CN100534897C - Sintered body of titanium compound - Google Patents
Sintered body of titanium compound Download PDFInfo
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- CN100534897C CN100534897C CNB2004800374625A CN200480037462A CN100534897C CN 100534897 C CN100534897 C CN 100534897C CN B2004800374625 A CNB2004800374625 A CN B2004800374625A CN 200480037462 A CN200480037462 A CN 200480037462A CN 100534897 C CN100534897 C CN 100534897C
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- titanium compound
- titanium
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Abstract
Disclosed is a sintered body of a titanium compound obtained by sintering the titanium compound. Also disclosed is a method for producing such a sintered body of a titanium compound. A titanium compound represented by the formula (1) or (2) below is sintered. [Ca10(PO4)6]TiO3.nH2O (1) [Ca10(PO4)6]TiO2(OH)2 (2) (In the formulae, n is an integer of 0-3.) The thus-obtained sintered body is substantially composed of perovskite and whitlockite.
Description
Technical field
The present invention relates to novel titanium compound.The invention still further relates to the sintered compact and preparation method thereof of the titanium compound of sintered titanium compound formation.And, the invention still further relates to artificial bone, artificial joint material, artificial teeth material, artificial tooth root (in plant) material that the sintered compact by above-mentioned titanium compound constitutes.The invention still further relates to artificial bone, joint prosthesis, artificial tooth, the artificial tooth root of the sintered compact that contains above-mentioned titanium compound.
Background technology
Apatite biological body adaptability excellence can directly combine with osseous tissue, so be widely used as the material of artificial bone or artificial tooth root.Wherein, calcium hydroxyapatite (calcium hydroxyapatite) is the main component of organism sclerous tissueses such as bone or tooth, so be one of the most frequently used starting material.In addition, bata-tricalcium phosphate (hereinafter referred to as " β-TCP "), is replaced with new bone after the implantable bioartificial body is interior easily easily by bone resorption.
In addition, the titanium excellent strength, reactive low to organism is widely used as the material (spy opens clear 63-143057 communique) of joint prosthesis or artificial tooth root.
And, wish that in a single day materials such as joint prosthesis or artificial tooth root implant after, with the osseous tissue mortise, become one with this osseous tissue.
But,, be difficult to osseous tissue integrated though titanium reactive low to organism as mentioned above is low with the affinity of bio-tissue.
Therefore, in order to improve the adaptability of titanium and osseous tissue, attempt with phosphatic rock lining titanium surface (for example, the spy opens flat 3-186272 communique).
But, at present, even, still can not be met the organism adaptability that needs in such cases.
In addition, as other matrix materials that use phosphatic rock and titanium, proposed to utilize the titanium compound (spy opens the 2000-327315 communique, the spy opens the 2001-302220 communique) of coprecipitation method preparation.This titanium compound is Powdered, and the material that this titanium compound of sintering forms is not also understood.
In addition, the known β-TCP etc. and so on that exists in inorganic substance is difficult to independent agglomerating inorganic substance.And, at present also not with inorganic substance and above-mentioned titanium compound mixed sintering.
Summary of the invention
Problem of the present invention provides sintered compact of the titanium compound that the sintered titanium compound obtains and preparation method thereof.In addition, the present invention also provides sintered compact that the mixture of sintered titanium compound and inorganic substance obtains and preparation method thereof.
Discoveries such as the inventor can obtain the sintered compact of titanium compound by sintered titanium compound under given conditions, and described sintered compact is suitable as the material of artificial bone etc., thereby has finished the present invention.In addition, discoveries such as the inventor can obtain sintered compact by the mixture that sintering under given conditions contains titanium compound and inorganic substance, and described sintered compact is suitable as the material of artificial bone etc., thereby has finished the present invention.
That is, the present invention is the titanium compound shown in following formula (1) or (2).
[Ca
10(PO
4)
6]TiO
3·nH
2O (1)
[Ca
10(PO
4)
6]TiO
2(OH)
2 (2)
(in the formula, n represents 0～3 integer.)
The sintered compact that the present invention obtains for the sintered titanium compound.
The present invention is above-mentioned sintered compact, and wherein, titanium compound is the compound shown in formula (1) or (2).
The present invention is above-mentioned sintered compact, and wherein, titanium compound is by add the compound that alkali prepares its co-precipitation in the solution that contains calcium ion, titanium ion and phosphate anion.
The present invention is a sintered compact, it is characterized in that, this sintered compact contains uhligite and whitlockite.
The present invention is a sintered compact, it is characterized in that, this sintered compact is made up of uhligite and whitlockite in fact.
The present invention is above-mentioned sintered compact, it is characterized in that, uhligite and whitlockite obtain by the sintered titanium compound.
The present invention is above-mentioned sintered compact, and wherein titanium compound is the compound shown in formula (1) or (2).
The present invention is above-mentioned sintered compact, and wherein, titanium compound is by add the compound that alkali prepares its co-precipitation in the solution that contains calcium ion, titanium ion and phosphate anion.
The present invention is the preparation method of sintered compact, it is characterized in that, this method is the sintered titanium compound.
The present invention is above-mentioned preparation method, and wherein, titanium compound is the compound shown in formula (1) or (2).
The present invention is above-mentioned preparation method, and wherein, titanium compound is by add the compound that alkali prepares its co-precipitation in the solution that contains calcium ion, titanium ion and phosphate anion.
The present invention is above-mentioned preparation method, it is characterized in that, this method is to carry out sintering above under 800 ℃ the temperature.
The present invention is above-mentioned preparation method, it is characterized in that, this method is to carry out sintering in atmosphere of inert gases and/or under the decompression.
The present invention is above-mentioned preparation method, it is characterized in that, rare gas element is xenon and/or argon.
The present invention is above-mentioned preparation method, it is characterized in that, this method is to be less than or equal to 10
-4Carry out sintering under the pressure of Pa.
The present invention is a sintered compact, and this sintered compact is to obtain by the mixture that sintering contains titanium compound and inorganic substance.
The present invention is above-mentioned sintered compact, and wherein titanium compound is the compound shown in formula (1) or (2).
The present invention is above-mentioned sintered compact, and wherein, titanium compound is by add the compound that alkali prepares its co-precipitation in the solution that contains calcium ion, titanium ion and phosphate anion.
The present invention is above-mentioned sintered compact, and wherein, inorganic substance are to be selected from least a in the following compound: calcium hydroxyapatite, calcium fluorapatite, bata-tricalcium phosphate, type alpha tricalcium phosphate, tetracalcium phosphate, metal titanium, titanium oxide and platinum.
The present invention is the preparation method of sintered compact, it is characterized in that, this method is the mixture that sintering contains titanium compound and inorganic substance.
The present invention is above-mentioned preparation method, and wherein, titanium compound is the compound shown in formula (1) or (2).
The present invention is above-mentioned preparation method, and wherein, titanium compound is by add the compound that alkali prepares its co-precipitation in the solution that contains calcium ion, titanium ion and phosphate anion.
The present invention is above-mentioned preparation method, and wherein, inorganic substance are to be selected from least a in the following compound: calcium hydroxyapatite, calcium fluorapatite, bata-tricalcium phosphate, type alpha tricalcium phosphate, tetracalcium phosphate, metal titanium, titanium oxide and platinum.
The present invention is above-mentioned preparation method, it is characterized in that, this method is to carry out sintering above under 800 ℃ the temperature.
The present invention is above-mentioned preparation method, it is characterized in that, this method is to carry out sintering in atmosphere of inert gases and/or under the decompression.
The present invention is above-mentioned preparation method, it is characterized in that, rare gas element is xenon and/or argon.
The present invention is above-mentioned preparation method, it is characterized in that, this method is to be less than or equal to 10
-4Carry out sintering under the pressure of Pa.
The present invention is artificial bone, artificial joint material, artificial teeth material or artificial tooth root material, it is characterized in that, described material is made of above-mentioned sintered compact.
The present invention is artificial bone, joint prosthesis, artificial tooth or artificial tooth root, it is characterized in that, wherein contains above-mentioned sintered compact.
Description of drawings
The X-ray diffraction result of titanium compound sintered compact of the present invention is represented on the last hurdle of Fig. 1, and the X-ray diffractogram of whitlockite is represented in intermediate hurdles, and the X-ray diffractogram of uhligite is represented on following hurdle.
Fig. 2 represents the sintering temperature of sintered compact of titanium compound and the relation of Vickers micro-hardness.
Fig. 3 represents the Vickers micro-hardness of sintered compact of the mixture of titanium compound and β-TCP.
Embodiment
Titanium compound of the present invention is the compound with following formula (1) or (2) expression, and has the metatitanic acid apatite structure.
[Ca
10(PO
4)
6]TiO
3·nH
2O (1)
[Ca
10(PO
4)
6]TiO
2(OH)
2 (2)
(in the formula, n represents 0～3 integer.)
In formula (1), n is 0～3 integer, is preferably 1 or 2.
Titanium compound of the present invention for example can utilize and add the coprecipitation method preparation that alkali makes its co-precipitation in the solution that contains calcium ion, titanium ion and phosphate anion.More specifically, for example, in the aqueous solution that is dissolved with nitrocalcite and titanium sulfate and small amount of alkali composition, add phosphoric acid, add ammoniacal liquor then, regulating pH is about 9, the suspension that obtains was stirred 4～8 hours down at 80～100 ℃, can obtain the dispersion liquid of titanium compound thus.By filtering this liquid, washing, dry filter thing can prepare the powder of titanium compound of the present invention.Need to prove, when dissolving nitrocalcite and titanium sulfate,, can suppress the generation of calcium sulfate by adding a spot of alkali composition.
Reaction formula in such cases is as follows.
[reaction formula 1]
Or
[Ca
10(PO
4)
6]TiO
2(OH)
2 (2)
Preparation method to the sintered compact of titanium compound of the present invention describes below.
The sintered compact of titanium compound of the present invention can be by being prepared at the powder that surpasses 800 ℃ sintering temperature titanium compound.Being less than or equal under 800 ℃ the temperature, can not make the titanium compound sintering sometimes, or the easy disintegration of the sintered compact behind the sintering.
For the upper limit of sintering temperature, so long as can sintered titanium the temperature of compound get final product, be not particularly limited, preferably carry out sintering being less than or equal under 1500 ℃ the temperature.
In addition, the sintered compact of titanium compound of the present invention preferably in atmosphere of inert gases and/or the decompression under the sintered titanium compound.Preferred xenon of the rare gas element of Shi Yonging and/or argon herein.In addition, the pressure during sintering preferably is less than or equal to normal atmosphere (10
5Pa), more preferably be less than or equal to 10Pa, be more preferably less than or equal 10
-2Pa most preferably is less than or equal to 10
-4Pa.In such cases, can only form atmosphere of inert gases or only form decompression state, but preferably after forming atmosphere of inert gases, reduce pressure.
For sintering time, as long as can obtain the sintered compact of titanium compound, be not particularly limited, for example, can enumerate more than or equal to 15 minutes, be preferably greater than or equal 12 hours, more preferably more than or equal to 24 hours, more preferably greater than or equal 48 hours, have the high more tendency of hardness of the long more sintered compact of sintering time.In addition, the upper limit of sintering time is not particularly limited, can be according to the suitably decisions such as hardness of sintered compact, for example, can enumerate and be less than or equal to 72 hours, preferably be less than or equal to 36 hours.
For example, under atmospheric pressure under 30 minutes the situation of sintering, preferably at 1250 ℃～1450 ℃ following sintering, 10
-4Under the Pa under 30 minutes the situation of sintering, preferably at 850～1350 ℃ of following sintering.
The sintered compact of titanium compound of the present invention contains uhligite (Perovskite (CaTiO
3)) and whitlockite (Whitlockite (Ca
3(PO
4)
2)).In such cases, consider, do not contain type alpha tricalcium phosphate (below, be called " α-TCP "), anatase titanium dioxide or hydroxyapatite etc. in the sintered compact of preferred titanium compound in fact from the hardness angle.
Reaction formula in such cases is as follows.
[reaction formula 2]
[Ca
10(PO
4)
6]TiO
3·nH
2O (1)
Or
Below sintering being contained the sintered compact that the mixture of titanium compound and inorganic substance obtains describes.
As long as mixing with titanium compound, the inorganic substance that use among the present invention obtain sintered compact, be not particularly limited, for example, can enumerate calcium hydroxyapatite, calcium fluorapatite, β-TCP, α-TCP, tetracalcium phosphate, metal titanium, titanium oxide and platinum etc., wherein, aspect bio-tissue, replacing easily, consider, preferably β-TCP with osseous tissue.In addition, above-mentioned inorganic substance can use separately or use mixing more than 2 kinds or 2 kinds.
The sintered compact of the mixture of titanium compound of the present invention and inorganic substance can prepare by the mixture that contains titanium compound and inorganic substance at the sintering temperature that surpasses 800 ℃.
Blending ratio for titanium compound and inorganic substance, as long as can obtain the sintered compact of mixture, be not particularly limited, can enumerate titanium compound: the weight ratio of inorganic substance is 99: 1～1: 99, preferred 95: 5～30: 70, more preferably 90: 10～50: 50.
The rare gas element that uses during sintering, pressure, temperature range, time etc. suitably determine according to the character of the inorganic substance that use or its blending ratio, the roughly the same condition of condition in the time of can adopting with the sintered compact for preparing above-mentioned titanium compound.
The preparation of＜titanium compound 〉
Approximately dissolving 0.1 molar nitric acid calcium (Ca (NO in the 500ml water
3)
2) and 0.1 mol sulfuric acid titanium (TiSO
4) after, neutralize with alkali.Next, the phosphoric acid (H that adds 0.06 mole
3PO
4) after, add ammoniacal liquor, regulate pH=9.0, stirred 6 hours down at 100 ℃.The precipitation that filter, drying obtains obtains the powder of compound shown in about 10g formula (1) or the formula (2).
The sintering of＜titanium compound 〉
The powder of the titanium compound that obtains with distilled water stir about 3g embodiment 1, in the mould of packing into, air-dry after the moulding.Formed body after air-dry is put into moisture eliminator, and drying is 24 hours under 100 ℃.The exsiccant test portion is put into the vacuum heat treatment machine, in normal atmosphere down or in the vacuum (10
-4Pa), keeping at each temperature 30 minutes, make its sintering.After stopping heating, place, make it restore to room temperature.Need to prove, after agglomerating test portion placement in a vacuum, returning to room temperature, take out behind the inclosure argon gas.Utilizing X-ray diffraction that the sintered compact of the titanium compound that obtains is carried out crystallization resolves.Fig. 1 represents in a vacuum, the X-ray diffraction result of 1300 ℃ of following agglomerating sintered compacies.The X-ray diffractogram of uhligite and whitlockite also is shown among Fig. 1 in addition, in the lump.Its result is summarized in table 1.
As shown in Table 1, under atmospheric pressure, when under 1300 ℃ and 1400 ℃, carrying out sintering, can obtain the sintered compact formed by uhligite and whitlockite in fact, in a vacuum, when under 900 ℃～1300 ℃, carrying out sintering, can obtain the sintered compact of forming by uhligite and whitlockite in fact.
In addition, because the sintered compact of above-mentioned titanium compound comes down to be made up of uhligite and whitlockite, so also proved reaction by above-mentioned reaction formula, the titanium compound shown in formula (1) or (2) has been transformed into uhligite and whitlockite.
[table 1]
Utilize the powder of the titanium compound of coprecipitation method preparation with distilled water stir about 3g, in the mould of packing into, air-dry after the moulding.Air-dry formed body is put into moisture eliminator, and drying is 24 hours under 100 ℃.The exsiccant test portion is put into the vacuum heat treatment machine, in normal atmosphere down or in the vacuum (10
-4Pa), keeping at each temperature 15 minutes, make its sintering.After stopping heating, place, make it restore to room temperature.Need to prove, after agglomerating test portion placement in a vacuum, returning to room temperature, take out behind the inclosure argon gas.The Vickers micro-hardness of the sintered compact of the titanium compound that mensuration obtains.The result as shown in Figure 2.
As shown in Figure 2, can obtain the sintered compact of the big titanium compound of hardness.And, compare with under atmospheric pressure carrying out sintering, when carrying out sintering in a vacuum, can obtain the bigger sintered compact of hardness.
Embodiment 4
Be mixed with the powder of the titanium compound that utilizes coprecipitation method preparation with distilled water stir about 3g in the same manner with embodiment 3 and as the mixture of the β-TCP powder of inorganic substance, moulding makes its drying.10
-4Under the Pa pressure, the exsiccant test portion was kept 15 minutes down in 1350 ℃, make its sintering.Need to prove, relative amount of the mixture, the content of β-TCP is 25 weight %, stops heating, places, return to room temperature after, take out after enclosing argon gas.The Vickers micro-hardness of 3 different positionss of the mixture sintering body of the titanium compound that mensuration obtains and β-TCP.The result as shown in Figure 3.
As shown in Figure 3, mix with titanium compound, can make its sintering by being difficult to independent agglomerating β-TCP.In addition, the sintered compact of the titanium compound that obtains and the mixture of β-TCP is compared during with the independent sintering of titanium compound, has equal or higher hardness.
Utilizability on the industry
The sintering body hardness of titanium compound of the present invention is big, can be used as artificial bone, Artificial joint material, artificial teeth material or artificial tooth root material. In addition, of the present invention The sintering body of titanium compound through processing can be made into artificial bone, artificial joint, artificial tooth or Artificial tooth root. Make the sintering body of titanium compound of the present invention sinter into desirable artificial bone, The shape of artificial joint, artificial tooth or artificial tooth root can obtain artificial bone, artificial closing Joint, artificial tooth or artificial tooth root.
Claims (17)
1, a kind of preparation method of sintered compact is characterized in that, this method prepares sintered compact at the sintering temperature titanium compound that surpasses 800 ℃, and titanium compound is the compound shown in following formula (1) or (2),
[Ca
10(PO
4)
6]TiO
3·nH
2O (1)
[Ca
10(PO
4)
6]TiO
2(OH)
2 (2)
In the formula, n represents 0～3 integer.
2, the preparation method of sintered compact as claimed in claim 1, wherein, titanium compound is by add the compound that alkali prepares its co-precipitation in the solution that contains calcium ion, titanium ion and phosphate anion.
3, the preparation method of sintered compact as claimed in claim 1 or 2 is characterized in that, carries out sintering in atmosphere of inert gases and/or under the decompression.
4, the preparation method of sintered compact as claimed in claim 3 is characterized in that, rare gas element is xenon and/or argon gas.
5, the preparation method of sintered compact as claimed in claim 3 is characterized in that, is being less than or equal to 10
-4Carry out sintering under the pressure of Pa.
6, the preparation method of sintered compact as claimed in claim 4 is characterized in that, is being less than or equal to 10
-4Carry out sintering under the pressure of Pa.
7, a kind of preparation method of sintered compact is characterized in that, this method is to prepare sintered compact at the mixture that the sintering temperature that surpasses 800 ℃ contains titanium compound and inorganic substance, and titanium compound is the compound shown in following formula (1) or (2),
[Ca
10(PO
4)
6]TiO
3·nH
2O (1)
[Ca
10(PO
4)
6]TiO
2(OH)
2 (2)
In the formula, n represents 0～3 integer.
8, the preparation method of sintered compact as claimed in claim 7, wherein, titanium compound is by add the compound that alkali prepares its co-precipitation in the solution that contains calcium ion, titanium ion and phosphate anion.
9, as claim 7 or 8 described preparation methods, wherein, inorganic substance are to be selected from least a in the following compound: calcium hydroxyapatite, calcium fluorapatite, bata-tricalcium phosphate, type alpha tricalcium phosphate, tetracalcium phosphate, metal titanium, titanium oxide and platinum.
10, as claim 7 or 8 described preparation methods, it is characterized in that, in atmosphere of inert gases and/or under the decompression, carry out sintering.
11, preparation method as claimed in claim 9 is characterized in that, carries out sintering in atmosphere of inert gases and/or under the decompression.
12, the preparation method of sintered compact as claimed in claim 10 is characterized in that, rare gas element is xenon and/or argon gas.
13, the preparation method of sintered compact as claimed in claim 11 is characterized in that, rare gas element is xenon and/or argon gas.
14, preparation method as claimed in claim 10 is characterized in that, is being less than or equal to 10
-4Carry out sintering under the pressure of Pa.
15, preparation method as claimed in claim 11 is characterized in that, is being less than or equal to 10
-4Carry out sintering under the pressure of Pa.
16, preparation method as claimed in claim 12 is characterized in that, is being less than or equal to 10
-4Carry out sintering under the pressure of Pa.
17, preparation method as claimed in claim 13 is characterized in that, is being less than or equal to 10
-4Carry out sintering under the pressure of Pa.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003421387 | 2003-12-18 | ||
| JP421387/2003 | 2003-12-18 | ||
| JP208462/2004 | 2004-07-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1894162A CN1894162A (en) | 2007-01-10 |
| CN100534897C true CN100534897C (en) | 2009-09-02 |
Family
ID=37598206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800374625A Expired - Fee Related CN100534897C (en) | 2003-12-18 | 2004-12-10 | Sintered body of titanium compound |
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| Country | Link |
|---|---|
| CN (1) | CN100534897C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100572266C (en) * | 2007-12-28 | 2009-12-23 | 徐选春 | A kind of method of producing microcapsule tricalcium phosphate |
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2004
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| CN1894162A (en) | 2007-01-10 |
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