CN106187325B - Antifouling ceramics and preparation method thereof - Google Patents
Antifouling ceramics and preparation method thereof Download PDFInfo
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- CN106187325B CN106187325B CN201610532575.7A CN201610532575A CN106187325B CN 106187325 B CN106187325 B CN 106187325B CN 201610532575 A CN201610532575 A CN 201610532575A CN 106187325 B CN106187325 B CN 106187325B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
- C04B41/524—Multiple coatings, comprising a coating layer of the same material as a previous coating layer
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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Abstract
The present invention relates to a kind of antifouling ceramics and preparation method thereof.The antifouling ceramics include ceramic layer, bottoming unit, transition zone and the stain-proofing layer stacked gradually, the consistency of bottoming unit is less than the consistency of ceramic layer, and the side from close to the side of ceramic layer to far from ceramic layer, the consistency of bottoming unit is gradually reduced, bottoming unit includes the first prime coat being laminated on ceramic layer, the material of the material of first prime coat and the material identical of ceramic layer, transition zone includes nano silicon dioxide, and the material of stain-proofing layer is fluorochemical.The stain-proofing layer of upper antifouling ceramics is not easily to fall off.
Description
Technical field
The present invention relates to coating technique field, more particularly to a kind of antifouling ceramics and preparation method thereof.
Background technology
Currently, antifouling ceramics are will be on anti-soil film material vacuum vapor deposition and ceramic surface, so that ceramic surface is not allowed
It is easily dirty, but after long-time use, anti-soil film is easy to fall off.This is because ceramic surface and anti-soil film are to pass through Van der Waals force
Connection, this active force is extremely weak, is more easily damaged, so as to cause falling off for anti-soil film.
Invention content
Based on this, it is necessary to provide a kind of stain-proofing layer antifouling ceramics not easily to fall off.
In addition, further relating to a kind of preparation method of antifouling ceramics.
A kind of antifouling ceramics, including the ceramic layer, bottoming unit, transition zone and the stain-proofing layer that stack gradually, the bottoming list
The consistency of member is less than the consistency of the ceramic layer, and from close to the side of the ceramic layer to one far from the ceramic layer
The consistency of side, the bottoming unit is gradually reduced, and the bottoming unit includes the first bottoming being laminated on the ceramic layer
The material of layer, the material identical of the material and the ceramic layer of first prime coat, the transition zone includes nanometer titanium dioxide
The material of silicon, the stain-proofing layer is fluorochemical.
The material of the ceramic layer is selected from zirconium dioxide, alundum (Al2O3) and three oxidations two in one of the embodiments,
At least one of yttrium.
The fluorochemical is silicon fluoride, perfluoropolyether, fluorinated alkyl sulfonate or fluorine in one of the embodiments,
Carbon resin.
The thickness of first prime coat is 1~1000 nanometer in one of the embodiments,.
The bottoming unit further includes the second bottoming being laminated on first prime coat in one of the embodiments,
Layer, the material of second prime coat be selected from aluminium oxide, aluminium nitride, silicon nitride, silicon carbide, barium titanate, titanium oxide, zirconium oxide and
At least one of yttrium oxide, wherein the transition zone is laminated on second prime coat.
A kind of preparation method of antifouling ceramics, includes the following steps：
Bottoming unit is formed on ceramic layer, wherein close to the side of the ceramic layer to one far from the ceramic layer
The consistency of side, the bottoming unit is gradually reduced, and the bottoming unit includes the first bottoming being laminated on the ceramic layer
Layer, the material identical of the material and the ceramic layer of first prime coat；
Transition zone is formed on the bottoming unit, wherein the material of the transition zone includes nano silicon dioxide；
Stain-proofing layer is formed on the transition zone, wherein the material of the stain-proofing layer is fluorochemical.
Further include pair in one of the embodiments, before the step of forming the bottoming unit on the ceramic layer
The surface of the ceramic layer is polished, so that the roughness on the surface after the polishing of the ceramic layer is 0.1~50 nanometer.
The method for forming the bottoming unit on the ceramic layer in one of the embodiments, is vacuum sputtering or true
Sky vapor deposition；When vacuum sputtering forms the bottoming unit on the ceramic layer, power is 2000~4000W, and the work(
Rate gradually increases, and sputtering pressure is 0.1~1.5Pa, and 30~100 millimeters of target-substrate distance, argon flow amount is 100~250sccm,；When
When vacuum evaporation forms the bottoming unit on the ceramic layer, vacuum degree 10-1~10-6Pa, vapor deposition electric current be 100~
350 milliamperes, evaporation rate is 0.3~30nm/s, and the evaporation rate gradually increases.
The method for forming the transition zone on the bottoming unit in one of the embodiments, is vacuum sputtering or true
Sky vapor deposition；When vacuum sputtering forms the transition zone on the bottoming unit, power is 3000~4000W, sputtering pressure
For 0.5~2Pa, 30~100 millimeters of target-substrate distance, argon flow amount is 150~300sccm；When vacuum is steamed on the bottoming unit
When plating forms the transition zone, vacuum degree 10-1~10-6Pa, vapor deposition electric current be 150~400 milliamperes, evaporation rate be 0.1~
30nm/s。
The method for forming the stain-proofing layer on the transition zone in one of the embodiments, is vacuum evaporation；And institute
The technological parameter for stating vacuum evaporation is：Vacuum degree is 10-2~10-7Pa, vapor deposition electric current is 250~600 milliamperes, and evaporation rate is
0.1~30nm/s.
Above-mentioned antifouling ceramics are specifically laminated in the on ceramic layer by the way that bottoming unit, bottoming unit are arranged on ceramic layer
One prime coat, the consistency of bottoming unit are less than the consistency of ceramic layer, and in order to alleviate coating stress, from close to ceramic layer
Side to the side far from ceramic layer, the consistency of bottoming unit are gradually reduced, and the material identical of the first prime coat and ceramics
The material identical of layer so that the first prime coat can firmly be combined with ceramic layer, and the material of transition zone includes nano-silica
SiClx, since the molecular state of nano silicon dioxide is in tridimensional network, there is a large amount of different bond styles on surface
(there are 3 kinds of hydroxyls on the surface of general nano silicon dioxide to hydroxyl：Unmarried free silicone hydroxyl, adhesion association silicone hydroxyl and twin silicon hydroxyl
Base), since the material of bottoming unit is ceramic material, and ceramic material inherently contains metal oxide, i.e. bottoming unit contains
There are metal cation, the hydroxyl of nano-silica surface that can firmly be combined, be made with the metal cation of bottoming unit
It crossing between layer and bottoming unit and is keyed by chemistry so that transition zone is firmly combined with bottoming unit, meanwhile, by and in prevent
The material of pollution layer is fluorochemical, and dehydration can occur with the transition zone of nano-silica-containing for fluorochemical to tie
Siliceous functional group is synthesized, and the hydroxyl on the nano silicon dioxide in transition zone also can pass through dehydrogenation reaction shape with fluorochemical
It is also that stain-proofing layer and transition zone are greatly improved by chemistry key connection at siliceous functional group, i.e., between stain-proofing layer and transition zone
Binding force, in other words, the adjacent two layers of above-mentioned antifouling ceramics be all it is strong bonded together so that stain-proofing layer is not easy to take off
It falls.
Description of the drawings
Fig. 1 is the structural schematic diagram of the antifouling ceramics of an embodiment；
Fig. 2 is the flow chart of the preparation method of the antifouling ceramics of an embodiment.
Specific implementation mode
To facilitate the understanding of the present invention, below with reference to relevant drawings to invention is more fully described.In attached drawing
Give the preferred embodiment of the present invention.But the present invention can realize in many different forms, however it is not limited to herein
Described embodiment.Keep the understanding to the disclosure more saturating on the contrary, purpose of providing these embodiments is
It is thorough comprehensive.
Unless otherwise defined, all of technologies and scientific terms used here by the article and belong to the technical field of the present invention
The normally understood meaning of technical staff is identical.Used term is intended merely to description tool in the description of the invention herein
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term " and or " used herein includes one or more phases
Any and all combinations of the Listed Items of pass.
As shown in Figure 1, one kind antifouling ceramic 100, including the ceramic layer 110, bottoming unit 120, the transition zone that stack gradually
130 and stain-proofing layer 140.
The material of ceramic layer 110 be selected from aluminium oxide, aluminium nitride, silicon nitride, silicon carbide, barium titanate, titanium oxide, zirconium oxide and
At least one of yttrium oxide.The consistency of ceramic layer 110 is 96% or more.
The consistency of bottoming unit 120 is less than the consistency of ceramic layer 110, and the material of bottoming unit 120 is ceramic material.
Wherein, the side from close to the side of ceramic layer 110 to far from ceramic layer 110, the consistency of bottoming unit 120 are gradually reduced,
Bottoming unit 120 near ceramic layer 110 is close with 110 consistency of ceramic layer, is to preferably combine；Consistency reduces
It is in order to preferably chimeric with transition zone 130.Consistency near the side of ceramic layer 110 is 95% or more, bottoming unit
The consistency of 120 sides farthest from ceramic layer 110 is 90% or more.
Wherein, the thickness of bottoming unit 120 is 1~1000 nanometer.
Wherein, bottoming unit 120 includes the first prime coat 122 being laminated on ceramic layer 110 and is laminated in the first bottoming
The second prime coat 124 on layer 122.
The material identical of first prime coat 122 and ceramic layer 110, so that bottoming unit 120 can be secured with ceramic layer 110
Be bonded together.That is consistency of the first prime coat 122 close to the side of ceramic layer 110 is 95% or more.
The material of second prime coat 124 is selected from aluminium oxide, aluminium nitride, silicon nitride, silicon carbide, barium titanate, titanium oxide, oxidation
At least one of zirconium and yttrium oxide.
Wherein, the second prime coat 124 can be one, or multiple.The material of multiple second prime coats can phase
With can not also be identical.From a 122 farthest side of second prime coat 124 far from the first prime coat 122 of the first prime coat
Consistency be 90% or more.
Transition zone 130 is laminated on the second prime coat 124.The material of transition zone 130 includes nano silicon dioxide.And transition
The mass percentage of nano silicon dioxide in the material of layer 130 is 95~100%.Due to the molecularity of nano silicon dioxide
State is in tridimensional network, and there is the hydroxyl of a large amount of different bond styles, (surface of general nano silicon dioxide has 3 on surface
Kind hydroxyl：Unmarried free silicone hydroxyl, adhesion association silicone hydroxyl and twin silicone hydroxyl), and the hydroxyl energy of nano-silica surface
It is enough firmly to be combined with the metal cation of bottoming unit 120.In addition, nano silicon dioxide has been also impossible in preparation process
Full dehydration, and itself also easily adsorbs water, but also there is a large amount of hydroxyl on the surface of nano silicon dioxide.
Wherein, the grain size of nano silicon dioxide is 8~40 nanometers.
A small amount of aluminium oxide, yttrium oxide and zirconium oxide can also be contained in the material of transition zone 130.Wherein, transition zone 130
Thickness be 1~500 nanometer.
The material of stain-proofing layer 140 is fluorochemical.With nano silicon dioxide dehydration can occur for fluorochemical
To be combined into siliceous functional group, the binding force of stain-proofing layer 140 and transition zone 130 is greatly improved, as shown in formula (1)：
(formula 1)
Meanwhile the hydroxyl on the nano silicon dioxide in transition zone 130 can also be given birth to fluorochemical by dehydrogenation reaction
At siliceous functional group, as shown in formula (2)：
(formula 2)
Wherein, fluorochemical is silicon fluoride, perfluoropolyether, fluorinated alkyl sulfonate or fluorocarbon resin.Wherein, perfluor alkane
Base sulfonate can be (SO)3Si-C8F17、(SO)3Si-C18F37Or (SO)3Si-C5F11。
Wherein, the roughness of stain-proofing layer 140 is at 30 nanometers or more.The thickness of stain-proofing layer 140 is 1~500 nanometer；Stain-proofing layer
140 hardness is more than or equal to 2H；Pure water contact angle >=80 ° on 140 surface of stain-proofing layer；The hexadecane on 140 surface of stain-proofing layer connects
Feeler >=50 °.
In other embodiments, bottoming unit 120 may also be only one layer, at this point, the material of bottoming unit 120 and ceramics
The material identical of layer 110.At this point, transition zone 120 is directly laminated on bottoming unit 120.
For above-mentioned antifouling ceramics by the way that bottoming unit 120 is arranged on ceramic layer 110, bottoming unit 120 is specifically laminated in pottery
The first prime coat 122 on enamel coating 110, the consistency of bottoming unit 120 are less than the consistency of ceramic layer 110, and in order to alleviate
Coating stress, and the side from close to the side of ceramic layer 110 to far from ceramic layer 110, the consistency of bottoming unit 120 are gradual
Reduce, and the material identical of the material identical and ceramic layer 110 of the first prime coat 122 so that the first prime coat 122 can be with pottery
Enamel coating firmly combines, and the material of transition zone 130 includes nano silicon dioxide, since the molecular state of nano silicon dioxide is in
Tridimensional network, there is the hydroxyl of a large amount of different bond styles, (there are 3 kinds of hydroxyls on the surface of general nano silicon dioxide on surface
Base：Unmarried free silicone hydroxyl, adhesion association silicone hydroxyl and twin silicone hydroxyl), since the material of bottoming unit is ceramic material, and
Ceramic material inherently contains metal oxide, i.e. bottoming unit contains metal cation, the hydroxyl of nano-silica surface
It is firmly combined with the metal cation of bottoming unit 120, makes to connect by chemical bond between transition zone 130 and bottoming unit 120
It connecing so that transition zone 130 is firmly combined with bottoming unit 120, simultaneously as the material of stain-proofing layer 140 is fluorochemical,
Dehydration can occur with the transition zone 130 of nano-silica-containing for fluorochemical to be combined into siliceous functional group, and mistake
The hydroxyl on nano silicon dioxide crossed in layer 130 also can form siliceous functional group with fluorochemical by dehydrogenation reaction, i.e.,
It is also that the knot of stain-proofing layer 140 and transition zone 130 is greatly improved by chemistry key connection between stain-proofing layer 140 and transition zone 130
With joint efforts, in other words, above-mentioned antifouling ceramic 100 adjacent two layers be all it is strong bonded together so that stain-proofing layer 140 is not easy
It falls off.
And since the nano silicon dioxide in transition zone 130 can be with the fluorine of the end of the fluorochemical of stain-proofing layer 140
Change alkyl to combine so that above-mentioned antifouling ceramic 100 stain-proofing layer 140 has preferable wear-resisting property.
As shown in Fig. 2, the preparation method of the antifouling ceramics of an embodiment, can be used for preparing above-mentioned antifouling ceramics.This is anti-
The preparation method of dirty ceramics includes the following steps：
Step S210：Bottoming unit is formed on ceramic layer.
Wherein, the material of ceramic layer is selected from aluminium oxide, aluminium nitride, silicon nitride, silicon carbide, barium titanate, titanium oxide, zirconium oxide
And at least one of yttrium oxide.
Wherein, the consistency of bottoming unit is less than the consistency of ceramic layer.From close to the side of ceramic layer to separate ceramics
The side of layer, the consistency of bottoming unit are gradually reduced.
Wherein, bottoming unit includes the first prime coat being laminated on ceramic layer and be laminated on the first prime coat second
Prime coat.
The material identical of first prime coat and ceramic layer, so that bottoming unit can be securely bonded to one with ceramic layer
It rises.Consistency of first prime coat close to the side of ceramic layer is 95% or more.
The material of second prime coat is selected from aluminium oxide, aluminium nitride, silicon nitride, silicon carbide, barium titanate, titanium oxide, zirconium oxide
And at least one of yttrium oxide.The cause of a second prime coat side far from first prime coat farthest from the first prime coat
Density is 90% or more.
Wherein, the thickness of bottoming unit is 1~1000 nanometer.
Wherein, further include being polished to the surface of ceramic layer before the step of forming bottoming unit on ceramic layer, with
It is 0.1~50 nanometer to make the roughness on the surface after the polishing of ceramic layer, to be conducive to form bottoming on the surface of ceramic layer
Layer.
Wherein, the method being polished to the surface of ceramic layer is in mechanical polishing, chemical polishing and electrobrightening
It is at least one.
Wherein, the method that bottoming unit is formed on ceramic layer is vacuum sputtering or vacuum evaporation；When true on ceramic layer
When sky sputtering forms bottoming unit, power is 2000~4000W, and power gradually increases, and sputtering pressure is 0.1~1.5Pa, target
30~100 millimeters of cardinal distance, argon flow amount are 100~250sccm.Power gradually increases so that the consistency of prime coat gradually subtracts
It is small.
When vacuum evaporation forms bottoming unit on ceramic layer, vacuum degree 10-1~10-6Pa, vapor deposition electric current are 100
~350 milliamperes, evaporation rate is 0.3~30nm/s, and evaporation rate gradually increases, so that the consistency of prime coat is gradually reduced.
Step S220：Transition zone is formed on bottoming unit.
Wherein, the material of transition zone includes nano silicon dioxide.The grain size of nano silicon dioxide is 8~40 nanometers.
And the mass percentage of the nano silicon dioxide in the material of transition zone is 95~100%.Wherein, transition zone
Thickness is 1~500 nanometer.
Wherein, the method that transition zone is formed on prime coat is vacuum sputtering or vacuum evaporation；When true on bottoming unit
When sky sputtering forms transition zone, power is 3000~4000W, and sputtering pressure is 0.5~2Pa, 30~100 millimeters of target-substrate distance, argon
Throughput is 150~300sccm；When vacuum evaporation forms transition zone on bottoming unit, vacuum degree 10-1~10-6Pa,
It is 150~400 milliamperes that electric current, which is deposited, and evaporation rate is 0.1~30nm/s.
When bottoming unit is one layer, the material identical of the material and ceramic layer of entire bottoming unit.At this point, directly beating
Transition zone is formed in bill kept on file member.
Step S230：Stain-proofing layer is formed on transition zone.
Wherein, the thickness of stain-proofing layer is 1~500 nanometer.The material of stain-proofing layer is fluorochemical.Fluorochemical is fluorine
Silane, perfluoropolyether, fluorinated alkyl sulfonate or fluorocarbon resin.Wherein, fluorinated alkyl sulfonate can be (SO)3Si-C8F17、
(SO)3Si-C18F37Or (SO)3Si-C5F11。
Wherein, the method that stain-proofing layer is formed on transition zone is vacuum evaporation.The technological parameter of vacuum evaporation is：Vacuum degree
It is 10-2~10-7Pa, vapor deposition electric current are 250~600 milliamperes, and evaporation rate is 0.1~30nm/s.
Wherein, the roughness of stain-proofing layer is at 50 nanometers or less；The hardness of stain-proofing layer is more than or equal to 9H；Antifouling layer surface it is pure
100 ° of water contact angle ＞.
The preparation method of above-mentioned antifouling ceramics is simple, and obtained antifouling ceramic stain-proofing layer is not easily to fall off.
It is specific embodiment part below：
Embodiment 1
The preparation process of the antifouling ceramics of the present embodiment is as follows：
(1) surface of cleaning ceramic layer polishes the surface of ceramic layer using the method for mechanical polishing, so that ceramic layer
The roughness on surface is 35 nanometers.Wherein, the material of ceramic layer is zirconium oxide, and the consistency of ceramic layer is 96%.
(2) vacuum evaporation forms the first prime coat on the surface of ceramic layer after a polish, wherein vacuum degree 10-3Pa,
It is 220 milliamperes that electric current, which is deposited, and starting evaporation rate is 0.3nm/s, and evaporation rate gradually increases, and increases to after 3 hours
30nm/s, to obtain the first prime coat that consistency is gradually reduced on ceramic layer.The thickness of first prime coat is 500 nanometers.
Therein, the material of the first prime coat is zirconium oxide, and consistency of first prime coat close to the side of ceramic layer is 95%, far
The consistency of side from ceramic layer is 90%.
(3) vacuum evaporation forms transition zone on the first prime coat, wherein.Vacuum degree is 10-3Pa, vapor deposition electric current are 250
Milliampere, evaporation rate 0.75nm/s.Wherein, the material of transition zone is nano silicon dioxide, and the grain size of nano silicon dioxide is 8
~30 nanometers.Wherein, the thickness of transition zone is 250 nanometers.
(4) vacuum evaporation forms the stain-proofing layer that thickness is 250 nanometers on transition zone, wherein vacuum degree 10-5Pa steams
It is 450 milliamperes to plate electric current, evaporation rate 0.95nm/s.Wherein, the material of stain-proofing layer is silicon fluoride.
The roughness of the stain-proofing layer of the antifouling ceramics of the present embodiment is tested using scarification；Using a stroke square method adhesive tape test
The hardness of the stain-proofing layer of the present embodiment, wherein 1B indicates there is strip peeling, and entire cubic grid along notching edge stain-proofing layer
Also there are peeling, the grid that area of infection is 35~65%；2B indicates that along notching edge and cubic grid, coating has peeling,
The grid that area of infection is 15~35%；3B indicates the intersection along notching edge and notch, there is a small amount of disbonding, by
The grid that influence area is 5~15%；4B indicates that intersection has a small amount of disbonding, but area of infection is less than 5%；5B tables
Show that notching edge is completely smooth, neither one four directions grid peels off；0B is indicated, peels off and stripping situation ratio 1B is even worse；It adopts
The pure water contact angle on the surface of the stain-proofing layer of the antifouling ceramics of the present embodiment is tested with sessile drop method；Using based on hang plate angle-measuring method
Test the hexadecane contact angle on the surface of the stain-proofing layer of the antifouling ceramics of the present embodiment；The present embodiment is tested using scarification
The binding force of stain-proofing layer and ceramic layer.
The roughness of the stain-proofing layer of the antifouling ceramics of the present embodiment, hardness, pure water contact angle, hexadecane contact angle and
The data of the binding force of stain-proofing layer and ceramic layer are shown in Table 1.
Embodiment 2
The preparation process of the antifouling ceramics of the present embodiment is as follows：
(1) surface of cleaning ceramic layer polishes the surface of ceramic layer using the method for chemical polishing, so that ceramic layer
The roughness on surface is 0.1 nanometer.Wherein, the material of ceramic layer is aluminium oxide, and the consistency of ceramic layer is 97%.
(2) vacuum evaporation forms the first prime coat on surface after a polish, wherein vacuum degree 10-1Electric current is deposited in Pa
Be 350 milliamperes, starting evaporation rate be 1nm/s, evaporation rate gradually increases, and increases to 25nm/s after 0.5 hour, with
The first prime coat that consistency is gradually reduced is obtained on ceramic layer.And first prime coat thickness be 1 nanometer.Wherein, first dozen
The material of bottom is aluminium oxide, and consistency of first prime coat close to the side of ceramic layer is 95%, one far from ceramic layer
The consistency of side is 92%.
(3) vacuum sputtering forms transition zone on the first prime coat, wherein power 3000W, sputtering pressure 2Pa, target
30 millimeters of cardinal distance, argon flow amount 150sccm；Wherein, the mass percentage of the nano silicon dioxide in the material of transition zone
It is 95%, and the grain size of nano silicon dioxide is 8~40 nanometers.Wherein, the thickness of transition zone is 1 nanometer.
(4) vacuum evaporation forms the stain-proofing layer that thickness is 1 nanometer on transition zone, wherein vacuum degree 10-2Pa, vapor deposition
Electric current is 600 milliamperes, evaporation rate 0.1nm/s.Wherein, the material of stain-proofing layer is perfluoropolyether.
Obtained using 1 identical test method of embodiment the roughness of the stain-proofing layer of the antifouling ceramics of the present embodiment, hardness,
The data of the binding force of pure water contact angle, hexadecane contact angle and stain-proofing layer and ceramic layer are shown in Table 1.
Embodiment 3
The preparation process of the antifouling ceramics of the present embodiment is as follows：
(1) surface of cleaning ceramic layer polishes the surface of ceramic layer using the method for electrobrightening, so that ceramic layer
The roughness on surface is 50 nanometers.Wherein, the material of ceramic layer is yttrium oxide, and the consistency of ceramic layer is 96.5%.
(2) surface vacuum after a polish sputters to form prime coat, wherein initial power 2000W, and power gradually increases
Greatly, power is 4000W, sputtering pressure 1.5Pa, 100 millimeters, argon flow amount 100sccm of target-substrate distance, to make pottery after 5 hours
The prime coat that consistency is gradually reduced is obtained on enamel coating.Wherein, the thickness of prime coat is 1000 nanometers.The material of first prime coat
For yttrium oxide, and consistency of first prime coat close to the side of ceramic layer is 96%, the consistency of the side far from ceramic layer
It is 94%.
(3) vacuum sputtering forms transition zone on the first prime coat, wherein power 4000W, sputtering pressure 0.5Pa,
100 millimeters of target-substrate distance, argon flow amount 300sccm.Wherein, the material of transition zone is nano silicon dioxide, and nanometer titanium dioxide
The grain size of silicon is 20~40 nanometers.The thickness of transition zone is 500 nanometers.
(4) vacuum evaporation forms the stain-proofing layer that thickness is 500 nanometers on transition zone, wherein vacuum degree 10-7Pa steams
It is 250 milliamperes to plate electric current, evaporation rate 30nm/s.Wherein, the material of stain-proofing layer is (SO)3Si-C8F17。
Obtained using 1 identical test method of embodiment the roughness of the stain-proofing layer of the antifouling ceramics of the present embodiment, hardness,
The data of the binding force of pure water contact angle, hexadecane contact angle and stain-proofing layer and ceramic layer are shown in Table 1.
Embodiment 4
The preparation process of the antifouling ceramics of the present embodiment is as follows：
(1) then the surface of cleaning ceramic layer is then thrown the surface of ceramic layer first using mechanically polishing using electrolysis
Light, so that the roughness on the surface of ceramic layer is 40 nanometers.Wherein, the material of ceramic layer is aluminium oxide and zirconium oxide, ceramic layer
Consistency be 96%.
(2) surface vacuum after a polish is deposited to form the first prime coat, wherein vacuum degree 10-6Pa, vapor deposition electric current are
100 milliamperes, starting evaporation rate is 0.95nm/s, and evaporation rate gradually increases, and evaporation rate is 15nm/s after 5 hours, with
The first prime coat that consistency is gradually reduced is obtained on ceramic layer.And first prime coat thickness be 1000 nanometers.Wherein,
The material of one prime coat is zirconium oxide and aluminium oxide, and consistency of first prime coat close to the side of ceramic layer is 95%, far
The consistency of side from ceramic layer is 90%.
(3) vacuum evaporation forms transition zone on the first prime coat, wherein vacuum degree 10-1Pa, vapor deposition electric current are 150
Milliampere, evaporation rate 30nm/s.Wherein, the thickness of transition zone is 100 nanometers.The material of transition zone is nano silicon dioxide,
And the grain size of nano silicon dioxide is 25~30 nanometers.
(4) vacuum evaporation forms the stain-proofing layer that thickness is 200 nanometers, vacuum degree 10 on transition zone-7Electric current is deposited in Pa
It is 250 milliamperes, evaporation rate 1.25nm/s.Wherein, the material of stain-proofing layer is (SO)3Si-C18F37。
Obtained using 1 identical test method of embodiment the roughness of the stain-proofing layer of the antifouling ceramics of the present embodiment, hardness,
The data of the binding force of pure water contact angle, hexadecane contact angle and stain-proofing layer and ceramic layer are shown in Table 1.
Embodiment 5
The preparation process of the antifouling ceramics of the present embodiment is as follows：
(1) then the surface of cleaning ceramic layer is then thrown the surface of ceramic layer first using mechanically polishing using electrolysis
Light is using chemical polishing, so that the roughness on the surface of ceramic layer is 30 nanometers.Wherein, the material of ceramic layer be zirconium oxide,
The consistency of aluminium oxide and yttrium oxide, ceramic layer is 96%.
(2) when surface vacuum after a polish sputters to form the first prime coat, initial power 3000W, and power is gradual
Increase, 4000W, sputtering pressure 0.1Pa, 30 millimeters, argon flow amount 250sccm of target-substrate distance, to make pottery are increased to after 3 hours
The first prime coat that consistency is gradually reduced is obtained on enamel coating.And first prime coat thickness be 200 nanometers.Wherein, first dozen
The material of bottom is the material of ceramic layer, and consistency of first prime coat close to the side of ceramic layer is 95.5%, far from ceramics
The consistency of the side of layer is 93%.
(3) vacuum evaporation forms transition zone on the first prime coat, wherein vacuum degree 10-6Pa, vapor deposition electric current are 400
Milliampere, evaporation rate 0.1nm/s.Wherein, the mass percentage of the nano silicon dioxide in the material of transition zone is 98%,
And the grain size of nano silicon dioxide is 15~35 nanometers.The thickness of transition zone is 200 nanometers.
(4) vacuum evaporation forms the stain-proofing layer that thickness is 300 nanometers on transition zone, wherein vacuum degree 10-3Pa steams
It is 450 milliamperes to plate electric current, evaporation rate 10nm/s, wherein the material of stain-proofing layer is fluorocarbon resin.
Obtained using 1 identical test method of embodiment the roughness of the stain-proofing layer of the antifouling ceramics of the present embodiment, hardness,
The data of the binding force of pure water contact angle, hexadecane contact angle and stain-proofing layer and ceramic layer are shown in Table 1.
Embodiment 6
The preparation process of the antifouling ceramics of the present embodiment is as follows：
(1) surface of cleaning ceramic layer polishes the surface of ceramic layer using the method for mechanical polishing, so that ceramic layer
The roughness on surface is 45 nanometers.The material of ceramic layer is aluminium nitride, silicon nitride and silicon carbide, and the consistency of ceramic layer is
96%.
(2) surface vacuum after a polish sputters to form the first prime coat, initial power 2000W, and power gradually increases,
3000W, sputtering pressure 1Pa, 50 millimeters of target-substrate distance, argon flow amount 200sccm, in ceramic layer are increased to after 1 hour
On obtain the first prime coat that consistency is gradually reduced.Wherein, the material of the first prime coat is the material of ceramic layer, the first bottoming
Consistency of the layer close to the side of ceramic layer is 95%, and the thickness of the first prime coat is 100 nanometers.
(3) the second prime coat of vacuum sputtering on the first prime coat, initial power 3000W, power gradually increase, and 1 is small
When after increase to 4000W, sputtering pressure 1Pa, 50 millimeters, argon flow amount 200sccm of target-substrate distance, in the first prime coat
On obtain the second prime coat that consistency is gradually reduced.Wherein, the material of the second prime coat is barium titanate, and the second prime coat is separate
The consistency of the side of first prime coat is 91%, and the thickness of the second prime coat is 300 nanometers.
(4) vacuum sputtering forms transition zone, power 3500W, sputtering pressure 1Pa, target-substrate distance on the second prime coat
80 millimeters, argon flow amount 250sccm.Wherein, the material of transition zone is nano silicon dioxide, and the grain size of nano silicon dioxide
It is 18~40 nanometers.Wherein, the thickness of transition zone is 50 nanometers.
(4) vacuum evaporation forms the stain-proofing layer that thickness is 400 nanometers, vacuum degree 10 on transition zone-4Electric current is deposited in Pa
It is 300 milliamperes, evaporation rate 0.5nm/s.Wherein, the material of stain-proofing layer is (SO)3Si-C5F11。
Obtained using 1 identical test method of embodiment the roughness of the stain-proofing layer of the antifouling ceramics of the present embodiment, hardness,
The data of the binding force of pure water contact angle, hexadecane contact angle and stain-proofing layer and ceramic layer are shown in Table 1.
Embodiment 7
The preparation process of the antifouling ceramics of the present embodiment is as follows：
(1) surface of cleaning ceramic layer polishes the surface of ceramic layer using the method for mechanical polishing, so that ceramic layer
The roughness on surface is 45 nanometers.The material of ceramic layer is titanium oxide, aluminium nitride, aluminium oxide and zirconium oxide, the densification of ceramic layer
Degree is 96%.
(2) surface vacuum after a polish sputters to form the first prime coat, initial power 2000W, and power gradually increases,
2500W, sputtering pressure 1Pa, 50 millimeters of target-substrate distance, argon flow amount 200sccm, in ceramics are increased to after 0.5 hour
The first prime coat that consistency is gradually reduced is obtained on layer.Wherein, the material of the first prime coat be ceramic layer material, first dozen
Consistency of the bottom close to the side of ceramic layer is 95.5%, and the thickness of the first prime coat is 50 nanometers.
(3) one the second prime coat of vacuum sputtering, initial power 2500W, power gradually increase on the first prime coat,
3000W, sputtering pressure 1Pa, 50 millimeters, argon flow amount 200sccm of target-substrate distance, at first dozen are increased to after 1 hour
First the second prime coat that consistency is gradually reduced is obtained on bottom.Wherein, the material of the second prime coat be barium titanate, second
The thickness of prime coat is 100 nanometers.
(4) vacuum sputtering forms another the second prime coat on the second prime coat, initial power 3000W, power by
It is cumulative big, increase to 3500W after 2 hours, sputtering pressure 1Pa, 20 millimeters, argon flow amount 200sccm of target-substrate distance, with
Second the second prime coat that consistency is gradually reduced is obtained on first the second prime coat.Wherein, the material of the second prime coat
Consistency for aluminium nitride, side of second prime coat far from the first prime coat is 91%, and the thickness of the second prime coat is received for 250
Rice
(5) the vacuum sputtering formation transition zone on second the second prime coat, power 3500W, sputtering pressure 1Pa,
80 millimeters of target-substrate distance, argon flow amount 250sccm.Wherein, the material of transition zone is nano silicon dioxide, and nano silicon dioxide
Grain size be 18~40 nanometers.Wherein, the thickness of transition zone is 50 nanometers.
(6) vacuum evaporation forms the stain-proofing layer that thickness is 400 nanometers, vacuum degree 10 on transition zone-6Electric current is deposited in Pa
It is 300 milliamperes, evaporation rate 0.5nm/s.Wherein, the material of stain-proofing layer is (SO)3Si-C5F11。
Obtained using 1 identical test method of embodiment the roughness of the stain-proofing layer of the antifouling ceramics of the present embodiment, hardness,
The data of the binding force of pure water contact angle, hexadecane contact angle and stain-proofing layer and ceramic layer are shown in Table 1.
Embodiment 8
The preparation process of the antifouling ceramics of the present embodiment is as follows：
(1) surface of cleaning ceramic layer polishes the surface of ceramic layer using the method for mechanical polishing, so that ceramic layer
The roughness on surface is 45 nanometers.The material of ceramic layer is barium titanate, and the consistency of ceramic layer is 97%.
(2) surface vacuum after a polish sputters to form the first prime coat, initial power 2000W, and power gradually increases,
2200W, sputtering pressure 1Pa, 50 millimeters of target-substrate distance, argon flow amount 200sccm, in ceramics are increased to after 0.5 hour
The first prime coat that consistency is gradually reduced is obtained on layer.Wherein, the material of the first prime coat be ceramic layer material, first dozen
Consistency of the bottom close to the side of ceramic layer is 94%, and the thickness of the first prime coat is 50 nanometers.
(3) one the second prime coat of vacuum evaporation on the first prime coat, wherein vacuum degree 10-4Pa, vapor deposition electric current are
220 milliamperes, starting evaporation rate is 0.3nm/s, and evaporation rate gradually increases, and increases to 10nm/s after 3 hours, with the
First the second prime coat that consistency is gradually reduced is obtained on one prime coat.Wherein, the material of the second prime coat be aluminium oxide,
The consistency of aluminium nitride and silicon carbide, side of second prime coat far from the first prime coat is 91%, the thickness of the second prime coat
It is 200 nanometers.
(4) vacuum evaporation forms another the second prime coat on the second prime coat, wherein vacuum degree 10-4Pa, vapor deposition
Electric current is 220 milliamperes, and starting evaporation rate is 10nm/s, and evaporation rate gradually increases, and increase to after 2 hours 20nm/s with
Second the second prime coat that consistency is gradually reduced is obtained on first the second prime coat.Wherein, second the second bottoming
The material of layer is silicon nitride, titanium oxide, zirconium oxide and yttrium oxide.The thickness of second the second prime coat is 300 nanometers.
(5) vacuum sputtering forms the second prime coat of third on the second prime coat, wherein vacuum degree 10-4Pa, vapor deposition
Electric current is 220 milliamperes, and starting evaporation rate is 20nm/s, and evaporation rate gradually increases, and increases to 30nm/s after 2 hours,
To obtain the second prime coat of third that consistency is gradually reduced on second the second prime coat.Wherein, third second dozen
The material of bottom is aluminium nitride and barium titanate, and the consistency of side of second prime coat far from the first prime coat is 91%, third
The thickness of a second prime coat is 300 nanometers.
(6) the vacuum sputtering formation transition zone on the second prime coat of third, power 3500W, sputtering pressure 1Pa,
80 millimeters of target-substrate distance, argon flow amount 250sccm.Wherein, the material of transition zone is nano silicon dioxide, and nano silicon dioxide
Grain size be 18~40 nanometers.Wherein, the thickness of transition zone is 50 nanometers.
(7) vacuum evaporation forms the stain-proofing layer that thickness is 400 nanometers, vacuum degree 10 on transition zone-5Electric current is deposited in Pa
It is 300 milliamperes, evaporation rate 0.5nm/s.Wherein, the material of stain-proofing layer is (SO)3Si-C5F11。
Obtained using 1 identical test method of embodiment the roughness of the stain-proofing layer of the antifouling ceramics of the present embodiment, hardness,
The data of the binding force of pure water contact angle, hexadecane contact angle and stain-proofing layer and ceramic layer are shown in Table 1.
Comparative example 1
The preparation process of the antifouling ceramics of comparative example 1 is：
(1) surface of cleaning ceramic layer polishes the surface of ceramic layer using the method for mechanical polishing, so that ceramic layer
The roughness on surface is 35 nanometers.Wherein, the material of ceramic layer is zirconium oxide, and the consistency of ceramic layer is 96%.
(2) it is 250 nanometers of stain-proofing layer that vacuum evaporation, which forms thickness, on ceramic layer after a polish, wherein vacuum degree is
10-5Pa, vapor deposition electric current are 450 milliamperes, evaporation rate 0.95nm/s.Wherein, the material of stain-proofing layer is silicon fluoride.
Obtained using 1 identical test method of embodiment the roughness of the stain-proofing layer of the antifouling ceramics of comparative example 1, hardness,
The data of the binding force of pure water contact angle, hexadecane contact angle and stain-proofing layer and ceramic layer are shown in Table 1.
In table 1 be respectively Examples 1 to 6 it is antifouling ceramics and comparative example 1 antifouling ceramics stain-proofing layer roughness, firmly
The data of the binding force of degree, pure water contact angle, hexadecane contact angle and stain-proofing layer and ceramic layer.
Table 1
From table 1 it follows that the roughness of the stain-proofing layer of the antifouling ceramics of Examples 1 to 6 is all higher than or equal to comparison
The hardness of example 1, the antifouling ceramics of Examples 1 to 6 is at least 9H, is all higher than the antifouling ceramics of comparative example 1, and Examples 1 to 6
The pure water contact angle of antifouling ceramics is within the scope of 100~110 °, and hexadecane contact angle is within the scope of 60~70 °, i.e. embodiment 1
The binding force of~6 antifouling ceramics is best, and in above-mentioned pure water contact angle and hexadecane contact angular region, pure water contact angle
Bigger with hexadecane contact angle, binding force is better.
Meanwhile the binding force of the antifouling ceramics of Examples 1 to 6 is at least 3B, and comparative example 1 only has 1B, it is clear that implement
The antifouling ceramics tool of example 1~6 is well bonded.
Each technical characteristic of embodiment described above can be combined arbitrarily, to keep description succinct, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, it is all considered to be the range of this specification record.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection of the present invention
Range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. a kind of antifouling ceramics, which is characterized in that including ceramic layer, bottoming unit, transition zone and the stain-proofing layer stacked gradually, institute
The consistency for stating bottoming unit is less than the consistency of the ceramic layer, and from close to the side of the ceramic layer to the separate pottery
The consistency of the side of enamel coating, the bottoming unit is gradually reduced, and the bottoming unit includes being laminated on the ceramic layer
First prime coat, the material identical of the material and the ceramic layer of first prime coat, the material of the transition zone include to receive
The material of rice silica, the stain-proofing layer is fluorochemical.
2. antifouling ceramics according to claim 1, which is characterized in that the material of the ceramic layer is selected from aluminium oxide, nitridation
At least one of aluminium, silicon nitride, silicon carbide, barium titanate, titanium oxide, zirconium oxide and yttrium oxide.
3. antifouling ceramics according to claim 1, which is characterized in that the fluorochemical be silicon fluoride, perfluoropolyether,
Fluorinated alkyl sulfonate or fluorocarbon resin.
4. antifouling ceramics according to claim 1, which is characterized in that the thickness of first prime coat is received for 1~1000
Rice.
5. antifouling ceramics according to claim 1, which is characterized in that the bottoming unit further includes being laminated in described first
The material of the second prime coat on prime coat, second prime coat is selected from aluminium oxide, aluminium nitride, silicon nitride, silicon carbide, metatitanic acid
At least one of barium, titanium oxide, zirconium oxide and yttrium oxide, wherein the transition zone is laminated on second prime coat.
6. a kind of preparation method of antifouling ceramics, which is characterized in that include the following steps：
Bottoming unit is formed on ceramic layer, wherein close to the side of the ceramic layer to the side far from the ceramic layer, institute
The consistency for stating bottoming unit is gradually reduced, and the bottoming unit includes the first prime coat being laminated on the ceramic layer, institute
State the material identical of the material and the ceramic layer of the first prime coat；
Transition zone is formed on the bottoming unit, wherein the material of the transition zone includes nano silicon dioxide；
Stain-proofing layer is formed on the transition zone, wherein the material of the stain-proofing layer is fluorochemical.
7. the preparation method of antifouling ceramics according to claim 6, which is characterized in that described in being formed on the ceramic layer
Further include being polished to the surface of the ceramic layer, so that after the polishing of the ceramic layer before the step of bottoming unit
The roughness on surface is 0.1~50 nanometer.
8. the preparation method of antifouling ceramics according to claim 6, which is characterized in that described in being formed on the ceramic layer
The method of bottoming unit is vacuum sputtering or vacuum evaporation；When vacuum sputtering forms the bottoming unit on the ceramic layer
When, power is 2000~4000W, and the power gradually increases, and sputtering pressure is 0.1~1.5Pa, 30~100 milli of target-substrate distance
Rice, argon flow amount are 100~250sccm；When vacuum evaporation forms the bottoming unit on the ceramic layer, vacuum degree is
10-1~10-6Pa, vapor deposition electric current are 100~350 milliamperes, and evaporation rate is 0.3~30nm/s, and the evaporation rate gradually increases
Greatly.
9. the preparation method of antifouling ceramics according to claim 6, which is characterized in that form institute on the bottoming unit
The method for stating transition zone is vacuum sputtering or vacuum evaporation；When vacuum sputtering forms the transition zone on the bottoming unit
When, power be 3000~4000W, sputtering pressure be 0.5~2Pa, 30~100 millimeters of target-substrate distance, argon flow amount be 150~
300sccm；When vacuum evaporation forms the transition zone on the bottoming unit, vacuum degree 10-1~10-6Pa, vapor deposition electricity
Stream is 150~400 milliamperes, and evaporation rate is 0.1~30nm/s.
10. the preparation method of antifouling ceramics according to claim 6, which is characterized in that form institute on the transition zone
The method for stating stain-proofing layer is vacuum evaporation；And the technological parameter of the vacuum evaporation is：Vacuum degree is 10-2~10-7Pa, vapor deposition
Electric current is 250~600 milliamperes, and evaporation rate is 0.1~30nm/s.
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