CN102303977A - Method for preparing titanium-iron particle reinforced hydroxyapatite-based bioceramic material - Google Patents
Method for preparing titanium-iron particle reinforced hydroxyapatite-based bioceramic material Download PDFInfo
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- CN102303977A CN102303977A CN201110134929A CN201110134929A CN102303977A CN 102303977 A CN102303977 A CN 102303977A CN 201110134929 A CN201110134929 A CN 201110134929A CN 201110134929 A CN201110134929 A CN 201110134929A CN 102303977 A CN102303977 A CN 102303977A
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- hydroxy apatite
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Abstract
The invention discloses a method for preparing a titanium-iron particle reinforced hydroxyapatite-based bioceramic material and belongs to the technical field of materials. The method comprises the following steps: mixing titanium powder and iron powder, mixing and finely grinding by ball milling and obtaining composite powder; mixing the composite powder with hyaluronic acid (HA) powder to obtain mixed powder, uniformly mixing by ball milling in absolute ethanol serving as a medium, drying under a condition of a temperature of 80+/-5 DEG C to remove ethanol and obtaining HA/Ti-Fe powder; and subjecting HA/Ti-Fe powder to unidirectional press forming or cold isostatic press forming, sintering under vacuum conditions and obtaining the titanium-iron particle reinforced hydroxyapatite-based bioceramic material. The method disclosed by the invention is simple in process and low in cost, and can realize industrial production easily; and the prepared bioceramic material has excellent mechanical performance and biological performance.
Description
Technical field
The invention belongs to the material technology field, particularly a kind of preparation method of ferrotianium particle enhanced hydroxy apatite-base bioceramic material.
Background technology
Hydroxyapatite (HA) has good biocompatibility, biological activity, osteoconductive, so hydroxyapatite is being brought into play more and more important effect in the function aspects of reparation, replacement and the raising sclerous tissues of biological hard tissue.But, can't satisfy the requirement of body to its mechanical property because hydroxyapatite fragility is bigger.Metallic substance titanium (Ti) is the most extensive in clinical application at present because of its excellent mechanical property and biological property, and therefore comprehensive HA excellent biological compatibility and Ti favorable mechanical performance prepare the concern that matrix material enjoys domestic and international investigator.Mainly be to utilize powder metallurgic method to adopt hot-pressing sintering technique to prepare the HA/Ti matrix material at present, the report of preparation Ti-6Al-4V/HA matrix material is abroad also arranged.Though discover that the sintering process such as hot pressing that adopt can only be made the goods of simple shape, and cost is high through introducing the toughness that metal titanium (Ti) or its alloy can improve pure HA pottery.In addition, the decomposition of HA is brought out in the existence of Ti, and can continue to react with the degradation production of HA, causes having only the Ti of very small amount or almost not having Ti to remain in the matrix in the sintered compact of final formation.Therefore how the low-cost HA/Ti matrix material that obtains good mechanical performance, the easy control of shape becomes present urgent problem.
Summary of the invention
The objective of the invention is to existing hydroxyapatite (Ca
10(PO
4)
6(OH)
2) deficiency of based composite ceramic material on performance; A kind of preparation method of ferrotianium particle enhanced hydroxy apatite-base bioceramic material is provided; Through in the HA/Ti matrix material, introducing iron, and adopt vacuum sintering to prepare hydroxyapatite based composite ceramic material with good mechanical property and biology performance.
The preparation method of ferrotianium particle enhanced hydroxy apatite-base bioceramic material of the present invention carries out according to the following steps:
1, titanium valve and iron powder are mixed, titanium valve accounts for 50 ~ 80% of whole material gross weights, is that medium ball milling mixer mill is thin then with the dehydrated alcohol, and extremely all the particle size of materials is 1 ~ 5 μ m, processes composite granule;
2, composite granule and HA powder mixes are processed mixed powder; Composite granule accounts for 5 ~ 20% of mixed powder gross weight; Then with mixed powder with the dehydrated alcohol for the medium ball milling mixes, oven dry is removed ethanol and is obtained the HA/Ti-Fe powder under 80 ± 5 ℃ of conditions again;
3, with the HA/Ti-Fe powder through unidirectional compacting or the moulding of isostatic cool pressing mode, process biscuit;
4, biscuit is carried out sintering under vacuum condition, sintering temperature is 900 ~ 1200 ℃, and soaking time is 45 ~ 300min, obtains ferrotianium particle enhanced hydroxy apatite-base bioceramic material.
The initial particle size of above-mentioned titanium valve is 300 ~ 500 orders, and the initial particle size of iron powder is 300 ~ 500 orders.
The particle size of the Ti-Fe composite granule behind the above-mentioned ball milling is 1 ~ 5 μ m.
Above-mentioned HA powder particle size is 80 ~ 200mm.
Vacuum tightness during above-mentioned vacuum condition sintering is 10 ~ 50Pa.
Ferrotianium particle enhanced hydroxy apatite-base bioceramic material of the present invention is compared with traditional HA/Ti matrix material, has following characteristics:
1, introduce Fe in the hydroxy apatite-base bioceramic material, can suppress bioceramic material in use HA decomposition and with the reaction of Ti, toughness phase Ti has been retained in the HA matrix;
2, the Fe that introduces in the hydroxy apatite-base bioceramic material has promoted the diffusion of Ti atom, and surface reaction is under control, and through vacuum sintering cheaply, behind lower sintering temperature, the matrix material of gained has higher density;
3, the Ti-Fe enhanced granule is a kind of eggshell state structure of being made up of rich Ti shell and rich Fe nuclear of novelty in the bioceramic material in the HA matrix, and the toughness phase Ti of distribution shell has important effect to the raising of stupalith mechanical property; The blending ratio of ferrotianium is to confirm according to the Ti-Fe binary phase diagram
4, a small amount of Ti-Fe particulate adds bending strength, fracture toughness property and the anti-fatigue performance that just can obviously improve HA in the bioceramic material, and in addition, the introducing of Fe is improved the permanent stability of matrix material in the simulated body fluid environment.
Method technology of the present invention is simple, and cost is lower, easy realization of industrial production, and the biological ceramic composite material of preparation has good mechanical property and biology performance.
Description of drawings
Fig. 1 is the ferrotianium particle enhanced hydroxy apatite-base bioceramic material product micro-structure diagram in the embodiment of the invention 1;
Fig. 2 is the ferrotianium particle enhanced hydroxy apatite-base bioceramic material product micro-structure diagram in the embodiment of the invention 4.
Embodiment
The HA powder that adopts in the embodiment of the invention is commercial product.
The equipment that cold isostatic compaction is selected for use in the embodiment of the invention is vertical cold isostatic press, and the equipment that compression molding is selected for use is FY-1 type 100 t hydraulic press.
Titanium valve that adopts in the embodiment of the invention and iron powder are commercial product.
In the embodiment of the invention be medium when carrying out ball milling with the dehydrated alcohol, the consumption of dehydrated alcohol is as the criterion with the submergence material.
The equipment that sintering is selected for use in the embodiment of the invention is the vacuum retort furnace.
The void content of the ferrotianium particle enhanced hydroxy apatite-base bioceramic material for preparing in the embodiment of the invention is 0.3 ~ 10%, and relative density is 85 ~ 95%, and bending strength is 86 ~ 95MPa, and fracture toughness property is 0.6 ~ 1.4 MPam
1/2
Embodiment 1
Granularity is 300 ~ 500 purpose titanium valves and iron powder mixing, and titanium valve accounts for 50% of whole material gross weights, is that medium ball milling mixer mill is thin then with the dehydrated alcohol, and extremely all the particle size of materials is 1 ~ 5 μ m, processes composite granule;
With composite granule and particle size is that the HA powder mixes of 80 ~ 200mm is processed mixed powder, and composite granule accounts for 5% of mixed powder gross weight, then mixed powder is mixed for the medium ball milling with the dehydrated alcohol; Oven dry is removed ethanol and is obtained the HA/Ti-Fe powder under 80 ± 5 ℃ of conditions again;
With HA/Ti-Fe powder cold isostatic compaction under the 200MPa condition, dwell time 5min processes biscuit;
Biscuit is placed the vacuum retort furnace; In vacuum tightness is to carry out sintering under 10 ~ 50Pa condition; Sintering temperature is 900 ℃; Soaking time is 300min; Obtain ferrotianium particle enhanced hydroxy apatite-base bioceramic material, void content is 10%, and relative density is 85%; Bending strength is 86MPa, and fracture toughness property is 0.6 MPam
1/2Its microtexture as shown in Figure 1, the Ti-Fe particle is the constitutional features of eggshell state in the HA matrix, wherein white portion for nuclear, gray area is a shell; EDS shows that to the element distribution analysis result of eggshell state structure the nuclear district is rich Fe phase, and the shell district is rich Ti phase;
Ferrotianium particle enhanced hydroxy apatite-base bioceramic material is carried out external immersion test; The result shows that the solubleness of this stupalith in SBF compares obvious reduction with traditional HA/Ti matrix material; The surface has type phosphate ore material to form, and promptly this material had both had certain biologically stable and also had certain biological activity in the simulated body fluid environment.
Embodiment 2
Granularity is 300 ~ 500 purpose titanium valves and iron powder mixing, and titanium valve accounts for 60% of whole material gross weights, is that medium ball milling mixer mill is thin then with the dehydrated alcohol, and extremely all the particle size of materials is 1 ~ 5 μ m, processes composite granule;
With composite granule and particle size is that the HA powder mixes of 80 ~ 200mm is processed mixed powder, and composite granule accounts for 10% of mixed powder gross weight, then mixed powder is mixed for the medium ball milling with the dehydrated alcohol; Oven dry is removed ethanol and is obtained the HA/Ti-Fe powder under 80 ± 5 ℃ of conditions again;
With HA/Ti-Fe powder cold isostatic compaction under the 200MPa condition, dwell time 5min processes biscuit;
Biscuit is placed the vacuum retort furnace; In vacuum tightness is to carry out sintering under 10 ~ 50Pa condition; Sintering temperature is 1000 ℃; Sintering time is 200min; Obtain ferrotianium particle enhanced hydroxy apatite-base bioceramic material, void content is 0.3%, and relative density is 95%; Bending strength is 95MPa, and fracture toughness property is 0.8 MPam
1/2
Ferrotianium particle enhanced hydroxy apatite-base bioceramic material is carried out external immersion test; The result shows that the solubleness of this stupalith in SBF compares obvious reduction with traditional HA/Ti matrix material; The surface has type phosphate ore material to form, and promptly this material had both had certain biologically stable and also had certain biological activity in the simulated body fluid environment.
Embodiment 3
Granularity is 300 ~ 500 purpose titanium valves and iron powder mixing, and titanium valve accounts for 70% of whole material gross weights, is that medium ball milling mixer mill is thin then with the dehydrated alcohol, and extremely all the particle size of materials is 1 ~ 5 μ m, processes composite granule;
With composite granule and particle size is that the HA powder mixes of 80 ~ 200mm is processed mixed powder, and composite granule accounts for 15% of mixed powder gross weight, then mixed powder is mixed for the medium ball milling with the dehydrated alcohol; Oven dry is removed ethanol and is obtained the HA/Ti-Fe powder under 80 ± 5 ℃ of conditions again;
With the unidirectional compression moulding under the 200MPa condition in the mould of packing into of HA/Ti-Fe powder, process biscuit;
Biscuit is placed the vacuum retort furnace; In vacuum tightness is to carry out sintering under 10 ~ 50Pa condition; Sintering temperature is 1100 ℃; Sintering time is 100min; Obtain the ferrotianium particle and strengthen the hydroxy apatite-base biological ceramic composite material, void content is 5%, and relative density is 90%; Bending strength is 92MPa, and fracture toughness property is 1.2 MPam
1/2
Ferrotianium particle enhanced hydroxy apatite-base bioceramic material is carried out external immersion test, and the result shows the almost not dissolving in SBF of this stupalith, does not also observe newborn particulate deposition, shows splendid biologically stable.
Embodiment 4
Granularity is 300 ~ 500 purpose titanium valves and iron powder mixing, and titanium valve accounts for 80% of whole material gross weights, is that medium ball milling mixer mill is thin then with the dehydrated alcohol, and extremely all the particle size of materials is 1 ~ 5 μ m, processes composite granule;
With composite granule and particle size is that the HA powder mixes of 80 ~ 200mm is processed mixed powder, and composite granule accounts for 20% of mixed powder gross weight, then mixed powder is mixed for the medium ball milling with the dehydrated alcohol; Oven dry is removed ethanol and is obtained the HA/Ti-Fe powder under 80 ± 5 ℃ of conditions again;
With HA/Ti-Fe powder cold isostatic compaction under the 200MPa condition, the dwell time is 5min, processes biscuit;
Biscuit is placed the vacuum retort furnace; In vacuum tightness is to carry out sintering under 10 ~ 50Pa condition; Sintering temperature is 1200 ℃; Sintering time is 45min; Obtain ferrotianium particle enhanced hydroxy apatite-base bioceramic material, void content is 3%, and relative density is 91%; Bending strength is 91MPa, and fracture toughness property is 1.4 MPam
1/2Its microtexture as shown in Figure 2, the Ti-Fe particle is the constitutional features of eggshell state in the HA matrix, wherein white portion for nuclear, gray area is a shell; EDS shows that to the element distribution analysis result of eggshell state structure the nuclear district is rich Fe phase, and the shell district is rich Ti phase;
Ferrotianium particle enhanced hydroxy apatite-base bioceramic material is carried out external immersion test, and the result shows the almost not dissolving in SBF of this stupalith, does not also observe newborn particulate deposition, shows splendid biologically stable.
Claims (4)
1. the preparation method of a ferrotianium particle enhanced hydroxy apatite-base bioceramic material is characterized in that carrying out according to the following steps:
(1) titanium valve and iron powder are mixed, titanium valve accounts for 50 ~ 80% of whole material gross weights, is that medium ball milling mixer mill is thin then with the dehydrated alcohol, and extremely all the particle size of materials is 1 ~ 5 μ m, processes composite granule;
(2) composite granule and HA powder mixes are processed mixed powder; Composite granule accounts for 5 ~ 20% of mixed powder gross weight; Then with mixed powder with the dehydrated alcohol for the medium ball milling mixes, oven dry is removed ethanol and is obtained the HA/Ti-Fe powder under 80 ± 5 ℃ of conditions again;
(3) with unidirectional compression moulding of HA/Ti-Fe powder or cold isostatic compaction, process biscuit;
(4) biscuit is carried out sintering under vacuum condition, sintering temperature is 900 ~ 1200 ℃, and sintering time is 45 ~ 300min, obtains ferrotianium particle enhanced hydroxy apatite-base bioceramic material.
2. the preparation method of a kind of ferrotianium particle enhanced hydroxy apatite-base bioceramic material according to claim 1, the granularity that it is characterized in that described titanium valve is 300 ~ 500 orders, the granularity of described iron powder is 300 ~ 500 orders.
3. the preparation method of a kind of ferrotianium particle enhanced hydroxy apatite-base bioceramic material according to claim 1 is characterized in that described HA powder particle size is 80 ~ 200mm.
4. the preparation method of a kind of ferrotianium particle enhanced hydroxy apatite-base bioceramic material according to claim 1, the vacuum tightness when it is characterized in that carrying out sintering under the described vacuum condition of step (4) is 10 ~ 50Pa.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602844A (en) * | 2013-11-19 | 2014-02-26 | 四川大学 | Preparation method of porous biomedical metal, ceramic or metal/ceramic composite material |
| CN104857566A (en) * | 2015-04-21 | 2015-08-26 | 昆明理工大学 | Preparation method of titanium-niobium-zirconium-based hydroxyapatite biological composite material |
| CN104894420A (en) * | 2015-04-21 | 2015-09-09 | 昆明理工大学 | Titanium-niobium-zirconium-based calcium pyrophosphate biological composite material preparation method |
| US10920300B2 (en) | 2015-07-29 | 2021-02-16 | Nippon Steel Corporation | Titanium composite material and titanium material for hot rolling |
| CN113088958A (en) * | 2021-03-09 | 2021-07-09 | 中南大学 | Gradient composite bioactive ceramic coating material and preparation method thereof |
| CN113880568A (en) * | 2021-11-12 | 2022-01-04 | 四川大学 | In-situ doped graphene reinforced calcium phosphate composite ceramic and preparation method and application thereof |
| CN114474482A (en) * | 2022-03-24 | 2022-05-13 | 江西理工大学 | Preparation process of biological ceramic-degradable polymer composite granulation |
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| CN1654428A (en) * | 2005-02-22 | 2005-08-17 | 清华大学 | Method for preparing processable hydroxyapatite/Ti3SiC2 bioceramic composites |
| CN1935270A (en) * | 2006-10-17 | 2007-03-28 | 山东大学 | Hydroxy apatite-base composite bioceramic material, and its preparing process |
| CN101407414A (en) * | 2008-11-06 | 2009-04-15 | 上海交通大学 | Method for preparing calcium polyphosphate / tricalcium phosphate two-phase biological ceramic |
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| CN1654428A (en) * | 2005-02-22 | 2005-08-17 | 清华大学 | Method for preparing processable hydroxyapatite/Ti3SiC2 bioceramic composites |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103602844A (en) * | 2013-11-19 | 2014-02-26 | 四川大学 | Preparation method of porous biomedical metal, ceramic or metal/ceramic composite material |
| CN104857566A (en) * | 2015-04-21 | 2015-08-26 | 昆明理工大学 | Preparation method of titanium-niobium-zirconium-based hydroxyapatite biological composite material |
| CN104894420A (en) * | 2015-04-21 | 2015-09-09 | 昆明理工大学 | Titanium-niobium-zirconium-based calcium pyrophosphate biological composite material preparation method |
| US10920300B2 (en) | 2015-07-29 | 2021-02-16 | Nippon Steel Corporation | Titanium composite material and titanium material for hot rolling |
| CN113088958A (en) * | 2021-03-09 | 2021-07-09 | 中南大学 | Gradient composite bioactive ceramic coating material and preparation method thereof |
| CN113088958B (en) * | 2021-03-09 | 2021-12-28 | 中南大学 | Gradient composite bioactive ceramic coating material and preparation method thereof |
| CN113880568A (en) * | 2021-11-12 | 2022-01-04 | 四川大学 | In-situ doped graphene reinforced calcium phosphate composite ceramic and preparation method and application thereof |
| CN114474482A (en) * | 2022-03-24 | 2022-05-13 | 江西理工大学 | Preparation process of biological ceramic-degradable polymer composite granulation |
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Application publication date: 20120104 |