CN106669440B - A kind of modification method and modified ceramic film of ceramic membrane - Google Patents
A kind of modification method and modified ceramic film of ceramic membrane Download PDFInfo
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- CN106669440B CN106669440B CN201710001802.8A CN201710001802A CN106669440B CN 106669440 B CN106669440 B CN 106669440B CN 201710001802 A CN201710001802 A CN 201710001802A CN 106669440 B CN106669440 B CN 106669440B
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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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- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/28—Degradation or stability over time
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/38—Hydrophobic membranes
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Abstract
The present invention provides a kind of modification method of ceramic membrane and modified ceramic films.The modification method of the ceramic membrane are as follows: ceramic membrane is surface-treated, fresh ceramic membrane is obtained；Silane compound is coated to the surface of ceramic membrane by infusion process or sedimentation；Ceramic membrane after coating is heat-treated under protective atmosphere, modified modified ceramic film is obtained after Temperature fall.The modification method of ceramic membrane provided by the invention has that modification is simple, low raw-material cost, and modification not will cause the secondary pollution of environment；Has the features such as long-time stability are high, anti acid alkali performance is strong, ultra-hydrophobicity relative to common are machine maintenance exterior material by the modified ceramic film of modification preparation；It can be widely applied to the fields such as sea water desalination, water-oil separating, wastewater treatment.
Description
Technical field
The invention belongs to ceramic membrane surface processing technology fields, are related to the modification method and modified pottery of a kind of ceramic membrane
Porcelain film.
Background technique
Along with the development of productivity, the progress of science and technology, isolated method also conforms to the principle of simplicity to numerous, technology from rudimentary to advanced,
A kind of combination of the technique from method to kinds of processes, constantly innovates, improves technique, reduces cost, to meet the mankind to improvement
Life demand with rapid changepl. never-ending changes and improvements.In numerous isolation technics, UF membrane is that occur in early 20th century, is emerged rapidly after the sixties
A new isolation technics.UF membrane is to be separated under the action of extraneous motive force to target mixture, purify, be concentrated
A kind of separation technology.Film used in UF membrane is the semi-permeable membrane with selective penetrated property energy, and this film must have only
Moieties can pass through, some intransitable characteristics of substance.Membrane material for isolation technics will have the function of certain
Property, film it is hydrophobically modified be membrane material functionalization a kind of important means, separation of the hydrophobic film for aqueous solvent mixture
Have significant effect, such as the membrane distillation method in sea water desalination, based on hydrophobic separation membrane, using various waste heats,
Waste heat can efficiently obtain completely pure water under the driving of steam pressure difference.Moisture is gone for example in Petroleum Production again
It removes, hydrophobic film is blocked, is concentrated, separates as separation basis, moisture, and high-efficiency low energy consumption achievees the purpose that purifying.
The exploitation of China's shale gas use multistage fracturing technique, the evaluation method of each fracturing section first is that being shown using fluorescence
Track agent obtains the geological information of fracturing section by the change of fluorescence indicator spectral intensity, and the shale gas for evaluating fracturing section produces
Energy.It is returned in drain since fluorescence indicator is mixed in, and the ingredient for returning drain is very complicated, contains fracturing fluid, underground water, underground rock
The Multiple components such as soil.This makes in the measurement process of fluorescence indicator spectrum, the scattering light severe jamming fluorescence instruction of sample
The measurement of agent spectrum leads to spectroscopic data poor signal to noise, and analysis result is incorrect, or even can not analyze.So to use separation
Film separates the fluorescence indicator returned in drain, reduces the interference of other factors as far as possible.
Seperation film also can be applied to the purified treatment of oil/gas well waste water simultaneously, realizes and is recycled, and reduce disposal of pollutants.
Currently, general hydrophobic film is organic high molecular layer, because its macromolecule group is able to maintain good long-term dredge
Aqueous, still, the stability and corrosion resistance of organic film itself are hinder its application prospect the drawbacks of.Inorganic ceramic conduct
A kind of traditional material, always with its stability title, the oxide ceramics such as aluminium oxide, zirconium oxide, silica and silicon nitride, match
The nitride ceramics such as dragon have been applied to various fields, and the separate modes such as the ultrafiltration of UF membrane field, nanofiltration are also widely used.Section
Grinding also has applied to hydrophobic function seperation film, and concrete mode is the grafting of organic hydrophobic molecule, also obtains high point
From efficiency.But, it is similar to organic film, the stability of organic hydrophobic molecule is poor, hinders its development to business application.
Summary of the invention
It is directed to above-mentioned traditional organic polymer membrane stability difference problem in the prior art, it is an object of the invention to mention
The modified ceramic film of modification method and its preparation for a kind of ceramic membrane, to obtain a kind of dredging for good long-time stability
The inorganic ceramic membrane of aqueous modification enables inorganic ceramic hydrophobic membrane commercially to be applied.
The purpose of the present invention is achieved by the following technical programs:
The present invention provides a kind of modification method of ceramic membrane comprising following steps:
Ceramic membrane is surface-treated by step 1, obtains fresh ceramic membrane；
Silane compound is coated to the surface of ceramic membrane by step 2 by infusion process or sedimentation；
Ceramic membrane after applying in step 2 is heat-treated under protective atmosphere, obtains after Temperature fall by step 3
Modified modified ceramic film.
In the modification method of above-mentioned ceramic membrane, it is preferable that in step 1, the step of surface treatment are as follows: will be ceramic
Film, which is placed in strong base solution, boils 5-180min, is washed out drying.
In the modification method of above-mentioned ceramic membrane, it is preferable that the strong base solution may include potassium hydroxide solution, hydrogen
One of sodium hydroxide solution and calcium hydroxide solution etc. or a variety of combinations；
It is further preferred that the concentration of the potassium hydroxide solution or sodium hydroxide solution can be 1-10mol/L；The hydrogen
Calcium oxide solution can be saturated solution.
In the modification method of above-mentioned ceramic membrane, it is preferable that the silane compound may include chlorosilane
Close one of object, alkoxy silane compound and silicon fluoride class compound etc. or a variety of combinations；
It is further preferred that the silane compound may include dimethyl dichlorosilane (DMCS), dimethyldichlorosilane, poly- diformazan
One of base dichlorosilane, dichlorophenyl silane and silicon fluoride etc. or a variety of combinations.
In the modification method of above-mentioned ceramic membrane, it is preferable that the concentration of the silane compound is 10-200g/L.
In the modification method of above-mentioned ceramic membrane, it is preferable that in step 2, silane compound is coated to ceramics
The mode on the surface of film is infusion process, which is that silane compound is dissolved in solvent to obtain solution A, then will be ceramic
Film immersion then takes out drying in solution A.
In the modification method of above-mentioned ceramic membrane, it is preferable that the solvent may include normal heptane, ethyl alcohol, acetone, second
One of nitrile and benzene etc. or a variety of combinations.
In the modification method of above-mentioned ceramic membrane, it is preferable that in step 2, silane compound is coated to ceramics
The surface based fashion of film is sedimentation, which deposited on the surface of ceramic membrane after vaporizing silane compound.
In the modification method of above-mentioned ceramic membrane, it is preferable that further include applying silane in ceramic membrane surface in step 2
After class compound, it is passed through the step that ammonia carries out ammonolysis, in air hydrolysis or catalytic polymerization etc..
In the modification method of above-mentioned ceramic membrane, it is preferable that in step 3, the equipment of heat treatment is high temperature furnace, packet
Include alundum furnace, carbon shirt-circuiting furnace or tungsten coil furnace.
In the modification method of above-mentioned ceramic membrane, it is preferable that the heat treatment is the temperature of the ceramic membrane after applying
It is warming up to 300-800 DEG C with the rate of 0.5-6 DEG C/min, then keeps the temperature 0.5-8h again.
In the modification method of above-mentioned ceramic membrane, it is preferable that the flow of protective atmosphere is 100-500mL/min；Protection
Atmosphere includes reducing gas and/or non-reducing gas；Wherein, reducing gas includes one of hydrogen, ammonia and methane or more
The combination of kind；Non-reducing gas includes nitrogen and/or argon gas；
It is further preferred that the protective atmosphere is ammonia or the protective atmosphere is the mixing of nitrogen and hydrogen composition
Gas, wherein hydrogen mole percent level is 1mol%.
In the modification method of above-mentioned ceramic membrane, it is preferable that the ceramic membrane includes silicon nitride ceramics film, Sialon pottery
In porcelain film, alumina ceramic membrane, titanium dioxide ceramic film, zirconia ceramics film, silicon carbide ceramic membrane and silicon oxide ceramics film
One or more combinations.
The present invention also provides the modified ceramic films that the modification method of above-mentioned ceramic membrane is prepared.
The present invention also provides above-mentioned modified ceramic films as membrane separation assemblies at sea water desalination, water-oil separating or waste water
Application in reason etc..
It is optional after silane compound to be coated to the surface of ceramic membrane in the modification method of ceramic membrane of the present invention
The ammonolysis under ammonia atmosphere is selected, and is polymerize, is obtained by Si-O, the three-dimensional net structure of Si-N key composition, then again in protection gas
Pyrolysis is crosslinked under atmosphere；Or silane compound is applied directly to the surface of ceramic membrane, it is handed under protective atmosphere
Connection pyrolysis, to obtain the inorganic ceramic hydrophobic structure being made of Si, C, O, H element.
In the modification method of ceramic membrane of the present invention, the important function for the protective atmosphere taken is to protect and reduce one
A little harmful oxidation reactions, during being otherwise engaged in Polymer-pyrolysis acquisition inorganic ceramic film and nano particle, enhancing
The intensity of inorganic ceramic coating.For example, wherein ammonia can be poly- with raw chlorsilane substance generation ammonolysis reaction formation organosilicon
Object is closed, nitrogen can enter in the covalent skeleton of ceramics during pyrolysis forms ceramics, play the role of rock-steady structure.
In the modification method of ceramic membrane of the present invention, heat treatment temperature is 300-800 DEG C, is distinguished generally conventional only with dry
Dry (100 DEG C or so) processing, organosilicon alkyl compound are acted in 300 DEG C or so generation internal crosslinkings, can be sent out in higher temperature
Heat is decomposed, to occur from organosilicon alkyl compound to the transformation of inorganic ceramic structure.Therefore inorganic ceramic in this patent
Structure hydrophobic modification particle has more especially in terms of resistance to organic corrosion than organic silicon decorative layer in resistance to acid and alkali, high temperature resistant
Good stability has more high chemical stability and service life.
In the modification method of ceramic membrane of the present invention, ceramic membrane surface is modified to solid phase macroscopic view film forming, with common grafting
Mode is different, and the present invention is to form certain thickness silicone-based polymers film in ceramic membrane surface first.Then it is being heat-treated
During, silicone-based polymers are pyrolyzed into inorganic ceramic membrane structural membrane and nano particle, and ceramic membrane of the invention is repaired
The modified ceramic film for adoring method of modifying preparation is the hydrophobic ceramic film of pure inorganic structure.
In ceramic membrane modification method of the present invention, using organosilicon alkanes as the initial feed reacted, through overheating
Become inorganic ceramic structure after processing, therefore has in thermostabilization, chemical stability and have great advantage.
In the modification method of ceramic membrane of the present invention, obtained ceramic membrane surface decorative layer is by Si-O, Si-N, and Si-C is total
The strong three-dimensional inorganic network structure that valence link is formed by connecting, the ceramic membrane surface after heat treatment can clearly find inorganic ceramic
Nanoparticulate object makes ceramic membrane form multilayer coarse structure, improves the hydrophobicity and self-cleaning ability of ceramic membrane surface.Due to
Be inorganic coating and ceramic membrane combination it is very strong, in resistance to acid and alkali, high temperature resistant, especially than organic in terms of resistance to organic corrosion
Silicon class has better stability.So present invention hydrophobic ceramic film obtained has more preferable long-time stability and use
Service life.
In the modification method of ceramic membrane of the present invention, there is dredging for covalent linkage on the surface of obtained ceramic membrane surface decorative layer
Water base group has good hydrophobicity.
The present invention is pyrolyzed to form hydrophobically modified layer, low raw-material cost, modification using silicon chloride alkyl compound
Simply；Thermal modification process is a kind of growth course, and hydrophobic group, which is grown in ceramic membrane surface and combines, to be stablized, can be high for a long time
Effect is stabilized, and after experiment discovery ceramic membrane is handled 1 hour in 500 DEG C of air, hydrophobic angle has almost no change；Ceramic membrane exists
Organic solvent-benzene, 100mg/L humic acid are handled 72 hours in pH=2-12 aqueous solution；Hydrophobic angle is almost unchanged, and ceramic membrane is boiling
After impregnating 24 hours in water, ceramic membrane hydrophobic angle is almost unchanged.
It is inorganic nano porous structure that modified ceramic film of the invention, which is formed by decorative layer, and siloxicon nitrogen skeleton structure is steady
It is fixed and environmental-friendly, can practical application without will cause secondary pollution.
Hydrophobic structure is the silicon methyl group of end in modified ceramic film of the invention, this group is a kind of steady in chemistry
Fixed, the difficult structure destroyed, meanwhile, intensive methyl group provides good hydrophobicity, achievees the effect that super-hydrophobic.
Modification process of the present invention is simple, and instrument majority needed for modification can be processed voluntarily and be built, and modification effect is good, practical
Property it is high, can stablize that permanently effective performance is good, can be used as effective substitute of organic high molecular layer, have potential practical
Development prospect can be widely used for the devices such as sea water desalination, water-oil separating, wastewater treatment.
Modified ceramic film of the invention in film distilling seawater desalination device, can play can only by vapor, and
The effect of liquid solution cannot be passed through；Modified ceramic film of the invention is in oily-water seperating equipment, can play can only to lead to
Organic matter is crossed, and the effect of liquid solution cannot be passed through.
A kind of modification method of ceramic membrane provided by the invention has that modification is simple, low raw-material cost, repairs
Decorations process not will cause the secondary pollution of environment；By the modified ceramic film of modification preparation relative to common are machine maintenance exterior material
Has the features such as long-time stability are high, anti acid alkali performance is strong, ultra-hydrophobicity；It can be widely used for sea water desalination, water-oil separating, waste water
The devices such as processing.
Detailed description of the invention
Fig. 1 is the SEM comparison diagram of the film modified front and back film surface of silicon nitride ceramics in the embodiment of the present invention 1；
Fig. 2 is the hydrophobic angle test comparison chart of the film modified front and back film surface of silicon nitride ceramics in the embodiment of the present invention 1；
Fig. 3 is that modified silicon nitride ceramics film and common silicon fluoride modify the survey of ceramic membrane thermal stability in the embodiment of the present invention 1
Try comparison diagram；
Fig. 4 is silicon nitride ceramics membranization stability test result figure after modifying in the embodiment of the present invention 1；
Fig. 5 is the SEM figure of modified silicon nitride ceramics film surface in the embodiment of the present invention 2；
Fig. 6 is modified silicon nitride ceramics film hydrophobic angle test chart in the embodiment of the present invention 2；
Fig. 7 is the SEM figure of modified silicon nitride ceramics film surface in the embodiment of the present invention 3；
Fig. 8 is modified silicon nitride ceramics film hydrophobic angle test chart in the embodiment of the present invention 3；
Fig. 9 is the SEM figure of modified silicon nitride ceramics film surface in the embodiment of the present invention 4；
Figure 10 is modified silicon nitride ceramics film hydrophobic angle test chart in the embodiment of the present invention 4；
Figure 11 is the SEM figure of modified Sialon ceramic membrane surface in the embodiment of the present invention 5；
Figure 12 is modified Sialon ceramic membrane hydrophobic angle test chart in the embodiment of the present invention 5；
Figure 13 is the SEM figure of modified Sialon ceramic membrane surface in the embodiment of the present invention 6；
Figure 14 is modified Sialon ceramic membrane hydrophobic angle test chart in the embodiment of the present invention 6；
Figure 15 is modified Sialon ceramic membrane chemical stability test result figure in the embodiment of the present invention 6；
Figure 16 is the SEM figure of modified aluminas ceramic membrane surface in the embodiment of the present invention 7；
Figure 17 is modified aluminas ceramic membrane hydrophobic angle test chart in the embodiment of the present invention 7；
Figure 18 is modifying titanium dioxide ceramic membrane hydrophobic angle test chart in the embodiment of the present invention 8；
Figure 19 is modified zirconia ceramic membrane hydrophobic angle test chart in the embodiment of the present invention 9.
Specific embodiment
In order to which technical characteristic of the invention, purpose and beneficial effect are more clearly understood, now to skill of the invention
Art scheme carries out described further below, but should not be understood as that limiting the scope of the invention.
Embodiment 1
The present embodiment provides a kind of modification methods of ceramic membrane comprising following steps:
Silicon nitride ceramics film is surface-treated, processing method by step 1 are as follows: silicon nitride ceramics film is put into 5mol/L
Sodium hydroxide solution in boil 30min, with pure water washing and drying after taking-up, obtain fresh silicon nitride ceramics film；
The dimethyldichlorosilane of 2.5g dimethyl dichlorosilane (DMCS) and 2.5g is added in the normal heptane of 10mL by step 2,
It is uniformly mixing to obtain solution A；By above-mentioned fresh silicon nitride ceramics film immersion in solution A, drying is taken out；
Ceramic membrane after applying in step 2 is transferred to boron nitride porcelain boat, and boron nitride porcelain boat is placed in electricity by step 3
In the quartz chamber body for hindering silk furnace, carry out slow ammonia purging (ammonia speed is 100mL/min), it is complete by solid to ceramic membrane surface
Terminate after all standing, completes cladding on ceramic membrane surface at this time；It increases under ammonia atmosphere (gas flow are as follows: 300mL/min),
It is heat-treated with the heating rate of 3 DEG C/min, is warming up to 600 DEG C and keeps the temperature Temperature fall after 1h, obtained through hydrophobic modification
Modified silicon nitride ceramics film.
The modification silicon nitride ceramics film that the hydrophobic modification method of modifying that the present embodiment also provides above-mentioned ceramic membrane is prepared.
Experiment is compared to the present embodiment silicon nitride ceramics film and modified silicon nitride ceramics film.It is scanned Electronic Speculum respectively
Experiment and hydrophobic angle experiment.As a result as depicted in figs. 1 and 2.Fig. 1 is the film modified front and back film surface of the present embodiment silicon nitride ceramics
SEM comparison diagram；Fig. 2 is the film modified front and back film surface hydrophobic angle test comparison chart of the present embodiment silicon nitride ceramics.
As seen from Figure 1, the SEM of the silicon nitride ceramics film surface before the present embodiment modification schemes as shown in fig. 1A,
Silicon nitride ceramics film is made of rodlike silicon nitride grain；The SEM of modification silicon nitride ceramics film surface after modification schemes as shown in figure 1
Shown in b, silicon nitride grain is coated by nano particle, formed nanometer protrusion, EDS elemental analysis show bump be by silicon, carbon,
Nitrogen, oxygen element mainly form, and are a kind of inorganic matters of silicon skeleton structure, and various elements are uniformly distributed.
As seen from Figure 2, the hydrophobic angle test chart such as a institute in Fig. 2 of the silicon nitride ceramics film before the present embodiment modification
Show, hydrophobic angle is close to 0 degree, it was demonstrated that the silicon nitride ceramics film for modification is total hydrophilic；Modification silicon nitride ceramics after modification
For the hydrophobic angle test chart of film as shown in the b in Fig. 2, hydrophobic angle is 142 degree, forms hydrophobic structure, has reached hydrophobic modification and changed
The purpose of property.
Heat stability testing experiment is carried out to the modification silicon nitride ceramics film that the present embodiment obtains.It will modified silicon nitride ceramics
Film calcines (100-500 DEG C) 1 hour in air atmosphere, then tests the variation of its hydrophobic angle.It is modified with general silicon fluoride
Ceramic membrane is as a comparison sample.As a result as shown in figure 3, wherein common silicon fluoride modifies ceramic membrane hydrophobic angle after 300 DEG C of calcinings
It begins to decline, at 500 DEG C, loses hydrophobicity completely；And the ability at 500 DEG C of the modification silicon nitride ceramics film in the present embodiment
It slightly decreases, shows good thermal stability.
Chemical stability test experiments are carried out to the modification silicon nitride ceramics film of the present embodiment.First by the modification silicon nitride
Ceramic membrane modifies ceramic membrane sample as a comparison as in boiling water with common silicon fluoride, and it is complete then will to be modified silicon nitride ceramics film
It is immersed into benzene, 0.01MNaOH solution and 0.01M hydrochloric acid solution after 24 hours and tests the variation of its hydrophobic angle.As a result such as Fig. 4 institute
Show, silicon fluoride modifies ceramic membrane in boiling water after 5 hours, hydrophobic to become hydrophilic；And the and modification silicon nitride in the implementation case
Ceramic membrane is reduced only by 4 ° (a in Fig. 4) after 24 hours；And it is modified silicon nitride ceramics film and is totally submerged benzene (in Fig. 4
B), in the NaOH solution (c in Fig. 4) of 0.01M and the hydrochloric acid solution of 0.01M (d in Fig. 4), the hydrophobic ceramic after 24 hours
Film hydrophobic angle does not change substantially, shows good chemical stability.
Embodiment 2
The present embodiment provides a kind of modification methods of ceramic membrane comprising following steps:
Silicon nitride ceramics film is surface-treated, processing method by step 1 are as follows: silicon nitride ceramics film is put into 10mol/
1h is boiled in the potassium hydroxide solution of L, with pure water washing and drying after taking-up, obtains fresh silicon nitride ceramics film；
The dimethyldichlorosilane of 2.5g dimethyl dichlorosilane (DMCS) and 2.5g is added in the ethyl alcohol of 10mL, stirs by step 2
It mixes and uniformly obtains solution A；By above-mentioned fresh silicon nitride ceramics film immersion in solution A, drying is taken out；
Ceramic membrane after applying in step 2 is transferred to boron nitride porcelain boat, and boron nitride porcelain boat is placed in electricity by step 3
In the quartz chamber body for hindering silk furnace, carry out slow ammonia purging (ammonia speed is 100mL/min), it is complete by solid to ceramic membrane surface
Terminate after all standing, completes cladding on ceramic membrane surface at this time；Use mixed gas (moles the hundred of hydrogen of nitrogen and hydrogen instead
Dividing than content is 1mol%) atmosphere (gas flow are as follows: 100mL/min), it is heat-treated, is risen with the heating rate of 1 DEG C/min
Temperature is to 600 DEG C and keeps the temperature Temperature fall after 1h, obtains the modification silicon nitride ceramics film through hydrophobic modification.
The modification silicon nitride ceramics film that the hydrophobic modification method of modifying that the present embodiment also provides above-mentioned ceramic membrane is prepared.
Electron microscope experiment and contact angle experiments are scanned to the modified silicon nitride ceramics film of the present embodiment.As a result such as Fig. 5 and Fig. 6
It is shown.Fig. 5 is the SEM figure of the modified silicon nitride ceramics film surface of the present embodiment；Fig. 6 is that the modified silicon nitride ceramics film of the present embodiment is dredged
Water angle test chart.
As seen from Figure 5, the modification silicon nitride ceramics film after the present embodiment modification, silicon nitride grain is by nano particle packet
It covers, forms nanometer protrusion.
As seen from Figure 6, the hydrophobic angle test of the modification silicon nitride ceramics film after the present embodiment modification, contact angle are
140 degree, hydrophobic structure is formd, has achieved the purpose that hydrophobic modification is modified.
Thermal stability and chemical stability test, modification nitridation have been carried out to the modification silicon nitride ceramics film of the present embodiment
Silicon ceramic membrane hydrophobic angle slightly decreases after 500 DEG C of calcinings.Decline respectively in the NaOH solution for being impregnated into boiling water and 0.01M
6 ° and 5 °, hydrophobic angle is almost unchanged in the hydrochloric acid of benzene and 0.01M.
Embodiment 3
The present embodiment provides a kind of modification methods of ceramic membrane comprising following steps:
Silicon nitride ceramics film is surface-treated, processing method by step 1 are as follows: silicon nitride ceramics film is put into saturation
30min is boiled in calcium hydroxide solution, with pure water washing and drying after taking-up, obtains fresh silicon nitride ceramics film；
The dimethyldichlorosilane of 5g dimethyl dichlorosilane (DMCS) and 5g is added in the ethyl alcohol of 10mL by step 2, and stirring is equal
It is even to obtain solution A；By above-mentioned fresh silicon nitride ceramics film immersion in solution A, drying is taken out；
Ceramic membrane after applying in step 2 is transferred to boron nitride porcelain boat, and boron nitride porcelain boat is placed in electricity by step 3
In the quartz chamber body for hindering silk furnace, carry out slow ammonia purging (ammonia speed is 100mL/min), it is complete by solid to ceramic membrane surface
Terminate after all standing, completes cladding on ceramic membrane surface at this time；Increase ammonia atmosphere (gas flow are as follows: 500mL/min), with
The heating rate of 5 DEG C/min is heat-treated, and is warming up to 600 DEG C and is kept the temperature Temperature fall after 1h, obtains changing through hydrophobic modification
Property silicon nitride ceramics film.
The modification silicon nitride ceramics film that the hydrophobic modification method of modifying that the present embodiment also provides above-mentioned ceramic membrane is prepared.
Electron microscope experiment and contact angle experiments are scanned to the modified silicon nitride ceramics film of the present embodiment.As a result such as Fig. 7 and Fig. 8
It is shown.Fig. 7 is the SEM figure of the modified silicon nitride ceramics film surface of the present embodiment；Fig. 8 is that the modified silicon nitride ceramics film of the present embodiment is dredged
Water angle test chart.
As seen from Figure 7, the modification silicon nitride ceramics film after the present embodiment modification, the inorganic hydrophobic substance of formation is no longer
It is nano particle formula, but forms film, is attached to silicon nitride crystal surface.
As seen from Figure 8, the hydrophobic angle test of the modification silicon nitride ceramics film after the present embodiment modification, contact angle are
136 degree, hydrophobic structure is formd, has achieved the purpose that hydrophobic modification is modified.
Thermal stability and chemical stability test, modification nitridation have been carried out to the modification silicon nitride ceramics film of the present embodiment
Silicon ceramic membrane hydrophobic angle slightly decreases after 500 DEG C of calcinings.Decline respectively in the NaOH solution for being impregnated into boiling water and 0.01M
5 ° and 3 °, hydrophobic angle is almost unchanged in the hydrochloric acid of benzene and 0.01M.
Embodiment 4
The present embodiment provides a kind of modification methods of ceramic membrane comprising following steps:
Silicon nitride ceramics film is surface-treated, processing method by step 1 are as follows: silicon nitride ceramics film is put into 1mol/L
Sodium hydroxide solution in boil 3h, with pure water washing and drying after taking-up, obtain fresh silicon nitride ceramics film；
The dimethyldichlorosilane of 2.5g dimethyl dichlorosilane (DMCS) and 2.5g is added in the ethyl alcohol of 10mL, stirs by step 2
It mixes and uniformly obtains solution A；By above-mentioned fresh silicon nitride ceramics film immersion in solution A, drying is taken out；
Ceramic membrane after coating filmform in step 2 is transferred to boron nitride porcelain boat, and boron nitride porcelain boat is set by step 3
In in the quartz chamber body of resistance wire furnace, carrying out slow ammonia purging (ammonia speed is 100mL/min), consolidated to ceramic membrane surface
Body terminates after being completely covered, and completes cladding on ceramic membrane surface at this time；It is heat-treated, is risen with the heating rate of 3 DEG C/min
Temperature is to 700 DEG C and keeps the temperature Temperature fall after 0.5h, obtains the modified ceramic film through hydrophobic modification.
The modification silicon nitride ceramics film that the hydrophobic modification method of modifying that the present embodiment also provides above-mentioned ceramic membrane is prepared.
Electron microscope experiment and contact angle experiments are scanned to the modified silicon nitride ceramics film of the present embodiment.As a result such as Fig. 9 and figure
Shown in 10.Fig. 9 is the SEM figure of the modified silicon nitride ceramics film surface of the present embodiment；Figure 10 is the modified silicon nitride ceramics of the present embodiment
Film hydrophobic angle test chart.
As seen from Figure 9, the modification silicon nitride ceramics film after the present embodiment modification, silicon nitride grain is by nano particle packet
It covers, particle is shown slightly unevenly, but hydrophobic effect is good.
As seen from Figure 10, the hydrophobic angle test of the modification silicon nitride ceramics film after the present embodiment modification, contact angle are
133 degree, hydrophobic structure is formd, has achieved the purpose that hydrophobic modification is modified.
Thermal stability and chemical stability test, modification nitridation have been carried out to the modification silicon nitride ceramics film of the present embodiment
Silicon ceramic membrane hydrophobic angle slightly decreases after 500 DEG C of calcinings.Decline respectively in the NaOH solution for being impregnated into boiling water and 0.01M
4 ° and 2 °, hydrophobic angle is almost unchanged in the hydrochloric acid of benzene and 0.01M.
Embodiment 5
The present embodiment provides a kind of hydrophobic modification method of modifying of ceramic membrane comprising following steps:
Sialon ceramic membrane is surface-treated, processing method by step 1 are as follows: Sialon ceramic membrane is put into 5mol/L
Potassium hydroxide solution in boil 30min, with pure water washing and drying after taking-up, obtain fresh Sialon ceramic membrane；
2.5g dimethyl dichlorosilane (DMCS) is added in the normal heptane of 10mL, is uniformly mixing to obtain solution A by step 2, will be upper
It states fresh Sialon ceramic membrane to be impregnated in solution A, takes out drying；
Ceramic membrane after applying in step 2 is transferred to boron nitride porcelain boat, and boron nitride porcelain boat is placed in electricity by step 3
In the quartz chamber body for hindering silk furnace, slow ammonia purging (ammonia speed is 100mL/min) is carried out, to Sialon ceramic membrane surface quilt
Solid terminates after being completely covered, and completes cladding on ceramic membrane surface at this time；Be changed to nitrogen atmosphere (gas flow are as follows:
400mL/min), be heat-treated with the heating rate of 5 DEG C/min, be warming up to 600 DEG C and keep the temperature Temperature fall after 1h, obtain through
The modification Sialon ceramic membrane of hydrophobic modification.
The modification Sialon ceramic membrane that the hydrophobic modification method of modifying that the present embodiment also provides above-mentioned ceramic membrane is prepared.
Electron microscope experiment and hydrophobic angle experiment are scanned to the modified Sialon ceramic membrane of the present embodiment.As a result such as Figure 11 and figure
Shown in 12.Figure 11 is the SEM figure of the modified Sialon ceramic membrane surface of the present embodiment；Figure 12 is the modified Sialon ceramics of the present embodiment
Film hydrophobic angle test chart.
As seen from Figure 11, the modification Sialon ceramic membrane after the present embodiment modification, forms on the surface of ceramic crystalline grain
One layer of clad includes nutty structure and cladding membrane structure.Under heating state, chlorosilane can be changed into gas by liquid
State, in the ammonia for touching ceramic membrane surface, it may occur that ammonolysis reaction forms solid-state macromolecular structure, on the surface of ceramic membrane
Deposition growing film forming.It is pyrolyzed after heat treatment, forms inorganic hydrophobic structure clad.
As seen from Figure 12, the hydrophobic angle test of the modification Sialon ceramic membrane after the present embodiment modification, hydrophobic angle are
140 degree, hydrophobic structure is formd, has achieved the purpose that hydrophobic modification is modified.
Thermal stability and chemical stability test, the modification have been carried out to the modification Sialon ceramic membrane of the present embodiment
Sialon ceramic membrane hydrophobic angle slightly decreases after 400 DEG C of calcinings.Be impregnated into boiling water, 0.01M NaOH solution, benzene and
Decline 10 °, 8 °, 6 ° and 5 ° in the hydrochloric acid of 0.01M respectively.
Embodiment 6
The present embodiment provides a kind of hydrophobic modification method of modifying of ceramic membrane comprising following steps:
Sialon ceramic membrane is surface-treated, processing method by step 1 are as follows: Sialon ceramic membrane is put into 5mol/L
Sodium hydroxide solution in boil 30min, with pure water washing and drying after taking-up, obtain fresh Sialon ceramic membrane；
3mL dimethyl silicone polymer is added in the normal heptane of 25mL by step 2, and the positive silicic acid tetrem of 1mL is then added
Dibutyl tin dilaurate 0.5mL is added dropwise under stirring condition, is uniformly mixing to obtain solution A for rouge, and above-mentioned fresh Sialon is made pottery
In porcelain film immersion and solution A, drying is taken out；；
Ceramic membrane after applying in step 2 is transferred to boron nitride porcelain boat, and boron nitride porcelain boat is placed in electricity by step 3
In the quartz chamber body for hindering silk furnace, under nitrogen atmosphere (gas flow are as follows: 300mL/min), carried out with the heating rate of 3 DEG C/min
Heat treatment, is warming up to 500 DEG C and keeps the temperature Temperature fall after 1h, obtain the modification Sialon ceramic membrane through hydrophobic modification.
The modification Sialon ceramic membrane that the hydrophobic modification method of modifying that embodiment also provides above-mentioned ceramic membrane is prepared.
Electron microscope experiment and hydrophobic angle experiment are scanned to the modified Sialon ceramic membrane of the present embodiment.As a result such as Figure 13 and figure
Shown in 14.Figure 13 is the SEM figure of the modified Sialon ceramic membrane surface of the present embodiment；Figure 14 is the modified Sialon ceramics of the present embodiment
Film hydrophobic angle test chart.
As seen from Figure 13, the modification Sialon ceramic membrane after the present embodiment modification, forms on the surface of ceramic crystalline grain
It include the clad of particle and cladding membrane structure.Under heating state, the dimethyl silicone polymer of ceramic membrane surface is pyrolyzed
Process forms inorganic hydrophobic structure clad.
As seen from Figure 14, the hydrophobic angle test of the modification Sialon ceramic membrane after the present embodiment modification, hydrophobic angle are
140 degree, hydrophobic structure is formd, has achieved the purpose that hydrophobic modification is modified.
Chemical stability test is carried out to the modification Sialon ceramic membrane of the present embodiment, by modification Sialon ceramic membrane
The variation of its hydrophobic angle is tested after being impregnated into the hydrochloric acid solution of 100mg/L humic acid solution, the NaOH solution of 0.01M and 0.01M
Situation is totally submerged 100mg/L humic acid solution (a in Figure 15), the NaOH solution of 0.01M (in Figure 15 as shown in figure 15
C) and the hydrochloric acid solution of 0.01M in (d in Figure 15), the modification Sialon ceramic membrane hydrophobic angle after 24 hours has dropped respectively
2 °, 2 ° and 5 °, and the hydrophobic angle for being impregnated in benzene the modification Sialon ceramic membrane of (b in Figure 15) does not change substantially, shows
Good chemical stability out.Modification Sialon ceramic membrane hydrophobic angle slightly decreases after 500 DEG C of calcinings.
Embodiment 7
The present embodiment provides a kind of hydrophobic modification method of modifying of ceramic membrane comprising following steps:
Alumina ceramic membrane is surface-treated by step 1, processing method are as follows: alumina ceramic membrane is put into 2mol/L
Sodium hydroxide solution in heat 30min, with pure water washing and drying after taking-up, obtain fresh alumina ceramic membrane；
3mL dimethyl silicone polymer is dissolved into 25mL normal heptane by step 2, and 1mL tetraethyl silicate resin is then added,
Dibutyl tin dilaurate 0.5mL is added dropwise under stirring condition, obtains solution A；Above-mentioned fresh alumina ceramic membrane is impregnated in
In solution A, drying is taken out；
Ceramic membrane after applying in step 2 is transferred to boron nitride porcelain boat, and boron nitride porcelain boat is placed in electricity by step 3
In the quartz chamber body for hindering silk furnace, under nitrogen protection atmosphere (gas flow are as follows: 400mL/min), with the heating rate of 5 DEG C/min
It is heat-treated, is warming up to 600 DEG C and keeps the temperature Temperature fall after 1h, obtain the modified aluminas ceramic membrane through hydrophobic modification.
The present embodiment also provides the modified aluminas ceramic membrane that the hydrophobic modification method of modifying of above-mentioned ceramic membrane is prepared.
Electron microscope experiment and hydrophobic angle experiment are scanned to the present embodiment modified aluminas ceramic membrane.As a result such as Figure 16 and figure
Shown in 17.Figure 16 is that the SEM of the present embodiment modified aluminas ceramic membrane surface schemes；Figure 17 is the present embodiment modified aluminas ceramics
Film hydrophobic angle test chart.
As seen from Figure 16, the modified aluminas ceramic membrane after the present embodiment modification, forms on the surface of ceramic crystalline grain
It include the clad of grain structure.Under heating state, the dimethyl silicone polymer pyrolytic process of ceramic membrane surface is formed
Inorganic hydrophobic structure clad.
As seen from Figure 17, the hydrophobic angle test of the modified aluminas ceramic membrane after the present embodiment modification, hydrophobic angle are
130 degree, hydrophobic structure is formd, has achieved the purpose that hydrophobic modification is modified.
Chemical stability test has been carried out to the modified aluminas ceramic membrane of the present embodiment, has been totally submerged 100mg/L corruption
In the hydrochloric acid solution for growing acid solution, the NaOH solution of 0.01M and 0.01M, modified aluminas ceramic membrane after 24 hours it is hydrophobic
Angle has dropped 5 °, 7 ° and 6 ° respectively, and the hydrophobic angle for the modified aluminas ceramic membrane being impregnated in benzene does not change substantially, shows
Good chemical stability out.The modified aluminas ceramic membrane hydrophobic angle slightly decreases after 500 DEG C of calcinings.
Embodiment 8
The present embodiment provides a kind of hydrophobic modification method of modifying of ceramic membrane comprising following steps:
Titanium dioxide ceramic film is surface-treated, processing method by step 1 are as follows: ceramic membrane is put into the hydrogen of 1mol/L
10min is boiled in sodium hydroxide solution, with pure water washing and drying after taking-up, obtains fresh titanium dioxide ceramic film；
The dimethyldichlorosilane of 2.5g dimethyl dichlorosilane (DMCS) and 2.5g is added in the ethyl alcohol of 10mL, stirs by step 2
It mixes and uniformly obtains solution A；By above-mentioned fresh titanium dioxide ceramic film immersion in solution A, drying is taken out；It will be new after dipping
Fresh titanium dioxide ceramic film carries out slow ammonia purging (ammonia speed is 100mL/min), aluminium ceramic membrane surface quilt to be oxidized
Solid terminates after being completely covered；
Ceramic membrane after coating filmform in step 2 is transferred to boron nitride porcelain boat, and boron nitride porcelain boat is set by step 3
In in the quartz chamber body of resistance wire furnace, carrying out slow ammonia purging (ammonia speed is 100mL/min), consolidated to ceramic membrane surface
Body terminates after being completely covered, and completes cladding on ceramic membrane surface at this time；Increase ammonia atmosphere (gas flow are as follows: 300mL/
Min), it is heat-treated with the heating rate of 3 DEG C/min, is warming up to 600 DEG C and keeps the temperature Temperature fall after 1h, obtains repairing through hydrophobic
The modifying titanium dioxide ceramic membrane of decorations.
The modifying titanium dioxide ceramics that the hydrophobic modification method of modifying that the present embodiment also provides above-mentioned ceramic membrane is prepared
Film.
Hydrophobic angle test is carried out to the present embodiment modifying titanium dioxide ceramic membrane.As a result as shown in figure 18.
As seen from Figure 18, the modifying titanium dioxide ceramic membrane hydrophobic angle after the present embodiment modification is 143 degree, is formd
Hydrophobic structure has achieved the purpose that hydrophobic modification is modified.
Chemical stability test has been carried out to the modifying titanium dioxide ceramic membrane of the present embodiment, has been totally submerged 100mg/L
Modifying titanium dioxide ceramic membrane in the hydrochloric acid solution of humic acid solution, the NaOH solution of 0.01M and 0.01M after 24 hours is dredged
Water angle has dropped 8 °, 6 ° and 8 ° respectively, and the modifying titanium dioxide ceramic membrane hydrophobic angle being impregnated in benzene does not change substantially, exhibition
Reveal good chemical stability.The hydrophobic angle of the modifying titanium dioxide ceramic membrane slightly decreases after 500 DEG C of calcinings.
Embodiment 9
The present embodiment provides a kind of hydrophobic modification method of modifying of ceramic membrane comprising following steps:
Zirconia ceramics film is surface-treated, processing method by step 1 are as follows: ceramic membrane is put into the hydrogen-oxygen of 5mol/L
Change in sodium solution and boil 30min, with pure water washing and drying after taking-up, obtains fresh zirconia ceramics film；
3mL dimethyl silicone polymer is dissolved into 25mL normal heptane by step 2, and 1mL tetraethyl silicate resin is then added,
Dibutyl tin dilaurate 0.5mL is added dropwise under stirring condition, obtains solution A；By above-mentioned fresh zirconia ceramics film immersion in
In solution A, drying is taken out；
Ceramic membrane after coating filmform in step 2 is transferred to boron nitride porcelain boat, and boron nitride porcelain boat is set by step 3
In in the quartz chamber body of resistance wire furnace, under nitrogen protection atmosphere (gas flow are as follows: 300mL/min), with the heating of 3 DEG C/min
Rate is heat-treated, and is warming up to 600 DEG C and is kept the temperature Temperature fall after 1h, obtains the modified oxidized zircon ceramic through hydrophobic modification
Film.
Embodiment also provides the modified zirconia ceramic membrane that the hydrophobic modification method of modifying of above-mentioned ceramic membrane is prepared.
Hydrophobic angle test is carried out to the present embodiment modified zirconia ceramic membrane.As a result as shown in figure 19.
As seen from Figure 19, the modified zirconia ceramic membrane hydrophobic angle after the present embodiment modification is 135 degree, is formd thin
Water-bound has achieved the purpose that hydrophobic modification is modified.
Chemical stability test has been carried out to the modified zirconia ceramic membrane of the present embodiment, has been totally submerged 100mg/L corruption
Grow the modified zirconia ceramic membrane hydrophobic angle point in the hydrochloric acid solution of acid solution, the NaOH solution of 0.01M and 0.01M after 24 hours
7 °, 6 ° and 9 ° are not had dropped, and the hydrophobic angle for the modified zirconia ceramic membrane being impregnated in benzene does not change substantially, shows good
Good chemical stability.The modified zirconia ceramic membrane hydrophobic angle slightly decreases after 400 DEG C of calcinings.
In conclusion a kind of modification method of ceramic membrane provided by the invention has, modification is simple, raw material at
This is cheap, and modification not will cause the secondary pollution of environment；By the modified ceramic film of modification preparation relative to common are
Machine maintenance exterior material has the features such as long-time stability are high, anti acid alkali performance is strong, ultra-hydrophobicity.
Claims (15)
1. a kind of modification method of ceramic membrane comprising following steps:
Ceramic membrane is surface-treated by step 1, obtains fresh ceramic membrane；
Silane compound is coated to the surface of ceramic membrane by step 2 by infusion process or sedimentation；
Ceramic membrane after applying in step 2 is heat-treated under protective atmosphere, obtains after Temperature fall through repairing by step 3
The modified ceramic film of decorations；
Wherein, in step 1, the step of surface treatment are as follows: ceramic membrane is placed in strong base solution and boils 5-180min, then
Wash drying；
It further include being passed through the step of ammonia carries out ammonolysis after ceramic membrane surface applies silane compound in step 2；
The heat treatment is that the temperature of the ceramic membrane after coating is warming up to 300-800 DEG C with the rate of 0.5-6 DEG C/min, then
0.5-8h is kept the temperature again.
2. the modification method of ceramic membrane according to claim 1, which is characterized in that the strong base solution includes hydrogen-oxygen
Change one of potassium solution, sodium hydroxide solution and calcium hydroxide solution or a variety of combinations.
3. the modification method of ceramic membrane according to claim 2, it is characterised in that: the potassium hydroxide solution or hydrogen
The concentration of sodium hydroxide solution is 1-10mol/L；The calcium hydroxide solution is saturated solution.
4. the modification method of ceramic membrane according to claim 1, it is characterised in that: the silane compound includes
One of chlorosilane compound, alkoxy silane compound and silicon fluoride class compound or a variety of combinations.
5. the modification method of ceramic membrane according to claim 4, it is characterised in that: the silane compound includes
One of dimethyl dichlorosilane (DMCS), dimethyldichlorosilane, poly dimethyl dichlorosilane, dichlorophenyl silane and silicon fluoride are more
The combination of kind.
6. the modification method of ceramic membrane according to claim 4, it is characterised in that: the silane compound it is dense
Degree is 10-200g/L.
7. the modification method of ceramic membrane according to claim 1, it is characterised in that: in step 2, by silanes
The mode that compound is coated to ceramic membrane surface is infusion process, which is that silane compound is dissolved in solvent to obtain
Solution A, then ceramic membrane is impregnated in solution A, then take out drying.
8. the modification method of ceramic membrane according to claim 7, it is characterised in that: the solvent include normal heptane,
One of ethyl alcohol, acetone, acetonitrile and benzene or a variety of combinations.
9. the modification method of ceramic membrane according to claim 1, it is characterised in that: in step 2, by silanes
The mode that compound is coated to ceramic membrane surface is sedimentation, which is to deposit to ceramics after vaporizing silane compound
On the surface of film.
10. the modification method of ceramic membrane according to claim 1, which is characterized in that in step 3, heat treatment
Equipment is high temperature furnace, including alundum furnace, carbon shirt-circuiting furnace or tungsten coil furnace.
11. the modification method of ceramic membrane according to claim 1, which is characterized in that the flow of protective atmosphere is
100-500mL/min；Protective atmosphere includes reducing gas and/or non-reducing gas；Wherein, reducing gas includes hydrogen, ammonia
With one of methane or a variety of combinations；Non-reducing gas includes nitrogen and/or argon gas.
12. the modification method of ceramic membrane according to claim 11, which is characterized in that the protective atmosphere is ammonia
Gas or the protective atmosphere are the gaseous mixture of nitrogen and hydrogen composition, wherein hydrogen mole percent level is 1mol%.
13. the modification method of ceramic membrane according to claim 1, it is characterised in that: the ceramic membrane includes nitridation
Silicon ceramic membrane, Sialon ceramic membrane, alumina ceramic membrane, titanium dioxide ceramic film, zirconia ceramics film, silicon carbide ceramic membrane and
One of silicon oxide ceramics film or a variety of combinations.
14. the modified ceramic film that the modification method of the described in any item ceramic membranes of claim 1-13 is prepared.
15. modified ceramic film is as membrane separation assemblies in sea water desalination, water-oil separating or wastewater treatment described in claim 14
In application.
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| CN115414798B (en) * | 2022-08-19 | 2024-03-29 | 电子科技大学长三角研究院(湖州) | Preparation method and application of silicon nitride-based ceramic separation membrane with micro-nano composite fiber structure |
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