CN101934096B - Ca-P biological glass-ceramic compound nano biological ceramic and preparation method thereof - Google Patents
Ca-P biological glass-ceramic compound nano biological ceramic and preparation method thereof Download PDFInfo
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- CN101934096B CN101934096B CN 201010220485 CN201010220485A CN101934096B CN 101934096 B CN101934096 B CN 101934096B CN 201010220485 CN201010220485 CN 201010220485 CN 201010220485 A CN201010220485 A CN 201010220485A CN 101934096 B CN101934096 B CN 101934096B
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Abstract
The invention provides Ca-P biological glass-ceramic compound nano biological ceramic which is prepared from 1-7 parts of alumina powder body and 1-8 parts of zirconia powder body in the proportion by weight through the following steps of: making the alumina powder body and the zirconia powder body into a matrix and then making 62-72 parts of matrix and 28-38 parts of Ca-P biological glass-ceramic powder body permeate with each other in the proportion by weight. The invention also provides a preparation method for the nano biological ceramic. The compound nano biological ceramic has the characteristics of high mechanical behavior, high processability, good three-dimensional size adaptability, good biocompatibility and good bioactivity, can be used as a good bone substitute to be used for bone defect repair and is especially suitable for the bone defect repair of long bones, joints and the like under the conditions of high load and abrasion.
Description
Technical field
The present invention relates to compound aluminium oxide-zirconium oxide base nano-biological cerimic of a kind of Ca-P bio-microcrystal glass and preparation method thereof, belong to the preparing technical field of high strength bioceramic material.
Background technology
The bone defect repair is one of the important heat subject of research that deepened continuously since a century always, with regard to the application of bone grafting material, except should be able to the repairing bone defect zone, and the osseous tissue that finally reaches chummage district on structure and the mechanical performance consistent outside, enough intensity, potential vigor also should be arranged, and in tissue, have no adverse reaction (nontoxic, non-immunogenicity, not carcinogenic, teratogenesis not) etc.From body spongy bone one to being so-called goldstandard for filling bone defects.For now, generally adopt freshly in body bone and homogeneous allogenic bone, but pain easily takes place and infects complication (8--10%) in the autologous bone transplanting district; Immunological rejection and communicate illness can appear in the heteroplastic transplantation bone, and the two source is all limited.Therefore, seeking desirable bone transplantation substitute material has great importance for the damaged reparation of bone.The effect of bone alternate material is the defective of repairing osseous tissue, mainly contains hydroxyapatite, bio-vitric, devitrified glass etc. at present, and with the composite of organic materials such as collagen protein, organic polymer.Inorganic substitution material is mainly as the skeleton of implant into body, and osteocyte and collagen fiber are grown thereon, finally becomes the part of live body bone.Because bone alternate material will be subjected to the effect of dynamic load behind implant into body, so except biocompatibility, material is had higher mechanical property requirements.
Present homogenous material has its certain merits and demerits, as, hydroxyapatite (HA) is the main inorganic constituents of natural bone tissue, can have excellent biological compatibility and bone conductibility as the substitute implant into body of natural bone.But because fine and close hydroxyapatite mechanical strength is lower, comprcssive strength 400MPa-917MPa, bending strength 80MPa-150MPa, and processing characteristics is poor, and mechanical performance and natural bone can not be mated fully, have limited its range of application to a certain extent.
Bio-vitric (Bioglass) has good chemical stability, biocompatibility, but compare with body bone tissue, elastic modelling quantity is very high, fragility is big, fracture toughness and mechanical strength are lower, comprcssive strength is similar substantially to hydroxyapatite with bending strength, single also very difficult as the application of bone replacing material, therefore normal employing and the compound mode of high-strength material are used clinically.Bio-vitric also is commonly used for coating for metal surfaces material and bone filler in addition.
Bio-microcrystal glass (Bioglass Ceramics) is a kind of new material that grows up on the bio-vitric basis, bio-vitric is handled the bio-microcrystal glass that obtains by crystallization and had both been kept excellent biological compatibility and biological activity, has also significantly improved mechanical property.Most typical in the bio-microcrystal glass material is with the A-W bio-microcrystal glass, and the many of dense form replace for bone, but rarely seen artificial vertebrae, the report of intervertebral disc, artificial rib etc. of successfully being used for.The porous type sintered body is commonly used to repair cranium jaw portion's bony defect and correction deformity and cosmetic surgery art.Corpuscular material then generally is used for the control of alveolar ridge atrophy, the filling of tooth nest, bone defect repairing and protect marrow, lid marrow etc.Though and zirconium oxide-hydroxyapatite composite ceramics intensity is higher than pure ha, wearability still is difficult to satisfy the strength demand of joint, long bone; Ball and socket joint or long bone have very high required precision aspect three-dimensional dimension, and adopt the method for ordinary sinter molding, and its shrinkage factor is up to about 15%～20%, and precision is restive.Though aluminium oxide, zirconia ceramics intensity are higher, belong to bio-inert material, not biologically active.Above-mentioned several bioactive materials is only applicable to the bone filling reparation of bone defect basically, does not see the report that is applied to long bone or osteoarticular defect repair.
In sum, prior biological pottery (hydroxyapatite, bio-vitric, devitrified glass etc.) low, the poor toughness of mechanical strength, not wear-resistant, poor processability is used limited under high capacity such as long bone, joint and the demanding condition of mechanical compatibility.
Summary of the invention
Technical scheme of the present invention has provided compound bioceramic of a kind of aluminium oxide-zirconium oxide base Ca-P bio-microcrystal glass and preparation method thereof.
The invention provides the compound nano-biological cerimic of a kind of Ca-P bio-microcrystal glass, it is that alumina powder jointed and Zirconium powder by following weight proportion is prepared into matrix, is prepared from the infiltration of Ca-P bio-microcrystal glass powder body high-temperature liquid-phase:
Alumina powder jointed 1-7 part, Zirconium powder 1-8 part;
Wherein the weight proportion of matrix and Ca-P bio-microcrystal glass is:
Matrix 62-72 part, Ca-P bio-microcrystal glass 28-38 part.
Further preferably, it is that alumina powder jointed and Zirconium powder by following weight proportion is prepared into matrix, is prepared from the infiltration of Ca-P bio-microcrystal glass powder body high-temperature liquid-phase:
1 part of alumina powder jointed 1 part, Zirconium powder;
Wherein the weight proportion of matrix and Ca-P bio-microcrystal glass is:
72 parts of matrixes, 28 parts of Ca-P bio-microcrystal glass.
It is to be matrix by alumina powder jointed, Zirconium powder, and through molding, drying, sintering, the infiltration of Ca-P bio-microcrystal glass powder body high-temperature liquid-phase makes the nano combined bioceramic of Ca-P bio-microcrystal glass infiltration.
Wherein, the component of described bio-vitric is Na
2O-Cao-La
2O
3-TiO
2-ZrO
2-P
2O
5-SiO
2-B
2O
3, wherein, Na
2The amount of O and CaO accounts for the 38%-42% of bio-vitric total amount; TiO
2And ZrO
2Amount account for the 4%-8% of bio-vitric total amount; La
2O
3Amount account for the 9%-15% of bio-vitric total amount, P
2O
5Account for the 19%-21% of bio-vitric total amount, SiO
2, B
2O
3Amount account for the 23%-34% of bio-vitric total amount, 1450 ℃ of-1500 ℃ of fusions of platinum crucible are made into glass powder through pulverizing, its granularity is 50 orders-100 orders.
Further preferably, Na in the component of described bio-vitric
2O and CaO account for 40% of bio-vitric total amount; TiO
2And ZrO
2Account for 6% of bio-vitric total amount; La
2O
3Account for 12% of bio-vitric total amount, P
2O
5, SiO
2And B
2O
3Account for 42% of bio-vitric total amount.
The present invention also provides a kind of method for preparing described nano-biological cerimic, and it comprises the steps:
A, alumina powder jointed, the Zirconium powder of preparation, preparation in proportion adds dispersant and is prepared into distributed slurry;
Wherein alumina powder jointed, Zirconium powder includes micron, submicron, nano level α-Al
2O
3, ZrO
2, nano alumina powder jointed preparation: with Al (NO
3)
3Be presoma, be mixed with solution, with NH
3Aqueous solution control pH ≈ 9 handles alcohol washing, lyophilization, sintering through hydro-thermal method; Nano zirconium oxide powder preparation: with ZrOCl
2.8H
2O is presoma, adds 6%-8%MolY (NO
3)
3, be mixed with the mixed solution of molar concentration scope 0.8mol～1.2mol/L, with NH
3Aqueous solution is made precipitant, and control pH ≈ 9 makes zirconium, yttrium colloid handle through hydro-thermal method, the alcohol washing, and lyophilization, sintering obtains the stabilized nano Zirconium powder;
B, with the described slip of a step injection forming in the artificial bone model; 1110 ℃ of-1350 ℃ of presintering; Be prepared into nanometer micropore skeleton matrix;
C, Ca-P bio-vitric and nanometer micropore skeleton are carried out the nanometer assembling, the Ca-P bio-vitric forms nano level microcrystalline film with liquid infiltration among the porous skeleton hole under 1100 ℃ of-1300 ℃ of temperature, 850 ℃ of insulations 0.5 hour, carry out controlled micro crystallization and handle, namely get nano-biological cerimic.
Wherein, the amount that contains alumina in Nano level and nanoscale Zirconium powder in described alumina powder jointed, the Zirconium powder of a step accounts for powder body total amount 15%～25%.
Wherein, α-Al in the described distributed slurry of a step
2O
3, ZrO
2Weight percentage be 85%～90%; Described dispersant is by a kind of in polyvinyl alcohol, Polyethylene Glycol, arabic gum, polyacrylic acid, citric acid, sodium citrate, the polyacrylamide or aqueous solution that several are formed, and the dispersant total amount accounts for the 0.1%-2% of slip total amount.
Wherein, the described sintering temperature of b step is 1100 ℃～1350 ℃ pre-burnings.
The present invention also provides the utilization of this nano-biological cerimic in preparation long bone or osteoarticular impairment renovation material.
The present invention adopts the osmotic ceramic forming technique, high strength, the high-wearing feature of zirconium oxide, aluminium oxide are combined with the biological activity of Ca-P bio-microcrystal glass, overcome the defective of Ca-P bio-microcrystal glass on mechanical property, make material can keep good biological activity, has the favorable mechanical performance again, bending strength can reach 500MPa-700MPa, and toughness reaches 4MPa/m
-1/2-5.6MPa/m
-1/2, the sinter molding shrinkage factor can have good processing characteristics less than 0.5%, can be used as the bone alternate material under high capacity, the conditions easy to wear such as long bone, joint.This material main feature is to utilize bio-microcrystal glass to coat the blapharoplast surface with form of film, can form biocompatibility good binding interface with osseous tissue.
The present invention adopts nano combined and the ceramic making technology, makes the biologically active artificial bone substitution material of a kind of high bioactivity, high strength, high-wearing feature, high accuracy and tool machinability.The complex of the whole homogeneous of the present invention, the equally distributed bioceramic of component that has high strength, toughness simultaneously can be used as bone renovating material and is directly used in the bone defect repair.The nano combined bioceramic of preparation is made up of nanocrystal, utilizes nanotechnology, has the good mechanical performance, can be used as the alternative material of bone for the bone defect repair.
Description of drawings
Fig. 1 bioceramic fabricating technology of the present invention route flow process
Fig. 2 aluminium oxide, zirconia base body opening crack distribute
Matrix cross-section morphology before the infiltration of Fig. 3 bio-vitric
Complex cross-section morphology behind Fig. 4 bio-vitric matrix permeability
The specific embodiment
Embodiment one: the preparation of the nano combined bioceramic of the present invention
With Al (NO
3)
3Be presoma, be mixed with certain density solution, with NH
3Aqueous solution control pH handles through hydro-thermal method, the alcohol washing, and lyophilization, 1400 ℃ of sintering are prepared into α-Al
2O
3Powder body, mean diameter 2.5 μ m.With ZrOCl
2.8H
2O or Zr (NO
3)
4.12H
2O is presoma, adds 9%MolY (NO
3)
3, be mixed with certain density mixed solution, with NH
3Aqueous solution is made precipitant, and control PH ≈ 9 makes zirconium, yttrium colloid handle through hydro-thermal method, the alcohol washing, and lyophilization, 1250 ℃ of sintering obtain partially stabilized Zirconium powder, its average particle size 40nm.Add part and be nano aluminium oxide, the nano zirconium oxide powder that disperse distributes, its micron, submicron particle constitute rigid backbone jointly, and it adds the total amount 15%～25% that nano-powder accounts for powder body.α-Al
2O
3Powder body and PZT-ZrO
2Carry out multistage grating according to closelypacked principle, aluminium oxide: zirconic weight ratio is 7: 3; Add organic dispersing agent Polyethylene Glycol, polyacrylic acid and sodium citrate, it adds quality and is followed successively by 1.5%, 0.3%, 0.15% of matrix material; Utilize its steric effect to improve slip uniformity, dispersibility and suspension, after the slip preparation, namely according to application target preformation biscuit body, forming the continuous nanometer micropore that communicates with each other in 2 hours through 1200 ℃ of insulations is main skeleton.Through 1230 ℃ of pre-burnings, namely be made into the micropore matrix.Fig. 2 is that aluminium oxide, zirconia base body opening crack distribute.Select the bio-vitric system for use, its component is Na
2O-CaO-La
2O
3TiO
2-ZrO
2-P
2O
5-SiO
2-B
2O
3, screening glass formation range, 1450 ℃ of-1500 ℃ of fusions of platinum crucible are made into glass powder through pulverizing, and its granularity is 50 orders-100 orders.Na
2The total amount 40% of O, CaO; TiO
2, ZrO
2The total amount of thing is 6%; La
2O
3Total amount be 12%, P
2O
5, SiO
2, B
2O
3Total amount be 42%.At 1200 ℃, the Ca-P bio-vitric is infiltrated in the liquid phase mode among the micropore that communicates with each other, and glass infiltration complex is carried out controlled micro crystallization handle, be about to it 850 ℃ of insulations 0.5 hour, namely be made into the nano combined bioceramic of Ca-P bio-microcrystal glass infiltration.After measured, matrix is 65%, Ca-P bio-microcrystal glass 35% (mass ratio) mutually.(Fig. 3 and Fig. 4 are respectively the scanning electron microscopic observation diagram before and after the glass infiltration.
Embodiment two: the preparation of the nano combined bioceramic of the present invention
Method with embodiment one prepares aluminium oxide and Zirconium powder, aluminium oxide and Zirconium powder are preparation in 1: 1 according to mass ratio, powder granularity carries out multistage grating by closelypacked principle, selecting Polyethylene Glycol, polyacrylic acid, polyacrylamide for use is organic dispersing agent, it adds quality and is followed successively by 0.5% of matrix material, 0.2%, 0.7%; Utilize its steric effect to improve slip uniformity, dispersibility and suspension, after the slip preparation, namely according to application target preformation biscuit body, through 1210 ℃ of pre-burnings, namely be made into the micropore matrix.After measured, matrix is 72%, Ca-P bio-microcrystal glass 28% (mass ratio) mutually.At 1190 ℃, the Ca-P bio-microcrystal glass is infiltrated in the liquid phase mode among the micropore that communicates with each other, namely be made into the nano combined bioceramic of Ca-P bio-microcrystal glass infiltration.
Embodiment three: the preparation of the nano combined bioceramic of the present invention
Method with embodiment one prepares aluminium oxide and Zirconium powder, aluminium oxide and Zirconium powder are preparation in 2: 8 according to mass ratio, powder granularity carries out multistage grating by closelypacked principle, selecting arabic gum, sodium citrate for use is organic dispersing agent, it adds quality and is followed successively by 0.7%, 0.2% of matrix material; Utilize its steric effect to improve slip uniformity, dispersibility and suspension, after the slip preparation, namely according to application target preformation biscuit body, through 1220 ℃ of pre-burnings, namely be made into the micropore matrix.After measured, matrix is 62%, Ca-P bio-microcrystal glass 38% (mass ratio) mutually.At 1200 ℃, the Ca-P bio-microcrystal glass is infiltrated in the liquid phase mode among the micropore that communicates with each other, namely be made into the nano combined bioceramic of Ca-P bio-microcrystal glass infiltration.
Measure bending strength and the fracture toughness of the nano-biological cerimic of embodiment 1-3 preparation respectively, concrete outcome is as follows:
Nano-biological cerimic bending strength and fracture toughness that the Ca-P bio-microcrystal glass of the different embodiments of table 1 is compound
| Embodiment one | Embodiment two | Embodiment three | |
| Bending strength (MPa) | 615 | 635 | 590 |
| Fracture toughness (MPa/m -1/2) | 5.12 | 5.45 | 5.14 |
In sum, the present invention adopts the osmotic ceramic forming technique, high strength, the high-wearing feature of zirconium oxide, aluminium oxide are combined with the biological activity of Ca-P bio-microcrystal glass, overcome the defective of Ca-P bio-microcrystal glass on mechanical property, make material can keep good biological activity, have the favorable mechanical performance again, bending strength can reach 500MPa-700MPa, and toughness reaches 4MPa/m
-1/2-5.6MPa/m
-1/2, the sinter molding shrinkage factor can have good processing characteristics less than 0.5%, can be used as the bone alternate material under high capacity, the conditions easy to wear such as long bone, joint.
Claims (1)
1. nano-biological cerimic that the Ca-P bio-microcrystal glass is compound is characterized in that: it is that alumina powder jointed and Zirconium powder by following weight proportion is prepared into matrix, is prepared from Ca-P biological glass powder height temperature liquid infiltration:
Alumina powder jointed 1-7 part, Zirconium powder 1-8 part;
Wherein the weight proportion of matrix and Ca-P bio-vitric is:
Matrix 62-72 part, Ca-P bio-vitric 28-38 part;
The component of described bio-vitric is Na
2O-CaO-La
2O
3-TiO
2-ZrO
2-P
2O
5-SiO
2-B
2O
3,Wherein, Na in the component of described bio-vitric
2O and CaO account for 40% of bio-vitric total amount; TiO
2And ZrO
2Account for 6% of bio-vitric total amount; La
2O
3Account for 12% of bio-vitric total amount, P
2O
5, SiO
2And B
2O
3Account for 42% of bio-vitric total amount, 1450 ℃ of-1500 ℃ of fusions of platinum crucible are made into glass powder through pulverizing, and its granularity is 50 orders-100 orders.
2, nano-biological cerimic according to claim 1 is characterized in that: it is that alumina powder jointed and Zirconium powder by following weight proportion is prepared into matrix, is prepared from Ca-P biological glass powder height temperature liquid infiltration:
1 part of alumina powder jointed 1 part, Zirconium powder;
Wherein the weight proportion of matrix and Ca-P bio-vitric is:
72 parts of matrixes, 28 parts of Ca-P bio-vitrics.
3, a kind of method for preparing claim 1 or 2 described nano-biological cerimics, it comprises the steps:
A, alumina powder jointed, the Zirconium powder of preparation, preparation in proportion adds dispersant and is prepared into distributed slurry;
B, with the described slip of a step injection forming in the artificial bone model; 1110 ℃ of-1350 ℃ of presintering; Be prepared into nanometer micropore skeleton matrix;
C, Ca-P bio-vitric and nanometer micropore skeleton are carried out the nanometer assembling, the Ca-P bio-vitric forms nano level microcrystalline film with liquid infiltration among the porous skeleton hole under 1100 ℃ of-1300 ℃ of temperature, handle 850 ℃ of controlled micro crystallizations, namely get nano-biological cerimic.
4, preparation method according to claim 3 is characterized in that: ZrO in the described distributed slurry of a step
2, α-Al
2O
3, weight percentage be 85%～90%; Described dispersant is by a kind of in polyvinyl alcohol, Polyethylene Glycol, arabic gum, polyacrylic acid, citric acid, sodium citrate, the polyacrylamide or aqueous solution that several are formed, and the dispersant total amount accounts for the 0.1%-2% of slip total amount.
5, preparation method according to claim 3 is characterized in that: the described pre-sintering temperature of b step is 1230 ℃.
6, claim 1 or the 2 described nano-biological cerimics utilization in preparation long bone or osteoarticular impairment renovation material.
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| WO2013019099A1 (en) * | 2011-08-03 | 2013-02-07 | Universiti Sains Malaysia | Nanostructured carbonated hydroxy apatite and method and system for making the same |
| CN104446386B (en) * | 2014-11-10 | 2016-05-18 | 新昌县镜岭镇康柳电子元件厂 | Be used for aluminium oxide ceramics of hip joint and preparation method thereof |
| CN104446387B (en) * | 2014-11-10 | 2016-05-18 | 宁夏康诚机电产品设计有限公司 | For capital aluminium oxide ceramics and preparation method thereof |
| CN108558393B (en) * | 2018-01-18 | 2021-05-28 | 东莞信柏结构陶瓷股份有限公司 | Wear-resistant zirconia ceramic |
| CN114522107A (en) * | 2020-11-23 | 2022-05-24 | 松山湖材料实验室 | Dental adhesive and method for preparing dental product |
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| CN1032423C (en) * | 1986-10-20 | 1996-07-31 | 丸野重雄 | Biological adaptability composite and its preparation method |
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| CN1322842C (en) * | 1999-07-20 | 2007-06-27 | 四川大学 | Method for making or repairing tooth crown or bridge with high-strength cuttable osmotic ceramic |
| CN1226053C (en) * | 2000-08-07 | 2005-11-09 | 松下电工株式会社 | Artificial joint made from zirconia-alumina composite ceramic |
| DE10244439A1 (en) * | 2002-09-24 | 2004-03-25 | Mathys Orthopädie GmbH | Endoprosthesis component used as an artificial joint comprises a ceramic material containing aluminum oxide and zirconium (di)oxide |
| EP1679089A4 (en) * | 2003-10-30 | 2009-11-04 | Kyocera Corp | Biological member and method for manufacturing thereof |
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