CN103819182A - Calcium borate silicate biological material as well as preparation and application thereof - Google Patents

Abstract

Translated fromChinese

本发明涉及一种硼硅酸钙生物材料、制备及其应用，采用固相合成或湿化学合成方法，合成得到纯相的硼硅酸钙Ca₁₁Si₄B₂O₂₂粉体，将硼硅酸钙粉体压制成型得到硼硅酸钙陶瓷块体。将硼硅酸钙粉体或硼硅酸钙陶瓷块体在模拟体液(SBF)中浸泡一定时间进行矿化，一段时间后，粉体或者陶瓷表面即可沉积类骨磷灰石层，且研究发现矿化得到的羟基磷灰石的厚度随着浸泡时间的延长而增加。本发明制备得到的硼硅酸钙粉体或者陶瓷材料具有良好的生物学性能，是一种很具潜力的生物和医用材料，可以用作骨组织的修复、填充以及齿科修复材料。

The present invention relates to a calcium borosilicate biomaterial, its preparation and application. The pure-phase calcium borosilicate Ca₁₁ Si₄ B₂ O₂₂ powder is synthesized by solid-phase synthesis or wet chemical synthesis, and the borosilicate The calcium borosilicate powder is compressed to obtain a calcium borosilicate ceramic block. Soak calcium borosilicate powder or calcium borosilicate ceramic block in simulated body fluid (SBF) for a certain period of time for mineralization. After a period of time, a bone-like apatite layer can be deposited on the surface of the powder or ceramic, and the research It was found that the thickness of mineralized hydroxyapatite increased with the immersion time. The calcium borosilicate powder or ceramic material prepared by the invention has good biological properties, is a biological and medical material with great potential, and can be used as bone tissue repairing, filling and dental repairing material.

Description

A kind of calcium borosilicate biomaterial, preparation and application thereof

Technical field

The present invention relates to calcium borosilicate biomaterial, preparation method and application thereof, being particularly related to one has adsorption and can induce biomineralization material of hydroxyapatite remineralization and preparation method thereof and application hydroxyapatite (HAP), belong to Materials science, bionics and biomedical crossing domain, relate to a kind of simulation human internal environment, adopt biomineralization method deposited hydroxyl apatite spontaneously in the aqueous solution, the coating obtaining not only has good biological activity, and can also significantly improve the bonding force of coating.

Background technology

Along with the raising of people's oral Health consciousness, the clinical technology demand for the treatment of the odontopathy causing because of demineralization increases sharply.The organic substrate such as tooth ENAMELIN and dentin phosphoprotein in human body plays an important role in the demineralization of tooth and the equilibrium process of remineralization, uses the material treatment demineralization disease of simulation organic substrate function to become a kind of important means.Rebuilding mineral dental hard tissue structure and mechanical property is a problem demanding prompt solution, has important clinical value and higher social benefit in bone tissue engineer field.

Hydroxyapatite is the important inorganic constituent element of biological hard tissue, is mainly present in the mineralising structures such as bone, tooth and brachiopod shell.Research discovery, in tissue or organ that organism is different, degree, crystalline size, pattern and the packaging assembly of hydroxyapatite mineral mineralising are different.

Calcium phosphate salt have and vertebrate sclerous tissues, mineral composition and structure as similar in bone, tooth etc., have good biocompatibility, has no side effect, a kind of biology and medical material of having very much potentiality, can be as reparation, filling and the gear division repair materials of osseous tissue.But also there is certain deficiency, as hydroxyapatite good stability in vivo, be difficult for being degraded and absorbed, and biological activity is not high.Calcium phosphate ceramics biological activity is not high.Borate calcining temperature is low, and energy consumption is low, is conducive to save energy, and in mineralisation process, material surface easily forms hole, is more conducive to the formation of hydroxyapatite.Therefore the biomaterial of studying this Ca of being rich in, B, Si has certain meaning.

Up to the present, pure phase silicic-boric acid calcium ceramic material and preparation method thereof, especially pure phase calcium borosilicate Ca₁₁si₄b₂o₂₂stupalith has no report as biomaterial.

Summary of the invention

Technical problem to be solved by this invention is to provide one and has absorption hydroxyapatite (HAP) concurrently and induce the calcium borosilicate Ca of hydroxyapatite remineralization function₁₁si₄b₂o₂₂biomaterial and preparation method thereof, for the gear division diseases such as treatment or anticaries, dentin hypersensitiveness (DH) provide new medical material.

For reaching above object, the technical solution used in the present invention is to provide a kind of calcium borosilicate biomaterial, and its chemical formula is Ca₁₁si₄b₂o₂₂.

The preparation method of a kind of calcium borosilicate biomaterial as above, adopts high temperature solid-state method, comprises the following steps:

(1) with calcium ions Ca²⁺compound, containing silicon ion Si⁴⁺compound and boracic ion B³⁺compound be raw material, by general formula Ca₁₁si₄b₂o₂₂the stoichiometric ratio of middle corresponding element takes each raw material, grinds and mixes, and obtains mixture;

(2) be precalcining 1～2 time under the air atmosphere condition of 300～900 ℃ in temperature by mixture, the precalcining time is 1～10 hour, after naturally cooling, grinds and mixes;

(3) mixture step (2) being obtained is to calcine under the air atmosphere condition of 900～1450 ℃ in temperature, and calcination time is 4～15 hours, after naturally cooling, grinds and mixes, and obtains a kind of Powdered calcium borosilicate biomaterial.

In above-mentioned high temperature solid-state method, the precalcining temperature of step (2) is 350～900 ℃, and the precalcining time is 3～9 hours; The calcining temperature of step (3) is 950～1450 ℃, and calcination time is 5～15 hours.

The preparation method of a kind of calcium borosilicate biomaterial as above, also can adopt chemical solution method, comprises the following steps:

(1) with calcium ions Ca²⁺compound, containing silicon ion Si⁴⁺compound and boracic ion B³⁺compound be raw material, by general formula Ca₁₁si₄b₂o₂₂the stoichiometric ratio of middle corresponding element takes each raw material, is dissolved in respectively in rare nitric acid, then adds respectively dehydrated alcohol, with deionized water dilution, stirs and obtains each material solution;

(2) by boracic ion B³⁺, calcium ions Ca²⁺material solution join successively containing silicon ion Si⁴⁺material solution in, then add dehydrated alcohol, stir 1～10 hour, be ripening 24～96 hours under the condition of 30～80 ℃ in temperature, then be drying treatment under the condition of 70～200 ℃ in temperature;

(3) product step (2) being obtained is placed in retort furnace, precalcining 1～2 time under air atmosphere, and precalcining temperature is 300～750 ℃, the precalcining time is 3～10 hours;

(4) after product naturally cooling step (3) being obtained, grind and mix, adopt method for calcinating to prepare Powdered calcium borosilicate, or adopt pressure forming method to prepare solid state calcium borosilicate.

Adopt chemical solution method, the described churning time of step (2) is 2～6 hours, and Aging Temperature is 50～80 ℃, and digestion time is 48～72 hours, and drying temperature is 100～150 ℃; The precalcining temperature of step (3) is 350～750 ℃, and calcination time is 4～9 hours.The method for calcinating that step (4) is described, its processing condition are: in air atmosphere, calcine, calcining temperature is 750～1100 ℃, and calcination time is 7～16 hours, after naturally cooling, grind and obtain a kind of Powdered calcium borosilicate; Described pressure forming method is the one in dry-pressing or isostatic cool pressing; The processing condition of dry-pressing formed method are: in powder, add binding agent, under the condition that is 2～20Mpa at pressure; The processing condition of cold isostatic pressing method are: in powder, add binding agent, under the condition that is 150～250MPa at pressure, pressurize is after 5～10 minutes, then is placed in retort furnace, be to calcine under the air atmosphere of 750～1100 ℃ in temperature, calcination time is 7～16 hours.Described binding agent is polyvinyl alcohol water solution, and polyvinyl alcohol water solution concentration is 5～10wt%, and the add-on of polyvinyl alcohol water solution is powder quality 1/10～2/10.

The calcium ion Ca that contains of the present invention²⁺compound be the one in calcium oxide, calcium hydroxide, calcium carbonate, nitrocalcite, calcium chloride, caoxalate; The described silicon ion Si that contains⁴⁺compound be the one in silicon-dioxide, silicic acid, tetraethoxy; The described boron ion B that contains³⁺compound be the one in boron trioxide, boric acid, tributyl borate.

Technical solution of the present invention also comprises the application of described calcium borosilicate biomaterial, calcium borosilicate biomaterial is placed in to simulated body fluid and carries out mineralising processing, obtains class bone hydroxyapatite, as reparation, filling and the gear division repair materials of osseous tissue.

Compared with prior art scheme, technical solution of the present invention advantage is:

1, the calcium borosilicate Ca that prepared by the present invention₁₁si₄b₂o₂₂biomaterial has good biocompatibility, has no side effect, and is a kind of desirable biology and medical material, can be as reparation, filling and the gear division repair materials of osseous tissue.

2, calcium borosilicate Ca provided by the invention₁₁si₄b₂o₂₂biomaterial has the function of absorption hydroxyapatite (HAP) and induction hydroxyapatite remineralization concurrently.

3, calcium borosilicate Ca provided by the invention₁₁si₄b₂o₂₂biomaterial raw material sources are abundant, cheap, and preparation technology is simple, easy handling, and energy consumption and product cost are lower.

4, the calcium borosilicate Ca that prepared by the present invention₁₁si₄b₂o₂₂biomaterial is compared with other biomaterial, and preparation process is simple, and product easily collecting is without waste water and gas discharge, environmentally friendly.

5, the calcium borosilicate Ca that prepared by the present invention₁₁si₄b₂o₂₂biomaterial has certain physical strength, can be for osseous tissue material.

Accompanying drawing explanation

Fig. 1 is Ca prepared by the embodiment of the present invention 1 technical scheme₁₁si₄b₂o₂₂x-ray powder diffraction collection of illustrative plates;

Fig. 2 is the Ca preparing by the embodiment of the present invention 1 technical scheme₁₁si₄b₂o₂₂the X-ray powder diffraction collection of illustrative plates of the hydroxyapatite obtaining after mineralising;

Fig. 3 is the Ca preparing by the embodiment of the present invention 1 technical scheme₁₁si₄b₂o₂₂sEM figure before powder mineralising;

Fig. 4 is the Ca preparing by the embodiment of the present invention 1 technical scheme₁₁si₄b₂o₂₂eDS figure after powder mineralising 3h;

Ca prepared by Fig. 5 embodiment of the present invention 2 technical schemes₁₁si₄b₂o₂₂sEM figure before powder mineralising;

Fig. 6 is the Ca preparing by the embodiment of the present invention 2 technical schemes₁₁si₄b₂o₂₂eDS figure after powder mineralising 1h;

Fig. 7 is the Ca preparing by the embodiment of the present invention 3 technical schemes₁₁si₄b₂o₂₂x-ray powder diffraction collection of illustrative plates;

Fig. 8 is the Ca preparing by the embodiment of the present invention 3 technical schemes₁₁si₄b₂o₂₂the SEM figure of powder mineralising after 5 hours;

The Ca that Fig. 9 is prepared by the embodiment of the present invention 9 technical schemes₁₁si₄b₂o₂₂sEM figure before pottery mineralising;

Referring to accompanying drawing 10, it is the Ca preparing by embodiment of the present invention technical scheme₁₁si₄b₂o₂₂the SEM of ceramic disks mineralising after 1 hour figure, SEM test result shows, after soaking simulated body fluid 30 minutes, the starting of calcium borosilicate powder surface has hydroxyapatite;

The Ca that Figure 10 is prepared by the embodiment of the present invention 8 technical schemes₁₁si₄b₂o₂₂sEM figure after pottery mineralising 30 minutes;

Figure 11 is the Ca preparing by the embodiment of the present invention 8 technical schemes₁₁si₄b₂o₂₂the SEM figure of pottery mineralising after 5 hours;

Figure 12 is the Ca preparing by the embodiment of the present invention 8 technical schemes₁₁si₄b₂o₂₂the SEM figure of pottery mineralising after 10 hours.

Embodiment

Below in conjunction with drawings and Examples, the invention will be further described.

Embodiment 1: preparation Ca₁₁si₄b₂o₂₂

According to chemical formula Ca₁₁si₄b₂o₂₂, take respectively calcium carbonate CaCO₃: 2.75 grams, silicon-dioxide SiO₂: 0.609 gram, boric acid H₃bO₃: 0.3092 gram, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 350 ℃, calcination time 3 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, calcining again in air atmosphere, and temperature is 850 ℃, calcination time 9 hours, is then chilled to room temperature, takes out sample; After finally it fully being ground again, be placed in retort furnace and calcine in air, calcining temperature is 1450 ℃, and calcination time is 15 hours, obtains powder shaped Ca₁₁si₄b₂o₂₂.By the Powdered Ca obtaining₁₁si₄b₂o₂₂be placed in simulated body fluid (SBF) and soak, carry out mineralising, observe the variation of soaking for some time rear surface pattern, judge whether surface has bone like apatite layer to form.

Simulated body fluid contains the ion close with human plasma and ionic group concentration, and it forms referring to table 1:

Table 1

Referring to accompanying drawing 1, it is the X-ray powder diffraction collection of illustrative plates that the present embodiment technical scheme is prepared sample, and XRD test result shows, prepared material C a₁₁si₄b₂o₂₂for monophase materials, exist mutually without any other impurity thing.

Referring to accompanying drawing 2, it is that the present embodiment technical scheme is prepared Ca₁₁si₄b₂o₂₂the X-ray powder diffraction collection of illustrative plates of sample after mineralising, XRD test result shows, prepared material C a₁₁si₄b₂o₂₂after mineralising, form hydroxyapatite, and be monophase materials, exist mutually without any other impurity thing.

The Ca that prepare by embodiment of the present invention technical scheme referring to accompanying drawing 3₁₁si₄b₂o₂₂sEM figure before powder mineralising, this material crystal property is good, and size distribution is even, and median size is 50 microns of left and right.

The Ca that prepare by embodiment of the present invention technical scheme referring to accompanying drawing 4₁₁si₄b₂o₂₂eDS after powder mineralising 3h figure, the Ca/P of this material is 1.72, very approaching with hydroxyapatite.

Embodiment 2: preparation Ca₁₁si₄b₂o₂₂

According to chemical formula Ca₁₁si₄b₂o₂₂, take respectively calcium oxide CaO:2.0563 gram, silicon-dioxide SiO₂: 0.812 gram, boron trioxide B₂o₃: 0.2321 gram, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 400 ℃, calcination time 4 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, calcining again in air atmosphere, and 900 ℃ of temperature, calcination time 8 hours, is then chilled to room temperature, takes out sample; After finally it fully being ground again, be placed on air calcination in retort furnace, calcining temperature is 1400 ℃, and calcination time is 14 hours, obtains powder shaped Ca₁₁si₄b₂o₂₂.By the Powdered Ca obtaining₁₁si₄b₂o₂₂be placed in simulated body fluid (SBF) and soak, carry out mineralising, observe the variation of soaking for some time rear surface pattern, judge whether surface has bone like apatite layer to form.Similar to embodiment 1 with structure properties main after mineralising before its mineralising.

The Ca that prepare by embodiment of the present invention technical scheme referring to accompanying drawing 5₁₁si₄b₂o₂₂sEM figure before powder mineralising, this material crystal property is good, and size distribution is even, and median size is 50 microns of left and right.Accompanying drawing 6 is the Ca that prepare by embodiment of the present invention technical scheme₁₁si₄b₂o₂₂eDS after powder mineralising 1h figure, the Ca/P of this material is 1.74, very approaching with hydroxyapatite.

Embodiment 3: preparation Ca₁₁si₄b₂o₂₂

According to chemical formula Ca₁₁si₄b₂o₂₂, take respectively calcium hydroxide Ca (OH)₂: 2.7167 grams, silicon-dioxide SiO₂: 0.812 gram, boric acid H₃bO₃: 0.4122 gram, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 450 ℃, calcination time 5 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, calcining again in air atmosphere, and 800 ℃ of temperature, calcination time 7 hours, is then chilled to room temperature, takes out sample; After finally it fully being ground again, be placed on air calcination in retort furnace, calcining temperature is 1350 ℃, and calcination time is 13 hours, obtains powder shaped Ca₁₁si₄b₂o₂₂.By the Powdered Ca obtaining₁₁si₄b₂o₂₂be placed in simulated body fluid (SBF) and soak, carry out mineralising, observe the variation of soaking for some time rear surface pattern, judge whether surface has bone like apatite layer to form.Similar to embodiment 1 with the main structure properties after mineralising before its mineralising.

Referring to accompanying drawing 7, it is that the present embodiment technical scheme is prepared Ca₁₁si₄b₂o₂₂the X-ray powder diffraction collection of illustrative plates of sample after mineralising, XRD test result shows, prepared material C a₁₁si₄b₂o₂₂for monophase materials, exist mutually without any other impurity thing.

Referring to accompanying drawing 8, it is the Ca preparing by embodiment of the present invention technical scheme₁₁si₄b₂o₂₂the SEM of powder after 5 hours figure, SEM test result shows, after soaking simulated body fluid 5 hours, calcium borosilicate powder surface hydroxyapatite layer has very large thickness.Calcium borosilicate Ca is described₁₁si₄b₂o₂₂biomaterial has good biological activity.

Embodiment 4: preparation Ca₁₁si₄b₂o₂₂

According to chemical formula Ca₁₁si₄b₂o₂₂, take respectively calcium sulfate CaSO₄2H₂o:3.7878 gram, silicon-dioxide SiO₂: 0.4872 gram, boric acid H₃bO₃: 0.2474 gram, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 500 ℃, calcination time 6 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, calcining again in air atmosphere, and 750 ℃ of temperature, calcination time 6 hours, is then chilled to room temperature, takes out sample; After finally it fully being ground again, be placed on air calcination in retort furnace, calcining temperature is 1300 ℃, and calcination time is 12 hours, obtains powder shaped Ca₁₁si₄b₂o₂₂.By the Powdered Ca obtaining₁₁si₄b₂o₂₂be placed in simulated body fluid (SBF) and soak, carry out mineralising, observe the variation of soaking for some time rear surface pattern, judge whether surface has bone like apatite layer to form.Similar to embodiment 1 with the main structure properties after mineralising before its mineralising.

Embodiment 5: preparation Ca₁₁si₄b₂o₂₂

According to chemical formula Ca₁₁si₄b₂o₂₂, take respectively nitrocalcite Ca (NO₃)₂4H₂o:3.711 gram, silicon-dioxide SiO₂: 0.348 gram, boric acid H₃bO₃: 0.1767 gram, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 550 ℃, calcination time 7 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, calcining again in air atmosphere, and 700 ℃ of temperature, calcination time 6 hours, is then chilled to room temperature, takes out sample; After finally it fully being ground again, be placed on air calcination in retort furnace, calcining temperature is 1250 ℃, and calcination time is 11 hours, obtains powder shaped Ca₁₁si₄b₂o₂₂.By the Powdered Ca obtaining₁₁si₄b₂o₂₂be placed in simulated body fluid (SBF) and soak, carry out mineralising, observe the variation of soaking for some time rear surface pattern, judge whether surface has bone like apatite layer to form.Similar to embodiment 1 with the main structure properties after mineralising before its mineralising.

Embodiment 6: preparation Ca₁₁si₄b₂o₂₂

According to chemical formula Ca₁₁si₄b₂o₂₂, take respectively calcium chloride CaCl₂: 3.052 grams, silicon-dioxide SiO₂: 0.609 gram, boric acid H₃bO₃: 0.3092 gram, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 600 ℃, calcination time 8 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, calcining again in air atmosphere, and 650 ℃ of temperature, calcination time 6 hours, is then chilled to room temperature, takes out sample; After finally it fully being ground again, be placed on air calcination in retort furnace, calcining temperature is 950 ℃, and calcination time is 5 hours, obtains powder shaped Ca₁₁si₄b₂o₂₂.By the Powdered Ca obtaining₁₁si₄b₂o₂₂be placed in simulated body fluid (SBF) and soak, carry out mineralising, observe the variation of soaking for some time rear surface pattern, judge whether surface has bone like apatite layer to form.Similar to embodiment 1 with the main structure properties after mineralising before its mineralising.

Embodiment 7: preparation Ca₁₁si₄b₂o₂₂

According to chemical formula Ca₁₁si₄b₂o₂₂, take respectively caoxalate CaC₂o₄: 3.5228 grams, silicon-dioxide SiO₂: 0.609 gram, boric acid H₃bO₃: 0.3092 gram, after grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 350 ℃, calcination time 5 hours, is then cooled to room temperature, takes out sample; By the raw material of calcining for the first time, fully mixed grinding is even again, calcining again in air atmosphere, and 800 ℃ of temperature, calcination time 7 hours, is then chilled to room temperature, takes out sample; After finally it fully being ground again, be placed on air calcination in retort furnace, calcining temperature is 1100 ℃, and calcination time is 10 hours, obtains powder shaped Ca₁₁si₄b₂o₂₂.By the Powdered Ca obtaining₁₁si₄b₂o₂₂be placed in simulated body fluid (SBF) and soak, carry out mineralising, observe the variation of soaking for some time rear surface pattern, judge whether surface has bone like apatite layer to form.Similar to embodiment 1 with the main structure properties after mineralising before its mineralising.

Embodiment 8: preparation Ca₁₁si₄b₂o₂₂

According to chemical formula Ca₁₁si₄b₂o₂₂, take respectively calcium carbonate CaCO₃: 1.8334 grams, boron trioxide B₂o₃: 0.1161 gram, tetraethoxy Si (OC₂h₅)₄: 1.3889 grams, first, the calcium carbonate taking, boron trioxide are dissolved in respectively in appropriate dilute nitric acid solution, and in the tetraethoxy taking, add the ethanol of equivalent and the salpeter solution of 5 times of volumes, dilute with deionized water, stir simultaneously.Secondly, to be dissolved completely after, by the boracic ion B of gained³⁺, calcium ions Ca²⁺solution, add successively containing silicon ion Si⁴⁺in solution, then add a certain amount of dehydrated alcohol, stir 2h, ageing 48h, be placed in 100 ℃ of baking ovens and be dried.After grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 350 ℃, calcination time 4 hours; Calcining for the second time, temperature is 750 ℃, calcination time 9 hours, is then chilled to room temperature, takes out sample.Then in powder, adding concentration is 0.3339 gram of the polyvinyl alcohol water solution of 5 wt%, boric acid silico-calcium powder is ground, sieved, then take 2 grams of powders, at dry-pressing 4MPa or isostatic cool pressing 150MPa forming under the pressure, make the biscuit of ceramics of 3 millimeters of 20 millimeters of thickness of diameter.Finally boric acid silico-calcium biscuit of ceramics is placed on to air calcination in retort furnace, calcining temperature is 1050 ℃, and calcination time is 15 hours, obtains Ca₁₁si₄b₂o₂₂ceramic disks.By the Ca obtaining₁₁si₄b₂o₂₂ceramic disks is made standard mechanics test specimens product, tests its mechanical property, and bending strength is 35.8MPa, and Young's modulus is 17.2GPa.By the Ca obtaining₁₁si₄b₂o₂₂ceramic disks is placed in simulated body fluid (SBF) soaks, and carries out mineralising, observes the variation of soaking for some time rear surface pattern, judges Ca₁₁si₄b₂o₂₂whether ceramic disks surface has bone like apatite layer to form, and evaluates its biological activity.The calcium borosilicate ceramic disks of having soaked different time sections is taken out from simulated body fluid, use deionized water clean surface, then dry at 70 ℃, observe the variation of surface topography with SEM.

Referring to accompanying drawing 9, be the Ca preparing by embodiment of the present invention technical scheme₁₁si₄b₂o₂₂sEM figure before pottery mineralising, this material crystal property is good.

Referring to accompanying drawing 10, it is the Ca preparing by embodiment of the present invention technical scheme₁₁si₄b₂o₂₂the SEM of ceramic disks mineralising after 1 hour figure, SEM test result shows, after soaking simulated body fluid 30 minutes, the starting of calcium borosilicate powder surface has hydroxyapatite.

Referring to accompanying drawing 11, it is the Ca preparing by embodiment of the present invention technical scheme₁₁si₄b₂o₂₂the SEM of ceramic disks mineralising after 10 hours figure, SEM test result shows, after soaking simulated body fluid 5 hours, trichoid hydroxyapatite that a large amount of hole of calcium borosilicate powder surface has newly been deposited is filled.

Referring to accompanying drawing 12, it is the Ca preparing by embodiment of the present invention technical scheme₁₁si₄b₂o₂₂the SEM of ceramic disks mineralising after 10 hours figure, SEM test result shows, after soaking simulated body fluid 10 hours, the thickness of calcium borosilicate powder surface hydroxyapatite layer further increases.Calcium borosilicate Ca is described₁₁si₄b₂o₂₂biomaterial has good biological activity.

Embodiment 9: preparation Ca₁₁si₄b₂o₂₂

According to chemical formula Ca₁₁si₄b₂o₂₂, take respectively calcium carbonate CaCO₃: 1.8334 grams, tributyl borate C₁₂h₂₇bO₃: 0.7672 gram, tetraethoxy Si (OC₂h₅)₄: 1.3889 grams, first, the dissolution of calcium carbonate taking, in appropriate dilute nitric acid solution, and is added respectively to the ethanol of equivalent and the salpeter solution of 6 times of volumes in the tetraethoxy taking and tributyl borate, dilute with deionized water, stir simultaneously.Secondly, to be dissolved completely after, by the boracic ion B of gained³⁺, calcium ions Ca²⁺solution, add successively containing silicon ion Si⁴⁺in solution, then add a certain amount of dehydrated alcohol, stir 6 hours, ageing 72 hours, be placed in 150 ℃ of baking ovens and be dried.After grinding in agate mortar and mixing, select air atmosphere to calcine for the first time, temperature is 300 ℃, calcination time 5 hours; Calcining for the second time, temperature is 700 ℃, calcination time 8 hours, is then chilled to room temperature, takes out sample.Then in powder, adding concentration is 0.3990 gram of the polyvinyl alcohol water solution of 10wt%, boric acid silico-calcium powder is ground, sieved, then take 2 grams of powders, at dry-pressing 10MPa or isostatic cool pressing 250MPa forming under the pressure, make the biscuit of ceramics of 3 millimeters of 20 millimeters of thickness of diameter.Finally boric acid silico-calcium biscuit of ceramics is placed on to air calcination in retort furnace, calcining temperature is 800 ℃, and calcination time is 8 hours, obtains Ca₁₁si₄b₂o₂₂ceramic disks.By the Ca obtaining₁₁si₄b₂o₂₂ceramic disks is made standard mechanics test specimens product, tests its mechanical property, and bending strength is 36.0MPa, and Young's modulus is 16.9GPa.By the Ca obtaining₁₁si₄b₂o₂₂ceramic disks is placed in simulated body fluid (SBF) soaks, and carries out mineralising, observes the variation of soaking for some time rear surface pattern, judges Ca₁₁si₄b₂o₂₂whether ceramic disks surface has bone like apatite layer to form, and evaluates its biological activity.It takes out the calcium borosilicate ceramic disks of having soaked different time sections from simulated body fluid, uses deionized water clean surface, then dry at 70 ℃, observes the variation of surface topography with SEM.Main structure properties after its mineralising is similar to embodiment 8.

Claims (10)

1. a calcium borosilicate biomaterial, is characterized in that: its chemical formula is Ca₁₁si₄b₂o₂₂.

2. the preparation method of a kind of calcium borosilicate biomaterial as claimed in claim 1, is characterized in that adopting high temperature solid-state method, comprises the following steps:

With calcium ions Ca²⁺compound, containing silicon ion Si⁴⁺compound and boracic ion B³⁺compound be raw material, by general formula Ca₁₁si₄b₂o₂₂the stoichiometric ratio of middle corresponding element takes each raw material, grinds and mixes, and obtains mixture;

Be precalcining 1～2 time under the air atmosphere condition of 300～900 ℃ in temperature by mixture, the precalcining time is 1～10 hour, after naturally cooling, grinds and mixes;

The mixture that step (2) is obtained is to calcine under the air atmosphere condition of 900～1450 ℃ in temperature, and calcination time is 4～15 hours, after naturally cooling, grinds and mixes, and obtains a kind of Powdered calcium borosilicate biomaterial.

3. the preparation method of a kind of calcium borosilicate biomaterial according to claim 2, is characterized in that: the described calcium ion Ca that contains²⁺compound be the one in calcium oxide, calcium hydroxide, calcium carbonate, calcium sulfate, nitrocalcite, calcium chloride, caoxalate; The described silicon ion Si that contains⁴⁺compound be the one in silicon-dioxide or silicic acid; The described boron ion B that contains³⁺compound be the one in boron trioxide or boric acid.

4. the preparation method of a kind of calcium borosilicate biomaterial according to claim 2, is characterized in that: the precalcining temperature of step (2) is 350～900 ℃, and the precalcining time is 3～9 hours; The calcining temperature of step (3) is 950～1450 ℃, and calcination time is 5～15 hours.

5. the preparation method of a kind of calcium borosilicate biomaterial as claimed in claim 1, is characterized in that adopting chemical solution method, comprises the following steps:

With calcium ions Ca²⁺compound, containing silicon ion Si⁴⁺compound and boracic ion B³⁺compound be raw material, by general formula Ca₁₁si₄b₂o₂₂the stoichiometric ratio of middle corresponding element takes each raw material, is dissolved in respectively in rare nitric acid, then adds respectively dehydrated alcohol, with deionized water dilution, stirs and obtains each material solution;

By boracic ion B³⁺, calcium ions Ca²⁺material solution join successively containing silicon ion Si⁴⁺material solution in, then add dehydrated alcohol, stir 1～10 hour, be ripening 24～96 hours under the condition of 30～80 ℃ in temperature, then be drying treatment under the condition of 70～200 ℃ in temperature;

The product that step (2) is obtained is placed in retort furnace, precalcining 1～2 time under air atmosphere, and precalcining temperature is 300～750 ℃, the precalcining time is 3～10 hours;

(4) after product naturally cooling step (3) being obtained, grind and mix, adopt method for calcinating to prepare Powdered calcium borosilicate, or adopt pressure forming method to prepare solid state calcium borosilicate.

6. the preparation method of a kind of calcium borosilicate biomaterial according to claim 5, is characterized in that: the described calcium ion Ca that contains²⁺compound be the one in calcium oxide, calcium hydroxide, calcium carbonate, nitrocalcite, calcium chloride, caoxalate; The described silicon ion Si that contains⁴⁺compound be the one in silicon-dioxide, silicic acid, tetraethoxy; The described boron ion B that contains³⁺compound be the one in boron trioxide, boric acid, tributyl borate.

7. the preparation method of a kind of calcium borosilicate biomaterial according to claim 5, it is characterized in that: the described churning time of step (2) is 2～6 hours, Aging Temperature is 50～80 ℃, and digestion time is 48～72 hours, and drying temperature is 100～150 ℃; The precalcining temperature of step (3) is 350～750 ℃, and calcination time is 4～9 hours.

8. the preparation method of a kind of calcium borosilicate biomaterial according to claim 5, it is characterized in that: the method for calcinating that step (4) is described, its processing condition are: in air atmosphere, calcine, calcining temperature is 750～1100 ℃, calcination time is 7～16 hours, after naturally cooling, grinds and obtains a kind of Powdered calcium borosilicate; Described pressure forming method is the one in dry-pressing or isostatic cool pressing; The processing condition of dry-pressing formed method are: in powder, add binding agent, under the condition that is 2～20Mpa at pressure; The processing condition of cold isostatic pressing method are: in powder, add binding agent, under the condition that is 150～250MPa at pressure, pressurize is after 5～10 minutes, then is placed in retort furnace, be to calcine under the air atmosphere of 750～1100 ℃ in temperature, calcination time is 7～16 hours.

9. the preparation method of a kind of calcium borosilicate biomaterial according to claim 8, it is characterized in that: described binding agent is polyvinyl alcohol water solution, polyvinyl alcohol water solution concentration is 5～10wt%, and the add-on of polyvinyl alcohol water solution is powder quality 1/10～2/10.

10. by the application of a kind of calcium borosilicate biomaterial claimed in claim 1, it is characterized in that: calcium borosilicate biomaterial is placed in to simulated body fluid and carries out mineralising processing, obtain class bone hydroxyapatite, as reparation, filling and the gear division repair materials of osseous tissue.

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