CN1267159C - Biological living being in medical use for Embeded to human body, and preparation method - Google Patents
Biological living being in medical use for Embeded to human body, and preparation method Download PDFInfo
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- CN1267159C CN1267159C CN 200310108348 CN200310108348A CN1267159C CN 1267159 C CN1267159 C CN 1267159C CN 200310108348 CN200310108348 CN 200310108348 CN 200310108348 A CN200310108348 A CN 200310108348A CN 1267159 C CN1267159 C CN 1267159C
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Abstract
The present invention relates to a medical biological body to be transplanted into human bodies and a preparation method thereof. The medical biological body to be transplanted into human bodies is prepared by compounding a Ca-Si-P-Mg four-element bioglass coating and metal, more specifically to a novel medical biological body to be transplanted into human bodies is prepared by depositing Ca-Si-P-Mg four-element bioglass on the surface of a titanium alloy (Ti-6Al-4V) substrate. The present invention is characterized in that the bioglass coating is composed of a glass phase, wherein the glass phase contains the micro crystals of calcium phosphate and calcium silicate. The thermal expansion coefficient of the bioglass coating approaches to the expansion coefficient of the titanium alloy substrate. The thickness of the bioglass coating is from 300 mu m to 600 mu m, and the porosity of the bioglass coating is from 11.0 % to 12.5 %. The shearing strength of the bioglass coating and the titanium alloy substrate can be up to 19 to 26Mpa. The results of human body simulated body fluid (SBF) immersion and animal experiments show that the bioglass coating on the surface of the medical biological body to be transplanted into human bodies has good bioactivity and biocompatibility.
Description
Technical field
The present invention relates to a kind of new medical bio implant and preparation method, or rather, utilize the plasma jet spraying technology, Ca-Si-P-Mg quaternary system bio-vitric is deposited on titanium alloy-based surface, be prepared into a kind of high strength medical bio implant.Belong to the biomaterial for medical purpose field.
Technical background
Titanium alloy material (Ti-6Al-4V) has better biocompatibility and excellent mechanical property, is widely used in substituting of plastic surgery and human body hard tissue in early days.But this alloy material lacks biological activity, can not form chemical bonding with osseous tissue after implanting.Hydroxyapatite (HA) has superior bioactive and biocompatibility, can combine closely with osseous tissue in human body.But hydroxyapatite (HA) block materials mechanical strength is poor, the load that can not bear bone.Utilizing the plasma jet spraying technology at present both at home and abroad, in titanium alloy-based surface spraying hydroxyapatite coating, is the effective ways that improve medical bio implant biological activity and mechanical property.But because the thermal coefficient of expansion of hydroxyapatite thermal coefficient of expansion and titanium alloy material differs greatly (the hydroxyapatite thermal coefficient of expansion is 16.4 * 10-6/ ℃-18.6 * 10-6/ ℃), cause hydroxyapatite coating internal stress bigger, the poor bonding strength of coating and titanium alloy substrate makes coating be easy to come off from matrix surface.
The little Kubo professor of Japan is on the basis of bio-vitric at research Ca-Si-P-Mg, and by being that bio-vitric is heat-treated at 1050 ℃ to Ca-Si-P-Mg, the A-W glass ceramics has been invented in preparation.This glass ceramics is made up of calcium phosphate and calcium silicates crystalline phase, has superior bioactive and mechanical strength.And the coexistence of calcium phosphate and calcium silicates crystalline phase, its thermal coefficient of expansion might be approaching with titanium alloy material, can improve the binding ability of coating and titanium alloy substrate.
Summary of the invention
The present invention has overcome the above-mentioned shortcoming of prior art, by component design and adjustment to (45S) bio-vitric and A-W glass ceramics, develop a kind of Ca-Si-P-Mg quaternary system bio-vitric, this bio-vitric thermal coefficient of expansion is 9.61 * 10-6/ ℃-10.84 * 10-6/ ℃, with the thermal coefficient of expansion comparison match of titanium alloy substrate, help combining of coating and matrix.
The object of the invention is to utilize the plasma jet spraying technology, the Ca-Si-P-Mg quaternary system bio-vitric of special component design is deposited on titanium alloy-based surface, be prepared into medical bio implants such as artificial joint that the surface coats the bio-vitric coating, pelvis, blade plate, screw, tooth root, coating and matrix bond are firm.
Bio-vitric coating of the present invention is made up of uncrystallized glassy phase, contains calcium phosphate and calcium silicates micro-crystallization.
Bio-vitric coating layer thickness of the present invention is 300 μ m-600 μ m.The coating porosity is 11.0%-12.5%, and the shear strength between coating and matrix is 19-26Mpa.The coating micropore size is between 5-10 μ m.
Ca-Si-P-Mg quaternary system bio-vitric coating of the present invention has no side effect in human body, no mutagenicity, and technology is simple, and is with low cost.
Concrete technology of the present invention is: with the Ca-Si-P-Mg quaternary system bio-vitric of fusion method preparation, its component is: (Wt%)
SiO2 35-42
CaO 30-40
P2O5 10-20
MgO 4-8
F 0-2
Plasma jet spraying coating process of the present invention is:
Plasma spray coating master gas N2 or Ar flow are the 30-46 standard liter/min
Plasma spray coating gas (H2) flow is the 5-10 standard liter/min
Spray distance 90-120mm
Powder carrier gas N2 or Ar flow are the 2-10 standard liter/min
Powder feeding rate 18g-25g/min
Spraying current 420A-500A
Spray voltage 75V-88V
Description of drawings
Fig. 1 is the electron micrograph that the invention provides glass coating.As seen from the figure, coating has loose structure.The micropore size is at the 5-10 micrometer range.This microcellular structure helps that osseous tissue is grown into and combines closely with its formation.
Fig. 2 is that glass coating provided by the invention and glass coating soak the XRD figure after three days in human body simulation body fluid.As seen from the figure, glass coating presents the non-crystalline glass phase, wherein contains the small crystalline substance of calcium phosphate and calcium silicates.And soak glass coating after three days, the crystalline phase of carbonic acid hydroxyapatite is very ripe, illustrates that glass coating has superior bioactive in human body simulation body fluid.
Fig. 3 is that bio-vitric provided by the invention soaks the stereoscan photograph after three days in human body simulation body fluid.As seen from the figure, coating surface generates a large amount of typical carbonic acid hydroxyapatite crystal, illustrates that glass coating has superior bioactive in human body simulation body fluid.
Fig. 4 is that bio-vitric coating artificial tooth root provided by the invention is implanted Canis familiaris L. oral cavity bone stereoscan photograph after six months.T: titanium alloy, S: bio-vitric coating, B: osseous tissue.The bio-vitric coating combines very closely with titanium alloy substrate and osseous tissue as seen from the figure, joins together with osseous tissue, forms tabular closely bone.This explanation glass coating has superior bioactive and biocompatibility in vivo, can form the bone bonding with osseous tissue.
The specific embodiment
Excellent characteristics of the present invention and effect can be described from the following example, but they are not that the present invention is imposed any restrictions.
Embodiment 1 is according to chemical composition: (Wt%)
SiO2 40.9
CaO 39.2
P2O5 13.0
MgO 6.4
F 0.2
After the powder that is mixed with stirs, through 1410 ℃ of high-temperature fusion, pour quenching in the water then rapidly into, the spraying powder is made in oven dry.Utilize the plasma jet spraying technology, the bio-vitric powder is deposited in medical titanium alloy base (Ti-6Al-4V) the artificial tooth root implantation body of cleaning with blasting treatment (implantation body's diameter is 4mm), spraying parameter is:
Plasma spray coating master gas (N2) flow is 40 standard liter/min
Plasma spray coating gas (H2) flow is 6 standard liter/min
Spray distance 100mm
Powder carrier gas (N2) flow is 3 standard liter/min
Powder feeding rate 20g
Spraying current 430A
Spray voltage 85V
This glass coating artificial tooth root implantation body, coating is made up of glassy phase, wherein contains calcium phosphate and calcium silicates micro-crystallization.Coating layer thickness is about 400 μ m, and thermal coefficient of expansion is 10.49 * 10-6/ ℃.Coating was soaked in simulated body fluid (SBF) after three days, and coating surface generates a large amount of carbonate-hydroxylapatite crystalline phases that contain.Fig. 1 is the XRD figure of glass coating, as seen from the figure, does not soak glass coating and presents the non-crystalline glass phase.Fig. 2 is the glass coating of immersion after three days, and the crystalline phase of hydroxyapatite is very ripe, illustrates that glass coating has good biological activity in human body simulation body fluid (SBF).Fig. 3 is Electronic Speculum (SEI) photo that bio-vitric soaked in human body simulation body fluid (SBF) three days, can clearly find from figure, and the surface generates a large amount of hydroxyapatite crystal, illustrates that glass coating has superior bioactive and biocompatibility.
Embodiment 2 is according to chemical composition: (Wt%)
SiO2 41.0
CaO 40.0
P2O5 13.0
MgO 6.0
After the powder that is mixed with stirs, through 1410 ℃ of high-temperature fusion, pour quenching in the water then rapidly into, the spraying powder is made in oven dry.Utilize the plasma jet spraying technology, the bio-vitric powder is deposited on medical titanium alloy base (Ti-6Al-4V) the artificial joint implant that cleans with blasting treatment.Spraying parameter is:
Plasma spray coating master gas (N2) flow is 45 standard liter/min
Plasma spray coating gas (H2) flow is 6 standard liter/min
Spray distance 110mm
Powder carrier gas (N2) flow is 3 standard liter/min
Powder feeding rate 20g
Spraying current 450A
Spray voltage 85V
This glass coating artificial joint implant, coating layer thickness are 500 μ m, and coating combines well with titanium alloy-based, and shear strength reaches 25.17Mpa, and thermal coefficient of expansion is 10.49 * 10-6/ ℃.Coating is made up of glassy phase, contains calcium phosphate and calcium silicates micro-crystallization.The result of glass coating in zoopery can be referring to accompanying drawing 4, and Fig. 4 illustrates that glass coating has superior bioactive and biocompatibility, and no toxicity can form the bone bonding with osseous tissue, implants and has formed tabular closely bone after six months.
Claims (3)
1. medical bio implant, it is made up of bio-vitric coating and titanium alloy substrate, and titanium alloy substrate is Ti-6Al-4V, it is characterized in that:
(1) percentage composition of described bio-vitric coating weight is:
SiO
2 35-42
CaO 30-40
P
2O
5 1-20
MgO 4-8
F 0-2
(2) described bio-vitric coating is made up of glassy phase, wherein contains calcium phosphate and calcium silicates micro-crystallization.
2. by the described medical bio implant of claim 1, the thickness that it is characterized in that the bio-vitric coating is 300 μ m-600 μ m, and the pore size of coating is between 5-10 μ m.
3. preparation is as the method for claim 1 or 2 any described medical bio implants of claim, comprise matrix cleaning, sandblast, it is characterized in that the plasma jet spraying parameter is:
Plasma spray coating master gas N
2Or the Ar flow is the 30-46 standard liter/min
Plasma spray coating gas H
2Flow is the 5-10 standard liter/min
Spray distance 90-120mm
Powder carrier gas N
2Or the Ar flow is the 2-10 standard liter/min
Powder feeding rate 18g-25g/min
Spraying current 420A-500A
Spray voltage 75V-88V
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310108348 CN1267159C (en) | 2003-10-31 | 2003-10-31 | Biological living being in medical use for Embeded to human body, and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200310108348 CN1267159C (en) | 2003-10-31 | 2003-10-31 | Biological living being in medical use for Embeded to human body, and preparation method |
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| CN1539512A CN1539512A (en) | 2004-10-27 |
| CN1267159C true CN1267159C (en) | 2006-08-02 |
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| CN 200310108348 Expired - Fee Related CN1267159C (en) | 2003-10-31 | 2003-10-31 | Biological living being in medical use for Embeded to human body, and preparation method |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101015711B (en) * | 2007-02-07 | 2010-05-19 | 北京大学 | Medical implantation material capable of by degraded by body fluid and its preparing process |
| CN101554491B (en) * | 2009-05-27 | 2012-10-03 | 四川大学 | Method for preparing bioactive glass coating by liquid-phase thermal spray |
| CN101927034A (en) * | 2009-12-25 | 2010-12-29 | 成都华西一为生物植体科技有限公司 | Bone repair implant coated with strontium-doped calcium polyphosphate coating and preparation method thereof |
| CN101862231B (en) * | 2010-05-12 | 2013-05-08 | 中国人民解放军第四军医大学 | Method for preparing prosthesis with tantalum coating |
| CN101837145B (en) * | 2010-06-22 | 2013-01-09 | 上海交通大学 | High-toughness corrosion-resistant magnesium alloy implanted material capable of being degraded in organism |
| CN101884807B (en) * | 2010-06-24 | 2013-06-26 | 同济大学 | Preparation method for borate antibacterial glass coating with bioactivity and application thereof |
| CN106913905B (en) * | 2015-12-24 | 2020-02-14 | 中国科学院上海硅酸盐研究所 | Cerium dioxide doped calcium silicate coating with good degradation resistance and antibacterial performance and preparation method and application thereof |
| CN114558177B (en) * | 2022-03-11 | 2022-10-04 | 大博医疗科技股份有限公司 | Implant with bioactive coating and manufacturing method thereof |
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2003
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