CN117598800B - Preparation method of low-brittleness dental crown composite material - Google Patents
Preparation method of low-brittleness dental crown composite material Download PDFInfo
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- CN117598800B CN117598800B CN202311650298.6A CN202311650298A CN117598800B CN 117598800 B CN117598800 B CN 117598800B CN 202311650298 A CN202311650298 A CN 202311650298A CN 117598800 B CN117598800 B CN 117598800B
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- carboxymethyl cellulose
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- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000005245 sintering Methods 0.000 claims abstract description 35
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 18
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 10
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 14
- 238000005452 bending Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000005548 dental material Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 210000000214 mouth Anatomy 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 208000025157 Oral disease Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 210000004195 gingiva Anatomy 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C13/00—Dental prostheses; Making same
- A61C13/0003—Making bridge-work, inlays, implants or the like
- A61C13/0006—Production methods
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C13/00—Dental prostheses; Making same
- A61C13/0003—Making bridge-work, inlays, implants or the like
- A61C13/0022—Blanks or green, unfinished dental restoration parts
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C13/00—Dental prostheses; Making same
- A61C13/08—Artificial teeth; Making same
- A61C13/081—Making teeth by casting or moulding
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
- A61C13/00—Dental prostheses; Making same
- A61C13/08—Artificial teeth; Making same
- A61C13/09—Composite teeth, e.g. front and back section; Multilayer teeth
-
- 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
-
- 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
- A61K6/84—Preparations for artificial teeth, for filling teeth or for capping teeth comprising metals or alloys
- A61K6/842—Rare earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/105—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing inorganic lubricating or binding agents, e.g. metal salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
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- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Mechanical Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Dentistry (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Fluid Mechanics (AREA)
- Composite Materials (AREA)
- Dental Preparations (AREA)
Abstract
The invention relates to the technical field of ceramic composite materials, in particular to a preparation method of a low-brittleness dental crown composite material. The low-brittleness dental crown composite material is prepared by mixing zirconium oxide, ruthenium oxide, silica sol and carboxymethyl cellulose-cobalt powder compound, ball milling, pressing, cold isostatic pressing, presintering and secondary sintering. By adding the silica sol and the carboxymethyl cellulose-cobalt powder compound into the raw materials, the mechanical properties such as fracture toughness, bending strength and the like of the composite are improved, the requirements of medicine on the performance of dental materials can be met, meanwhile, the presintering temperature is reduced, the workability after presintering is improved, and the use of resources is reduced.
Description
Technical Field
The invention relates to the technical field of ceramic composite materials, in particular to a preparation method of a low-brittleness dental crown composite material.
Background
The damage and the lack of teeth not only affect the normal chewing function of people, but also affect the appearance and appearance, and along with the continuous progress of technology and the increasing living standard of people, the tooth repairing material also needs to meet the aesthetic requirements and the comfort requirements of people from the original requirement of only meeting the strength and the function. At present, the dental restoration materials commonly used in modern medicine are mainly metal porcelain materials and all-porcelain materials, and the metal porcelain materials have higher strength, but the metal ions can be released in the oral cavity, so that the gingiva is blackened and even the oral cavity is diseased; the all-ceramic material has good biocompatibility, good combination property and attractive appearance, and is widely focused as a novel dental repair material.
According to the different base materials, the dental all-ceramic material can be divided into alumina ceramic, silica ceramic, zirconia ceramic and the like, and in many all-ceramic restoration materials, the zirconia ceramic has special stress-induced phase change toughening effect, so that the mechanical property of the zirconia ceramic is far higher than that of other all-ceramic restoration materials, and meanwhile, the zirconia ceramic has the advantages of low heat conductivity, good corrosion resistance, high transmittance, excellent biocompatibility and the like, and becomes a main stream material for manufacturing all-ceramic crowns and bridges at present. At present, the common preparation method of the all-ceramic zirconia dental crown is to obtain zirconia ceramic blocks from zirconia powder through the processes of compression molding, presintering and the like, and then perform secondary sintering to improve the compactness and mechanical strength of the zirconia ceramic blocks, but the existing zirconia material still has the defects of insufficient strength, complex processing technology, higher brittleness and the like, and the defects of the existing zirconia material still do not completely meet the requirements of wide clinical application.
The invention improves toughness and mechanical strength of the composite all-ceramic material by introducing carbon nano tubes, tiC and alloy, wherein the carbon nano tubes are introduced by taking the alloy as an adhesive, the problem of agglomeration of the carbon nano tubes in the sintering process of the composite all-ceramic material is solved by the existence of the alloy, the carbon nano tubes are uniformly distributed in TiC-Y-TZP ceramic, good interface combination is realized, mechanical properties of the composite ceramic material are improved, and the introduction of the alloy is also beneficial to the improvement of mechanical properties. However, the alloy releases metal ions in the oral cavity, resulting in darkening of gums and even oral lesions. Most importantly, the patent directly sinters TiC-Y-TZP and Co-Ge-Zr alloy-carbon nanotubes at 1450-1650 ℃, which will give the finished product a poor machinability.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a low-brittleness dental crown composite material, so as to solve the problems of high brittleness and low pre-sintering processability of the traditional zirconia dental crown composite material.
Based on the above purpose, the invention provides a preparation method of a low-brittleness dental crown composite material, which comprises the following preparation steps:
S1: adding carboxymethyl cellulose and cobalt powder into deionized water, stirring for 3-5h, and drying to obtain carboxymethyl cellulose-cobalt powder compound;
preferably, the weight ratio of the carboxymethyl cellulose to the cobalt powder is 10:0.5-1;
Preferably, the drying is performed at 100-150 ℃;
S2: mixing zirconium oxide, ruthenium oxide, silica sol and carboxymethyl cellulose-cobalt powder compound, ball milling for 3-5 hours, then standing for 24-36 hours at room temperature, drying, grinding, and sieving with a 100-200 mesh sieve to obtain mixed powder;
Preferably, the weight ratio of the zirconia, the ruthenium oxide, the silica sol and the carboxymethyl cellulose-cobalt powder compound is 97:3:10-15:5-7;
s3: putting the mixed powder into a die, slowly pressurizing and exhausting gas, and then performing cold isostatic pressing to obtain a blank;
s4: presintering the blank in a vacuum environment to obtain a presintered dental crown composite material;
s5: and (3) performing secondary sintering on the presintered dental crown composite material to obtain the dental crown composite material with low brittleness.
Preferably, the average particle size of the cobalt powder is 50-70nm.
Preferably, the average particle size of the zirconia is 2-3 mu m, the specific surface area is 11-14 m 2/g, the average particle size of the ruthenium oxide is 0.2-0.5 mu m, and the purity is 99.99%.
Preferably, the silica sol is an alkaline silica sol, the silica content is 30% and the pH is 9.
Preferably, the pressurizing pressure in the step S3 is 3-4 MPa, and the pressure maintaining time is 25-35S.
Preferably, the cold isostatic pressure in step S3 is 180-220 MPa.
Preferably, the pre-sintering in the step S4 adopts gradient heating, firstly, the temperature is kept for 3-5 hours from room temperature to 500-600 ℃ at a heating rate of 5-10 ℃/min, then the temperature is raised to 700-800 ℃ at a heating rate of 1-3 ℃/min, the temperature is kept for 2-4 hours, and finally the temperature is lowered to 300-350 ℃ at a cooling rate of 9-11 ℃/min, and then the temperature is cooled to the room temperature along with a furnace.
Preferably, the temperature of the secondary sintering in the step S5 is 1400-1450 ℃, and the temperature rising rate is 4-6 ℃/min.
The invention has the beneficial effects that:
(1) The low-brittleness dental crown composite material provided by the invention has the advantages that the carboxymethyl cellulose-cobalt powder is added into the raw materials to act as an adhesive, the fracture toughness and the bending strength can be improved, the mechanical property is excellent, and meanwhile, the composite material can be used as a second phase to inhibit crack propagation, so that the fracture toughness and the bending strength of the material are improved.
(2) According to the low-brittleness dental crown composite material, the silica sol is added into the raw materials to serve as an auxiliary binder, so that on one hand, the use amount of carboxymethyl cellulose is reduced, the degumming step is avoided, and the fracture toughness and the bending strength can be improved in cooperation with carboxymethyl cellulose-cobalt powder; on the other hand, the pre-sintering temperature can be lowered, so that the workability after pre-sintering is improved, and the shrinkage rate of secondary sintering is suppressed.
(3) The low-brittleness dental crown composite material has excellent mechanical property, the fracture toughness performance of the composite material reaches 6.45 Mpa.m 1/2, the bending strength of the composite material reaches 773MPa, the shrinkage rate of the composite material after secondary sintering can reach 10.59 percent at the lowest, and the pre-sintering temperature of the composite material is lower, so that the processable type after pre-sintering is improved, and the aim of saving resources is also achieved.
Detailed Description
The present invention will be further described in detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent.
Example 1: a preparation method of a low-brittleness dental crown composite material comprises the following specific preparation steps:
(1) Adding 10g of carboxymethyl cellulose and 0.5g of cobalt powder with the average particle size of 50nm into deionized water, stirring for 3 hours, and drying at 100 ℃ to obtain a carboxymethyl cellulose-cobalt powder compound;
(2) 93g of zirconium oxide with the average particle size of 2 mu m and the specific surface area of 11.1 m 2/g, 3g of ruthenium oxide with the average particle size of 0.2 mu m, 10g of alkaline silica sol and 5g of carboxymethyl cellulose-cobalt powder compound are mixed and ball-milled for 3 hours, then placed for 24 hours at room temperature, dried, ground and sieved by a 100-mesh sieve to obtain mixed powder;
(3) Putting the mixed powder into a die, slowly pressurizing to 3 MPa, exhausting gas, keeping the pressure for 25s, and then performing cold isostatic pressing to obtain a blank body, wherein the pressure is 180 MPa;
(4) Presintering the blank in a vacuum environment, keeping the temperature for 3 hours from room temperature to 500 ℃ at a heating rate of 5 ℃/min, then heating to 700 ℃ at a heating rate of 1 ℃/min, keeping the temperature for 2 hours, and finally cooling to 300 ℃ at a cooling rate of 9 ℃/min, and then cooling to room temperature along with a furnace to obtain a presintered dental crown composite material;
(5) And (3) performing secondary sintering on the presintered dental crown composite material, wherein the secondary sintering temperature is 1400 ℃, and the heating rate is 4 ℃/min, so as to obtain the dental crown composite material with low brittleness.
Example 2: a preparation method of a low-brittleness dental crown composite material comprises the following specific preparation steps:
(1) Adding 10g of carboxymethyl cellulose and 0.8g of cobalt powder with the average particle size of 60nm into deionized water, stirring for 4 hours, and drying at 130 ℃ to obtain a carboxymethyl cellulose-cobalt powder compound;
(2) 93g of zirconium oxide with the average particle size of 2.5 mu m and the specific surface area of 12.8m 2/g, 3g of ruthenium oxide with the average particle size of 0.4 mu m, 13g of alkaline silica sol and 6g of carboxymethyl cellulose-cobalt powder compound are mixed and ball-milled for 4 hours, then placed for 30 hours at room temperature, dried, ground and sieved by a 150-mesh sieve to obtain mixed powder;
(3) Putting the mixed powder into a die, slowly pressurizing to 3.5 MPa, exhausting gas, keeping the pressure for 30s, and then performing cold isostatic pressing to obtain a blank body, wherein the pressure is 200 MPa;
(4) Presintering the blank in a vacuum environment, keeping the temperature for 4 hours from room temperature to 550 ℃ at a heating rate of 8 ℃/min, then heating to 750 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 3 hours, and finally cooling to 330 ℃ at a cooling rate of 10 ℃/min, and then cooling to room temperature along with a furnace to obtain a presintered dental crown composite material;
(5) And (3) performing secondary sintering on the presintered dental crown composite material, wherein the secondary sintering temperature is 1430 ℃, and the heating rate is 5 ℃/min, so as to obtain the dental crown composite material with low brittleness.
Example 3: a preparation method of a low-brittleness dental crown composite material comprises the following specific preparation steps:
(1) Adding 10g of carboxymethyl cellulose and 1g of cobalt powder with the average particle size of 50-70nm into deionized water, stirring for 5h, and drying at 150 ℃ to obtain a carboxymethyl cellulose-cobalt powder compound;
(2) 93g of zirconium oxide with the average particle size of 3 mu m and the specific surface area of 13.8 m 2/g, 3g of ruthenium oxide with the average particle size of 0.5 mu m, 15g of alkaline silica sol and 7g of carboxymethyl cellulose-cobalt powder compound are mixed and ball-milled for 5 hours, then placed for 36 hours at room temperature, dried, ground and screened by a 200-mesh sieve to obtain mixed powder;
(3) Putting the mixed powder into a die, slowly pressurizing to 4 MPa, exhausting gas, keeping the pressure for 35s, and then performing cold isostatic pressing to obtain a blank body, wherein the pressure is 220 MPa;
(4) Presintering the blank in a vacuum environment, keeping the temperature for 5 hours from room temperature to 600 ℃ at a heating rate of 10 ℃/min, then heating to 800 ℃ at a heating rate of 3 ℃/min, keeping the temperature for 4 hours, and finally cooling to 350 ℃ at a cooling rate of 11 ℃/min and then cooling to room temperature along with a furnace to obtain a presintered dental crown composite material;
(5) And (3) performing secondary sintering on the presintered dental crown composite material, wherein the secondary sintering temperature is 1450 ℃, and the heating rate is 6 ℃/min, so as to obtain the dental crown composite material with low brittleness.
Comparative example 1: a preparation method of a dental crown composite material comprises the following specific preparation steps:
the difference from example 3 is that cobalt powder was not added in step (1), and the rest of the steps were the same as in example 2.
Comparative example 2: a preparation method of a dental crown composite material comprises the following specific preparation steps:
the difference from example 3 is that no silica sol was added in step (2), and the rest of the steps are the same as in example 2.
Comparative example 3: a preparation method of a dental crown composite material comprises the following specific preparation steps:
The difference from example 3 is that no silica sol is added in step (2), the temperature rising rate of 5-10deg.C/min for pre-sintering in step (4) is from room temperature to 700-800deg.C, the temperature is kept for 3-5h, then the temperature is raised to 1000-1150 deg.C at the temperature rising rate of 1-3deg.C/min, the temperature is kept for 2-4h, finally the temperature is lowered to 550-600deg.C at the temperature lowering rate of 9-11deg.C/min, and then the furnace is cooled to room temperature, and the rest steps are the same as those in example 2.
Comparative example 4: a preparation method of a dental crown composite material comprises the following specific preparation steps:
The difference from example 3 is that the temperature rising rate of 5-10 ℃/min of the pre-sintering temperature in step (4) is from room temperature to 700-800 ℃, the temperature is kept for 3-5h, then the temperature is raised to 1000-1150 ℃ at the temperature rising rate of 1-3 ℃/min, the temperature is kept for 2-4h, finally the temperature is lowered to 550-600 ℃ at the temperature lowering rate of 9-11 ℃/min, then the furnace is cooled to the room temperature, and the rest steps are the same as those in example 2.
Performance test:
Fracture toughness: the samples obtained in the examples and the comparative examples were tested by indentation, and the test results are shown in table 1;
flexural strength: the samples obtained in examples and comparative examples were tested by a three-point flexural strength test method, the span of the sample was 14 mm, the width was 5 mm, the thickness was 1.5 mm, the surface of the sample was polished and chamfered with 1500 sandpaper before testing, and the maximum load at flexural fracture of the sample was measured.
The processing method comprises the following steps: according to the friction and wear performance of the test sample, the machinability of the sample is indirectly reflected, firstly, a sample wafer subjected to friction and wear test is weighed, then the diameter of the wafer sample is measured, and the cross-sectional area of the sample is calculated; and then placing the sample into a friction and wear testing machine, selecting silicon carbide as a counter-grinding part, wherein the rotating speed of the sample is 30rpm, the testing time is 30s, and the calculation formula of the wear amount is as follows:
T=（M1-M2）/A
wherein T: grinding amount per unit area, mg/mm 2;M1: the mass of the sample before grinding, g; m 2: the mass g of the sample after grinding; a: friction area of sample, mm 2
Shrinkage ratio: the diameters of the samples obtained in the examples and the comparative examples before and after sintering were measured by a screw micrometer, and the linear shrinkage after pre-sintering and secondary sintering was calculated by taking the average value ten times. The calculation of the linear shrinkage is as follows:
S=×100%
wherein S represents the linear shrinkage; d 1 represents the diameter before sintering, mm; d 2 represents the diameter after sintering, mm.
TABLE 1 Performance test results
Data analysis: the low-brittleness dental crown composite material has excellent mechanical property, the fracture toughness performance of the composite material reaches 6.45 Mpa.m 1/2, the bending strength of the composite material reaches 773MPa, the minimum shrinkage rate of the composite material after secondary sintering can reach 10.59%, more importantly, the machinability after pre-sintering of the composite material is greatly improved, the abrasion loss after pre-sintering of the composite material can reach 5.42 mg.mm -2, the pre-sintering temperature is reduced while the requirements of dental materials on the mechanical property are met, and the resource saving effect is achieved while the machinability is increased.
As can be seen from example 3 and comparative examples 1 to 4, the low brittleness dental crown composite material of the present invention can exert very excellent effects by adding cobalt powder and silica sol to raw materials, mainly because carboxymethyl cellulose-cobalt powder not only acts as a binder, but also can improve fracture toughness and flexural strength, has excellent mechanical properties, and can inhibit crack propagation as a second phase, thereby improving fracture toughness and flexural strength of the material; the silica sol is used as an auxiliary binder, so that the using amount of carboxymethyl cellulose is reduced, the fracture toughness and the bending strength can be improved in cooperation with carboxymethyl cellulose-cobalt powder, and most importantly, the pre-sintering temperature can be reduced, the processability after pre-sintering is improved, and the shrinkage rate of secondary sintering is inhibited; after the silica sol and the cobalt powder are added, the two samples are prepared at the presintering temperature of 700-800 ℃ and 1000-1150 ℃ and have basically the same mechanical properties, and the effect of saving resources is achieved while the machinability of the samples is improved.
Those of ordinary skill in the art will appreciate that: the discussion of any of the embodiments above is merely exemplary and is not intended to suggest that the scope of the invention (including the claims) is limited to these examples; the technical features of the above embodiments or in the different embodiments may also be combined within the idea of the invention, the steps may be implemented in any order and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The present invention is intended to embrace all such alternatives, modifications and variances which fall within the broad scope of the appended claims. Therefore, any omission, modification, equivalent replacement, improvement, etc. of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a low-brittleness dental crown composite material, which is characterized by comprising the following preparation steps:
S1: adding carboxymethyl cellulose and cobalt powder into deionized water, stirring for 3-5h, and drying to obtain carboxymethyl cellulose-cobalt powder compound;
S2: mixing zirconium oxide, ruthenium oxide, silica sol and carboxymethyl cellulose-cobalt powder compound, ball milling for 3-5 hours, then standing for 24-36 hours at room temperature, drying, grinding, and sieving with a 100-200 mesh sieve to obtain mixed powder;
s3: putting the mixed powder into a die, slowly pressurizing and exhausting gas, and then performing cold isostatic pressing to obtain a blank;
s4: presintering the blank in a vacuum environment to obtain a presintered dental crown composite material;
s5: performing secondary sintering on the presintered dental crown composite material to obtain a dental crown composite material with low brittleness;
in the step S2, the weight ratio of the zirconia, the ruthenium oxide, the silica sol and the carboxymethyl cellulose-cobalt powder compound is 97:3:10-15:5-7.
2. The method for preparing a low brittleness dental crown composite material according to claim 1, wherein said cobalt powder has an average particle size of 50-70nm.
3. The method for preparing a dental crown composite material having low brittleness according to claim 1, wherein the average particle size of the zirconia is 2-3 μm, the specific surface area is 11-14 m 2/g, the average particle size of the ruthenium oxide is 0.2-0.5 μm, and the purities are 99.99%.
4. The method of preparing a low brittleness dental crown composite according to claim 1, wherein said silica sol is an alkaline silica sol, having a silica content of 30%, and a pH of 9.
5. The method for preparing a dental crown composite material having low brittleness according to claim 1, wherein the pressurizing pressure in the step S3 is 3 to 4 MPa and the dwell time is 25 to 35S.
6. The method of preparing a low brittleness dental crown composite material according to claim 1, wherein said cold isostatic pressing pressure in step S3 is 180-220 MPa.
7. The method for preparing a low brittleness dental crown composite material according to claim 1, wherein the presintering in the step S4 adopts gradient heating, firstly, heating from room temperature to 500-600 ℃ at a heating rate of 5-10 ℃/min, preserving heat for 3-5 hours, then heating to 700-800 ℃ at a heating rate of 1-3 ℃/min, preserving heat for 2-4 hours, and finally cooling to 300-350 ℃ at a cooling rate of 9-11 ℃/min, and then cooling to room temperature with a furnace.
8. The method for preparing a dental crown composite material having low brittleness according to claim 1, wherein the secondary sintering temperature in the step S5 is 1400-1450 ℃ and the heating rate is 4-6 ℃/min.
9. The method for preparing a dental crown composite material with low brittleness according to claim 1, wherein the weight ratio of carboxymethyl cellulose to cobalt powder in the step S1 is 10:0.5-1.
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| US5401695A (en) * | 1994-01-24 | 1995-03-28 | Rohm And Haas Company | Process for preparing ceramic products |
| WO2018039620A1 (en) * | 2016-08-26 | 2018-03-01 | Sabic-Gapt | Method of making a ceramic composite material by cold sintering |
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