CN106007802B - A kind of resin penetration ceramic composite and preparation method thereof - Google Patents
A kind of resin penetration ceramic composite and preparation method thereof Download PDFInfo
- Publication number
- CN106007802B CN106007802B CN201610349596.5A CN201610349596A CN106007802B CN 106007802 B CN106007802 B CN 106007802B CN 201610349596 A CN201610349596 A CN 201610349596A CN 106007802 B CN106007802 B CN 106007802B
- Authority
- CN
- China
- Prior art keywords
- resin
- ceramic
- ceramics
- ceramic body
- network structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—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 organic materials
- C04B41/48—Macromolecular compounds
- C04B41/483—Polyacrylates
-
- 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
- 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
-
- 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
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/82—Coating or impregnation with organic materials
- C04B41/83—Macromolecular compounds
Abstract
The present invention provides a kind of resin penetration ceramic composites, solidified by the hybrid resin of ceramic body and infiltration in the ceramic body porous network structure, ceramic body has porous network structure, ceramic body includes the tetragonal phase zirconium oxide of stabilized with yttrium oxide, and hybrid resin includes the mixture and thermal curing agents of methyl acrylic ester compound.Resin penetration ceramic composite provided by the invention is constituted with the resin of porous ceramic network structure and infiltration in ceramic network structure, using ceramics as matrix, it is possible to prevente effectively from the volume change of composite material in the curing process, and then overcome conventional particles toughened resin based composites and be easy to cure shrinkage, introduce the defect of residual stress；By way of infiltration, hybrid resin, which is capable of forming, has the ceramic matric composite of excellent mechanical performance with the mutually perforative resin network structure of ceramic network structure, composition.
Description
Technical field
The invention belongs to materials of bone tissue technical field more particularly to a kind of resin penetration ceramic composite and its systems
Preparation Method.
Background technique
Oral health and national life quality are closely bound up, and according to World Health Organization's recent statistics, mouth disease is arranged
For the third-largest disease after cancer and cranial vascular disease.The illness rate of the various stomatopathys in studies have shown that China is up to
97.6%, it is concentrated mainly on the stomatopathys such as saprodontia and periodontitis.Third National oral health epidemiological investigation result is shown
China human mortality caries incidence is 40%, and each patient is averagely related to 2-3 tooth.As population structure aging and people are to life
The raising of quality requirement, the demand of oral restoration treatment and research just expand rapidly.Currently, being used for the composite material of gear division reparation
Research formd the direction with important research and Practical significance, while developing advanced composite material (ACM) and synthesis side
The optimization of method is also current materials of bone tissue research emphasis.
Ceramic material and composite material combination CAD/CAM technology are being widely used in gear division reparation field in recent years.It is main at present
There is ceramic material of two classes for gear division reparation, is respectively: glass ceramics and polycrystalline ceramics (Li R.W.K., et.al,
J.Prosthodont.Res.,2014,58,208-216)。
Glass ceramics, such as Lithium silicate glass ceramics, although having excellent biocompatibility and aesthetic properties,
Brittleness is big, and mechanical property is poor.And the polycrystalline ceramics with higher intensity and toughness, such as alumina-based ceramic or oxidation zirconium base
Ceramics, with the defect opaque, hardness is high and modulus is high.It is opaque for materials of bone tissue, mean aesthetic properties
Difference；In order to make up this defect, porcelain poor mechanical property would generally be adornd in top ceramic layer plus decorations porcelain during reparation
And it is poor with the binding performance of dummy, the failure of entire dummy is finally easily caused, the hardness of polycrystalline ceramics is usually
The repair materials of 2-4 times of enamel, excessively high hardness will wear the natural tooth of surrounding, damage to natural tooth；
Secondly, the Young's modulus of dentine is 20-25GPa in human teeth, well below zirconium oxide (200GPa) and aluminium oxide (340-
Young's modulus 390GPa), this significant difference will cause negatively transmitting of the power in repair materials and natural tooth
Influence (Ziskind D., et.al, J.Struct.Biol., 2011,174,23-30；White S.N.,et.al,
J.Prosthet.Dent.,2005,94,125-131；Mangalaraja R.V.,et.al,Mater.Sci.Eng.A,2003,
343,71-73)。
In order to which mechanical property and aesthetic properties to be preferably combined together, composite material is introduced into gear division in 1960s and repairs
Multiple field, and people are being dedicated to improving their performance always after this.(Ferracane J.L.,et.al,
Dent.Mater., 2005,21,36-42) however, since the bond distance of covalent bond is far smaller than the intermolecular bond distance between monomer,
Inorganic particle toughened resin based composites have significant shrinkage after hardening, and this distinctive shrinkage is compound
Residual stress can be introduced in material repair process, be detached from dummy so as to cause repair materials, it is compound seriously to limit resin base
The extensive use (Ferracane J.L., et.al, Dent.Mater., 2011,27,29-38) of material.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of resin penetration ceramic composite, tree provided by the invention
Rouge osmotic ceramic composite material is constituted with the resin of porous ceramic network structure and infiltration in ceramic network structure, is overcome
The shrinkage of conventional particles toughened resin based composites, is easy to introduce the defect of residual stress.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of resin penetration ceramic composites, and the composite material is by ceramic body and infiltration in institute
The hybrid resin stated in the porous network structure of ceramic body solidifies, and the ceramic body has porous network structure,
The ceramic body includes the tetragonal phase zirconium oxide of stabilized with yttrium oxide, and the hybrid resin includes methyl acrylic ester compound
Mixture and thermal curing agents.
Preferably, the ceramic body further includes di-iron trioxide, moles the hundred of di-iron trioxide in the ceramic body
Divide than being 0~3mol%.
Preferably, the thermal curing agents are benzoyl peroxide.
Preferably, the mixture of the methyl acrylic ester compound is bisphenol-A glycerine dimethacrylate, three
One of (ethylene glycol) dimethylacrylate, methacrylate and polymethyl methacrylate are a variety of.
The present invention provides a kind of preparation methods of resin penetration ceramic composite, comprising the following steps:
(1), it is thermally cured agent to mix with the mixture of methyl acrylic ester compound, obtains hybrid resin；
(2), the hybrid resin that the step (1) obtains is infiltrated into ceramic body, obtains the ceramics that infiltration has resin；
(3), the infiltration for obtaining the step (2) has the ceramics of resin to solidify, and obtains resin penetration Ceramic Composite
Material.
Preferably, the ceramic body preparation method the following steps are included:
A, the tetragonal phase zirconium oxide ceramics and di-iron trioxide of stabilized with yttrium oxide are mixed, obtains mixed material；
B, the obtained mixed material of the step a is ground, obtains presoma powder；
C, the obtained presoma powder of the step b is once suppressed, obtains biscuit of ceramics precursor；
D, the biscuit of ceramics precursor for obtaining the step c carries out secondary compacting, obtains biscuit of ceramics；
E, the obtained biscuit of ceramics of the step d is sintered, obtains ceramic body.
Preferably, the mass fraction of thermal curing agents is 0.5~2% in the hybrid resin.
Preferably, the time of infiltration described in step (2) be 2~for 24 hours.
Preferably, the environment of infiltration described in step (2) is vacuum environment.
Preferably, step (3) the cured temperature be 50~100 DEG C, the cured time be 2~for 24 hours.
The present invention provides a kind of resin penetration ceramic composites, and the composite material is by ceramic body and infiltration in institute
The hybrid resin stated in the porous network structure of ceramic body solidifies, and the ceramic body has porous network structure,
The ceramic body includes the tetragonal phase zirconium oxide of stabilized with yttrium oxide, and the hybrid resin includes methyl acrylic ester compound
Mixture and thermal curing agents.Resin penetration ceramic composite provided by the invention is with porous ceramic network structure and infiltration
Resin in ceramic network structure is constituted, and using ceramics as matrix, effectively avoids the volume of composite material during the sintering process
Variation, and then the shrinkage of conventional particles toughened resin based composites is overcome, it is easy to introduce the defect of residual stress；With
The hybrid resin of the form of infiltration can sufficiently occupy the porous network structure of ceramic body, and the toughening for playing hybrid resin is special
Property, and avoid hybrid resin that volume change occurs in the curing process as matrices of composite material；Resin penetration ceramics, it is ingenious
Two kinds of network structures being intertwined are utilized in ground, i.e. resin network structure, ceramic network structure, this structure overcomes resin
The cure shrinkage defect of based composites, and can effectively improve the mechanical property of composite material.The embodiment of the present invention
The result shows that resin penetration composite material provided by the invention, bending strength with higher, fracture toughness, while have compared with
Low hardness and elastic modulus is a kind of novel gear division repair composite material with broad prospect of application.
The present invention also provides the preparation method of composite material described in above-mentioned technical proposal, preparation side provided by the invention
Method is thermally cured agent and mixes with the mixture of methyl acrylic ester compound, obtains hybrid resin, then seep hybrid resin
Thoroughly into ceramic body, the ceramics that infiltration has resin are obtained, by way of infiltration, hybrid resin is capable of forming and ceramic network
The ceramic network structure of the mutually perforative resin network structure of structure, sintering combines resin network structure therethrough to constitute tool
There is the ceramic matric composite of excellent mechanical performance, and effectively overcomes the cure shrinkage performance of polymer matrix composites.
In addition, grinding is uniformly mixed the zirconium oxide in ceramic slurry with di-iron trioxide；It, can be true by once suppressing
The biscuit of ceramics for protecting acquisition certain size further increases the compactness of biscuit of ceramics, in conjunction with secondary compacting convenient for resin
Infiltration makes full use of ceramic network structure and resin network structure, and then improves subsequent acquired resin penetration Ceramic Composite material
The mechanical property of material；By sintering, the porous network structure with some strength is prepared；Methyl acrylic ester compound mixes
Close object be proportionally uniformly mixed, add benzoyl peroxide, by the addition of benzoyl peroxide, colourless mixed solution by
Fade to it is faint yellow, reach improve resin penetration composite material aesthetic properties.
Detailed description of the invention
The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
Fig. 1 is the XRD spectra of ceramic body in 1-4 of embodiment of the present invention resin penetration ceramic composite preparation process；
Fig. 2 is the SEM figure of ceramic body in 1-4 of embodiment of the present invention resin penetration ceramic composite preparation process；
Fig. 3 is the sample photo for the resin penetration ceramic composite that 5-8 of the embodiment of the present invention is provided；
Fig. 4 is the SEM figure of ceramic body in 5-8 of embodiment of the present invention resin penetration ceramic composite preparation process.
Specific embodiment
The present invention provides a kind of resin penetration ceramic composites, and the composite material is by ceramic body and infiltration in institute
The hybrid resin stated in the porous network structure of ceramic body solidifies, and the ceramic body has porous network structure,
The ceramic body includes the tetragonal phase zirconium oxide of stabilized with yttrium oxide, and the hybrid resin includes methyl acrylic ester compound
Mixture and thermal curing agents.
Resin penetration ceramic composite provided by the invention, with porous ceramic network structure and infiltration in ceramic network
Resin in structure is constituted, and using ceramics as matrix, effectively avoids the volume change of composite material during the sintering process, Jin Erke
The shrinkage for having taken conventional particles toughened resin based composites is easy to introduce the defect of residual stress.
Resin penetration ceramic composite provided by the invention, including ceramic body, the ceramic body have porous
Network structure, heretofore described ceramic body aperture are preferably 1~3 μm, and the gap of the ceramic body is uniformly distributed；It is described
Ceramic body includes the tetragonal phase zirconium oxide of stabilized with yttrium oxide, i.e. 3Y-TZP.The present invention is to the source of the 3Y-TZP without spy
It is different to require, using 3Y-TZP well-known to those skilled in the art；In an embodiment of the present invention, 3Y-TZP can be used
Commercial goods, the technical solution well known to those skilled in the art for preparing 3Y-TZP can also be used and voluntarily prepare.In the present invention
Embodiment in, the 3Y-TZP is purchased from Tokyo Tosoh company (Tosoh Co., Tokyo, Japan).
In the present invention, the ceramic body is it is also preferable to include di-iron trioxide, di-iron trioxide in the ceramic body
Molar percentage is preferably 0~2mol%, further preferably 0.1~1.9mol%, can be specific in the embodiment of the present invention
For 0.1mol%, 0.2mol%, 0.3mol%, 0.5mol%, 0.8mol%, 1.2mol%, 1.5mol% or 1.8mol%.
Resin penetration ceramic composite provided by the invention, including permeating the porous network structure in the ceramic body
In hybrid resin, the hybrid resin includes the mixture and thermal curing agents of methyl acrylic ester compound.In the present invention
In, the thermal curing agents are preferably benzoyl peroxide, and the mass fraction of the thermal curing agents in hybrid resin is preferably 0.5
~2%, further preferably 0.8~1.5%.In the embodiment of the present invention, the matter of the thermal curing agents in the hybrid resin
Measuring score can be specially 1.0%, 1.2%, 1.4%, 1.6% or 1.8%.
In the present invention, the mixture of the methyl acrylic ester compound is preferably bisphenol-A glycerol dimethyl allene
One of acid esters, three (ethylene glycol) dimethylacrylates, methacrylate and polymethyl methacrylate are a variety of；This
In invention, when the mixture of methyl acrylic ester compound is bisphenol-A glycerine dimethacrylate and three (ethylene glycol) two
When methacrylate, the matter of the bisphenol-A glycerine dimethacrylate and described three (ethylene glycol) dimethylacrylate
Amount can be specially 1:1.2,1:1.3 or 1:1.4 in the embodiment of the present invention than being preferably 1:1~1:1.5.
The present invention provides a kind of preparation methods of resin penetration ceramic composite, comprising the following steps:
(1), it is thermally cured agent to mix with the mixture of methyl acrylic ester compound, obtains hybrid resin；
(2), the hybrid resin that the step (1) obtains is infiltrated into ceramic body, obtains the ceramics that infiltration has resin；
(3), the infiltration for obtaining the step (2) has the ceramics of resin to solidify, and obtains resin penetration Ceramic Composite
Material.
In the present invention, the thermal curing agents are mixed with the mixture of the methyl acrylic ester compound,
It is spare to obtain hybrid resin.The present invention does not have particular/special requirement to the mixed process, and use is well-known to those skilled in the art
Hybrid mode；The thermal curing agents and the mixture of the methyl acrylic ester compound in embodiments of the present invention
Hybrid mode can be specially the mode of normal agitation or magnetic agitation, to the speed of the normal agitation or the magnetic agitation
There is no particular/special requirement.
In the present invention, the mixture of the methyl acrylic ester compound is preferably bisphenol-A glycerol dimethyl allene
One of acid esters, three (ethylene glycol) dimethylacrylates, methacrylate and polymethyl methacrylate are a variety of；This
In invention, when the mixture of methyl acrylic ester compound is bisphenol-A glycerine dimethacrylate and three (ethylene glycol) two
When methacrylate, the matter of the bisphenol-A glycerine dimethacrylate and described three (ethylene glycol) dimethylacrylate
Amount can be specially 1:1.2,1:1.3 or 1:1.4 in the embodiment of the present invention than being preferably 1:1~1:1.5.
In the present invention, the thermal curing agents are preferably benzoyl peroxide, the thermal curing agents in hybrid resin
Mass fraction is preferably 0.5~2%, and further preferably 0.8~1.5%.In the embodiment of the present invention, in the hybrid resin
The mass fraction of the thermal curing agents can be specially 1.0%, 1.2%, 1.4%, 1.6% or 1.8%.
The preparation method of the ceramic body preferably includes following steps:
A, the tetragonal phase zirconium oxide ceramics and di-iron trioxide of stabilized with yttrium oxide are mixed, obtains mixed material；
B, the obtained mixed material of the step a is ground, obtains presoma powder；
C, the obtained presoma powder of the step b is once suppressed, obtains biscuit of ceramics precursor；
D, the biscuit of ceramics precursor for obtaining the step c carries out secondary compacting, obtains biscuit of ceramics；
E, the obtained biscuit of ceramics of the step d is sintered, obtains ceramic body.
The present invention preferably mixes the tetragonal zircite ceramic of stabilized with yttrium oxide with di-iron trioxide, obtains mixed material.
The present invention does not have particular/special requirement to the mixed mode, using hybrid mode well-known to those skilled in the art, originally
The mode of mixing described in inventive embodiments can be specially the mode of magnetic agitation.In the present invention, di-iron trioxide is mixing
Molar percentage in material is preferably 0~2mol%, further preferably 0.1~1.9mol%, in the embodiment of the present invention
Can be specially 0.1mol%, 0.2mol%, 0.3mol%, 0.5mol%, 0.8mol%, 1.2mol%, 1.5mol% or
1.8mol%.The addition of di-iron trioxide of the present invention, the color of the color and natural tooth that on the one hand can make composite material is more
Be it is close, have better aesthetic properties, the mechanical property of composite material on the other hand can be improved.
After obtaining mixed material, the present invention preferably grinds the mixed material, obtains precursor powder.In this hair
In bright, the mode of grinding is preferably wet-milling, and the medium of the wet-milling is preferably alcohol, and the present invention is to the additive amount of alcohol without spy
It is different to require, add wet grinding media dosage well-known to those skilled in the art；The revolving speed of grinding of the present invention is preferably
250~500rpm, further preferably 300~450rmp；In the present invention, the time of the grinding be preferably 2~for 24 hours, into
One step is preferably 5~20h.In the present invention, after completing to the grinding of the mixed material, the partial size of precursor powder is preferably
50~100 mesh, further preferably 60~80 mesh.
After obtaining precursor powder, the present invention is once suppressed the presoma powder, obtains biscuit of ceramics
Precursor.When not adding di-iron trioxide in the present invention, the tetragonal zircite ceramic of stabilized with yttrium oxide is directly preferably carried out one
Secondary compacting obtains biscuit of ceramics precursor.In the present invention before the primary compacting, preferably the precursor powder is done
It is dry.In the present invention, the time of the drying be preferably 2~for 24 hours, further preferably 10~15h；The temperature of the drying is excellent
It is selected as 50~80 DEG C, further preferably 55~75 DEG C.
The equipment that the present invention uses the primary compacting does not have special limitation, and use is well known to those skilled in the art
Tablet press machine.In the present invention, the pressure once suppressed is preferably 2~10MPa, further preferably 3.5~
7.5MPa；In the present invention, the dwell time once suppressed is preferably 2~4min, is once suppressed in the embodiment of the present invention
Dwell time can be specially 2.5min, 3min or 3.5min.
After obtaining biscuit of ceramics precursor, the biscuit of ceramics precursor is carried out secondary compacting by the present invention, is obtained comparatively dense
Biscuit of ceramics.In the present invention, the secondary compacting is by the way of isostatic cool pressing well-known to those skilled in the art, institute
The pressure for stating secondary compacting is preferably 150~220MPa, further preferably 180~200MPa；In the present invention, described secondary
The dwell time of compacting is preferably 0.5~3min, the dwell time once suppressed in the embodiment of the present invention can be specially 1.0min,
1.5min or 2min.
After obtaining the biscuit of ceramics of secondary compacting, the present invention is preferably sintered the biscuit of ceramics, obtains ceramic blank
Body.In the present invention, sintering preferably partially sinter mode, present invention preferably employs it is well-known to those skilled in the art with it is complete
Dense sintering is corresponding to be partially sintered, lower than the temperature of complete dense sintering.In the present invention, the temperature of the sintering is preferred
It is 1000~1150 DEG C, can is specially 1050 DEG C, 1080 DEG C, 1100 DEG C or 1120 DEG C in the embodiment of the present invention；In the present invention,
The time of the sintering is preferably 2~4h, can be specially 2.5h, 2.7h, 2.9h, 3.0h, 3.2h in an embodiment of the present invention
Or 3.5h.The present invention does not have particular/special requirement to sintering atmosphere, using sintering atmosphere well-known to those skilled in the art, originally
Sintering atmosphere can be specially to be sintered under air atmosphere in inventive embodiments.
After the present invention obtains ceramic body, hybrid resin described in above-mentioned technical proposal is infiltrated into the ceramic body
In, obtain the ceramics that infiltration has resin.In the present invention, it is preferred to be permeated by the way of vacuum infiltration, the vacuum is seeped
Saturating vacuum degree is preferably -0.1MPa；In the present invention, the time of the infiltration be preferably 2~for 24 hours, further preferably 5~
20h；It in embodiments of the present invention, can be specially 8h, 10h, 12h, 14h, 16h or 18h.
The present invention by infiltration, obtain infiltration have the ceramics of resin after, by it is described infiltration there are the ceramics of resin to solidify,
Obtain resin penetration ceramic composite.In the present invention, the cured temperature is preferably 50~100 DEG C, further preferably
It is 60~85 DEG C, most preferably 65~75 DEG C；The cured time is preferably 2~for 24 hours, further preferably 5~20h, and most
Preferably 10~15h.In the present invention, it is preferred to be solidified by the way of vacuum solidification, specifically adopted in the embodiment of the present invention
Cured mode is carried out in vacuum drying oven well-known to those skilled in the art.
The present invention provides a kind of resin penetration ceramic composites, and the composite material is by ceramic body and infiltration in institute
The hybrid resin stated in the porous network structure of ceramic body solidifies, and the ceramic body has porous network structure,
The ceramic body includes the tetragonal phase zirconium oxide of stabilized with yttrium oxide, and the hybrid resin includes methyl acrylic ester compound
Mixture and thermal curing agents.Resin penetration ceramic composite provided by the invention is with porous ceramic network structure and infiltration
Resin in ceramic network structure is constituted, and using ceramics as matrix, effectively avoids the volume of composite material during the sintering process
Variation, and then the shrinkage of conventional particles toughened resin based composites is overcome, it is easy to introduce the defect of residual stress；With
The hybrid resin of the form of infiltration can sufficiently occupy the porous network structure of ceramic body, and the toughening for playing hybrid resin is special
Property, and avoid the cure shrinkage occurred when matrix of the hybrid resin as composite material；Resin penetration ceramics, dexterously utilize
Two kinds of network structures being intertwined, i.e. resin network structure, ceramic network structure, it is compound that this structure overcomes resin base
The cure shrinkage defect of material, and can effectively improve the mechanical property of composite material.
The present invention also provides the preparation method of composite material described in above-mentioned technical proposal, preparation side provided by the invention
Method is thermally cured agent and mixes with the mixture of methyl acrylic ester compound, obtains hybrid resin, then seep hybrid resin
Thoroughly into ceramic body, the ceramics that infiltration has resin are obtained, by way of infiltration, hybrid resin is capable of forming and ceramic network
The ceramic network structure of the mutually perforative resin network structure of structure, sintering combines resin network structure therethrough to constitute tool
There is the ceramic matric composite of excellent mechanical performance, and effectively overcomes the cure shrinkage performance of polymer matrix composites.
In addition, grinding is uniformly mixed the zirconium oxide in ceramic slurry with di-iron trioxide；It, can be true by once suppressing
The biscuit of ceramics for protecting acquisition certain size further increases the compactness of biscuit of ceramics, in conjunction with secondary compacting convenient for resin
Infiltration makes full use of ceramic network structure and resin network structure, and then improves subsequent acquired resin penetration Ceramic Composite material
The mechanical property of material；By sintering, the porous network structure with some strength is prepared；Methyl acrylic ester compound mixes
Close object be proportionally uniformly mixed, add benzoyl peroxide, by the addition of benzoyl peroxide, colourless mixed solution by
Fade to it is faint yellow, reach improve resin penetration composite material aesthetic properties.
Resin penetration ceramic composite provided by the invention and preparation method thereof is carried out below with reference to embodiment detailed
Explanation, but they cannot be interpreted as limiting the scope of the present invention.
In following embodiment gained sample mechanics properties testing method it is as follows: using universal testing machine according to
The bending strength and fracture toughness of ISO4049 standardized test specimen.Bending strength is tested, with golden steel blade by resin penetration
Zirconia ceramics sample is cut into 2 × 3 × 16mm3Batten, sample upper and lower surface is polished using abrasive pastes later, each sample
Test 22 battens.For fracture toughness, resin penetration zirconia ceramics sample is cut into 2 × 4 × 16mm with golden steel blade3's
Batten cuts the notch of about 2mm long, 22 battens of each sample test in batten side with diamant.For consistency and elasticity mould
Amount, is tested, after polishing sample according to polishing technology well-known to those skilled in the art, at random using Nanoindentation
10 points are tested, depth of cup is fixed as 500nm.
Embodiment 1
Powder is compressed to biscuit of ceramics precursor using tablet press machine by the 3Y-TZP for weighing 4.5g, pressure 4MPa, when pressure maintaining
Between be 3min；Finer and close biscuit of ceramics is obtained using isostatic cool pressing compacting zirconia ceramics biscuit, pressure 220MPa is protected
The pressure time is 1min；Biscuit of ceramics is sintered to obtain ceramic body is spare, and wherein sintering temperature is in air atmosphere
1000 DEG C, soaking time 2h.The bisphenol-A glycerine dimethacrylate and three (ethylene glycol) diformazans for being 1:1 by mass ratio
Base acrylate is mixed, and stirs 2h using magnetic agitation；Above-mentioned hybrid resin relaying is added in curing agent benzoyl peroxide
Continuous stirring 2h, obtains resin solution, and according to the mass fraction meter for accounting for hybrid resin, the additional amount of curing agent is 1%；It will be spare
Ceramic body immerses in resin solution, is placed in the vacuum environment that vacuum degree is -0.1MPa, permeates 4h；By the pottery of infiltration resin
Porcelain billet body, which is placed in vacuum drying oven, to be solidified, and solidification temperature is 70 DEG C, curing time 2h, obtains resin penetration zirconium oxide composite wood
Material.
1000 DEG C of corresponding SEM scheme institute to the XRD diagram for the ceramic body being sintered in the embodiment preparation process as shown in figure 1
Show, ceramic body composition is correct known to You Tuzhong peak position, is tetragonal phase zirconium oxide；Ceramic body in the present embodiment preparation process
SEM scheme as shown in a in Fig. 2, as known in the figure due to partially sintering, ceramic body be porous network structure, ceramic crystalline grain
About 0.1 μm.
1 sample of embodiment in the mechanical property such as table 1 of the resin penetration zirconium oxide composite material sample of embodiment preparation
Shown in corresponding data, bending strength is shown up to 121.8 ± 10.1MPa, fracture toughness is up to 1.6 ± 0.3MPa × m1/2,
Hardness is 1.7 ± 0.2GPa, and elasticity modulus is 34.2 ± 2.7GPa.
Embodiment 2
Powder is compressed to biscuit of ceramics precursor using tablet press machine by the 3Y-TZP for weighing 4.5g, pressure 4MPa, when pressure maintaining
Between be 3min；Using the obtained biscuit of ceramics of isostatic cool pressing compacting zirconia ceramics biscuit, wherein pressure is 220MPa, when pressure maintaining
Between be 1min；Ceramic body biscuit is sintered in air atmosphere to obtain ceramic body, sintering temperature is 1050 DEG C, heat preservation
Time is 2h.By mass ratio be 1:1 bisphenol-A glycerine dimethacrylate and three (ethylene glycol) dimethylacrylates into
Row mixing stirs 2h using magnetic agitation, obtains resin solution；Curing agent benzoyl peroxide is added in above-mentioned resin solution
Continue to stir 2h, according to the mass fraction meter for accounting for hybrid resin, the additional amount of curing agent is 1%；Ceramic body is immersed and is mixed
It in resin solution, is placed in vacuum environment, permeates 4h；The material of infiltration resin is placed in vacuum drying oven and is solidified, solidification temperature
It is 70 DEG C, curing time 2h obtains resin penetration zirconium oxide composite material.
The XRD spectra for the ceramic body that the embodiment is sintered is as shown in figure 1 shown in spectrogram corresponding to 1050 DEG C, by this
Ceramic body composition is correct known to figure, is tetragonal phase zirconium oxide；The SEM figure for the ceramic body being sintered in the present embodiment is as schemed
In 2 shown in b, ceramic body sample needed for the resin penetration ceramic composite prepared as known in the figure by the embodiment is more
The network structure in hole.
2 sample of embodiment in the mechanical property such as table 1 of the resin penetration zirconium oxide composite material sample of embodiment preparation
Shown in corresponding data, the bending strength of sample is shown up to 113.1 ± 6.3MPa, fracture toughness is up to 1.5 ± 0.4MPa
×m1/2, hardness is 1.7 ± 0.2GPa, and elasticity modulus is 34.2 ± 3.5GPa.
Embodiment 3
Powder is compressed to biscuit of ceramics precursor, pressure 4MPa, pressure maintaining using tablet press machine by the 3Y-TZP for weighing 4.5g
Time is 3min；Biscuit of ceramics, pressure 220MPa are obtained using isostatic cool pressing compacting zirconia ceramics biscuit, the dwell time is
1min；Biscuit of ceramics is sintered in air atmosphere, sintering temperature is 1100 DEG C, and soaking time 2h obtains ceramic blank
Body.Mass ratio is mixed for the bisphenol-A glycerine dimethacrylate of 1:1 and three (ethylene glycol) dimethylacrylates
It closes, stirs 2h using magnetic agitation；Curing agent benzoyl peroxide is added in above-mentioned hybrid resin and continues to stir 2h, is set
Lipoprotein solution, according to the mass fraction meter for accounting for hybrid resin, the additional amount of curing agent is 1%；The ceramics of pre-sintering are immersed into resin
It in solution, is placed in vacuum environment, permeates 4h；The material of infiltration resin is placed in vacuum drying oven and is solidified, solidification temperature 70
DEG C, curing time 2h obtains resin penetration zirconium oxide composite material.
The XRD spectra for the ceramic body sample that the embodiment is sintered is as shown in figure 1 shown in spectrogram corresponding to 1100 DEG C,
Ceramic body composition is correct as known in the figure, is tetragonal phase zirconium oxide；Pottery needed for the present embodiment resin penetration ceramic composite
The SEM of porcelain billet body sample schemes as shown in c in Fig. 2, the resin penetration Ceramic Composite material prepared as known in the figure by the embodiment
Ceramic body sample needed for expecting is porous network structure.
3 sample of embodiment in the mechanical property such as table 1 of the resin penetration zirconium oxide composite material sample of embodiment preparation
Shown in corresponding data, show the bending strength of sample up to 184.0 ± 9.8MPa, fracture toughness up to 2.6 ± 0.1MPa ×
m1/2, hardness is 1.9 ± 0.6GPa, and elasticity modulus is 44.2 ± 4.3GPa.
Embodiment 4
Powder is compressed to biscuit of ceramics precursor using tablet press machine by the 3Y-TZP for weighing 4.5g, pressure 4MPa, when pressure maintaining
Between be 3min；Ceramic body, pressure 220MPa, dwell time are obtained using isostatic cool pressing compacting zirconia ceramics biscuit precursor
For 1min；Biscuit of ceramics is sintered in air atmosphere, sintering temperature is 1150 DEG C, soaking time 2h.By mass ratio
Example is that the bisphenol-A glycerine dimethacrylate of 1:1 and three (ethylene glycol) dimethylacrylates are mixed, and is stirred using magnetic force
Agitating mixes 2h, obtains resin solution；Curing agent benzoyl peroxide is added in above-mentioned hybrid resin and continue to stir 2h, according to accounting for
The mass fraction meter of hybrid resin, the additional amount of curing agent are 1%；The ceramics of pre-sintering are immersed in resin solution, are placed in true
In Altitude, 4h is permeated；The material of infiltration resin is placed in vacuum drying oven and is solidified, solidification temperature is 70 DEG C, and curing time is
2h obtains resin penetration zirconium oxide composite material.
The XRD spectra for the ceramic body sample that the embodiment is sintered is as shown in figure 1 shown in spectrogram corresponding to 1150 DEG C,
Ceramic body composition is correct as known in the figure, is tetragonal phase zirconium oxide；The SEM for the ceramic body sample that the present embodiment is sintered
Ceramic body sample needed for the resin penetration ceramic composite that figure is prepared as shown in d in Fig. 2, as known in the figure by the embodiment
Product are porous network structures.As shown in the SEM figure of ceramic body in Fig. 2 resin penetration ceramic composite preparation process, with
The raising of sintering temperature, less, about 0.1 μm, but porosity is gradually reduced, crystal boundary is gradually for the crystallite dimension variation of sample
Increase.
Shown in mechanical property data as corresponding to 4 sample of embodiment in table 1 of the sample of embodiment preparation, display gained
The bending strength of sample is up to 240.3 ± 7.4MPa, and fracture toughness is up to 3.7 ± 0.2MPa × m1/2, hardness be 3.1 ±
0.2GPa, elasticity modulus are 58.8 ± 2.0GPa.
Embodiment 5
Powder is placed in ball grinder by the 3Y-TZP for weighing 4.5g, and dehydrated alcohol is added as ball-milling medium and carries out ball milling,
Rotational speed of ball-mill is 250rpm, and time 10h obtains precursor powder；For 24 hours in 70 DEG C of dryings by the precursor powder；Use tabletting
Precursor powder is compressed to biscuit of ceramics precursor, pressure 4MPa, dwell time 3min by machine；Oxygen is suppressed using isostatic cool pressing
Change zircon ceramic biscuit precursor, pressure 220MPa, dwell time 1min obtain biscuit of ceramics；By biscuit of ceramics in air gas
It is sintered under atmosphere, sintering temperature is 1150 DEG C, soaking time 2h.The bisphenol-A glycerol dimethyl propylene for being 1:1 by mass ratio
Olefin(e) acid ester and three (ethylene glycol) dimethylacrylates are mixed, and are stirred 2h using magnetic agitation, are obtained resin solution；It will consolidate
Agent benzoyl peroxide, which is added in above-mentioned hybrid resin, to be continued to stir 2h, according to the mass fraction meter for accounting for hybrid resin, solidification
The additional amount of agent is 1%；The ceramics of pre-sintering are immersed in resin solution, are placed in vacuum environment, 4h is permeated；By infiltration resin
Material be placed in vacuum drying oven and solidify, solidification temperature is 70 DEG C, curing time 2h, obtains resin penetration zirconium oxide composite wood
Material.
The photo for the sintering ceramic body sample that the embodiment obtains is as shown in a in Fig. 3, its color is white as known in the figure
Chalk color differs farther out with natural color of teeth；The present embodiment is sintered the SEM spectrogram of ceramic body sample as shown in a and b in Fig. 4,
Ceramic body sample needed for the resin penetration ceramic composite prepared as known in the figure by the embodiment is porous network
Structure.
In the mechanical property table 2 of the sample of embodiment preparation shown in data corresponding to 5 gained sample of embodiment, display
In 1150 DEG C of sintering temperatures, Fe is not adulterated2O3, for the bending strength of gained sample up to 240.3 ± 7.4MPa, fracture toughness can
Up to 3.7 ± 0.2MPa × m1/2, hardness is 3.1 ± 0.2GPa, and elasticity modulus is 58.8 ± 2.0GPa.
Embodiment 6
Weigh 3Y-TZP and Fe2O3Total 4.5g, wherein Fe2O3Powder is placed in ball grinder by content 0.1mol%, is added
Dehydrated alcohol carries out ball milling as ball-milling medium, and rotational speed of ball-mill 250rpm, time 10h obtain precursor powder；Before this
Body powder is driven to dry for 24 hours in 70 DEG C；Precursor powder is compressed to biscuit of ceramics precursor, pressure 4MPa, pressure maintaining with tablet press machine
Time is 3min；Zirconia ceramics biscuit precursor is suppressed using isostatic cool pressing, pressure 220MPa, dwell time 1min are obtained
To biscuit of ceramics；Biscuit of ceramics is sintered in air atmosphere, wherein sintering temperature is 1150 DEG C, and soaking time obtains for 2h
To ceramic body.The bisphenol-A glycerine dimethacrylate and three (ethylene glycol) dimethylacrylates for being 1:1 by mass ratio
It is mixed, stirs 2h using magnetic agitation, obtain resin solution；Above-mentioned hybrid resin is added in curing agent benzoyl peroxide
In continue to stir 2h, according to the mass fraction meter for accounting for hybrid resin, the additional amount of curing agent is 1%；Ceramic body is immersed and is set
It in lipoprotein solution, is placed in vacuum environment, permeates 4h；The material of infiltration resin is placed in vacuum drying oven and is solidified, solidification temperature is
70 DEG C, curing time 2h obtains resin penetration zirconium oxide composite material.
The photo of the sample for the sintered body that the embodiment obtains is as shown in b in Fig. 3, its color is yellowish as known in the figure
Color is close with natural color of teeth；The SEM figure such as Fig. 4 of ceramic body needed for the present embodiment resin penetration ceramic composite
Shown in middle c and d, ceramic body sample needed for the resin penetration ceramic composite prepared as known in the figure by the embodiment is
Porous network structure.
The mechanical property of the sample of embodiment preparation is as shown in the corresponding data of 6 gained sample of embodiment in table 2, as a result
Show to be sintered by 1150 DEG C of temperature, adulterates 0.1mol%Fe2O3The bending strength of sample obtained by situation up to 242.6 ±
10MPa, fracture toughness is up to 3.8 ± 0.2MPa × m1/2, hardness is 4.0 ± 0.6GPa, and elasticity modulus is 72.3 ± 6.4GPa.
Embodiment 7
Weigh 3Y-TZP and Fe2O3Total 4.5g, wherein Fe2O3Content is 0.2mol%, and powder is placed in ball grinder, is added
Enter dehydrated alcohol as ball-milling medium and carry out ball milling, rotational speed of ball-mill 250rpm, time 10h obtain precursor powder；It should
Precursor powder is dried for 24 hours in 70 DEG C；Precursor powder is compressed to biscuit of ceramics precursor with tablet press machine, pressure 4MPa is protected
The pressure time is 3min；Using isostatic cool pressing suppress zirconia ceramics biscuit precursor, pressure 220MPa, dwell time 1min,
Obtain biscuit of ceramics；Biscuit of ceramics is sintered in air atmosphere, wherein sintering temperature is 1150 DEG C, and soaking time is
2h obtains ceramic body.The bisphenol-A glycerine dimethacrylate and three (ethylene glycol) dimethyl propylenes for being 1:1 by mass ratio
Olefin(e) acid ester is mixed, and is stirred 2h using magnetic agitation, is obtained resin solution；Above-mentioned tree is added in curing agent benzoyl peroxide
Continue to stir 2h in lipoprotein solution, according to the mass fraction meter for accounting for hybrid resin, the additional amount of curing agent is 1%；By ceramic body
It immerses in resin solution, is placed in vacuum environment, permeate 4h；The material of infiltration resin is placed in vacuum drying oven and is solidified, is solidified
Temperature is 70 DEG C, and curing time 2h obtains resin penetration zirconium oxide composite material.
The photo of the resin penetration zirconium oxide composite material sample of embodiment preparation is as shown in c in Fig. 3, as known in the figure
Its color be it is faint yellow, be close with natural color of teeth；Ceramic body needed for the present embodiment resin penetration ceramic composite
SEM scheme as shown in e and f in Fig. 4, ceramic body needed for resin penetration ceramic composite is in the present embodiment as known in the figure
Porous network structure.
In the mechanical property table 2 of the sample of embodiment preparation shown in data corresponding to 7 gained sample of embodiment, as a result
Show to adulterate 0.1mol%Fe at 1150 DEG C of sintering temperature2O3The bending strength of gained sample is broken up to 336.8 ± 12.7MPa
Toughness is split up to 3.9 ± 0.3MPa × m1/2, hardness is 4.7 ± 0.3GPa, and elasticity modulus is 88.2 ± 3.7GPa.
Embodiment 8
Weigh 3Y-TZP and Fe2O3Total 4.5g, Fe2O3Powder is placed in ball grinder by content 0.3mol%, is added anhydrous
Ethyl alcohol carries out ball milling as ball-milling medium, and rotational speed of ball-mill 250rpm, time 10h obtain precursor powder；By the presoma
Powder is dried for 24 hours in 70 DEG C；Precursor powder is compressed to biscuit of ceramics precursor, pressure 4MPa, dwell time with tablet press machine
For 3min；Zirconia ceramics biscuit precursor is suppressed using isostatic cool pressing, pressure 220MPa, dwell time 1min are made pottery
Porcelain biscuit；Biscuit of ceramics is sintered in air atmosphere, sintering temperature is 1150 DEG C, and soaking time is that 2h obtains ceramic blank
Body.Mass ratio is mixed for the bisphenol-A glycerine dimethacrylate of 1:1 and three (ethylene glycol) dimethylacrylates
It closes, stirs 2h using magnetic agitation, obtain resin solution；Curing agent benzoyl peroxide is added in above-mentioned hybrid resin and is continued
2h is stirred, according to the mass fraction meter for accounting for hybrid resin, the additional amount of curing agent is 1%；Ceramic body is immersed into resin solution
In, it is placed in vacuum environment, permeates 4h；The material of infiltration resin is placed in vacuum drying oven and is solidified, solidification temperature is 70 DEG C, Gu
The change time is 2h, obtains resin penetration zirconium oxide composite material.
The photo of the sample of the resin penetration zirconium oxide composite material of embodiment preparation, can by the figure as shown in d in Fig. 3
Know its color be it is faint yellow, be close with natural color of teeth；Ceramic blank needed for the present embodiment resin penetration ceramic composite
The SEM of body schemes as shown in g and h in Fig. 4, the resin penetration ceramic composite being sintered as known in the figure by the embodiment
Required ceramic body sample is porous network structure.By ceramic body in Fig. 4 resin penetration ceramic composite preparation process
SEM figure shown in, with the raising of sintering temperature, the crystallite dimension variation of sample less, about 0.1 μm, but porosity by
Decrescence small, crystal boundary gradually increases.
Shown in mechanical property data as corresponding to 8 gained sample of embodiment in table 2 of the sample of embodiment preparation, doping
0.3mol%Fe2O3Bending strength through 1150 DEG C of sintering gained samples is up to 370.9 ± 15.1MPa, and fracture toughness is up to 5.4
±0.4MPa×m1/2, hardness is 8.0 ± 0.4GPa, and elasticity modulus is 129.3 ± 10.5GPa.
Mechanical property of the table 1 through resin penetration ceramic composite obtained by different sintering temperatures
As can be seen from Table 1, the resin penetration ceramic composite excellent in mechanical performance being prepared, bending strength are broken
It is higher to split toughness, elasticity modulus and hardness number；When sintering temperature is 1000 DEG C, 1050 DEG C and 1100 DEG C, bending strength,
There is no significant differences for fracture toughness, elasticity modulus and hardness, when sintering temperature reaches 1150 DEG C, bending strength, fracture
Toughness, elasticity modulus and hardness, which have, greatly to be improved.
The mechanical property of resin penetration ceramic composite obtained by 2 di-iron trioxide difference doping of table
As can be seen from Table 2, the resin penetration ceramic composite excellent in mechanical performance being prepared, bending strength are broken
It is higher to split toughness, elasticity modulus and hardness number；With the increase of di-iron trioxide doping, the resin penetration that is prepared
Bending strength, fracture toughness, elasticity modulus and the hardness of ceramic composite gradually rise.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (1)
1. a kind of resin penetration ceramic composite, it is characterised in that be prepared via a method which: weigh 3Y-TZP and
Fe2O3Total 4.5g, wherein Fe2O3Content is 0.2mol%, and powder is placed in ball grinder, and dehydrated alcohol is added and is situated between as ball milling
Matter carries out ball milling, and rotational speed of ball-mill 250rpm, time 10h obtain precursor powder；By the precursor powder in 70 DEG C of dryings
24h；Precursor powder is compressed to biscuit of ceramics precursor, pressure 4MPa, dwell time 3min with tablet press machine；Using cold etc.
Static pressure suppression zirconia ceramics biscuit precursor, pressure 220MPa, dwell time 1min obtain biscuit of ceramics；By ceramic element
Base is sintered in air atmosphere, and wherein sintering temperature is 1150 DEG C, and soaking time 2h obtains ceramic body, by quality
The bisphenol-A glycerine dimethacrylate and three (ethylene glycol) dimethylacrylates that ratio is 1: 1 are mixed, and magnetic force is utilized
Stirring stirring 2h, obtains resin solution；Curing agent benzoyl peroxide is added in above-mentioned resin solution and continues to stir 2h, according to
The mass fraction meter of hybrid resin is accounted for, the additional amount of curing agent is 1%；Ceramic body is immersed in resin solution, vacuum is placed in
In environment, 4h is permeated；The material of infiltration resin is placed in vacuum drying oven and is solidified, solidification temperature is 70 DEG C, curing time 2h,
Obtain resin penetration zirconium oxide composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610349596.5A CN106007802B (en) | 2016-05-24 | 2016-05-24 | A kind of resin penetration ceramic composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610349596.5A CN106007802B (en) | 2016-05-24 | 2016-05-24 | A kind of resin penetration ceramic composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106007802A CN106007802A (en) | 2016-10-12 |
| CN106007802B true CN106007802B (en) | 2019-09-17 |
Family
ID=57093506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610349596.5A Active CN106007802B (en) | 2016-05-24 | 2016-05-24 | A kind of resin penetration ceramic composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106007802B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106747430A (en) * | 2017-01-22 | 2017-05-31 | 韩雨桐 | A kind of resin penetration 3Y TZP composites and preparation method thereof |
| CN106830928B (en) * | 2017-02-09 | 2020-05-29 | 中国科学院上海硅酸盐研究所 | Composite ceramic material and manufacturing method and application thereof |
| CN108524291A (en) * | 2018-05-07 | 2018-09-14 | 清华大学 | A kind of resin penetration silicate composite material and its preparation and application |
| CN108578250B (en) * | 2018-05-07 | 2023-07-11 | 清华大学 | Resin-permeable silicate composite material and preparation and application thereof |
| CN108451773A (en) * | 2018-05-07 | 2018-08-28 | 清华大学 | A kind of resin penetration silicate composite material and its preparation and application |
| CN109503209A (en) * | 2018-12-28 | 2019-03-22 | 广东昭信照明科技有限公司 | A kind of preparation method of novel multi-through hole densifying materials |
| CN110327220A (en) * | 2019-05-29 | 2019-10-15 | 北京交通大学 | Zirconium oxide-resin bicontinuous composites, using and preparation method thereof |
| CN112295871A (en) * | 2019-07-31 | 2021-02-02 | 共享智能铸造产业创新中心有限公司 | Technology for pressurizing and permeating reinforcer on surface of mould and container |
| CN113105234B (en) * | 2021-04-16 | 2022-08-16 | 深圳陶陶科技有限公司 | Zirconia composite material, ceramic product, preparation method and application thereof |
| CN113563116B (en) * | 2021-07-21 | 2022-12-02 | 佛山欧神诺陶瓷有限公司 | Composite ceramic tile and preparation method and application thereof |
| CN114213021B (en) * | 2021-12-23 | 2024-03-19 | 温州医科大学附属口腔医院 | Gradient bionic dental ceramic |
| CN115340413B (en) * | 2022-10-17 | 2023-03-28 | 新明珠集团股份有限公司 | Porous ceramic plate, porous composite ceramic plate and preparation method thereof |
| CN115974588B (en) * | 2022-12-28 | 2023-12-22 | 爱迪特（秦皇岛）科技股份有限公司 | Resin-permeated ceramic with antibacterial function and preparation method thereof |
| CN116120092B (en) * | 2022-12-30 | 2024-03-19 | 爱迪特（秦皇岛）科技股份有限公司 | High-strength resin-infiltrated ceramic composite material and preparation method thereof |
| CN115894001B (en) * | 2023-03-10 | 2023-05-09 | 湖南康纳新材料有限公司 | High-hardness wear-resistant resin-infiltrated ceramic composite material and preparation method and application thereof |
| CN116698632B (en) * | 2023-07-20 | 2023-11-03 | 龙华相位新材料(绵阳)股份有限公司 | Method for testing folding endurance of optical film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058655B (en) * | 2013-01-18 | 2014-09-10 | 秦皇岛爱迪特高技术陶瓷有限公司 | Gradient transparent zirconium oxide dental ceramic and preparation method thereof |
| CN104909745B (en) * | 2015-06-23 | 2017-03-22 | 成都贝施美生物科技有限公司 | Preparation method for uniform gradient-colour zirconium oxide porcelain blocks |
-
2016
- 2016-05-24 CN CN201610349596.5A patent/CN106007802B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| "聚甲基丙烯酸甲酯-氧化锆复合材料经CAD-CAM制作牙科修复体的研究";李石保等;《口腔材料学研究》;20050131;第40卷(第1期);23-26 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106007802A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106007802B (en) | A kind of resin penetration ceramic composite and preparation method thereof | |
| EP2352480B1 (en) | Dental ceramic article, process for production and use thereof | |
| US20180221118A1 (en) | Multi sectional dental zirconia milling block, process of production and use thereof | |
| US11839665B2 (en) | High strength and translucency dental ceramic materials, devices, and methods | |
| CN109414309A (en) | The method and green body of manufacture coloring green body | |
| US9872746B2 (en) | Translucency enhancing solution for zirconia ceramics | |
| WO2012023601A1 (en) | Sintered zirconia, and sintering composition and calcined object therefor | |
| CN100398489C (en) | Cuttable colored zirconium oxide ceramics and its use | |
| JP2017530939A (en) | Parts kit containing dental mill blank and coloring solution | |
| WO2018155459A1 (en) | Zirconia object to be cut for dental cutting work and method of manufacturing zirconia object to be cut, and transparency improving liquid for zirconia object to be cut for dental cutting work and method of manufacturing transparency improving liquid | |
| EP2968076A1 (en) | Fluorescence imparting coloring solution for dental ceramics | |
| CN107903557A (en) | Gear division reparation machinable resin penetration glass ceramic material and preparation method thereof | |
| US20200062653A1 (en) | Highly Translucent Zirconia Material, Device, Methods Of Making The Same, And Use Thereof | |
| CN108814991B (en) | Bionic enamel material and manufacturing method for manufacturing bionic tooth by using same | |
| Seesala et al. | Monolith dental bridge by soft machining of dried ceramic dough | |
| CN1151766C (en) | High-strength material with excellent machinability for repairing tooth | |
| Tian et al. | Mechanical Properties and Microstructure of Alumina‐Glass Composites | |
| CN106747430A (en) | A kind of resin penetration 3Y TZP composites and preparation method thereof | |
| CN113511894B (en) | Zirconia ceramic for tooth veneering and preparation method thereof | |
| CN116120092B (en) | High-strength resin-infiltrated ceramic composite material and preparation method thereof | |
| US20230202931A1 (en) | Method and composition to produce high translucency dental ceramics | |
| CN115894001B (en) | High-hardness wear-resistant resin-infiltrated ceramic composite material and preparation method and application thereof | |
| KR20110027345A (en) | Manufacturing method of extra hard stone for dentistry | |
| CN116606135A (en) | Yttria-stabilized tetragonal polycrystalline zirconia composite ceramic material containing alumina and strontium aluminate, and preparation method and application thereof | |
| CN116253562A (en) | Resin-infiltrated ceramic composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |