CN108689699A - A kind of high-flexibility artificial bone joint ceramic composite and preparation method - Google Patents
A kind of high-flexibility artificial bone joint ceramic composite and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of high-flexibility artificial bone joint ceramic composite and preparation methods, and raw material is by following components and mass percentage composition:Hydroxyapatite 30-40%, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder 30-40%, ceramic whisker 5-10%, nano-titanium oxide 5-10%, oyster shell powder 0-10%, magnesia 0-10%, calcium oxide 0-10%;The Zirconia reinforced alumina powder includes that the aluminium oxide of 60-70wt% and the zirconium oxide of 30-40wt% prepare mixed gel by coprecipitation, then are prepared by spray drying;The yttrium stable zirconium oxide powder is made of the zirconium oxide of 97wt% and the yttrium oxide of 3wt%.Artificial bone joint ceramic composite prepared by the present invention has excellent biocompatibility and flexibility, shock resistance is excellent, and thermal stability and corrosion resistance are good, and bending strength can reach 1250-1400MPa, and fracture toughness can reach 16.5-17.5MPa/m2, compressive strength reaches 750-900HV, can alternative metals or ceramic system for artificial bone or joint.
Description
Technical field
The present invention artificial skeletal joint Ceramic Composite technical field more particularly to a kind of high-flexibility artificial bone joint
With ceramic composite and preparation method.
Background technology
With the increase of joint damage caused by the aggravation of aging of population and various damages, often lead on joint structure
It changes, can only partly relieve pain symptom using drug therapy merely, it is difficult to improve function of joint.And prosthetic replacement
Can reach and relieve pain, stablize joint, correction deformity, improve the purpose of function of joint.As caused by rheumatoid arthritis
Pain, oldness abarticulation etc., are performed the operation by joint prosthesis, can apparent orthotic joint deformity, make original stiff joint
Restore normal function.Arthralgia caused by many diseases and severe dysfunction are suitable for performing the operation using prosthetic replacement,
The whole world has about 800,000 people to receive artificial operation on joint every year, and has the tendency that increasing year by year.Joint prosthesis is performed the operation
One of the most successful operation that twentieth century medically obtains, and treat one of the best method of joint diseases.
However, for the artificial joint prosthesis clinically used at present, mostly uses metal or ceramics are made, metal or ceramics
Joint biofacies content in human body is relatively low, and movement is realized in joint by the stress generated conduction is hit, and stimulates bone growth,
If using metal joint, easy ting produce " stress shielding " can not conduct, and the bone of joint part is due to a lack of thorn in the course of time
Swash and is easy " to dissolve " atrophy.In addition, there is also heavy metal ion allergy, metal erosion, polyethylene wear, imagings for metal joint
The hidden danger such as interfere, overhaul in early days.And although ceramic bone joint hardness is higher, do not have flexibility, then anti-impact force is poor, one
Denier, which is crushed its powder, will be embedded in musculature, cause secondary injury.
It is more and more with the demand of joint prosthesis, to the properties of joint prosthesis, as biocompatibility, intensity,
More stringent requirements are proposed for flexibility, interface binding power, therefore develops a kind of high-flexibility artificial bone joint Ceramic Composite
Material has great importance.
Invention content
The purpose of the present invention is to provide high-flexibility artificial bone joint ceramic composite and preparation methods, can increase
The biocompatibility of joint prosthesis and flexibility and the growth for promoting coupled joint tissue by force.
To achieve the above object, the present invention provides the following technical solutions:
A kind of high-flexibility artificial bone joint ceramic composite, raw material is by following components and mass percentage composition:Hydroxyl
Base apatite 30-40%, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder 30-40%, ceramic whisker 5-10% receive
Rice titanium oxide 5-10%, oyster shell powder 0-10%, magnesia 0-10%, calcium oxide 0-10%;The Zirconia reinforced alumina powder
The zirconium oxide of aluminium oxide and 30-40wt% including 60-70wt% prepares mixed gel by coprecipitation, then passes through spray drying
It is prepared;The yttrium stable zirconium oxide powder is made of the zirconium oxide of 97wt% and the yttrium oxide of 3wt%.
Further, raw material is by following components and mass percentage composition:Hydroxyapatite 35-40%, Zirconium oxide plasticizing
Alumina powder or yttrium stable zirconium oxide powder 35-40%, ceramic whisker 8-10%, nano-titanium oxide 8-10%, oyster shell powder 0-
5%, magnesia 0-5%, calcium oxide 0-5%;The Zirconia reinforced alumina powder includes the aluminium oxide and 30- of 60-70wt%
The zirconium oxide of 40wt% prepares mixed gel by coprecipitation, then is prepared by spray drying;The yttrium stable zirconium oxide
Powder is made of the zirconium oxide of 97wt% and the yttrium oxide of 3wt%.
Further, the ceramic whisker is silicon carbide, aluminium borate whisker mixture.
A kind of preparation method of high-flexibility artificial bone joint ceramic composite includes the following steps:(1)By hydroxyl
Base apatite, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder, oyster shell powder, nano magnesia, calcium oxide are pressed
It is mixed according to weight proportion, dispersant, deionized water stirring 30-60min is added, uniform stirring is configured to slurry;(2)Nanometer is added
Then titanium oxide carries out ball milling, wherein the ratio of material and ball is 1:(0.5-1.5);(3)Ceramic whisker and bonding agent is added
Constant temperature is stirred 4-6h, the spray-dried granulation material for obtaining can be used for subsequent forming;(4)By spray-dried granulation
Expect die-filling, cold isostatic compaction;(5)Molding blank is subjected to high temperature firing, 1100-1300 DEG C of firing temperature, heating rate 5-8
DEG C/min, after the highest temperature keeps the temperature 1-2h, natural cooling is taken out, and high-flexibility artificial bone joint Ceramic Composite material is obtained
Material.
Further, the dispersant is citric acid, macromolecule dispersing agent acrylamide or triethanolamine, the bonding
Agent is gum arabic.
Further, step(5)Middle calcination temperature is 1180 DEG C, 6 DEG C/min of heating rate.
Hydroxyapatite (HAP) is the main inorganic composition of human body and animal skeleton.It can be realized with body tissue on interface
Chemical keyness bonding has certain solubility in vivo, can discharge the ion harmless to body, can participate in being metabolized in vivo, right
Osteoproliferation has stimulation or inducing action, can promote the reparation of defective tissue, shows bioactive.Hydroxyapatite is human body bone
The host inorganic constituent of bone tissue.After implanting, calcium and the phosphorus material surface that can dissociate are systemically absorbed, and raw
Grow new tissue.
Zirconia reinforced alumina ceramic(Abbreviation Ceramic Composite, ZTA), matter is white, corrosion-resistant, chemical stability is good.Oxidation
Aluminium hardness is big, zirconium oxide good toughness, and two kinds of materials form the excellent complex of high intensity, high tenacity, and purposes is more extensive.
There is higher flexural strength and fracture toughness at normal temperatures, thus toughened zirconia ceramics have outstanding wear-resisting property.
The specific ratio of two kinds of materials can be adjusted according to the actual operation requirements of user.Zirconia reinforced alumina ceramic performance is better than
99 aluminium oxide ceramics, price are far below zirconia ceramics again;Many incompetent occasions of aluminium oxide ceramics have embodied ratio
Zirconia ceramics more preferably cost performance.
Yttrium stable zirconium oxide is a kind of ceramic material, changes the phase transformation temperature model of zirconium dioxide by addition yttrium oxide
It encloses, generates stable at room temperature cubic crystal and tetragonal crystal.The excellent crystal grain of yttrium stable zirconium oxide makes the pottery produced
Porcelain density is intensive, without many stomatas, has excellent mechanical strength, corrosion-resistant, impact flexibility, thermal shock resistance and extremely low heat conduction
Performance.
Ceramic whisker is that have monocrystal fiber and polycrystalline fibre by the whisker that raw material manufactures of special cermacis raw material.With special type
Ceramic raw material, which is the whisker of raw material manufacture, has monocrystal fiber and polycrystalline fibre (generally by the small crystalline substance of 5 × 10-3~5 × 10-2 μm
Grain is constituted).There are aluminium oxide, silicon carbide (SiC), boron carbide (B4C), zirconium dioxide, aluminium nitride (A1N) and silicon nitride (Si3N4)
Whisker etc..With high intensity, high elastic modulus, low-density, the high performances such as heat-resisting.It is divided into long fibre, fixed length by the length of fiber
Fiber and staple fiber etc..By method of manufacturing technology difference, it is divided into crystal growth, vapour deposition process, precursor process, chemical conversion
Method, fusion method etc..As toughened and reinforced material.
Magnesia is the oxide of magnesium, a kind of ionic compound.It is a kind of white solid under room temperature.Magnesia is with periclase
Form is present in nature, is the raw material of smelting magnesium.Magnesia is basic anhydride, and the general character with basic anhydride belongs to
Cementitious material.Magnesia is also widely used in rubber for metallurgical, smelting, the manufacture of advanced magnesia brick, refractory material and moisturizing material
Glue, rubber slab, rubber product, pharmaceuticals industry, food service industry, plastic plate accelerating agent, the plasticizer of fiberglass and silicon steel sheet
Face coat paint, paper production, steel ball polishing, leather processing, insulating materials, grease, dyestuff, ceramics, drier, resin,
Fire retardant etc..
Titanium dioxide is white solid or powdered amphoteric oxide, is a kind of white inorganic pigment, is had nontoxic, most
A kind of good opacity, best whiteness and brightness, it is considered to be the best white pigment of performance in the world now.Titanium white
Adhesion strength is strong, has been not easy chemical change, is snow-white forever.Be widely used in coating, plastics, papermaking, printing ink, chemical fibre,
The industry such as rubber, cosmetics.Its fusing point is very high, is also used to manufacture fireproof glass, glaze, enamel, clay, heat safe reality
Test vessel etc..
By by hydroxyapatite, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder, ceramics in the present invention
The mixing such as whisker, nano-titanium oxide, oyster shell powder, magnesia, calcium oxide, hydroxyapatite on the Nomenclature Composition and Structure of Complexes with people's bone and
Tooth is closely similar, and hydroxyapatite can make osteocyte be attached to its surface, with the growth of new bone, this connection area by
Gradually atrophy, and hydroxyapatite by crystal outer layer become bone a part, new bone can from Hydroxapatite implant body with
Growth is sought connections with along implant surfaces or internal run-through hole in green bone junction.Hydroxyapatite bioactive ceramics are typical
Bioactive ceramics can be woven on interface with group after implanting and form chemical keyness bonding, have higher mechanical property,
Resolvability is relatively low in human physiological environment.Although hydroxyapatite as artificial bone joint material biofacies content compared with
Height, but bending strength and fracture toughness are relatively low, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder are than common
Aluminium oxide ceramics or zirconia ceramics flexibility are stronger, and combine and act synergistically by ceramic whisker, greatly strengthen people
The dispersion toughening effect of the toughness of work skeletal joint ceramic composite, magnesia and nano-titanium oxide, also substantially increases pottery
The flexibility and bending strength of porcelain composite material, therefore ceramic composite prepared by the present invention has preferable biocompatibility
And mechanical property, it is a kind of preferable artificial bone joint material.
Compared with prior art, the beneficial effects of the invention are as follows:
Artificial bone joint ceramic composite prepared by the present invention has excellent biocompatibility and flexibility, impact resistance
Can be excellent, and thermal stability and corrosion resistance are good, and bending strength can reach 1250-1400MPa, and fracture toughness can reach
To 16.5-17.5MPa/m2, compressive strength reaches 750-900HV, can alternative metals or ceramic system for artificial bone or joint.
The present invention changes former ceramic material by the toughening effect of ceramic whisker, nano-titanium oxide and magnesia
Structural behaviour, the excellent performance of comprehensive hydroxyapatite and ceramic material, and the brittleness of ceramic material is overcome, the present invention passes through
Hydroxyapatite, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder, ceramic whisker, nano-titanium oxide, oyster shell
The high-flexibility artificial bone joint ceramic composite hardness that powder, magnesia, calcium oxide coordinate other auxiliary agents to prepare is high, has
Excellent toughness and wearability.
Specific implementation mode
Embodiment 1
The present embodiment high-flexibility artificial bone joint is made with ceramic composite of the raw material of following parts by weight:Hydroxy-apatite
30 parts of stone, 30 parts of Zirconia reinforced alumina powder, 10 parts of silicon carbide, aluminium borate whisker mixture, 10 parts of nano-titanium oxide, oxygen
Change 10 parts of magnesium, 10 parts of calcium oxide;
Preparation method:(1)By hydroxyapatite, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder, oyster shell powder,
Nano magnesia, calcium oxide are mixed according to weight proportion, and dispersant, deionized water stirring 30-60min is added, and uniform stirring is matched
Slurry is made;(2)Nano-titanium oxide is added, then carries out ball milling, wherein the ratio of material and ball is 1:(0.5-1.5);(3)Add
Enter silicon carbide, aluminium borate whisker mixture and bonding agent constant temperature and is stirred 4-6h, it is spray-dried to obtain can be used for subsequently
The granulation material of molding;(4)Die-filling, the cold isostatic compaction by spray-dried granulation material;(5)Molding blank is subjected to high temperature
Firing, 1100 DEG C of firing temperature, 8 DEG C/min of heating rate, after the highest temperature keeps the temperature 1-2h, natural cooling is taken out, and Gao Rou is obtained
Toughness artificial bone joint ceramic composite.
Embodiment 2
The present embodiment high-flexibility artificial bone joint is made with ceramic composite of the raw material of following parts by weight:Hydroxy-apatite
40 parts of stone, 40 parts of Zirconia reinforced alumina powder, 5 parts of silicon carbide, aluminium borate whisker mixture, 5 parts of nano-titanium oxide, oxidation
5 parts of magnesium, 5 parts of calcium oxide;
Preparation method:(1)By hydroxyapatite, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder, oyster shell powder,
Nano magnesia, calcium oxide are mixed according to weight proportion, and dispersant, deionized water stirring 30-60min is added, and uniform stirring is matched
Slurry is made;(2)Nano-titanium oxide is added, then carries out ball milling, wherein the ratio of material and ball is 1:(0.5-1.5);(3)Add
Enter silicon carbide, aluminium borate whisker mixture and bonding agent constant temperature and is stirred 4-6h, it is spray-dried to obtain can be used for subsequently
The granulation material of molding;(4)Die-filling, the cold isostatic compaction by spray-dried granulation material;(5)Molding blank is subjected to high temperature
Firing, 1100 DEG C of firing temperature, 8 DEG C/min of heating rate, after the highest temperature keeps the temperature 1-2h, natural cooling is taken out, and Gao Rou is obtained
Toughness artificial bone joint ceramic composite.
Embodiment 3
The present embodiment high-flexibility artificial bone joint is made with ceramic composite of the raw material of following parts by weight:Hydroxy-apatite
35 parts of stone, 35 parts of Zirconia reinforced alumina powder, 8 parts of silicon carbide, aluminium borate whisker mixture, 4 parts of oyster shell powder, nano oxygen
Change 8 parts of titanium, 5 parts of magnesia, 5 parts of calcium oxide;
Preparation method:(1)By hydroxyapatite, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder, oyster shell powder,
Nano magnesia, calcium oxide are mixed according to weight proportion, and dispersant, deionized water stirring 30-60min is added, and uniform stirring is matched
Slurry is made;(2)Nano-titanium oxide is added, then carries out ball milling, wherein the ratio of material and ball is 1:(0.5-1.5);(3)Add
Enter silicon carbide, aluminium borate whisker mixture and bonding agent constant temperature and is stirred 4-6h, it is spray-dried to obtain can be used for subsequently
The granulation material of molding;(4)Die-filling, the cold isostatic compaction by spray-dried granulation material;(5)Molding blank is subjected to high temperature
Firing, 1100 DEG C of firing temperature, 8 DEG C/min of heating rate, after the highest temperature keeps the temperature 1-2h, natural cooling is taken out, and Gao Rou is obtained
Toughness artificial bone joint ceramic composite.
Embodiment 4
The present embodiment high-flexibility artificial bone joint is made with ceramic composite of the raw material of following parts by weight:Hydroxy-apatite
35 parts of stone, 35 parts of Zirconia reinforced alumina powder, 8 parts of silicon carbide, aluminium borate whisker mixture, 4 parts of oyster shell powder, nano oxygen
Change 8 parts of titanium, 5 parts of magnesia, 5 parts of calcium oxide;
Preparation method:(1)By hydroxyapatite, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder, oyster shell powder,
Nano magnesia, calcium oxide are mixed according to weight proportion, and dispersant, deionized water stirring 30-60min is added, and uniform stirring is matched
Slurry is made;(2)Nano-titanium oxide is added, then carries out ball milling, wherein the ratio of material and ball is 1:(0.5-1.5);(3)Add
Enter silicon carbide, aluminium borate whisker mixture and bonding agent constant temperature and is stirred 4-6h, it is spray-dried to obtain can be used for subsequently
The granulation material of molding;(4)Die-filling, the cold isostatic compaction by spray-dried granulation material;(5)Molding blank is subjected to high temperature
Firing, 1100 DEG C of firing temperature, 6 DEG C/min of heating rate, after the highest temperature keeps the temperature 1-2h, natural cooling is taken out, and Gao Rou is obtained
Toughness artificial bone joint ceramic composite.
Embodiment 5
The present embodiment high-flexibility artificial bone joint is made with ceramic composite of the raw material of following parts by weight:Hydroxy-apatite
35 parts of stone, 35 parts of Zirconia reinforced alumina powder, 8 parts of silicon carbide, aluminium borate whisker mixture, 4 parts of oyster shell powder, nano oxygen
Change 8 parts of titanium, 5 parts of magnesia, 5 parts of calcium oxide;
Preparation method:(1)By hydroxyapatite, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder, oyster shell powder,
Nano magnesia, calcium oxide are mixed according to weight proportion, and dispersant, deionized water stirring 30-60min is added, and uniform stirring is matched
Slurry is made;(2)Nano-titanium oxide is added, then carries out ball milling, wherein the ratio of material and ball is 1:(0.5-1.5);(3)Add
Enter silicon carbide, aluminium borate whisker mixture and bonding agent constant temperature and is stirred 4-6h, it is spray-dried to obtain can be used for subsequently
The granulation material of molding;(4)Die-filling, the cold isostatic compaction by spray-dried granulation material;(5)Molding blank is subjected to high temperature
Firing, 1180 DEG C of firing temperature, 6 DEG C/min of heating rate, after the highest temperature keeps the temperature 1-2h, natural cooling is taken out, and Gao Rou is obtained
Toughness artificial bone joint ceramic composite.
In above-described embodiment dispersant be citric acid, macromolecule dispersing agent acrylamide or triethanolamine, binder be Ah
Draw uncle's natural gum.
By high-flexibility artificial bone joint ceramic composite and metal, ceramic artificial bone made from embodiment 1-5
Bone joint material carries out contrast test, and performance is as follows:
The different specimen material mechanical property tables of table 1
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Titanium alloy metal material | General ceramic material |
| Bending strength/MPa | 1255 | 1268 | 1300 | 1358 | 1400 | 1240 | 1450 |
| Fracture toughness/MPa/m2 | 16.6 | 17.0 | 17.1 | 16.9 | 17.5 | 14.1 | 13.0 |
| Compressive strength/HV | 770 | 790 | 800 | 830 | 900 | 720 | 950 |
Embodiment 1-3 comparisons, hydroxyapatite, Zirconia reinforced alumina powder, the mass ratio of ceramic whisker are different, embodiment
Ceramic composite bending strength, fracture toughness and compressive strength are good compared with Examples 1 and 2 in 3;Embodiment 4 and embodiment 3 compare
Compared with heating rate is different, and ceramic composite bending strength, fracture toughness and compressive strength are compared with embodiment 3 in embodiment 4
Height, embodiment 5 and embodiment 4 compare, and calcination temperature is different, in embodiment 5 ceramic composite bending strength, fracture toughness with
And compressive strength is high compared with embodiment 4, studies have shown that the quality of hydroxyapatite, Zirconia reinforced alumina powder, ceramic whisker
Proportioning, calcination temperature and heating rate are the several principal elements for influencing ceramic composite mechanical property, conventional ceramic material
Though the bending strength and compressive strength of material are slightly higher compared with ceramic composite, fracture toughness is minimum, Ceramic Composite of the present invention
Material comprehensive performance is best, is the favorable substitutes of artificial bone joint metal or general ceramic material.
The better embodiment of this patent is explained in detail above, but this patent is not limited to above-mentioned embodiment party
Formula, one skilled in the relevant art within the scope of knowledge, can also be under the premise of not departing from this patent objective
It makes a variety of changes.
Claims (6)
1. a kind of high-flexibility artificial bone joint ceramic composite, which is characterized in that raw material is by following components and quality
Percentage forms:Hydroxyapatite 30-40%, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder 30-40%, ceramics
Whisker 5-10%, nano-titanium oxide 5-10%, oyster shell powder 0-10%, magnesia 0-10%, calcium oxide 0-10%;The zirconium oxide increases
Tough alumina powder includes that the aluminium oxide of 60-70wt% and the zirconium oxide of 30-40wt% prepare mixed gel by coprecipitation, then
It is prepared by spray drying;The yttrium stable zirconium oxide powder is made of the zirconium oxide of 97wt% and the yttrium oxide of 3wt%.
2. high-flexibility artificial bone according to claim 1 joint ceramic composite, which is characterized in that raw material by
Following components and mass percentage composition:Hydroxyapatite 35-40%, Zirconia reinforced alumina powder or yttrium stable zirconium oxide
Powder 35-40%, ceramic whisker 8-10%, nano-titanium oxide 8-10%, oyster shell powder 0-5%, magnesia 0-5%, calcium oxide 0-5%;
The Zirconia reinforced alumina powder includes that the aluminium oxide of 60-70wt% and the zirconium oxide of 30-40wt% pass through co-precipitation legal system
Standby mixed gel, then be prepared by spray drying;The yttrium stable zirconium oxide powder by 97wt% zirconium oxide and 3wt%
Yttrium oxide composition.
3. high-flexibility artificial bone according to claim 1 joint ceramic composite, which is characterized in that the pottery
Porcelain whisker is silicon carbide, aluminium borate whisker mixture.
4. high-flexibility artificial bone as described in claim 1 joint ceramic composite, which is characterized in that preparation method
Include the following steps:(1)By hydroxyapatite, Zirconia reinforced alumina powder or yttrium stable zirconium oxide powder, oyster shell powder,
Nano magnesia, calcium oxide are mixed according to weight proportion, and dispersant, deionized water stirring 30-60min is added, and uniform stirring is matched
Slurry is made;(2)Nano-titanium oxide is added, then carries out ball milling, wherein the ratio of material and ball is 1:(0.5-1.5);(3)Add
Enter ceramic whisker and bonding agent constant temperature is stirred 4-6h, the spray-dried granulation material for obtaining can be used for subsequent forming;
(4)Die-filling, the cold isostatic compaction by spray-dried granulation material;(5)Molding blank is subjected to high temperature firing, firing temperature
1100-1300 DEG C, 5-8 DEG C of heating rate/min, after the highest temperature keeps the temperature 1-2h, natural cooling is taken out, and high-flexibility people is obtained
Work skeletal joint ceramic composite.
5. the preparation method of high-flexibility artificial bone according to claim 3 joint ceramic composite, feature
It is, the dispersant is citric acid, macromolecule dispersing agent acrylamide or triethanolamine, and the binder is Arabic sets
Glue.
6. the preparation method of high-flexibility artificial bone according to claim 3 joint ceramic composite, feature
It is, step(5)Middle calcination temperature is 1180 DEG C, 6 DEG C/min of heating rate.
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| CN112341218B (en) * | 2020-11-05 | 2022-04-12 | 中民驰远实业有限公司 | Method for preparing high-performance magnesium-zirconium composite ceramic tile by spark plasma sintering |
| CN112299843A (en) * | 2020-11-13 | 2021-02-02 | 娄底市安地亚斯电子陶瓷有限公司 | Auxiliary robot zirconia ceramic skeleton and forming process thereof |
| CN112826979A (en) * | 2021-02-25 | 2021-05-25 | 泉州新致美义齿有限公司 | Implant bridge prosthesis and preparation method thereof |
| CN112826979B (en) * | 2021-02-25 | 2023-02-24 | 泉州新致美义齿有限公司 | Planting bridge prosthesis and preparation method thereof |
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