such as that there are material reuse degree is low, environment easy to pollute.
In conclusion that there are micro-nano compound structures is generally unstable for the water-oil separationg film of the prior art, micro-/particle of receiving easily is ground
It damages and falls off, and reuse the technological deficiency of low, the easy to pollute environment of degree.
Summary of the invention
First aspect present invention provides a kind of micro-nano compound structure intensity height, and micro-/ nano particle is not easy to wear and falls off,
It is reusable, the free of contamination water-oil separationg film for carrying out water-oil separating.
Second aspect of the present invention provides that a kind of preparation process flow is simple, industrial controllability is strong carries out oil
The preparation method of the water-oil separationg film of water separation.
In view of this, this application provides a kind of preparation methods of water-oil separationg film, comprising the following steps:
Step 1 mixes ceramic powder, solvent and acid-base modifier, obtains ceramic powder slurry；
Step 2, by the ceramic powder slurry and organic acid hybrid reaction, obtain the first reactant；
Step 3 emulsifies the mixing of first reactant, surfactant and organic solvent, obtains the second reaction
Object；
Second reactant is successively formed and is dried by step 4, obtains ceramic membrane biscuit；
The ceramic membrane biscuit is sintered by step 5, obtains porous ceramic film；
Hydrophobic layer is arranged in the surface of the water-oil separating ceramic membrane by step 6, obtains water-oil separationg film.
Preferably, by adding acid-base modifier, the pH value of solvent is adjusted, to improve ceramic powder molten in step 1
The pH of the solution rate of agent, solvent is lower than 7, and ceramic powder can be improved in the solution rate and dissolubility of solvent, so that
A small amount of solvent can incorporate a large amount of ceramic powder under acid condition.
Preferably, the acid-base modifier is selected from the strong acid or weak acid and sodium hydroxide etc. such as hydrochloric acid, sulfuric acid, nitric acid
Highly basic.More preferably, the acid-base modifier is selected from hydrochloric acid and sodium hydroxide.
Preferably, the pH range is 3.0~7.0 in step 1.
It is furthermore preferred that the pH range is 4.3~6.0 in step 1.
Preferably, in step 1, the pH is 5.3.
Preferably, in step 1, the ceramic powder be selected from aluminium oxide, zirconium oxide, Zirconia reinforced alumina ceramic,
One of boron nitride, silicon nitride and aluminium nitride are a variety of；The solvent is selected from deionized water or/and alcohol.
Preferably, in step 1, the solid concentration of the ceramic powder in the ceramic powder slurry be 5vol%~
80vol%.
More preferably, the solid concentration of the ceramic powder in the ceramic powder slurry is 30vol% in step 1
~60vol%.
It is described to be mixed into ball milling mixing preferably, in step 1, the Ball-milling Time is 0.5~for 24 hours, the ball milling
Revolving speed is 200~600r/min.
It is furthermore preferred that the Ball-milling Time is 5~12h in step 1, the revolving speed of the ball milling is 250~350r/min.
Wherein, the acid-base modifier forms chemical coordination reaction for adjusting pH, and ball milling mixing is reunited to break up,
To provide the dispersibility of ceramic powder slurry.
Preferably, the organic acid is selected from propionic acid or/and valeric acid in step 2；The additive amount of the organic acid are as follows: every
Organic acid described in gram described ceramic powder addition 0.01mmol-0.1mmol；The incorporation time of the hybrid reaction is 2-10 points
Clock.
Preferably, be stirred the ceramic powder slurry with organic acid hybrid reaction in step 2, it is described to stir
The time mixed is 0.05~0.5h, and the revolving speed of the stirring is 200~300r/min.
It should be noted that the application discovery carries out ceramic powder slurry and organic acid hybrid reaction to ceramic powder
Moditied processing, so that the surface grafting carboxyl functional group of the ceramic powder of ceramic powder slurry, repairs ceramic powder with realizing
Decorations processing, is also convenient for subsequent the second reactant for being emulsified into microlayer model shape.
Preferably, in step 3, the surfactant be selected from polyvinyl alcohol, polyethylene glycol, sodium stearyl sulfate and
One of odium stearate is a variety of；The organic solvent is selected from one of normal octane, hexadecane and n-hexane or a variety of.
Preferably, in step 3, additive amount of the polyvinyl alcohol in second reactant are as follows: described in every gram
The polyvinyl alcohol of solvent addition 0.1wt%~10wt%；Percent by volume of the organic solvent in second reactant
≤ 95%, wherein the solvent is deionized water or/and alcohol.
It should be noted that the application has found, through-hole controls volume of the polyvinyl alcohol in second reactant
Percentage can control the aperture of the porous structure of water-oil separationg film, specifically, the polyvinyl alcohol is in second reactant
Accounting is bigger, and the aperture of water-oil separationg film is smaller.
Preferably, mixing first reactant, surfactant and organic solvent includes that stirring is mixed in step 3
It closes, the time of the stirring is 0.05h~0.5h.
It should be noted that please referring to Figure 11, Figure 11 is three before the application water-oil separationg film sintering provided by the present application
Simulation drawing is tieed up, discovery carries out emulsion foam processing, surface-active after mixing the first reactant, surfactant and organic solvent
Organic solvent (such as one of normal octane, hexadecane and n-hexane or a variety of) is divided into countless small oil droplets, ceramic powder by agent
Body coats small oil droplet and forms self assembly (ceramic powder cladding organic solvent), organic solvent after organic solvent volatilization or/and evaporation
Occupied hole just forms the hole of water-oil separationg film, that is to say, that the first reactant is that surface modification has carboxyl functional group
Ceramic powder realizes self-assembling function to the coating function of microlayer model, forms the microlayer model of ceramic powder cladding organic solvent,
After organic solvent volatilization in microlayer model, the porous engraved structure of the three-dimensional network of formation rule.
Specifically, under the action of by surfactant and organic solvent, so that surface modification has the pottery of carboxyl functional group
Porcelain powder realizes self assembly in ceramic powder slurry, forms the honeycomb micro-meter scale oil drops group of aligned transfer, will emulsify
Ceramic slurry afterwards is formed and is sintered.
Preferably, the molding is congealed into including traditional moulds molding, 3D printing molding, injection forming, note in step 4
Type, die cast or tape casting.
Wherein, the ceramic film preparation that complicated shape can be achieved is formed using 3D printing.
Preferably, the 3D printing is shaped to free direct write molding 3D printing molding in step 4.
Preferably, the drying is to remove the second reactant solvent after molding or liquid substance, example in step 4
Such as oil droplet；It is dried for follow-up sintering；The drying is natural drying or oven drying；The time of the natural drying is
72h。
Preferably, the temperature of the sintering is 1000 DEG C~1700 DEG C in step 5；The sintering temperature 800 DEG C with
Under, the heating rate of the sintering is no more than 10 DEG C/min, and for the sintering temperature at 800 DEG C or more, the heating of the sintering is fast
Degree is no more than 5 DEG C/min, keeps the temperature two hours at maximum temperature.
More preferably, the temperature of the sintering is 1200 DEG C~1700 DEG C in step 5；The sintering temperature 800 DEG C with
Under, the heating rate of the sintering is no more than 10 DEG C/min, and for the sintering temperature at 800 DEG C or more, the heating of the sintering is fast
Degree is no more than 5 DEG C/min, keeps the temperature two hours at maximum temperature.
Preferably, the material of the hydrophobic layer is selected from dimethyl silicone polymer, stearic acid, polytetrafluoroethyl-ne in step 6
One of alkene, polysilazane and trimethoxy (17 fluorine decyl of 1H, 1H, 2H, 2H-) silane are a variety of.
More preferably, the material of the hydrophobic layer is selected from dimethyl silicone polymer in step 6.
Preferably, including: vapour deposition process, object by the method for the surface setting hydrophobic layer of the water-oil separating ceramic membrane
Reason coating or infusion method.
Wherein, hydrophobic layer is set on the surface of the water-oil separating ceramic membrane, so that the water-oil separating ceramic membrane is water
It can not pass through, the water-oil separationg film of passable super-hydrophobic-super oleophylic of oil.
Wherein, the temperature of the vapor deposition is 200 DEG C~300 DEG C.
Preferably, the temperature of the vapor deposition is 235 DEG C.
Wherein, the physics coating and the temperature impregnated are room temperature.
Second aspect of the present invention discloses a kind of water-oil separationg film, including water-oil separating made from preparation method described above
Film.
Specifically, this application provides the preparation method of specific water-oil separationg film, using deionized water as solvent, oxidation
Aluminium ceramic powder is gradually added under ultrasound environments and stirring environment as powder body material, mixed proportion for 58vol% powder, and
PH gradually is adjusted with HCl, pH is adjusted and is lower than 5.0, ball milling mixing, ball-milling treatment time and revolving speed are set to 12h, 300r/
min；Then, the suspension after ball milling is diluted to the slurry sample of 46vol% with deionized water, using propionic acid as organic acid point
Son, and it is being added with stirring propionic acid energetically；Then, surface modification PVA and organic solvent normal octane are added, under stirring
First plus PVA, normal octane, stirring foaming 10min are added after mixing；Adopt the molding system for being molded with a mold and realizing biscuit of ceramics
It is standby, drying condition, time 72h are used as using spontaneously drying；1550 DEG C of sintering processes are carried out after demoulding；It is selected after grind away
PDMS as hydrophobic molecule, using vapor deposition method realize hydrophobic molecule in the uniform coating of ceramic membrane body surface face and inside and
Coating.
As can be seen from the above technical solutions, the application has the following advantages:
This application provides a kind of water-oil separationg films to be conducive to the surface modification carboxyl grafting functional group of ceramic powder
Ceramic powder after modification realizes self assembly in certain circumstances, i.e., surfactant is organic solvent (such as normal octane, 16
One of alkane and n-hexane are a variety of) countless small oil droplets are divided into, ceramic powder coats small oil droplet and forms self assembly (ceramic powder
Body coats organic solvent), hole occupied by organic solvent just forms the hole of water-oil separationg film after organic solvent volatilization or/and evaporation
Therefore hole after the final slurry after emulsification is formed and is sintered, then in surface setting hydrophobic layer, is formed with super close
Oil-super-hydrophobic, water-oil separating is high-efficient, high-strength light, wear-resistant pressure-resistant, and it is environmentally protective, can repeatedly use have it is more
The water-oil separationg film of pore structure.Meanwhile the preparation method of the water-oil separationg film of the application is simple, it can adding by control raw material
For dosage to control the aperture of water-oil separationg film, industrial controllability is strong.Experiment shows the water-oil separationg film oil of the application
Water separation is high-efficient, compression strength is big, so that its structural strength is high, surface micronano particle is not easy to wear, will not fall off；Grease
Seperation film has porous structure, the specifically porous engraved structure of three-dimensional grid of the rule of ordered arrangement；And its structure three-dimensional
Controllably, the arbitrary size ratio in aperture and through-hole in porous structure can be realized by the additive amount of raw material；And water-oil separationg film can
It is pollution-free to reuse.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 characterizes Test Drawing for the super hydrophobic contact angle for the water-oil separationg film that the application provides embodiment 1；
Fig. 2 characterizes Test Drawing for the super oleophylic contact angle for the water-oil separationg film that the application provides embodiment 1；
Fig. 3 carries out water-oil separating wettability pictorial diagram for the water-oil separationg film that the application provides embodiment 1；
Fig. 4 carries out water-oil separating wettability pictorial diagram for the product that the application provides comparative example 1；
Fig. 5 provides the schematic diagram of the oil-water separation test of the water-oil separationg film of embodiment 1 for the application, wherein a is simultaneously
Oil droplet 1 and water droplet 2 are added dropwise on toward the water-oil separationg film of embodiment 1, b is the water-oil separationg film that oil droplet 1 passes through embodiment 1, water droplet 2
The water-oil separationg film of embodiment 1 is not passed through, c is the surface for the water-oil separationg film that water droplet 2 rests on embodiment 1 with drops；
Fig. 6 is that the water-oil separationg film (PVA1wt%) of the embodiment of the present application amplifies 100 times of scanning electron microscope (SEM) photograph；
Fig. 7 is that the water-oil separationg film (PVA1wt%) of the embodiment of the present application amplifies 200 times of scanning electron microscope (SEM) photograph；
Fig. 8 is that the water-oil separationg film (PVA1wt%) of the embodiment of the present application amplifies 400 times of scanning electron microscope (SEM) photograph；
Fig. 9 is that the water-oil separationg film (PVA1wt%) of the embodiment of the present application amplifies 1200 times of scanning electron microscope (SEM) photograph；
Figure 10 is that the water-oil separationg film (PVA1wt%) of the embodiment of the present application amplifies 10000 times of scanning electron microscope (SEM) photograph；
Figure 11 is the three-dimensional simulation figure before the application water-oil separationg film sintering provided by the present application.
Specific embodiment
The present invention provides a kind of water-oil separationg films and preparation method thereof, efficiently solve the water-oil separationg film of the prior art
It is generally unstable that there are micro-nano compound structures, and micro-/particle of receiving is easy to wear and falls off, and reuse degree is low, ring easy to pollute
The technological deficiency in border.
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Wherein, it is commercially available or self-control that following embodiment is raw materials used；Ceramic powder: α-Al2O3, purchased from big bright aluminium oxide
TM-DAR (partial size 0.2um；Density 3.98g/ml；Japanese big bright chemistry)；Propionic acid: chemical formula CH3CH2COOH, purity 99%,
MW is 74.08, lark prestige science and technology；Polyvinyl alcohol: PVA, alcoholysis degree 99.0-99.4mol%；Viscosity: 12.0-16.0mPa.s；MW
It is 44.05；Aladdin Reagent Company；Normal octane: C8H18Purity 96%, MW 114.23；Aladdin Reagent Company；Poly dimethyl
Siloxanes: PDMS, 184 silicon rubber, Dow corning SYLGARD；Polyethylene glycol: HO (CH2CH2O)nH average Mn is
6000, Aladdin Reagent Company；Methyl blue: molecular formula C37H27N3Na2O9S3, MW is 799.8 Mike woodss；Oil red O:Oil Red
O, 3,5-dimethylphenyl, molecular formula C26H24N4O, MW 408.495, Mai Kelin.
SEM uses scanning electron microscope SU 8220, Hitachi, Japan.
Contact-angle measurement uses XG-CAM contact angle measurement, and Contact Angle Meter Shang Haixuan, which is lost, creates analysis industry
Equipment Co., Ltd.
Consistency uses Archimedes's drainage, heated at constant temperature platform, assay balance, PTX-FA electronic analytical balance；
USA.HZ&HUAZHI, Kang ZhouHZ Electronics Co., Ltd., the U.S..
Sintering experiment uses Muffle furnace TSX1700 type, western nit (Beijing) electric furnace Co., Ltd.
Polishing experiments use MP-2B polisher lapper, Laizhou City Weiyi Experiment Machine Co., Ltd..
Embodiment 1
The embodiment of the present application provides a kind of water-oil separationg film, and specific preparation process is as follows:
One, the preparation of ceramic powder slurry
1, α-Al is gradually added into deionized water under the action of stirring is with ultrasound according to the additive amount of table 12O3Powder
Body, finally configuring solid content with hydrochloric acid regulation pH is 53.7vol%, the aluminum oxide suspension that pH is 5.36.Wherein, emulsion foam
Afterwards, deionized water 16.2vol%, α-Al2O3Powder is 27.6vol%.
2, in the ratio of ratio of grinding media to material 1:1, alumina balls abrading-ball is added, wherein ball milling ball Φ 10mm, Φ 5mm ball milling ball ratio
For 1:1.With one night of planetary ball mill ball milling (revolving speed 300r/min).
3, ball milling ball is removed after ball milling, obtains ceramic powder slurry.
Two, the moditied processing of ceramic powder slurry
1, will add deionized water in the ceramic powder slurry of step 1 to be diluted to solid content is 46vol%；
By the propionic acid of every gram of alumina powder addition 0.04mmol, and it is added dropwise under stiring.Stirring is realized to ceramics
The moditied processing of powder obtains the first reactant.
Three, emulsion foam is handled
1, the first reactant of step 2 is divided into 6 parts, every part of first reactant adds polyvinyl alcohol, marks respectively
Are as follows: PVA0wt%, PVA1wt%, PVA2wt%, PVA3wt%, PVA4wt% and PVA10wt%, i.e. PVA0wt% are polyethylene
The additive amount of alcohol is the polyvinyl alcohol that 0, PVA1wt% is every gram of deionized water addition 0.01g in the first reactant, PVA2wt%
Add the polyvinyl alcohol of 0.02g for every gram of deionized water in the first reactant, PVA3wt% be in the first reactant every gram go from
The polyvinyl alcohol of sub- water addition 0.03g, PVA4wt% are the polyethylene that every gram of deionized water adds 0.04g in the first reactant
Alcohol, PVA10wt% are the polyvinyl alcohol that every gram of deionized water adds 0.1g in the first reactant；Later according to volume basis score
Not Tian Jia the normal octane of 70vol% be stirred foaming, mixing time is 7 minutes.Through normal octane all circulates in suspension
Stroke lotion.Be the first reactant volume and addition normal octane volume ratio be 3:7, obtain the polyethylene of various concentration
Second reactant of alcohol, be denoted as respectively PVA0wt%, PVA1wt%, PVA2wt%, PVA3wt%, PVA4wt% and
PVA10wt%, wherein as needed, adjusting ph value of emulsion with NaOH solution in the case of stirring is 4.4, until being suitble to 3D
The viscosity of printing.
Four, forming processes
1, take every kind of second reactant in previous step, by 3D printing molding equipment realize macroscopical biscuit of ceramics at
Type and drying process, it is dry to be spontaneously dried at room temperature to be placed in, obtain ceramic membrane biscuit, be denoted as respectively PVA0wt%,
PVA1wt%, PVA2wt%, PVA3wt%, PVA4wt% and PVA10wt%.
Five, it is sintered
1, it takes every kind of ceramic membrane biscuit of previous step to be sintered, obtains porous ceramic film, be denoted as respectively
PVA0wt%, PVA1wt%, PVA2wt%, PVA3wt%, PVA4wt% and PVA10wt%；Sintering parameter are as follows: sintering temperature
800 DEG C with the speed of 10 DEG C/min hereinafter, heated up；Temperature is heated up at 800-1550 DEG C with the speed of 3.75 DEG C/min, is reached
2 hours are kept the temperature after 1550 DEG C, is then cooled down, temperature is cooled down, later with furnace at 800-1550 DEG C with the speed of 3.75 DEG C/min
It is cold.
Six, water-oil separating ceramic membrane hydrophobic treatment
1, every kind of porous ceramic film in previous step is taken to be polished with 200 mesh Buddha's warrior attendant mills, production piece thickness is 0.8mm
Ceramic for filtration membrane sample, (take every kind of ceramic for filtration membrane sample to be placed in culture dish 1, PDMS liquid by 235 DEG C of vapor depositions
Body glue is placed in culture dish 2, covers culture dish 1,2 with beaker inversion, and beaker mouth is suitably sealed with masking foil, whole later to set
Slow heating is warming up to 235 DEG C in Muffle furnace, keeps the temperature 8 hours, and the PDMS in culture dish 2 forms steam, in ceramic for filtration film
The surface evaporation of sample simultaneously deposits one layer of PDMS molecular layer, and vapor deposition parameter is to be warming up to 235 DEG C with 7.8 DEG C/min, 235
8 hours are kept the temperature at DEG C, cold with furnace later), one layer of PDMS (dimethyl silicone polymer) molecule is plated in sample surfaces, realizes and dredges
Water process obtains 6 kinds of water-oil separationg films, is denoted as PVA0wt%, PVA1wt%, PVA2wt%, PVA3wt%, PVA4wt% respectively
And PVA10wt%.
Table 1
Measure the property of the average pore sizes of 6 kinds of water-oil separationg films obtained, contact angle, water-oil separating efficiency and compression strength
Can, the results are shown in Table 2.
Table 2
| Average pore size (μm) | Contact angle (O) | Water-oil separating efficiency (%) | Compression strength (MPa) | |
| PVA0% | 137.5 | 147.64 | 99.87 | It is unstable |
| PVA1% | 18.0 | 152.85 | 99.86 | 51.136 |
| PVA2% | 11.1 | 152.57 | 99.87 | 45.872 |
| PVA3% | 15.5 | 152.47 | 99.87 | 44.752 |
| PVA4% | 10.3 | 152.75 | 99.91 | 36.767 |
| PVA10% | 7.8 | 153.35 | 99.91 | 25.608 |
As known from Table 2, when adding the polyvinyl alcohol water solution that concentration is 0wt%, obtained water-oil separationg film pressure resistance
Spend unstable, and the average pore size of water-oil separationg film is excessive, and gap is unevenly distributed weighing apparatus, and the contact angle of oil droplet is too small.With poly- second
The concentration of enol increases, and water-oil separationg film average pore size is smaller and smaller.Compression strength is all relatively high, and water contact angle is above super
150 ° of hydrophobic boundary, water-oil separating efficiency reaches 99.8% or more.
Electronic Speculum detection is scanned to the water-oil separationg film (PVA1%) of the present embodiment, as a result as Figure 6-9, Fig. 6 is
The water-oil separationg film (PVA1wt%) of the embodiment of the present application amplifies 100 times of scanning electron microscope (SEM) photograph, and Fig. 7 is the oil of the embodiment of the present application
Water seperation film (PVA1wt%) amplifies 200 times of scanning electron microscope (SEM) photograph, and Fig. 8 is the water-oil separationg film of the embodiment of the present application
(PVA1wt%) amplify 400 times of scanning electron microscope (SEM) photograph, Fig. 9 is that the water-oil separationg film (PVA1wt%) of the embodiment of the present application is amplified
1200 times of scanning electron microscope (SEM) photograph, Figure 10 are that the water-oil separationg film (PVA1wt%) of the embodiment of the present application amplifies 10000 times of scanning
Electron microscope, from Fig. 6-10 it is found that the water-oil separationg film (PVA1wt%) of the embodiment of the present application has the three of the rule of ordered arrangement
The porous engraved structure of grid is tieed up, Figure 10 is it is found that it is found that the self-assembling method heap of the application under 10000 times of surface sweeping electron microscope
The porous structure that pile comes out, the crystal grain on hole wall can be stacked to the firm hole shell of precise alignment, so macroscopic aspect just has
High-intensitive compressive property, and be porous structure, so there is high-strength light performance.
Embodiment 2
The super-hydrophobic and super oil-wet behavior for measuring the water-oil separationg film of the embodiment of the present application 1, please refers to Fig. 1-2, and Fig. 1 is this
Application provides the super-hydrophobic Test Drawing of the water-oil separationg film of embodiment 1, and Fig. 2 provides the water-oil separationg film of embodiment 1 for the application
Super oleophylic Test Drawing, from Fig. 1-2 it is found that the water-oil separationg film of the embodiment of the present application 1 has super-hydrophobic and super oil-wet behavior.
Comparative example 1
The application comparative example provides a kind of water-oil separationg film of control, the preparation step of specific preparation step such as embodiment 1
Rapid type, difference are the hydrophobic treatment without 1 step 6 of embodiment, remaining step is same as Example 1, and comparative example is made
1 product.
Embodiment 3
Fig. 5 is please referred to, Fig. 5 provides the schematic diagram of the oil-water separation test of the water-oil separationg film of embodiment 1 for the application,
In, Fig. 5 a is simultaneously toward dropwise addition oil droplet 1 and water droplet 2 in the water-oil separationg film of embodiment 1, and Fig. 5 b is that oil droplet 1 passes through embodiment 1
Water-oil separationg film, water droplet 2 do not pass through the water-oil separationg film of embodiment 1, and Fig. 5 c rests on embodiment 1 for water droplet 2 with drops
The surface of water-oil separationg film.According to the process of Fig. 5, oil-water separation test also is carried out to the product of comparative example 1, result in kind is as schemed
Shown in 3 and Fig. 4, Fig. 3 carries out the pictorial diagram after oil-water separation test for the water-oil separationg film that the application provides embodiment 1, and Fig. 4 is
The product that the application provides comparative example 1 carries out the pictorial diagram after oil-water separation test, from Fig. 3-4 it is found that without 1 step of embodiment
The comparative example 1 that rapid six hydrophobic treatment obtains does not have the performance of water-oil separating.
The description of the present application and term " first " in above-mentioned attached drawing, " second ", " third ", " the 4th " etc. are (if deposited
) it is to be used to distinguish similar objects, without being used to describe a particular order or precedence order.It should be understood that use in this way
Data are interchangeable under appropriate circumstances, so that embodiments herein described herein for example can be in addition to illustrating herein
Or the sequence other than those of description is implemented.In addition, term " includes " and " having " and their any deformation, it is intended that
Cover it is non-exclusive include, for example, containing the process, method, system, product or equipment of a series of steps or units need not limit
In step or unit those of is clearly listed, but may include be not clearly listed or for these process, methods, produce
The other step or units of product or equipment inherently.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of water-oil separationg film, which comprises the following steps:
Step 1 mixes ceramic powder, solvent and acid-base modifier, obtains ceramic powder slurry；
Step 2, by the ceramic powder slurry and organic acid hybrid reaction, obtain the first reactant；
Step 3 emulsifies the mixing of first reactant, surfactant and organic solvent, obtains the second reactant；
Second reactant is successively formed and is dried by step 4, obtains ceramic membrane biscuit；
The ceramic membrane biscuit is sintered by step 5, obtains porous ceramic film；
Hydrophobic layer is arranged in the surface of the water-oil separating ceramic membrane by step 6, obtains water-oil separationg film.
2. preparation method according to claim 1, which is characterized in that in step 1, the ceramic powder be selected from aluminium oxide,
One of zirconium oxide, Zirconia reinforced alumina ceramic, boron nitride, silicon nitride and aluminium nitride are a variety of；The solvent is selected from
Deionized water or/and alcohol.
3. preparation method according to claim 1, which is characterized in that described in the ceramic powder slurry in step 1
The solid concentration of ceramic powder is 5vol%~80vol%.
4. preparation method according to claim 1, which is characterized in that in step 2, the organic acid be selected from propionic acid or/and
Valeric acid；The additive amount of the organic acid are as follows: organic acid described in every gram of ceramic powder addition 0.01mmol-0.1mmol；It is described
The incorporation time of hybrid reaction is 2-10 minutes.
5. preparation method according to claim 1, which is characterized in that in step 3, the surfactant is selected from polyethylene
One of alcohol, polyethylene glycol, sodium stearyl sulfate and odium stearate are a variety of；The organic solvent is selected from normal octane, ten
One of six alkane and n-hexane are a variety of.
6. preparation method according to claim 5, which is characterized in that in step 3, the polyvinyl alcohol is anti-described second
Answer the additive amount in object are as follows: the polyvinyl alcohol of every gram of solvent addition 0.1wt%~10wt%；The organic solvent is in institute
State percent by volume≤95% in the second reactant.
7. preparation method according to claim 1, which is characterized in that in step 5, the temperature of the sintering is 1000 DEG C~
1700℃；The sintering temperature is at 800 DEG C hereinafter, the heating rate of the sintering is no more than 10 DEG C/min, the sintering temperature
At 800 DEG C or more, the heating rate of the sintering is no more than 5 DEG C/min, keeps the temperature two hours at maximum temperature.
8. preparation method according to claim 1, which is characterized in that in step 6, the material of the hydrophobic layer is selected from poly- two
In methylsiloxane, stearic acid, polytetrafluoroethylene (PTFE), polysilazane and trimethoxy (17 fluorine decyl of 1H, 1H, 2H, 2H-) silane
It is one or more.
9. preparation method according to claim 1, which is characterized in that the surface of the water-oil separating ceramic membrane is arranged and dredges
The method of water layer includes: vapour deposition process, physics coating or infusion method.
10. a kind of water-oil separationg film, which is characterized in that be made including preparation method as described in any one of claims 1-9
Water-oil separationg film.
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| CN113842787A (en) * | 2021-09-29 | 2021-12-28 | 天津工业大学 | Halloysite nanotube-reinforced ultrathin ceramic membrane and preparation method thereof |
| CN114574049A (en) * | 2022-03-22 | 2022-06-03 | 东北石油大学 | Preparation method of organic/inorganic hybrid super-hydrophobic super-oleophylic anti-scaling coating |
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