CN101596326A - A kind of borate biological glass ceramics and its preparation method and application - Google Patents

Abstract

The present invention relates to a kind of devitrified glass, specifically about a kind of borate biological microcrystalline glass and its production and application.Technical scheme of the present invention is as follows: a kind of borate biological microcrystalline glass, this devitrified glass is composed of the following components by weight percentage: B₂O₃30-60%, Na₂O 10-40%, CaO 10-30%, P₂O₅10-30%, F 0-2%, described Na₂O and CaO weight ratio are 1: 2, described CaO and P₂O₅Weight ratio is 1: 2.Advantage of the present invention shows: the borate biological microcrystalline glass crystalline phase mainly is that phosphorus sodium calcium stone is β-NaCaPO₄, glassy phase is a sodium calcium boron glass.Sodium calcium boron glass degradation rate in SBF solution is very high, can make material rapider hydroxyapatite material that is transformed in body fluid, generates the rate adjusted of hydroxyapatite.

Description

A kind of borate biological microcrystalline glass and its production and application

Technical field

The present invention relates to a kind of devitrified glass, specifically about a kind of borate biological microcrystalline glass and its production and application.

Background technology

At the beginning of the seventies in 19th century, professor Hench of Univ Florida USA has found bioactivity glass, and is applied to biomedical sector first, thereby has started a brand-new biomaterial research field.This class material has the incomparable advantage of metal, macromolecule and bio-inert material as biomedical material, combine firmly with sclerotin on every side, there is not rejection in the implantable bone, harmless, nontoxic, mechanical strength is than the natural skeleton height, and no intensity fatigue phenomenon in human body, characteristics such as easily sterilization and processing and forming be easy.

Develop some biologically actives, the higher bioactivity glass of mechanical strength in recent years, 45S5 glass with professor's Hench exploitation is representative, mostly be the glass of calcic and phosphorus, behind such glass implantation skeleton, the phosphate anion that exists in the calcium ion of glass surface stripping and body fluid combines and generates the calcium phosphate layer, and the calcium phosphate layer with the bone surface area of new bone combines securely whereby.But bio-vitric degradation rate in human body is too fast, has influenced its long durability, and intensity is lower, uses limited.For this reason, relevant scientific worker handles by the controlled micro crystallization of glass by adjusting glass ingredient with on the basis that keeps the bioactivity glass advantage, improves its chemical stability, comparatively typically has:

(1) mentioning composition wt% among the United States Patent (USP) P3981736 is SiO₂2 0-60%, P₂O₅5-40%, Na₂O 2.7-20%, K₂O 0.4-20%, MgO 2.9-30%, CaO 5-40%, the apatite devitrified glass of F 0.5-3%, owing to contain alkali metal ions such as K, Na, chemical stability is bad, just degraded fully before new osseous tissue forms behind the implant into body, mechanical property is relatively poor.

(2) the A/W bio-microcrystal glass is to propose (Bull Inst Chem Res Kyoto Univ in the eighties by the people such as Kokubo of Kyoto Univ Japan at first, 60 (1982) 260-268), it is named as the A/W devitrified glass owing to containing apatite mutually with the wollastonite crystallite.The AW devitrified glass is keeping the good bioactive while, owing to contain the fibrous wollastonite crystalline phase, mechanical property is greatly improved and near natural bone, and owing to do not contain alkali metal ions such as K, Na, degradation rate is low, even its mechanical property also shows extraordinary stability in body fluid.

(3) mentioning composition wt% among the United States Patent (USP) P5336642 is SiO₂42-70%, P₂O₅2-13%, Na₂O 6-12%, K₂O 3-10%, CaO 20-30%, the canasite devitrified glass of F 3-11%.

(4) German patent DE-4113021 is mentioned Na₂O-K₂O-MgO-CaO-Al₂O₃-SiO₂-P₂O₅-F system

Devitrified glass, this glass contains apatite, AlPO₄And other phosphate is as crystalline phase.Yet, Al in the glass³⁺The regeneration of osteocyte, Al have been disturbed in ionic existence³⁺Ion reaches finite concentration, and devitrified glass is transformed into apatite in body fluid will become very difficult.

(5) mentioning composition wt% among the United States Patent (USP) P7074730 is SiO₂29.5-70%, P₂O₅2-13%, Na₂O6-27.5%, CaO5.5-23%, F0-1.5% phosphorus sodium calcium stone devitrified glass is mainly used in the dentistry substitution material.

(6) Chinese patent literature CN1562834 discloses a kind of degradable multiporous bioactivity glass support and preparation method thereof, and the mass percent that this glass supporter is formed is CaO24-45%, SiO₂34-50%, Na₂O 0-25%, P₂O₅5-17%, MgO 0-5% and CaF₂0-1%.This support soaks the rear surface in human body simulation body fluid promptly have hydroxyapatite to generate, and shows to have good biological activity, is expected as sclerous tissues's impairment renovation material and external osseous tissue cultivation cytoskeleton material.

But, about in simulated body fluid SBF solution, not appearing in the newspapers by the borate biological microcrystalline glass of material surface generation hydroxyapatite rate adjusted.

Summary of the invention

The objective of the invention is to:

(1) provides a kind of borate biological microcrystalline glass;

(2) provide a kind of preparation method of borate biological microcrystalline glass;

(3) provide the application of borate biological microcrystalline glass

The objective of the invention is to realize: 2003 by following technical method, people such as Delbert E professor Day of inventor and Missouri, USA university have studied first and have not contained the application of silicon borate glass aspect biological, result of study shows with silicate bio-vitric 45S5 to be compared, and some borate glass is can be in body fluid rapider to be transformed into hydroxyapatite and to combine well with osseous tissue.On this basis, by repeatedly practising, find to form, prepare a kind of novel borate system bio-microcrystal glass by adjusting glass.The preparation method of devitrified glass is as follows: the pretreatment of (one) raw material.Consider the volatility of phosphoric acid, the introducing mode of phosphorus pentoxide has been carried out a series of research.The contrast experiment finds, with solid Metaphosphoric acid (HPO₃) when introducing, raw material is easy to deliquescence, the weighing poor accuracy is difficult for pulverizing, have no way of uniform mixing and be heated and during fusion of powder when it, and the generation lamination, volatilization loss is big.With phosphoric acid (H₃PO₄) impouring powder and directly founding, because phosphate forms not exclusively, free phosphoric acid is easy to volatilization, and easily infiltrates when low temperature in the pore of sidewall of crucible, reinforcement is to the erosion of refractory material, and produced moisture behind the phosphoric acid chemical reaction, causes foamed phenomenon.As for synthetic phosphate,, often can not make required glass ingredient because the content of phosphorus pentoxide is higher in the glass.Discover, the most favourable with partial synthesis phosphate and the common introducing of phosphorus pentoxide to founding of glass.The preprocessing process of raw material is as follows: carry out accurate weighing by glass formula, and load weighted raw material stirring is even, in the silica crucible of packing into, in Muffle furnace, be warming up to 180-250 ℃ with heating rate 1-2 ℃/min slowly, be incubated 4 hours.The purpose of pretreatment of raw material is the moisture of introducing in the raw material in order to remove (some raw material such as phosphorus pentoxide be the moisture absorption very easily); Make the raw material pre-reaction, prevent the excessive volatilization of phosphorus pentoxide in the high temperature melting process of next step glass.The blocks of solid of heat treatment gained promptly can be used for founding after crushed.(2) glass founds.After the pretreatment of raw material, from silica crucible, take out pulverizing and be ground to certain fineness, in platinum crucible, found.Glass melting temperature is 900 ℃-1200 ℃, and temperature retention time is 1-3 hour.The tentative experimental result of founding shows, during about 900 ℃ of borate salt glass, viscosity has reached the required numerical value of clarification, is the volatilization that reduces phosphorus pentoxide, and in conjunction with the characteristics of borate glass, it is suitable taking to found fast.The result shows that also when temperature retention time was no more than 1 hour, the glass of founding gained had defectives such as scum silica frost, calculus and bubble.When in the time of 900 ℃, prolonging more than the temperature retention time to 2 hour, can eliminate above-mentioned phenomenon substantially.(3) preparation of devitrified glass.Two kinds of situations are arranged in the preparation of devitrified glass: 1) melt is suppressed quenching between metal mold, precipitation of phosphorus sodium calcium stone crystal in cooling procedure; 2) melt is behind compacting quenching between metal mold, and under 600 ℃ of-800 ℃ of temperature heat treatment 0.5-10 hour, precipitation of phosphorus sodium calcium stone crystal.Crystallize depends on Na in the glass ingredient₂The ratio of O and CaO and P₂O₅Content.

Technical scheme of the present invention is as follows:

(1) a kind of borate biological microcrystalline glass, this devitrified glass is composed of the following components by weight percentage:

B₂O₃ 30-60％

Na₂O 10-40％

CaO 10-30％

P₂O₅ 10-30％

F 0-2％，

Described Na₂O and CaO weight ratio are 1: 2, described CaO and P₂O₅Weight ratio is 1: 2.

Described devitrified glass, this devitrified glass is composed of the following components by weight percentage:

B₂O₃ 40-50％

Na₂O 10-30％

CaO 10-20％

P₂O₅ 10-20％

F 0-1％，

Described Na₂O and CaO weight ratio are 1: 1.5, described CaO and P₂O₅Weight ratio is 1.5: 2.

This devitrified glass is composed of the following components by weight percentage:

B₂O₃ 45.7％

Na₂O 22％

CaO 19.9％

P₂O₅ 12.4％。

(2) devitrified glass preparation method, this method comprises by following steps to be formed:

(a) pretreatment of raw material: with raw material stirring, in the silica crucible of packing into, in Muffle furnace, be warming up to 180-250 ℃, be incubated 4 hours with heating rate 1-2 ℃/min slowly;

(b) founding of glass: take out to pulverize from silica crucible and grind, found in platinum crucible, glass melting temperature is 900 ℃-1200 ℃, and temperature retention time is 1-3 hour;

(c) preparation of devitrified glass: the melt that (b) step makes is suppressed quenching between metal mold, precipitation of phosphorus sodium calcium stone crystal in cooling procedure; Perhaps the melt that (b) step is made is behind compacting quenching between metal mold, and under 600 ℃ of-800 ℃ of temperature heat treatment 0.5-10 hour, precipitation of phosphorus sodium calcium stone crystal.

Raw material is warming up to 190 ℃ in described (a) step in Muffle furnace, (b) glass melting temperature is 1100 ℃ in the step, and temperature retention time is 2.5 hours, and (c) annealing temperature is 500 ℃ in the step, annealing time is 2 hours, and the glass after the annealing is at 2 hours devitrifications of glass of 700 ℃ of following heat treatments.

(3) described devitrified glass is as the application of artificial bone, artificial tooth, artificial joint.

Disclosed a kind of borate biological microcrystalline glass of the present invention and its production and application, its advantage shows: borate biological microcrystalline glass, crystalline phase mainly are that phosphorus sodium calcium stone is β-NaCaPO₄, glassy phase is a sodium calcium boron glass.Compare with before silicate or phosphate system bio-microcrystal glass, its major advantage exists: sodium calcium boron glass degradation rate in SBF solution is very high, can make material rapider hydroxyapatite material that is transformed in body fluid, generate the rate adjusted of hydroxyapatite.Phosphorus sodium calcium stone crystalline phase has bone conductibility, and degradation rate is lower in body fluid, has but guaranteed the intensity stabilization of material after implantation.Two kinds of reaction mechanisms of this of borate system devitrified glass make the degradation rate of material in body fluid to control by regulating crystalline phase and glassy phase ratio, thereby make material after implantation, osseous tissue growth rate and material degradation speed are consistent and become possibility, and it is stable that the intensity of material keeps.Borate biological microcrystalline glass preparation method (a) step: the purpose of pretreatment of raw material is the moisture of introducing in the raw material in order to remove (some raw material such as phosphorus pentoxide be the moisture absorption very easily); Make the raw material pre-reaction, prevent the excessive volatilization of phosphorus pentoxide in the high temperature melting process of next step glass.The blocks of solid of heat treatment gained promptly can be used for founding after crushed.Improved the borate biological microcrystalline glass productive rate.

The specific embodiment

Below will be by further illustrating related content of the present invention in conjunction with the embodiments, but embodiment does not limit its protection domain:

Embodiment 1

According to the accurate raw materials weighing of ratio of components shown in the table 1, with raw material stirring, in the silica crucible of packing into, in Muffle furnace, be warming up to 200 ℃ with 2 ℃/min of heating rate slowly, be incubated 4 hours; Take out to pulverize from silica crucible and grind, found in platinum crucible, glass melting temperature is 1200 ℃, and temperature retention time is 2 hours; The melt that makes is suppressed quenching between metal mold, in cooling procedure, be product of the present invention behind the precipitation of phosphorus sodium calcium stone crystal.The sample (being conventional specification requirement) that the cutting of devitrified glass sample, grinding, polishing is had certain thickness and diameter.Devitrified glass is founded and the test result of performance is shown in table 2.The transition temperature of glass and recrystallization temperature are to adopt the conventional test methodologies differential thermal analysis of glass industry to test, and test instrunment is the CRY-2CRY-1WRT-1 high temperature difference thermal analyzer of Shanghai balance equipment factory.

Usually, the bioactive appraisal procedure of material is that material is placed physiology simulated solution (SBF), measures it generates hydroxyapatite in SBF solution ability.Various ionic concentration are respectively in the SBF solution: Na⁺142.0mM, K⁺5.0mM, Mg²⁺1.5mM, Ca²⁺2.5mM, Cl^-148.8mM, HCO^-34.2mM and HPO4^2-1.0mM simulated body fluid is with NaCl, NaHCO₃, KCl, K₂HPO₄3H₂O, MgCl₂6H₂O, CaCl₂And Na₂SO₄Be dissolved in the deionized water solution ((CH₂OH)₃CNH₂) and HCl buffering pH value to 7.25.The bioactive sample that is evaluated as to microcrystal glass material in this experiment soaks the time that reaction surface generates hydroxyapatite (HA) in the SBF simulated body fluid.If glass is placed 24 hours rear surfaces down and just generated hydroxyapatite (HA) in the SBF simulated body fluid, then the biological activity of this glass is splendid, can use.The structural analysis of glass surface comprises SEM (JSM-6360LV) the type scanning electron microscope of Japanese JEOL company, and the commentaries on classics target X ray polycrystalline diffractometer D/MAX 2550VB/PC of the infrared absorption spectroscopy Nicolet Magna IR550 of U.S. Nicolet company and Japanese RIGAKU analyzes.Test result sees Table 2, soaks after 48 hours in simulated body fluid, and the devitrified glass surface has generated hydroxyapatite, shows that this devitrified glass has very high biological activity, and material promotes the osseous tissue growth as an alternative.

According to nineteen eighty-two American National Standards Institute (ANSI) and the evaluation biocompatibility experiment draft standard announced of dentistry association (ANSI/ADA), the experimental technique of estimating biocompatibility has general toxicity test (oral medication), cell culture method (cell toxicity test method), the test of acute general toxicity (intravenous injection), toxicity on inhalation test, hemolytic test, subcutaneous Implantation Test, bone to be implanted into test, hypersensitive test etc.Wherein, cell culture method is as the toxic means of test material, has easy, advantages such as sensitivity is high, save animal, reduction of expenditure, shortening biomaterial research cycle.Evaluation criterion to the biocompatibility of microcrystal glass material in this experiment mainly is to carry out cell culture with human body tumour cell SAOS-2.Test result shows there is not the death of cell, and on the contrary, cell just begins adherent absorption on material after 1 hour, and cell adsorbs fully and covers material surface and rapidly breeding growth after 48 hours.

Embodiment 2

According to the accurate raw materials weighing of ratio of components shown in the table 1, except pre-sintering temperature is 190 ℃, glass melting temperature is 1100 ℃, temperature retention time is 2.5 hours, melt is suppressed quenching between metal mold, outside the precipitation of phosphorus sodium calcium stone crystal, all the other are identical with embodiment 1 in cooling procedure.Test identically, the results are shown in table 2 with embodiment 1.In simulated body fluid, soak after 24 hours, the devitrified glass surface has generated hydroxyapatite, and the cell culture test result shows there is not the death of cell, cell just begins adherent absorption on material after 1 hour, cell adsorbs fully and covers material surface and rapidly breeding growth after 24 hours.

Embodiment 3

According to the accurate raw materials weighing of ratio of components shown in the table 1, except pre-sintering temperature is 210 ℃, glass melting temperature is 1000 ℃, and temperature retention time is 2 hours, and except annealing temperature is 500 ℃, annealing time is 2 hours.Glass after the annealing is outside 2 hours devitrifications of glass of 700 ℃ of following heat treatments, and all the other are identical with embodiment 1.Test identically, the results are shown in table 2 with embodiment 1.In simulated body fluid, soak after 24 hours, the devitrified glass surface has generated hydroxyapatite, and the cell culture test result shows there is not the death of cell, cell just begins adherent absorption on material after 1 hour, cell adsorbs fully and covers material surface and rapidly breeding growth after 24 hours.

The component of table 1 embodiment glass

Glass ingredient (wt%)	Embodiment 1	Embodiment 2	Embodiment 3
				Na2O	24	22	25.3
CaO	20.4	19.9	12
				P2O5	20	12.4	7
B2O3	35.6	45.7	55

F

0

0

0.7

The The performance test results of table 2 embodiment glass

Glass properties	Embodiment 1	Embodiment 2	Embodiment 3
				Pattern	The white crystallize	The white crystallize	Flint glass
Heat treatment	-	-	700 ℃, 2 hours
				Glass transformation temperature (℃)	-	-	500
The devitrification of glass temperature (℃)	-	-	670
				Soak the time that reaction surface generates hydroxyapatite (HA) in the SBF simulated body fluid	48	24	24

Obviously, borate biological microcrystalline glass of the present invention is on the bases of a large amount of experiments, is according to a class borate biological microcrystalline glass of creating with the theory, and it is to be crystalline phase with phosphorus sodium calcium stone, and sodium calcium boron glass is the material of host glass phase.This devitrified glass has very high biological activity and biocompatibility, can be used as substitution material and is used for aspects such as artificial bone, artificial tooth, artificial joint

Claims (6)

1, a kind of borate biological microcrystalline glass is characterized in that: this devitrified glass is composed of the following components by weight percentage:

B₂O₃ 30-60％

Na₂O 10-40％

CaO 10-30％

P₂O₅ 10-30％

F 0-2％，

Described Na₂O and CaO weight ratio are 1: 2

Described CaO and P₂O₅Weight ratio is 1: 2.

2, devitrified glass according to claim 1 is characterized in that: this devitrified glass is composed of the following components by weight percentage:

B₂O₃ 40-50％

Na₂O 10-30％

CaO 10-20％

P₂O₅ 10-20％

F 0-1％，

Described Na₂O and CaO weight ratio are 1: 1.5

Described CaO and P₂O₅Weight ratio is 1.5: 2.

3, devitrified glass according to claim 1 is characterized in that: this devitrified glass is composed of the following components by weight percentage:

B₂O₃ 45.7％

Na₂O 22％

CaO 19.9％

P₂O₅ 12.4％。

4, the method for preparing the described devitrified glass of claim 1 is characterized in that this method comprises by following steps to form:

(a) pretreatment of raw material: with raw material stirring, in the silica crucible of packing into, in Muffle furnace, be warming up to 180-250 ℃, be incubated 4 hours with heating rate 1-2 ℃/min slowly;

(b) founding of glass: take out to pulverize from silica crucible and grind, found in platinum crucible, glass melting temperature is 900 ℃-1200 ℃, and temperature retention time is 1-3 hour;

(c) preparation of devitrified glass: the melt that (b) step makes is suppressed quenching between metal mold, precipitation of phosphorus sodium calcium stone crystal in cooling procedure; Perhaps the melt that (b) step is made is behind compacting quenching between metal mold, and under 600 ℃ of-800 ℃ of temperature heat treatment 0.5-10 hour, precipitation of phosphorus sodium calcium stone crystal.

5, devitrified glass preparation method according to claim 1, it is characterized in that: (a) raw material is warming up to 190 ℃ in the step in Muffle furnace, (b) glass melting temperature is 1100 ℃ in the step, temperature retention time is 2.5 hours, (c) annealing temperature is 500 ℃ in the step, annealing time is 2 hours, and the glass after the annealing is at 2 hours devitrifications of glass of 700 ℃ of following heat treatments.

6, among the claim 1-3 arbitrary described devitrified glass as the application of artificial bone, artificial tooth, artificial joint.