CN107117962B - A kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology - Google Patents

A kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology Download PDF

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CN107117962B
CN107117962B CN201710307668.4A CN201710307668A CN107117962B CN 107117962 B CN107117962 B CN 107117962B CN 201710307668 A CN201710307668 A CN 201710307668A CN 107117962 B CN107117962 B CN 107117962B
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CN107117962A (en
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王衍根
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Zhongshan Ruifeng Medical Devices Co., Ltd.
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Abstract

The present invention relates to a kind of preparation methods of dental all-ceramics repair materials based on electrostatic self-assembled technology, belong to dental material technical field.The key technology of use is that the surface of zirconia material is made to coat one layer of titanium oxide sol particle by the method for electrostatic self-assembled, by the overlap joint of titanium oxide sol in sintering process, solve the problems, such as between zirconium oxide and other aggregates that thermal expansion coefficient is different and bring material is easy to crack.

Description

A kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology
Technical field
The present invention relates to a kind of preparation methods of dental all-ceramics repair materials based on electrostatic self-assembled technology, belong to dentistry Field of material technology.
Background technique
Dental polishing repair volume morphing color with it is naturally similar, when application, seems nature, true to nature that depth is welcome by patient.Pottery The densification of Porcelain veneer quality, wear-resisting, any surface finish, bacterial plaque are not easy to adhere to, and have good biocompatibility, use is safe.Therefore, Ceramics are the materials of commonly used production artificial tooth.Oral cavity ceramics are the most stable of materials of chemical property in oral cavity material, The effects of many chemical substances is resistant to without changing, for a long time under the conditions of oral environment, to various foods, beverage, saliva, The effect of body fluid, microorganism and its enzyme will not generate rotten, denaturation.Oral cavity ceramic material has preferable biology performance, Using safe and nontoxic in oral cavity.
Currently, its material mainly used is zirconium oxide, it has good biocompatibility, corrosion resistance, stability high Advantage, 50% or more, flexural strength improves zirconia content with the increase of zirconia content.High-intensitive aluminium porcelain is mainly used Make the primer of composite ceramic hat.Preparation method is usually to inject in mold after melting zirconia ceramics material, then be cooled to Precast body, then handled within specified temperatures by crystallization, crystalline phase and porcelain is precipitated, material is made to obtain sufficient intensity.Through It crosses the ceramic material cast after crystallization processing and is known as cast ceramic material.Glass ceramics is mostly used to be cast at present, Its casting technique uses investment casting or generally for lost wax process.
Oral cavity ceramic material is heat insulation body, and coefficient of thermal expansion and tooth body are close.But oral cavity ceramic material makes in sintering In the process, the precision of dummy is influenced there are biggish volume contraction.
Summary of the invention
The purpose of the present invention is: it is easy out in brittleness height, processing cutting process existing for solution dental all-ceramics repair materials The problem of splitting；The invention proposes a kind of preparation methods of dental all-ceramics repair materials based on electrostatic self-assembled technology, use Key technology be made by the method for electrostatic self-assembled zirconia material surface coat one layer of titanium oxide sol particle, pass through The overlap joint of titanium oxide sol in sintering process solves that thermal expansion coefficient between zirconium oxide and other aggregates is different and bring material Expect problem easy to crack.
Technical solution is:
A kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology, includes the following steps:
The pretreatment of powder: step 1 takes ZrO2Powder, SnO2Powder is dispersed in water respectively, is configured to solid content respectively For 10~15% slurry, slurry is filtered out after ball milling, the ZrO after spray drying, after respectively obtaining ball milling2、SnO2Powder Body；
The preparation of the ionic liquid of silane coupling agent grafting: in alcohols solvent, the silane of 2~4wt% is added in step 2 Coupling agent and 6~8% glyoxaline ion liquid, at 85~90 DEG C react 12~16h after, obtain silane coupling agent grafting The solution of ionic liquid；
Step 3, ZrO2The surface cationic of powder: by the ZrO after ball milling2Powder is immersed in silane coupling agent grafting It is handled in the solution of ionic liquid, obtains the ZrO of surface cationic2Powder；
Step 4, the preparation of the titanium oxide sol of negative electrical charge: by weight, by 30~45 parts of butyl titanate, sulfuric acid 10~12 parts and 350~450 parts of water of sodium are uniformly mixed, and after heating, sulfuric acid solution are added dropwise to the pH of system 4~5, is hydrolyzed Reaction；After being cooled to room temperature, 20~25 parts of hydroxy silicon oil are added, is modified reaction, reaction solution, which is concentrated under reduced pressure into volume, is Before 40~50%, it adds NaOH solution and adjusts pH to 9~11, obtain the titanium oxide sol of surface negative charge；
Step 5, the surface electrostatic self assembly of Zirconium powder: by the ZrO of surface cationic2Powder is slowly added to table In the titanium oxide sol of face negative electrical charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1:8~12, is added After continue to stir, then powder is filtered out, decompression drying, obtaining to surface has titania oxide supported Zirconium powder；
The compacting of green body: by weight, there are titania oxide supported Zirconium powder, 1 in 92~96 parts of surfaces by step 6 ~3 parts of SnO2Powder, 2~3 parts of polyvinyl alcohol, 3~5 parts of ethyl alcohol are uniformly mixed, and are carried out as powder mixture, and in a mold Dry-pressing formed, demoulding obtains green body；
Sintering: step 7 green body is calcined in air atmosphere, obtains full ceramic restoration material.
In the step 1, ZrO after high-energy ball milling2、SnO2The average grain diameter of powder is not more than 10 μm.
In the step 2, glyoxaline ion liquid is selected from chlorination -1- allyl -3- methylimidazole or chlorination 1- butyl - The mixing of one or more of 3- methylimidazole；The alcohols solvent is selected from methanol, ethyl alcohol, propylene glycol, butanol or isoamyl The mixing of one or more of alcohol.
In the step 3, ZrO2Powder and silane coupling agent grafting ionic liquid solution weight ratio be 1:2~ 4；Processing step refers to 3~6h of processing under the conditions of 75~80 DEG C.
In the step 4, the temperature of hydrolysis is 55~60 DEG C, and hydrolysis time is 2~4h；Modified-reaction Temperature is 35~40 DEG C, and the modified-reaction time is 1~3h.
In the step 5, whipping process feed liquid temperature is 40~50 DEG C, and mixing time is 5~10h.
In the step 6, dry-pressing formed 500~700MPa of pressure, 20~30s of pressing time.
In the step 7, sintering procedure is: being first warming up to 950~1100 DEG C with the rate of 3~5 DEG C/min and keeps the temperature 2 ~4 hours, room temperature is then cooled to the rate of 2~4 DEG C/min.
Beneficial effect
In preparation method of the invention, the effect of step 1 is that the partial size of powder is made to become smaller, equal conducive to the tissue of sintering process It homogenizes；The effect of step 2 is make ionic liquid silicane coupling agent surface grafted；The effect of step 3 is to pass through silane coupling agent Effect and zirconium surface be grafted；The effect of step 4 is that titanium oxide sol is prepared, wherein due to the effect of electric double layer, The surface of electronegative titanium oxide sol particle has one layer of positive charge, modified by the surface of hydroxy silicon oil, destroys electric double layer Effect, keeps particle surface negatively charged, and the purpose for adjusting pH is to make under alkaline condition, and particle is in negative electrical charge；The effect of step 5 It is the surface that titanium oxide sol is coated on to Zirconium powder by the method for electrostatic self-assembled, can obtains during the sintering process To the snap action of titanium oxide sol, the amalgamation between Zirconium powder and aggregate is improved；The effect of step 6 is by powder pressure Wet embryo body is made；The effect of step 7 is sinter molding.
The invention proposes a kind of preparation method of dental all-ceramics repair materials based on electrostatic self-assembled technology, use Key technology is that the surface of zirconia material is made to coat one layer of titanium oxide sol particle by the method for electrostatic self-assembled, passes through burning The overlap joint of titanium oxide sol during knot solves that thermal expansion coefficient between zirconium oxide and other aggregates is different and bring material Problem easy to crack.
Detailed description of the invention
Fig. 1 is the surface SEM figure for the dental prosthetic material that embodiment 3 is prepared；
Fig. 2 is the surface SEM figure for the dental prosthetic material that reference examples 1 are prepared.
Specific embodiment
Embodiment 1
The pretreatment of powder: step 1 takes ZrO2Powder, SnO2Powder is dispersed in water respectively, is configured to solid content respectively For 10% slurry, slurry is filtered out after ball milling, the ZrO after spray drying, after respectively obtaining ball milling2、SnO2Powder is high ZrO after energy ball milling2、SnO2About 5~10 μm of the average grain diameter of powder；
The preparation of the ionic liquid of silane coupling agent grafting: in ethanol, the silane coupling agent of 2wt% is added in step 2 Chlorination -1- allyl -3- the methylimidazole of KH550 and 6%, at 85 DEG C react 12h after, obtain silane coupling agent grafting from The solution of sub- liquid；
Step 3, ZrO2The surface cationic of powder: by the ZrO after ball milling2Powder is immersed in silane coupling agent grafting In the solution of ionic liquid, 3h, ZrO are handled under the conditions of 75 DEG C2The solution of powder and the ionic liquid of silane coupling agent grafting Weight ratio be 1:2, obtain the ZrO of surface cationic2Powder；
Step 4, the preparation of the titanium oxide sol of negative electrical charge: by weight, by 30 parts of butyl titanate, sodium sulphate 10 Part is uniformly mixed with 350 parts of water, after heating, sulfuric acid solution is added dropwise to the pH of system 4~5, reaction, hydrolysis is hydrolyzed Temperature be 55 DEG C, hydrolysis time is 2h；After being cooled to room temperature, 20 parts of hydroxy silicon oil are added, reaction is modified, it is modified The temperature of reaction is 35 DEG C, and the modified-reaction time is 1h, and reaction solution is concentrated under reduced pressure into 40% before volume is, is added NaOH solution adjusts pH to 91~1, obtains the titanium oxide sol of surface negative charge；
Step 5, the surface electrostatic self assembly of Zirconium powder: by the ZrO of surface cationic2Powder is slowly added to table In the titanium oxide sol of face negative electrical charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1:8, and addition finishes After continue to stir, whipping process feed liquid temperature is 40 DEG C, and mixing time is 5h, then powder is filtered out, and decompression drying obtains surface There is titania oxide supported Zirconium powder；
The compacting of green body: by weight, there are titania oxide supported Zirconium powder, 1 part in 92 parts of surfaces by step 6 SnO2Powder, 2 parts of polyvinyl alcohol, 3 parts of ethyl alcohol are uniformly mixed, and as powder mixture, and are carried out dry-pressing formed, are done in a mold Molded pressure 500MPa, pressing time 20s, demoulding, obtain green body；
Sintering: step 7 green body is calcined in air atmosphere, sintering procedure is: first with the rate liter of 3 DEG C/min Temperature is to 950 DEG C and keeps the temperature 2 hours, is then cooled to room temperature with the rate of 2 DEG C/min, obtains full ceramic restoration material.
Embodiment 2
The pretreatment of powder: step 1 takes ZrO2Powder, SnO2Powder is dispersed in water respectively, is configured to solid content respectively For 10~15% slurry, slurry is filtered out after ball milling, the ZrO after spray drying, after respectively obtaining ball milling2、SnO2Powder Body, ZrO after high-energy ball milling2、SnO2About 5~10 μm of the average grain diameter of powder；
The preparation of the ionic liquid of silane coupling agent grafting: in ethanol, the silane coupling agent of 4wt% is added in step 2 Chlorination -1- allyl -3- the methylimidazole of KH550 and 8%, at 90 DEG C react 16h after, obtain silane coupling agent grafting from The solution of sub- liquid；
Step 3, ZrO2The surface cationic of powder: by the ZrO after ball milling2Powder is immersed in silane coupling agent grafting In the solution of ionic liquid, 6h, ZrO are handled under the conditions of 80 DEG C2The solution of powder and the ionic liquid of silane coupling agent grafting Weight ratio be 1:4, obtain the ZrO of surface cationic2Powder；
Step 4, the preparation of the titanium oxide sol of negative electrical charge: by weight, by 45 parts of butyl titanate, sodium sulphate 12 Part is uniformly mixed with 450 parts of water, after heating, sulfuric acid solution is added dropwise to the pH of system 4~5, reaction, hydrolysis is hydrolyzed Temperature be 60 DEG C, hydrolysis time is 4h；After being cooled to room temperature, 25 parts of hydroxy silicon oil are added, reaction is modified, it is modified The temperature of reaction is 40 DEG C, and the modified-reaction time is 3h, and reaction solution is concentrated under reduced pressure into 50% before volume is, is added NaOH solution adjusts pH to 9~11, obtains the titanium oxide sol of surface negative charge；
Step 5, the surface electrostatic self assembly of Zirconium powder: by the ZrO of surface cationic2Powder is slowly added to table In the titanium oxide sol of face negative electrical charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1:12, has been added Continue to stir after finishing, whipping process feed liquid temperature is 50 DEG C, and mixing time is 10h, then powder is filtered out, and decompression drying obtains There is titania oxide supported Zirconium powder on surface；
The compacting of green body: by weight, there are titania oxide supported Zirconium powder, 3 parts in 96 parts of surfaces by step 6 SnO2Powder, 3 parts of polyvinyl alcohol, 5 parts of ethyl alcohol are uniformly mixed, and as powder mixture, and are carried out dry-pressing formed, are done in a mold Molded pressure 700MPa, pressing time 30s, demoulding, obtain green body；
Sintering: step 7 green body is calcined in air atmosphere, sintering procedure is: first with the rate liter of 5 DEG C/min Temperature is to 1100 DEG C and keeps the temperature 4 hours, is then cooled to room temperature with the rate of 4 DEG C/min, obtains full ceramic restoration material.
Embodiment 3
The pretreatment of powder: step 1 takes ZrO2Powder, SnO2Powder is dispersed in water respectively, is configured to solid content respectively For 10~15% slurry, slurry is filtered out after ball milling, the ZrO after spray drying, after respectively obtaining ball milling2、SnO2Powder Body, ZrO after high-energy ball milling2、SnO2About 5~10 μm of the average grain diameter of powder；
The preparation of the ionic liquid of silane coupling agent grafting: in ethanol, the silane coupling agent of 3wt% is added in step 2 Chlorination -1- allyl -3- the methylimidazole of KH550 and 7%, at 88 DEG C react 15h after, obtain silane coupling agent grafting from The solution of sub- liquid；
Step 3, ZrO2The surface cationic of powder: by the ZrO after ball milling2Powder is immersed in silane coupling agent grafting In the solution of ionic liquid, 5h, ZrO are handled under the conditions of 78 DEG C2The solution of powder and the ionic liquid of silane coupling agent grafting Weight ratio be 1:3, obtain the ZrO of surface cationic2Powder；
Step 4, the preparation of the titanium oxide sol of negative electrical charge: by weight, by 35 parts of butyl titanate, sodium sulphate 11 Part is uniformly mixed with 380 parts of water, after heating, sulfuric acid solution is added dropwise to the pH of system 4~5, reaction, hydrolysis is hydrolyzed Temperature be 58 DEG C, hydrolysis time is 3h；After being cooled to room temperature, 22 parts of hydroxy silicon oil are added, reaction is modified, it is modified The temperature of reaction is 38 DEG C, and the modified-reaction time is 2h, and reaction solution is concentrated under reduced pressure into 45% before volume is, is added NaOH solution adjusts pH to 9~11, obtains the titanium oxide sol of surface negative charge；
Step 5, the surface electrostatic self assembly of Zirconium powder: by the ZrO of surface cationic2Powder is slowly added to table In the titanium oxide sol of face negative electrical charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1:10, has been added Continue to stir after finishing, whipping process feed liquid temperature is 45 DEG C, and mixing time is 8h, then powder is filtered out, and decompression drying obtains table There is titania oxide supported Zirconium powder in face；
The compacting of green body: by weight, there are titania oxide supported Zirconium powder, 2 in 92~96 parts of surfaces by step 6 Part SnO2Powder, 3 parts of polyvinyl alcohol, 4 parts of ethyl alcohol are uniformly mixed, as powder mixture, and carry out in a mold it is dry-pressing formed, Dry-pressing formed pressure 600MPa, pressing time 25s, demoulding, obtain green body；
Sintering: step 7 green body is calcined in air atmosphere, sintering procedure is: first with the rate liter of 4 DEG C/min Temperature is to 980 DEG C and keeps the temperature 3 hours, is then cooled to room temperature with the rate of 3 DEG C/min, obtains full ceramic restoration material.
Reference examples 1
Difference with embodiment 3 is: not by way of electrostatic self-assembled in Zirconium powder area load titanium oxide, But a certain amount of titanium oxide powder is used to be added in the process of idiosome compacting directly as aggregate.
The pretreatment of powder: step 1 takes ZrO2Powder, SnO2Powder is dispersed in water respectively, is configured to solid content respectively For 10~15% slurry, slurry is filtered out after ball milling, the ZrO after spray drying, after respectively obtaining ball milling2、SnO2Powder Body, ZrO after high-energy ball milling2、SnO2About 5~10 μm of the average grain diameter of powder；
The preparation of the ionic liquid of silane coupling agent grafting: in ethanol, the silane coupling agent of 3wt% is added in step 2 Chlorination -1- allyl -3- the methylimidazole of KH550 and 7%, at 88 DEG C react 15h after, obtain silane coupling agent grafting from The solution of sub- liquid；
Step 3, ZrO2The surface cationic of powder: by the ZrO after ball milling2Powder is immersed in silane coupling agent grafting In the solution of ionic liquid, 5h, ZrO are handled under the conditions of 78 DEG C2The solution of powder and the ionic liquid of silane coupling agent grafting Weight ratio be 1:3, obtain the ZrO of surface cationic2Powder；
Step 4, the preparation of the titanium oxide sol of negative electrical charge: by weight, by 35 parts of butyl titanate, sodium sulphate 11 Part is uniformly mixed with 380 parts of water, after heating, sulfuric acid solution is added dropwise to the pH of system 4~5, reaction, hydrolysis is hydrolyzed Temperature be 58 DEG C, hydrolysis time is 3h；After being cooled to room temperature, 22 parts of hydroxy silicon oil are added, reaction is modified, it is modified The temperature of reaction is 38 DEG C, and the modified-reaction time is 2h, and reaction solution is concentrated under reduced pressure into 45% before volume is, is added NaOH solution adjusts pH to 9~11, obtains the titanium oxide sol of surface negative charge；
Step 5, the preparation of titanium oxide powder: taking the titanium oxide sol of 10 times of ZrO2 powder weight, after decompression drying, obtains Titanium oxide powder；
Step 6, the compacting of green body: by weight, the ZrO for the surface cationic that 92~96 parts of step 3 are obtained2Powder Titanium oxide powder that body, step 5 obtain, 2 parts of SnO2Powder, 3 parts of polyvinyl alcohol, 4 parts of ethyl alcohol are uniformly mixed, and are mixed as powder Object, and dry-pressing formed, dry-pressing formed pressure 600MPa, pressing time 25s are carried out in a mold, it demoulds, obtains green body；
Sintering: step 7 green body is calcined in air atmosphere, sintering procedure is: first with the rate liter of 4 DEG C/min Temperature is to 980 DEG C and keeps the temperature 3 hours, is then cooled to room temperature with the rate of 3 DEG C/min, obtains full ceramic restoration material.
Reference examples 2
Difference with embodiment 3 is: not carrying out to titanium oxide sol hydroxyl silicon oil modified.
The pretreatment of powder: step 1 takes ZrO2Powder, SnO2Powder is dispersed in water respectively, is configured to solid content respectively For 10~15% slurry, slurry is filtered out after ball milling, the ZrO after spray drying, after respectively obtaining ball milling2、SnO2Powder Body, ZrO after high-energy ball milling2、SnO2About 5~10 μm of the average grain diameter of powder；
The preparation of the ionic liquid of silane coupling agent grafting: in ethanol, the silane coupling agent of 3wt% is added in step 2 Chlorination -1- allyl -3- the methylimidazole of KH550 and 7%, at 88 DEG C react 15h after, obtain silane coupling agent grafting from The solution of sub- liquid；
Step 3, ZrO2The surface cationic of powder: by the ZrO after ball milling2Powder is immersed in silane coupling agent grafting In the solution of ionic liquid, 5h, ZrO are handled under the conditions of 78 DEG C2The solution of powder and the ionic liquid of silane coupling agent grafting Weight ratio be 1:3, obtain the ZrO of surface cationic2Powder；
Step 4, the preparation of the titanium oxide sol of negative electrical charge: by weight, by 35 parts of butyl titanate, sodium sulphate 11 Part is uniformly mixed with 380 parts of water, after heating, sulfuric acid solution is added dropwise to the pH of system 4~5, reaction, hydrolysis is hydrolyzed Temperature be 58 DEG C, hydrolysis time is 3h；After being cooled to room temperature, then 38 DEG C are warming up to, keep 2h, reaction solution is depressurized dense 45% be reduced to before volume is adds NaOH solution and adjusts pH to 9~11, and the titanium oxide for obtaining surface negative charge is molten Glue；
Step 5, the surface electrostatic self assembly of Zirconium powder: by the ZrO of surface cationic2Powder is slowly added to table In the titanium oxide sol of face negative electrical charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1:10, has been added Continue to stir after finishing, whipping process feed liquid temperature is 45 DEG C, and mixing time is 8h, then powder is filtered out, and decompression drying obtains table There is titania oxide supported Zirconium powder in face；
The compacting of green body: by weight, there are titania oxide supported Zirconium powder, 2 in 92~96 parts of surfaces by step 6 Part SnO2Powder, 3 parts of polyvinyl alcohol, 4 parts of ethyl alcohol are uniformly mixed, as powder mixture, and carry out in a mold it is dry-pressing formed, Dry-pressing formed pressure 600MPa, pressing time 25s, demoulding, obtain green body；
Sintering: step 7 green body is calcined in air atmosphere, sintering procedure is: first with the rate liter of 4 DEG C/min Temperature is to 980 DEG C and keeps the temperature 3 hours, is then cooled to room temperature with the rate of 3 DEG C/min, obtains full ceramic restoration material.
As can be seen from the table, full ceramic restoration material provided by the invention has preferable intensity and toughness；3 phase of embodiment For reference examples 1, due to by the titania oxide supported surface in zirconium oxide, can be improved its during the sintering process with other bones Conformability between material can preferably be such that the intensity of material and toughness improves by the snap action of titanium oxide；3 phase of embodiment For reference examples 2, titanium oxide sol is modified by hydroxy silicon oil, the electric double layer effect of sol surface can be offset It answers, improves the negative charge amount of sol particle, make preferably coat Zirconium powder during electrostatic self-assembled, mention The intensity and toughness of high material.
The surface electromicroscopic photograph for the full ceramic restoration material that embodiment 3 is prepared is as shown in Figure 1, it can be seen that surface is Mutually overlapped graininess, smooth zero defect；The material surface that reference examples 1 are prepared illustrates oxygen there are apparent crackle Changing titanium has the effect of the electrostatic self-assembled of zirconium oxide preferably to prevent material sintering cracking.

Claims (5)

1. a kind of preparation method of the dental all-ceramics repair materials based on electrostatic self-assembled technology, which is characterized in that including as follows Step:
The pretreatment of powder: step 1 takes ZrO2Powder, SnO2Powder is dispersed in water respectively, and being configured to solid content respectively is 10 ~15% slurry filters out slurry after ball milling, the ZrO after spray drying, after respectively obtaining ball milling2、SnO2Powder；
The preparation of the ionic liquid of silane coupling agent grafting: in alcohols solvent, the silane coupled of 2~4wt% is added in step 2 Agent and 6~8% glyoxaline ion liquid, at 85~90 DEG C react 12~16h after, obtain silane coupling agent grafting ion The solution of liquid；
Step 3, ZrO2The surface cationic of powder: by the ZrO after ball milling2Powder is immersed in the ion of silane coupling agent grafting It is handled in the solution of liquid, obtains the ZrO of surface cationic2Powder；Wherein ZrO2What powder and silane coupling agent were grafted The weight ratio of the solution of ionic liquid is 1:2~4, and processing step refers to 3~6h of processing under the conditions of 75~80 DEG C；
Step 4, the preparation of the titanium oxide sol of negative electrical charge: by weight, by 30~45 parts of butyl titanate, sodium sulphate 10 ~12 parts and 350~450 parts of water are uniformly mixed, and after heating, sulfuric acid solution are added dropwise to the pH of system 4~5, is hydrolyzed anti- It answers；After being cooled to room temperature, 20~25 parts of hydroxy silicon oil are added, reaction is modified, reaction solution is concentrated under reduced pressure into volume for it Preceding 40~50% add NaOH solution and adjust pH to 9~11, obtain the titanium oxide sol of surface negative charge；Wherein water The temperature of solution reaction is 55~60 DEG C, and hydrolysis time is 2~4h, and the temperature of modified-reaction is 35~40 DEG C, modified-reaction Time is 1~3h；
Step 5, the surface electrostatic self assembly of Zirconium powder: by the ZrO of surface cationic2Powder is slowly added to negative to surface In the titanium oxide sol of charge, the ZrO of surface cationic2The weight ratio of powder and colloidal sol is 1:8~12, and addition finishes After continue to stir, then powder is filtered out, decompression drying, obtaining to surface has titania oxide supported Zirconium powder；Wherein stirring temperature Degree is 40~50 DEG C, and mixing time is 5~10h；
The compacting of green body: by weight, there are titania oxide supported Zirconium powder, 1~3 part in 92~96 parts of surfaces by step 6 SnO2Powder, 2~3 parts of polyvinyl alcohol, 3~5 parts of ethyl alcohol are uniformly mixed, and as powder mixture, and carry out dry-pressing in a mold Molding, demoulding, obtains green body；
Sintering: step 7 green body is calcined in air atmosphere, obtains full ceramic restoration material.
2. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, special Sign is, in the step 1, ZrO after high-energy ball milling2、SnO2The average grain diameter of powder is not more than 10 μm.
3. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, special Sign is, in the step 2, glyoxaline ion liquid is selected from chlorination -1- allyl -3- methylimidazole or chlorination 1- butyl - The mixing of one or more of 3- methylimidazole；The alcohols solvent is selected from methanol, ethyl alcohol, propylene glycol, butanol or isoamyl The mixing of one or more of alcohol.
4. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, special Sign is, in the step 6, dry-pressing formed 500~700MPa of pressure, 20~30s of pressing time.
5. the preparation method of the dental all-ceramics repair materials according to claim 1 based on electrostatic self-assembled technology, special Sign is, in the step 7, sintering procedure is: being first warming up to 950~1100 DEG C with the rate of 3~5 DEG C/min and keeps the temperature 2 ~4 hours, room temperature is then cooled to the rate of 2~4 DEG C/min.
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CN107998905B (en) * 2017-12-20 2020-11-13 绍兴凯达纺织装饰品有限公司 Method for repairing macropores or cracks on surface of ceramic membrane
CN108439978A (en) * 2018-05-07 2018-08-24 内蒙古科技大学 A kind of yttria-stabilized zirconia powder and preparation method thereof and ceramics
CN112142462B (en) * 2020-09-02 2021-10-08 佳木斯大学 Method for manufacturing anti-inflammatory tooth restoration material with layer-by-layer self-assembly coating

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1658914A (en) * 2002-04-09 2005-08-24 艾斯特勒科技公司 Medical prosthetic devices having improved biocompatibility
CN101006944A (en) * 2007-01-31 2007-08-01 浙江大学 A method for assembling RGD on the surface of porous pure titanium dental implant
CN101322662A (en) * 2007-06-14 2008-12-17 浙江大学医学院附属口腔医院 Dental implant surface extracellular matrix biomimetic modification method
WO2010121101A2 (en) * 2009-04-17 2010-10-21 Research Triangle Institute Surface modification for enhanced silanation of ceramic materials
CN101926735A (en) * 2009-06-24 2010-12-29 四川大学 Fully ceramic dental prosthetic material and method for preparing same
CN102327645A (en) * 2011-09-26 2012-01-25 浙江大学 Preparation method of bionic coating carrying bioactive factors
CN104744038A (en) * 2015-03-31 2015-07-01 苏州维泰生物技术有限公司 Zicronia bioceramic used for making tooth root and preparation method thereof
CN105963143A (en) * 2016-07-01 2016-09-28 赵艳丽 Porcelain tooth material and preparation method thereof
CN106039396A (en) * 2016-07-01 2016-10-26 赵艳丽 Dental implant material and preparation method thereof
CN106512557A (en) * 2016-11-23 2017-03-22 南京悠谷知识产权服务有限公司 Method for preparing water treatment filter material based on non-aqueous gel injection molding technology

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1658914A (en) * 2002-04-09 2005-08-24 艾斯特勒科技公司 Medical prosthetic devices having improved biocompatibility
CN101006944A (en) * 2007-01-31 2007-08-01 浙江大学 A method for assembling RGD on the surface of porous pure titanium dental implant
CN101322662A (en) * 2007-06-14 2008-12-17 浙江大学医学院附属口腔医院 Dental implant surface extracellular matrix biomimetic modification method
WO2010121101A2 (en) * 2009-04-17 2010-10-21 Research Triangle Institute Surface modification for enhanced silanation of ceramic materials
CN101926735A (en) * 2009-06-24 2010-12-29 四川大学 Fully ceramic dental prosthetic material and method for preparing same
CN102327645A (en) * 2011-09-26 2012-01-25 浙江大学 Preparation method of bionic coating carrying bioactive factors
CN104744038A (en) * 2015-03-31 2015-07-01 苏州维泰生物技术有限公司 Zicronia bioceramic used for making tooth root and preparation method thereof
CN105963143A (en) * 2016-07-01 2016-09-28 赵艳丽 Porcelain tooth material and preparation method thereof
CN106039396A (en) * 2016-07-01 2016-10-26 赵艳丽 Dental implant material and preparation method thereof
CN106512557A (en) * 2016-11-23 2017-03-22 南京悠谷知识产权服务有限公司 Method for preparing water treatment filter material based on non-aqueous gel injection molding technology

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