CN109485459A - A kind of Nano tube of zirconium dioxide film coating of zirconia ceramics coating surface and the preparation method and application thereof - Google Patents
A kind of Nano tube of zirconium dioxide film coating of zirconia ceramics coating surface and the preparation method and application thereof Download PDFInfo
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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
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- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
- A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
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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
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
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Abstract
The invention discloses Nano tube of zirconium dioxide film coatings of a kind of zirconia ceramics coating surface and the preparation method and application thereof.The film coating includes zirconium micron membranes and ZrO2Nanotube layer, zirconium micron membranes are located at the zirconia ceramics and ZrO2Between nanotube layer, respectively with zirconia ceramics and ZrO2Nanotube layer engagement, for connecting zirconia ceramics and ZrO2Nanotube layer.The present invention is first plated with zirconium film on zirconia ceramics surface with ion-plating technique, then zirconium membrane part is oxidized to ZrO by anodic oxidation2Nanotube.After the present invention combines physical coating and electrochemical oxidation method, the film coating of nano tube structure is successfully prepared on the extremely strong zirconia ceramics surface of chemical inertness, bonding agent is effectively increased in zirconia ceramics wettability of the surface, the adhesive strength of zirconia ceramics and bonding agent can be remarkably reinforced, the adhesive property for greatly improving zirconia ceramics, realizes its wider clinical application in dental prosthesis.
Description
Technical field
The present invention relates to field of nanometer material technology, and in particular to the Nano tube of zirconium dioxide film of zirconia ceramics coating surface
Coating and the preparation method and application thereof.
Background technique
Dental zirconium oxide All-ceramic material (i.e. zirconia ceramics) is because it is with good mechanical property, aesthetic properties and biology
Compatibility is mainly used as dentistry crowns and bridges as a kind of ceramic material being most widely used in the aesthetic orthopaedics treatment of dental caries
The preferred material of body, the dummy made of the material are known as zirconium oxide ceramic dental crown bridge prosthesis.Zirconium oxide ceramic dental
Crowns and bridges external surface is in dental morphology, and inner surface is Nian Jie with the tooth after polishing preparation.
However zirconium oxide belongs to chemical inertness ceramic-like materials, limit the features such as by its compact structure and low chemical activity
System, zirconium oxide ceramic dental crown bridge prosthesis are clinically difficult to obtain ideal lasting bonding force, and bonding failure rate is higher, at
For one of the principal element for influencing its clinical application effect.
It has a large amount of researchs for improving zirconia ceramics adhesive property both at home and abroad, is modified to its surface, it is existing
There is the surface modifying method of zirconia ceramics to have air sand blower, laser-induced thermal etching, thermochemical method etc..These methods are by removal portion
Divide zirconium oxide ingredient to realize to " cutting down formula " roughening treatment on zirconia ceramics surface, can not only reduce zirconia ceramics certainly
Body mechanical strength, it is also limited to the raising effect of adhesive strength between zirconia ceramics and resin adhesive.
Summary of the invention
The purpose of the present invention is being directed to technological deficiency existing in the prior art, in a first aspect, a kind of coating is provided, the painting
Layer is in the ZrO of zirconia ceramics coating surface2Nano-tube film, adhesive strength significantly increase.The zirconia ceramics surface
The ZrO of plating2Nano-tube film coating, the film coating include zirconium micron membranes and ZrO2Nanotube layer, zirconium micron membranes are located at institute
State zirconia ceramics and ZrO2Between nanotube layer, respectively with zirconia ceramics and ZrO2Nanotube layer engagement, for connecting oxidation
Zircon ceramic and ZrO2Nanotube layer；Preferably, the ZrO2Nanotube layer is by ZrO2It is micro- that nanotube is arranged in zirconium in the form of an array
It is formed on rice film.
The thin film coating thicknesses are 500nm-2.5 μm, preferably 800nm-2 μm.
The ZrO2Nanotube caliber is 50-700nm, preferably 200-500nm, more preferable 300-500nm.
Zirconium dioxide is in tetragonal phase and monocline crystal phase in the film coating.
The film coating is using metal zirconium (Zr) as ion film plating target, first through ion plating method in zirconia ceramics
Surface is plated with zirconium (Zr) film, then with NH4F, water and ethylene glycol prepare electrolyte, respectively to plate the zirconia ceramics and graphite of zirconium film
For anode and cathode, the zirconium membrane part on zirconia ceramics surface is oxidized to by ZrO by anodizing2Nanotube layer, not by
The zirconium film of oxidation is as zirconium micron membranes and ZrO2The ZrO is collectively formed in nanotube layer2Nano-tube film coating.
Second aspect, the present invention provide a kind of preparation method of above-mentioned Nano tube of zirconium dioxide film coating, are included in oxygen
Change zircon ceramic surface and through ion plating method be plated with zirconium (Zr) film, through anodizing by the zirconium membrane part oxygen on zirconia ceramics surface
Turn to ZrO2Nanotube layer.
The ion plating method specifically: zirconia ceramics is swung wash, dry after, using vacuum coating equipment, with metal zirconium
(Zr) it is used as ion film plating target, zirconium film is plated on zirconia ceramics surface, obtains the zirconia ceramics for being coated with zirconium film；
Preferably, ion film plating parameter is base vacuum 2 × 10-3Pa, 200 DEG C of coating temperature, working gas is Ar gas, work
Make gas atmosphere be 0.8Pa, on-load voltage electric current be 21V, 80A, continuous coating 1-4 hours.
The anodizing specifically: the zirconia ceramics of zirconium film will be coated with as anode, graphite is as cathode, submergence
In the electrolytic solution, 30-50V constant DC voltage is loaded between anodic-cathodic, reacts 10-20min, zirconium membrane part is oxidized to
ZrO2Nanotube layer；
Preferably, the electrolyte is by NH4F is dissolved in the aqueous solution that water is made into 0.1-0.5wt%, and second two is then added
Alcohol obtains after stirring so that volumn concentration of the aqueous solution in ethylene glycol is 1vol%.
The third aspect, the present invention provide a kind of zirconia ceramics repair materials, have in the zirconia ceramics coating surface
Above-mentioned ZrO2Nano-tube film coating.
Fourth aspect, the present invention provides a kind of zirconium oxide ceramic dental crown bridge prosthesis, including is made of zirconia ceramics
Corona shape crown bridge prosthesis ontology, on the zirconia ceramics coating surface on the inside of the corona shape crown bridge prosthesis ontology has
State ZrO2Nano-tube film coating.
5th aspect, the present invention provide above-mentioned zirconia ceramics repair materials and are preparing zirconium oxide ceramic dental crowns and bridges
Application in body.
The present invention provides Nano tube of zirconium dioxide film coating of zirconia ceramics coating surface and preparation method thereof and answers
With being put forward for the first time and be plated with zirconium (Zr) film on zirconia ceramics surface with ion-plating technique, then by anodic oxidation by the ceramics
The zirconium membrane part on surface is oxidized to the ZrO of nano tubular structure2, as on zirconia ceramics surface, " growth " has gone out ZrO2Nanometer
Pipe.The present invention is by combining physical coating and electrochemical oxidation method, successfully in the extremely strong zirconium oxide pottery of chemical inertness
The film coating of nano tube structure is prepared on porcelain surface, effectively increases bonding agent in zirconia ceramics wettability of the surface, can
The adhesive strength of zirconia ceramics and bonding agent is remarkably reinforced, greatly improves the adhesive property of dental zirconium oxide ceramics, plays
Its wider clinical effectiveness.
Detailed description of the invention
Fig. 1 show the ZrO of zirconia ceramics coating surface of the present invention2The structural schematic diagram of nano-tube film coating；
Fig. 2 show the x-ray diffraction pattern for the Nano tube of zirconium dioxide film coating that embodiment 1 obtains；
Fig. 3, which is shown, is plated with ZrO2The zirconia ceramics of nano-tube film coating and the ultra small scale manufacture adhesive strength of bonding agent
Histogram；
Fig. 4 show ZrO in the Nano tube of zirconium dioxide film coating of embodiment 12The electromicroscopic photograph of nano-tube array；
Fig. 5 show ZrO in the Nano tube of zirconium dioxide film coating of embodiment 22The electromicroscopic photograph of nano-tube array；
Fig. 6 show bonding agent and is being plated with ZrO2The dynamic contact angle on the zirconia ceramics surface of nano-tube film coating
Curve graph；
Fig. 7, which is shown, is plated with ZrO2The three-point bending resistance intensity histograms of the zirconia ceramics of nano-tube film coating.
Specific embodiment
Currently, enamel can form honeycomb enamel fiber nano array structure by phosphoric acid acid etching, so as to resin
The bonding agent of material forms good adhesive effect.However, extensive as corona dummy in extremely strong, dentistry for chemical inertness
The zirconia ceramics used, and if how in zirconia ceramics surface simulation building enamel honeycomb enamel fiber nano-array
Structure is research original intention of the invention, especially constructs one layer on zirconia ceramics surface and do not destroy zirconia ceramics surface
" growth formula " coating of structure, rather than " cutting down formula " roughened surface is target of the inventor in exploratory development.
In the research of dentistry material, TiO can be prepared in the surfaces externally and internally of pure titanium implant by anodizing2
Nanotube, to effectively improve Integrated implant (Lv L, Liu Y, Zhang P, the et al.The nanoscale of planting body
geometry of TiO2nanotubes influences the osteogenic differentiation of human
adipose-derived stem cells by modulating H3K4trimethylation.[J].Biomaterials,
2015,39:193.).But the technology is applicable only to pure metal (such as pure titanium) surface, in the high dental zirconium oxide of chemical inertness
Ceramic surface " growth " nanotube, especially ZrO2Nano-pipe array thin film is not reported so far.
This invention address that probing into zirconia ceramics surface " growth " ZrO2Nano-pipe array thin film, by numerous studies
It is put forward for the first time a kind of Nano tube of zirconium dioxide film coating of zirconia ceramics coating surface, structure is as shown in Figure 1, the dioxy
Change zirconium nano-tube film coating 2 and be plated on 1 surface of zirconia ceramics, Nano tube of zirconium dioxide film coating 2 includes zirconium micron membranes 4
And ZrO2Nanotube layer 3, zirconium micron membranes 4 are located at zirconia ceramics 1 and ZrO2Between nanotube layer 3, and and ZrO2Nanotube layer 3
It is connected with zirconia ceramics 1.This is because ZrO2Nanotube layer 3 is that zirconium micron membranes 4 aoxidize to obtain through anode part, therefore also
The not oxidized zirconium micron membranes 4 in part are for connecting ZrO2Nanotube layer 3 and zirconia ceramics 1.Zirconium dioxide in film coating 2
In tetragonal phase and monocline crystal phase, ZrO2ZrO in nanotube layer 32Nanotube arranges in the form of an array, caliber 50-700nm, excellent
Select 200-500nm, more preferable 300-500nm.Nano tube of zirconium dioxide film coating 2 with a thickness of 500nm-2.5 μm, preferably
800nm-2μm.When defect of teeth or absence of tooth patient need to carry out zirconium oxide crowns and bridges, by the Nano tube of zirconium dioxide
The plating of film coating 2 is overlying on zirconium oxide ceramic dental crown bridge prosthesis inner surface, recycles the bonding agent of resinae by zirconium oxide
Ceramic dental crown bridge prosthesis carried out with enamel or dentine it is be bonded, complete zirconium oxide ceramic dental crown bridge prosthesis wear into
With cementation, achievees the purpose that restore tooth body anatomic form and rebuild meshing functionss.
The invention also provides the preparation sides of the Nano tube of zirconium dioxide film coating of the above zirconia ceramics coating surface
Method, using dental zirconium oxide ceramics as substrate, high purity metal Zr (99.9%) is used as ion film plating target, first uses ion film plating
Method is plated with zirconium (Zr) film on zirconia ceramics surface, then with NH4F, water and ethylene glycol prepare electrolyte, to plate the zirconium oxide of zirconium film
Ceramics and graphite are respectively anode and cathode, and the zirconium membrane part of ceramic surface is oxidized to ZrO by anodizing2Nanometer
Pipe, just looks like that " growth " goes out ZrO on zirconia ceramics surface2Nanotube.
Wherein, the principle of ion plating method are as follows: under vacuum conditions, gas discharge ionizes Zr atomic component, Zr from
Son is bombarded and is deposited on to zirconia ceramics surface, and the metal zirconium film of uniform compact is formed.The principle of anodizing
Are as follows: using high pure metal Zr piece as anode, graphite it is that cathode is inserted in organic electrolyte, certain direct current is added between the two poles of the earth
Pressure, reaction can grow ZrO on Zr piece surface after a certain period of time2Nano-tube array.First in the ion plating of zirconia ceramics surface
It is the metal Zr film in order to make electric conductivity is extremely low under room temperature zirconia ceramics surface deposition compact that embrane method, which is plated with zirconium (Zr) film,
To have good electric conductivity, alternative high pure metal Zr piece participates in anode as anode in the anodizing of next step
Oxidation reaction, so that " growth " goes out ZrO on zirconia ceramics surface2Nano-tube film coating.
By taking dental zirconium oxide potsherd as an example, ZrO is prepared2The process of nano-tube film coating specifically includes the following steps:
(1), the ion film plating of zirconium oxide
Dental zirconium oxide potsherd is after through deionized water, acetone, ethyl alcohol, successively ultrasound swings and washes, dries, lay flat be fixed on it is true
In empty coating machine reaction warehouse, ion film plating is carried out to the one side of zirconia ceramics piece upward.Adjustment filming parameter is base vacuum 2
×10-3Pa, 200 DEG C of coating temperature, working gas Ar gas (100%, 100sccm), operating air pressure 0.8Pa, 99.9% high-purity
Zr target on-load voltage electric current: 21V/80A continuous coating 1-4 hours in the above conditions, obtains the oxidation for being coated with uniform zirconium film
Zircon ceramic piece.
(2), anodic oxidation
Prepare electrolyte: by NH4F powder is dissolved in the aqueous solution that water is made into 0.1-0.5wt%, and ethylene glycol is then added, and makes
Obtaining volumn concentration of the aqueous solution in ethylene glycol is 1vol%, and magnetic agitation obtains electrolyte after 2 hours, injects electrolytic cell
In.The zirconia ceramics piece for being coated with zirconium film that step (1) is obtained is as anode, and graphite plate is as cathode, by zirconia ceramics
Piece is coated with the surface face cathode graphite of zirconium film, and is placed in parallel, and 30-50V constant DC voltage is loaded between anodic-cathodic, instead
Power supply is closed after answering 10-20min；It is successively swung with deionized water and dehydrated alcohol ultrasound after taking out zirconia ceramics piece and is washed 5min,
After dry 2h is placed in 50 DEG C of vacuum ovens obtain the zirconia ceramics that coating surface has Nano tube of zirconium dioxide film coating
Piece.
When needs are applied in corona shape zirconium oxide ceramic dental crown bridge prosthesis inner surface plating Nano tube of zirconium dioxide film
When layer, it is only necessary in step (1) ion film plating, by the occlusal surface court of corona shape crown bridge prosthesis ontology made of zirconia ceramics
Under, the corona shape crown bridge prosthesis body internal surface Nian Jie with tooth upward, using ion plating equipment to corona shape crowns and bridges
Body body internal surface carries out ion film plating, obtains the corona shape crown bridge prosthesis ontology that inner surface is coated with uniform zirconium film；Within table
Face is coated with the corona shape crown bridge prosthesis ontology of uniform zirconium film as anode, and graphite plate is as cathode, by corona shape crowns and bridges
Body ontology is coated with the inner surface face cathode graphite plate of zirconium film, and is placed in parallel, and it is constant straight that 30-50V is loaded between anodic-cathodic
Galvanic electricity pressure closes power supply after reacting 10-20min；Obtaining coating surface after ultrasound swings and washes and dry has Nano tube of zirconium dioxide
The zirconium oxide ceramic dental crown bridge prosthesis of film coating.
The Nano tube of zirconium dioxide film coating for being plated on zirconia ceramics surface is accredited as through X-ray diffraction (XRD)
The ZrO of tetragonal phase and monocline crystal phase2, electron scanning micrograph display zirconia ceramics surface, which is grown, ZrO2Nanotube
Array, average caliber is 50-700nm, and step instrument measures 500nm-2.5 μm of zirconium oxide nanotube thin film coating thicknesses.
Working principle of the present invention in zirconia ceramics coating surface Nano tube of zirconium dioxide film coating are as follows:
Zr(m)→Zr4++4e-Formula (1)
Zr4++4OH-→Zr(OH)4Formula (2)
Zr(OH)4-2H2O→ZrO2Formula (3)
By formula (1)-formula (3) it is found that under electric field action, the metal surface Zr of substrate can be quickly generated one layer it is new
ZrO2Oxide high-resistance barrier.Then the F in solution-And H+Start the ZrO to substrate2High-resistance barrier carries out simultaneously
Chemical attack and electrochemical corrosion form nano aperture structure under double action.
Below in conjunction with specific embodiment, the content of the present invention will be explained in more detail, and the present invention is further elaborated, but
These embodiments limit the invention absolutely not.
In order to detect the effect of embodiment in subsequent experimental, zirconia ceramics piece substitution oxygen is all made of in embodiment
Change the corona shape crown bridge prosthesis ontology of zircon ceramic dentistry crown bridge prosthesis.
Embodiment 1
1) zirconia ceramics surface ion plating
Dental zirconium oxide potsherd lies against Vacuum Deposition after successively ultrasound swings and washes, dries through deionized water, acetone, ethyl alcohol
In film machine reaction warehouse, make zirconia ceramics piece upward receive ion film plating on one side.Adjustment filming parameter be base vacuum 2 ×
10-3Pa, 200 DEG C of coating temperature, working gas Ar gas (100%, 100sccm), operating air pressure 0.8Pa, 99.9% high-purity Zr
Target on-load voltage electric current: 21V/80A, continuous coating 2.5 hours, obtain the zirconium oxide for being coated with uniform zirconium film in the above conditions
Potsherd.
2) anodic oxidation reactions
Prepare electrolyte: by NH4F, which is dissolved in deionized water, obtains NH4F concentration is the NH of 0.20%wt4F aqueous solution, then
To NH4Ethylene glycol is added in F aqueous solution, so that NH4Volumn concentration of the F aqueous solution in ethylene glycol is 1vol%, and magnetic force stirs
Electrolyte is obtained after mixing uniformly, and is injected into electrolytic cell.The zirconia ceramics piece for being coated with zirconium film that step (1) is obtained is made
For anode, zirconia ceramics piece is coated with the surface face graphite cathode of zirconium film as cathode by graphite plate, and is placed in parallel,
Constant Direct Current 30V voltage is loaded between anodic-cathodic, closes power supply after reacting 15min.Zirconia ceramics piece successively uses deionized water
It is swung with dehydrated alcohol ultrasound and washes 5min, be placed in 50 DEG C of vacuum ovens after dry 2h and obtain coating surface and have zirconium dioxide nanometer
The zirconia ceramics piece of pipe film coating.
The length of time of anodic oxidation is most important to preparing for zirconium oxide nanotube, lasting and sufficiently long anodic oxidation
Time could form nano tubular structure, but the too long reaction time can make nano-tube array by fluorine ion and hydrionic mistake
Degree corrodes and is damaged.
X-ray diffraction (XRD) detection is carried out to the zirconia ceramics piece surface after ion film plating, after anodic oxidation respectively,
As shown in Figure 2.Curve A is the X-ray diffraction on the zirconia ceramics piece surface after ion film plating as a result, identified ceramics in Fig. 2
The metal of on piece is metal Zr；In Fig. 2 curve B be anodic oxidation after zirconia ceramics piece surface X-ray diffraction as a result,
Zirconia ceramics on piece after identified anodic oxidation is ZrO2Nanotube, and be tetragonal phase and monocline crystal phase (in Fig. 2 " ■ "
Black square represents tetragonal phase, and "●" black circle represents monocline crystal phase).Electron scanning micrograph (as shown in Figure 4)
The growth of display zirconia ceramics surface has ZrO2Nano-tube array, average caliber 300nm.
Embodiment 2
1) zirconium film is plated in zirconia ceramics surface ion with 1 same procedure of embodiment
2) anodic oxidation reactions
It is only the constant DC voltage loaded between anodic-cathodic is 50V with embodiment 1.
Curve C is the X-ray diffraction on the zirconia ceramics piece surface after anodic oxidation as a result, identified anodic oxygen in Fig. 2
Zirconia ceramics on piece after changing reaction is the ZrO of tetragonal phase and monocline crystal phase2Nanotube.Electron scanning micrograph
Display zirconia ceramics surface growth (as shown in Figure 5) has ZrO2Nano-tube array, average caliber 500nm.
Embodiment 3
1) zirconium film is plated in zirconia ceramics surface ion with 1 same procedure of embodiment
2) anodic oxidation reactions
It is only the preparation of electrolyte specifically: by NH with embodiment 14F, which is dissolved in deionized water, obtains NH4F concentration is
The NH of 0.50wt%4F aqueous solution, then to NH4Ethylene glycol is added in F aqueous solution, so that NH4Volume of the F aqueous solution in ethylene glycol
Percentage composition is 1vol%, and magnetic agitation obtained electrolyte after 2 hours.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows that the growth of zirconia ceramics surface has ZrO2Nano-tube array, caliber
500-700nm。
Embodiment 4
1) zirconium film is plated in zirconia ceramics surface ion with 1 same procedure of embodiment
2) anodic oxidation reactions
It is only the preparation of electrolyte specifically: by NH with embodiment 14F, which is dissolved in deionized water, obtains NH4F concentration is
The NH of 0.10wt%4F aqueous solution, then to NH4Ethylene glycol is added in F aqueous solution, so that NH4Volume of the F aqueous solution in ethylene glycol
Percentage composition is 1vol%, and magnetic agitation obtained electrolyte after 2 hours.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows that there is ZrO on zirconia ceramics surface2Nanotube is formed, caliber 50-
100nm。
Embodiment 5
1) zirconium film is plated in zirconia ceramics surface ion with 1 same procedure of embodiment
2) anodic oxidation reactions
With embodiment 1, being only is 20min the anodic oxidation reactions time.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows that the growth of zirconia ceramics surface has ZrO2Nano-tube array, it is average
Caliber 500nm.
Embodiment 6
1) zirconium film is plated in zirconia ceramics surface ion with 1 same procedure of embodiment
2) anodic oxidation reactions
With embodiment 1, being only is 10min the anodic oxidation reactions time.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows that the growth of zirconia ceramics surface has ZrO2Nano-tube array, it is average
Caliber 100nm.
Embodiment 7
1) zirconia ceramics surface ion plating
With embodiment 1, being only is 1h the continuous coating time.
2) anodic oxidation reactions
With embodiment 1.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows that the growth of zirconia ceramics surface has ZrO2Nano-tube array, it is average
Caliber 300nm.
Embodiment 8
1) zirconia ceramics surface ion plating
With embodiment 1, being only is 4h the continuous coating time.
2) anodic oxidation reactions
With embodiment 1.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows that the growth of zirconia ceramics surface has ZrO2Nano-tube array, it is average
Caliber 450nm.
Embodiment 9
1) zirconia ceramics surface ion plating
With embodiment 1, being only is 2h the continuous coating time.
2) anodic oxidation reactions
With embodiment 1.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows that the growth of zirconia ceramics surface has ZrO2Nano-tube array, it is average
Caliber 400nm.
Embodiment 10
1) zirconia ceramics surface ion plating
With embodiment 1, being only is 3h the continuous coating time.
2) anodic oxidation reactions
With embodiment 1.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows that the growth of zirconia ceramics surface has ZrO2Nano-tube array, it is average
Caliber 350nm.
Comparative example 1
1) zirconia ceramics surface ion plating
With embodiment 1.
2) anodic oxidation reactions
It is only the preparation of electrolyte specifically: by NH with embodiment 14F, which is dissolved in deionized water, obtains NH4F concentration is
The NH of 0.05wt%4F aqueous solution, then to NH4Ethylene glycol is added in F aqueous solution, so that NH4Volume of the F aqueous solution in ethylene glycol
Percentage composition is 1vol%, and magnetic agitation obtained electrolyte after 2 hours.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is mainly metal
Zr, the ZrO of only a small amount of tetragonal phase2.Electron scanning micrograph shows zirconia ceramics surface without nano tube structure
Growth, it is seen that zirconium film is not corroded sufficiently by electrolyte, and zirconium membrane structure is also more complete, is oxidized to ZrO2Nanotube it is seldom,
The adhesive strength of itself and bonding agent can not be improved.
Comparative example 2
1) zirconia ceramics surface ion plating
With embodiment 1.
2) anodic oxidation reactions
It is only the preparation of electrolyte specifically: by NH with embodiment 14F, which is dissolved in deionized water, obtains NH4F concentration is
The NH of 0.60wt%4F aqueous solution, then to NH4Ethylene glycol is added in F aqueous solution, so that NH4Volume of the F aqueous solution in ethylene glycol
Percentage composition is 1vol%, and magnetic agitation obtained electrolyte after 2 hours.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is mainly cube
Phase ZrO2.Electron scanning micrograph shows that a small amount of ZrO is only left on zirconia ceramics surface2Nanotube, structure disturbance exist
A large amount of irregular cavities, the exposure of large area zirconia ceramics substrate, most of zirconium film and ZrO2Nano-tube array and zirconium oxide are made pottery
Porcelain sur-face peeling falls off, plating failure.
Comparative example 3
1) zirconia ceramics surface ion plating
With embodiment 1.
2) anodic oxidation reactions
With embodiment 1, being only is 8min the anodic oxidation reactions time.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is metal Zr.It sweeps
Retouching electron micrograph shows zirconia ceramics surface without ZrO2Nano-tube array is formed, and zirconium film corrodes not in the electrolytic solution
Foot, only there are a small amount of bowl configurations in visible zirconium film surface, can not improve the adhesive strength of itself and bonding agent.
Comparative example 4
1) zirconia ceramics surface ion plating
With embodiment 1.
2) anodic oxidation reactions
With embodiment 1, being only is 25min the anodic oxidation reactions time.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows the visible a large amount of flocculence complex compound coverings in zirconia ceramics surface
In nanotube surface and be jammed among nanotube lumen, it is difficult to observe nanotube pattern and diameter, can not improve its with it is bonding
The adhesive strength of agent.
Comparative example 5
1) zirconia ceramics surface ion plating
With embodiment 1.
2) anodic oxidation reactions
With embodiment 1, be only anodic oxidation reactions voltage be 60V.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows that the growth of zirconia ceramics surface has ZrO2Nano-tube array, it is average
Caliber 500nm, but visible a large amount of irregular cavities are formed in nano-tube array, and a large amount of nanometer tube walls have rupture defect,
The adhesive strength of itself and bonding agent can not be improved.
Comparative example 6
1) zirconia ceramics surface ion plating
With embodiment 1.
2) anodic oxidation reactions
With embodiment 1, be only anodic oxidation reactions voltage be 20V.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is tetragonal phase
With the ZrO of monocline crystal phase2.Electron scanning micrograph shows that there is a small amount of ZrO on zirconia ceramics surface2Nanotube is formed, average
Caliber 50nm or so, remaining ZrO2Itself and bonding agent can not be improved without obvious segment dislocation in the column structure of irregular structure
Adhesive strength.
Comparative example 7
1) zirconia ceramics surface ion plating
With embodiment 1, being only is 5h the continuous coating time.
2) anodic oxidation reactions
With embodiment 1.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is mainly cube
Phase ZrO2Ceramic bases and metal Zr.Electron scanning micrograph shows that there is a small amount of ZrO on zirconia ceramics surface2Nanotube is residual
It staying, average caliber 500nm, most of zirconium film and zirconia ceramics substrate are removed, and zirconium film falls off, exposure zirconia ceramics substrate,
Plating failure.
Comparative example 8
1) zirconia ceramics surface ion plating
With embodiment 1, being only is 0.5h the continuous coating time.
2) anodic oxidation reactions
With embodiment 1.
Qualification result: the zirconia ceramics on piece after X-ray diffraction (XRD) detection anodic oxidation reactions is mainly cube
Phase ZrO2Ceramic bases.Electron scanning micrograph shows zirconia ceramics surface without ZrO2Nanotube is formed, and zirconium membrane structure disappears
It loses, zirconia ceramics substrate is completely exposed, plating failure.
Experiment one: dental zirconium oxide ceramic surface ZrO2The adhesive property of nano-tube film coating detects
Detection method: there is ZrO using what universal testing machine test 1-10 of the embodiment of the present invention and comparative example 1-8 was obtained2
Adhesive strength between the zirconia ceramics of nanotube coatings and the bonding agent of resinae.Resin is detected using contact angle measurement
Bonding agent is in zirconia ceramics wettability of the surface.
It makes ultra small scale manufacture bonding test specimen production: being 0.8mm by internal diameter, the polyethylene pipe of high 2mm is fixed on ZrO2Nanotube
Coating surface or zirconia ceramics surface fill the resin dedicated bonding agent SA LUTING of dentistry, and photocuring in lumen
40s removes polyethylene tube wall, tests ultra small scale manufacture adhesive strength using universal testing machine.Using contact angle measurement, resin is detected
Dynamic contact angle of the bonding agent in sample surfaces.
Show embodiment 1 and embodiment 2 as sample as a result, in figure in figure: a) plating ZrO prepared by embodiment 12
The zirconia ceramics piece of nano-tube film coating；B) plating ZrO prepared by embodiment 22The zirconium oxide of nano-tube film coating is made pottery
Tile；C) the zirconia ceramics piece of aluminum oxide blast roughening treatment；D) without the zirconia ceramics piece of any surface treatment.
Fig. 3 shows the ultra small scale manufacture adhesive strength of different zirconia ceramics surfaces and resin adhesive.Fig. 6 shows resin bonding
Dynamic contact angle of the agent on zirconia ceramics surface.As can be seen from Figure, plating ZrO2The zirconium oxide of nano-tube film coating
Ceramics are higher with the ultra small scale manufacture adhesive strength of resin adhesive, and resin adhesive is in ZrO2The dynamic Contact on nanotube coatings surface
Angle is smaller.Illustrate: the ZrO that the present invention obtains2Nanotube coatings can be effective compared to the processing of conventional aluminium oxide blasted roughization
The wetability for improving zirconia ceramics and resin adhesive, to improve adhesive strength.
The experimental result of all laboratory samples is shown in Table 1.
The experimental result of table 1 experimental example 1-10 and comparative example 1-8
Test two, ZrO2Zirconia ceramics three-point bending resistance song intensity detection after nano-tube film coating treatment
Detection method: using universal testing machine test present invention gained plating ZrO2The zirconium oxide of nano-tube film coating is made pottery
The three-point bending resistance Qu Qiangdu of porcelain.
Test sample: a) plating ZrO prepared by embodiment 12The zirconia ceramics piece of nano-tube film coating；B) embodiment
The plating ZrO of 2 preparations2The zirconia ceramics piece of nano-tube film coating；C) the zirconium oxide pottery of aluminum oxide blast roughening treatment
Tile；D) without the zirconia ceramics piece of any surface treatment.Above four groups of zirconia ceramics pieces are prepared using cutting machine at a slow speed
At 20mm × 2mm × 4mm test specimen, three-point bending resistance Qu Qiangdu is tested using universal testing machine.
Testing result: referring to Fig. 7.Zirconia ceramics mechanical strength obviously drops after Fig. 7 shows aluminum oxide blast roughening treatment
It is low, and two kinds of plating ZrO prepared by the present invention2The zirconia ceramics mechanical strength of nano-tube film coating with without surface treatment oxygen
Change zircon ceramic no significant difference.
The result of other embodiments is no different with embodiment 2, will not repeat them here.
The above is only a preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications
Also the contents of the present invention be should be regarded as.
Claims (10)
1. a kind of ZrO of zirconia ceramics coating surface2Nano-tube film coating, which is characterized in that the film coating includes zirconium
Micron membranes and ZrO2Nanotube layer, zirconium micron membranes are located at the zirconia ceramics and ZrO2Between nanotube layer, respectively with zirconium oxide
Ceramics and ZrO2Nanotube layer engagement, for connecting zirconia ceramics and ZrO2Nanotube layer；Preferably, the ZrO2Nanotube
Layer is by ZrO2Nanotube is arranged on zirconium micron membranes in the form of an array and is formed.
2. ZrO according to claim 12Nano-tube film coating, which is characterized in that the thin film coating thicknesses are 500nm-
2.5 μm, preferably 800nm-2 μm.
3. ZrO according to claim 1 or claim 22Nano-tube film coating, which is characterized in that the ZrO2Nanotube caliber is
50-700nm, preferably 200-500nm, more preferable 300-500nm.
4. ZrO according to claim 32Nano-tube film coating, which is characterized in that zirconium dioxide is in the film coating
Tetragonal phase and monocline crystal phase.
5. -4 any ZrO according to claim 12Nano-tube film coating, which is characterized in that the film coating is with gold
Belong to zirconium (Zr) and be used as ion film plating target, is first plated with zirconium (Zr) film on zirconia ceramics surface through ion plating method, then with NH4F、
Water and ethylene glycol prepare electrolyte and pass through anodic oxidation respectively using the zirconia ceramics and graphite for plating zirconium film as anode and cathode
The zirconium membrane part on zirconia ceramics surface is oxidized to ZrO by method2Nanotube layer, not oxidized zirconium film as zirconium micron membranes and
ZrO2The ZrO is collectively formed in nanotube layer2Nano-tube film coating.
6. a kind of prepare any ZrO of claim 1-52The method of nano-tube film coating, which is characterized in that be included in oxygen
Change zircon ceramic surface and through ion plating method be plated with zirconium (Zr) film, through anodizing by the zirconium membrane part oxygen on zirconia ceramics surface
Turn to ZrO2Nanotube layer.
7. method according to claim 6, which is characterized in that the ion plating method specifically: zirconia ceramics, which is swung, to be washed,
After drying, using vacuum coating equipment, using metal zirconium (Zr) as ion film plating target, zirconium film is plated on zirconia ceramics surface,
Obtain the zirconia ceramics for being coated with zirconium film；
Preferably, ion film plating parameter is base vacuum 2 × 10-3Pa, 200 DEG C of coating temperature, working gas is Ar gas, work gas
Body air pressure be 0.8Pa, on-load voltage electric current be 21V, 80A, continuous coating 1-4 hours.
8. according to claim 6 or 7 the method, which is characterized in that the anodizing specifically: the oxygen of zirconium film will be coated with
Change zircon ceramic as anode, graphite in the electrolytic solution, loads 30-50V constant dc as cathode, submergence between anodic-cathodic
Pressure reacts 10-20min, zirconium membrane part is oxidized to ZrO2Nanotube layer；
Preferably, the electrolyte is by NH4F is dissolved in the aqueous solution that water is made into 0.1-0.5wt%, and ethylene glycol is then added, so that
Volumn concentration of the aqueous solution in ethylene glycol is 1vol%, is obtained after stirring.
9. a kind of zirconia ceramics repair materials, which is characterized in that have the right to require 1-5 in the zirconia ceramics coating surface
Any ZrO2Nano-tube film coating.
10. a kind of zirconium oxide ceramic dental crown bridge prosthesis, including the corona shape crown bridge prosthesis sheet made of zirconia ceramics
Body, which is characterized in that the zirconia ceramics coating surface on the inside of the corona shape crown bridge prosthesis ontology has the right to require 1-5
Any ZrO2Nano-tube film coating.
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