CN101791427B - Alkaline excitation nano silicon dioxide self-curing material with bioactivity and preparation method and application thereof - Google Patents
Alkaline excitation nano silicon dioxide self-curing material with bioactivity and preparation method and application thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 85
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 54
- 230000005284 excitation Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 27
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 23
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 23
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
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Abstract
The invention relates to an alkaline excitation nano silicon dioxide self-curing material with bioactivity and a preparation method and application thereof. The preparation method comprises the following steps of: mixing nano silicon dioxide powder with calcium hydroxide in a mol ratio of (1-4):1 to prepare alkaline excitation nano silicon dioxide self-curing powder; preparing a hardening liquid;adding the hardening liquid into the alkaline excitation nano silicon dioxide self-curing powder, wherein the ratio of the volume of the hardening liquid to the mass of the alkaline excitation nano silicon dioxide self-curing powder is (1-3):1 ml/g; and stirring the mixture to form a plastic slurry. The alkaline excitation nano silicon dioxide self-curing material has the characteristics of excellent bioactivity, random plasticity, injectability, self-curing, gradual degradation and medicament loading, can induce the formation of osteoid apatite, can be bonded with a bone tissue, has a simplepreparation method and controllable curing performance and injection performance, can be applied to repairing, filling and minimally invasive therapy of bone/tooth tissue defects, and simultaneously can load medicaments.
Description
Invention field
The present invention relates to a kind of alkaline excitation nano silicon dioxide self-curing powder body of biologically active, and contain a kind of biological activity alkaline excitation nano silicon dioxide self-curing material of this powder body and its production and use.Biological activity self-curing material that damaged filling is repaired more specifically to human body bone and dental tissue and preparation method thereof, and the application in orthopaedics, dentistry and minimally-invasive treatment.Belong to biomedical materials field.
Background technology
Along with osteopathias such as the incident osteoporosises of world population aging, and because damaged the growing with each passing day of bone that motion, accident and tumor resection cause, wherein damaged use bone reparation or the alternate material of needing of most of bone.In the such populous nation of China, along with aged tendency of population, young and middle-aged wound increase and development of science and technology, self-evident for the great demand of bone/dental tissue repair materials.But, up to the present, also can be really without any a kind of bone renovating material and the tissue coupling, it all exists certain defective.With advancing age, the function of human body descends, and the scholar generally believes the direction key of the development of following biomaterial for medical purpose is how to realize the regeneration organized.Realize the regeneration of tissue, key is the self-regeneration function of excitating organism, namely will control increment and the differentiation (Hench of in-house grandmother's cell or stem cell by biomaterial for medical purpose; Journal offthe European Ceramic Society 2008; 29 (7): 1257-1265).
In numerous hard tissue repairing materials, discover the bioactivity glass biologically active, spatial induction apatite can be connected with the bone formation bone, has osseous tissue binding ability preferably; Also have simultaneously the function of regulating and activating osteocyte, realize the regeneration of bone.Yet, also there are some problems in bioactivity glass in application facet, as bioactivity glass, use with bulk, in operation process, need cut processing to material or to tissue, make material and repair place size coupling, can bring the damage of the damaged and surrounding tissue of the secondary of tissue like this, limited its extensive use aspect hard tissue repair, especially the minimally-invasive treatment field.
Discover that in a large number bioactivity glass and osseous tissue binding ability induce osteoid apatite in the deposition of material surface based on its surperficial silicon hydroxyl.Simultaneously, the calcium that discharges, silicon ion can with the osteoblast effect, active cell gene expression promotes osteoblastic increment and differentiation, has realized the regeneration of bone.Thus can, induce apatite to form and promote that the increment of human body osteocyte, differentiation are the common denominators of some calcic-silicon components bioactive materials, this provides scientific basis for exploitation biologically active self-curing material.
Tricalcium silicate (self-curing bioactive tricalcium silicate material, Preparation method and use, 200510025824.5), dicalcium silicate (a kind of self solidified in situ biological activity material, preparation and application application number:, the patent No.: Z1200410067419.5) be topmost composition in the Portland cement, the pastel that adds an amount of distiller liquor preparation has the characteristics of any plasticity, self-curing.Studies show that tricalcium silicate and dicalcium silicate and bioactivity glass are similar, the formation of apatite also can be induced in its surface, has superior bioactive, can with the bone formation bonding.Current research shows that tricalcium silicate and dicalcium silicate not only have superior bioactive, also has the calcium of appropriateness and the release of silicon ion, and increment and the differentiation of osteocyte also had facilitation.Checking is induced apatite to form and is promoted that the increment of human body osteocyte, differentiation are the common denominators of some calcic-silicon components bioactive materials.Tricalcium silicate and dicalcium silicate can be used as the bioactive materials that the damaged filling of human body bone/dental tissue is repaired.But still there are some defective in tricalcium silicate and dicalcium silicate, on the one hand, the difficult preparation of tricalcium silicate and dicalcium silicate, preparation tricalcium silicate and dicalcium silicate need carry out under the high temperature of 1200 ℃ and 1450 ℃ respectively, and the crystal formation of tricalcium silicate and dicalcium silicate easily changes in extremely cold process, and difficult control; On the other hand, the aquation solidification process of tricalcium silicate and tricalcium silicate progress is slower, and solidifying needs the long time, can not adapt to the orthopaedics clinical practice preferably.
Nano silicon has huge specific surface area, and there is a large amount of silicon hydroxyls in the surface.Therefore, nano silicon has higher activity, generation and tricalcium silicate and the similar hydrated calcium silicate gel of dicalcium silicate hydrated product under the effect of water and alkali (as calcium hydroxide etc.).The self-curing powder body of nano silicon and calcium hydroxide, the pastel that adds the preparation of an amount of distiller liquor have any plasticity, characteristics such as curing voluntarily equally.When nano silicon under the effect of water and calcium hydroxide, the network structure depolymerization of nano silicon forms hydrated calcium silicate gel with calcium hydroxide, with the carrying out of reaction, the hydrated calcium silicate gel polymerizing curable forms the firming body with a large amount of micropores and intensity.It is similar with dicalcium silicate to tricalcium silicate, can induce the formation of osteoid apatite, can with the bone formation bonding, also have superior bioactive.The firming body of calcium hydroxide and nano silicon soaks in simulated body fluid (SBF), and material surface at first dissolves, Ca
2+And SiO
4 4+Enter solution, the surface forms the network gel layer that is rich in Si-OH, with the prolongation of soak time, solidifies the Ca (OH) of body weight remnants
2With the HCO in the simulated body fluid (SBF)
3 -Reaction, at the surface deposition calcium carbonate, unformed calcium phosphate is that the forming core spot deposition is in material surface with the Si-OH that the surface forms simultaneously.With the HPO in surface and the simulated body fluid (SBF)
4 2-, CO
3 2-Isoionic effect, the deposition of carbonate stops gradually, and unformed calcium phosphate constantly deposits, and changes into the osteoid apatite of crystal formation.Thereby the formation of osteoid apatite guaranteed with body bone tissue in the collagen bonding and the growth of extension, can form bonding with osseous tissue, have excellent biological activity.Calcium hydroxide excitation nano silicon dioxide bone cement is the biological activity self-curing material that a kind of novel damaged filling of bone/dental tissue is repaired, and it will have good application advantage and prospect at aspects such as orthopaedics, dentistry and minimally-invasive treatments.
Summary of the invention
The purpose of this invention is to provide a kind of alkaline excitation nano silicon dioxide self-curing powder body; Another object of the present invention provides a kind of alkaline excitation nano silicon dioxide self-curing material that contains the biologically active of above-mentioned powder body; The present invention also has a purpose to provide the preparation method of above-mentioned biologically active alkaline excitation nano silicon dioxide self-curing material; It is the application that discloses above-mentioned biological activity alkaline excitation nano silicon dioxide self-curing material that the present invention also has a purpose, to satisfy the needs of the damaged filling reparation of bone/dental tissue and minimally-invasive treatment aspect.
Technical scheme of the present invention is: a kind of alkaline excitation nano silicon dioxide self-curing powder body of biologically active is characterized in that being made up of calcium hydroxide and nano silicon; Wherein, the mol ratio of calcium hydroxide and nano silicon is (1～4): 1.
The particle diameter of preferred described nano silicon is 5～200nm.More preferably the particle diameter of nano silicon is 20～30nm.More little aquation and the rate of set that more is conducive to the plasticity slurry of nano-particle diameter that the present invention is used.
Nano silicon of the present invention can also can preferably adopt positive tetraethyl orthosilicate to be the nano silicon of the indefiniteness of raw material hydrolysis preparation for buying the medical grade nano silicon, and its preparation method is as follows:
Positive tetraethyl orthosilicate is joined in the dehydrated alcohol, and wherein the mole of positive tetraethyl orthosilicate and the volume ratio of dehydrated alcohol are 1-2.5mol/L, and hydrolysis is 1～3 hour in 70～80 ℃ water-bath; One-tenthization is after 1～7 day under the room temperature, inserts in 40～50 ℃ the vacuum drying oven dry; Dried sample is removed all organic components 150～200 ℃ of following heat treatments 5～8 hours.After the sample cooling, namely obtaining mean diameter is the armorphous nano silicon-dioxide powdery of 100～200nm.Ground 5～8 hours by vibromill again, can prepare particle diameter at the armorphous nano silicon dioxide of 20～30nm.
The present invention also provides a kind of biologically active alkaline excitation nano silicon dioxide self-curing material, it is characterized in that the plasticity slurry of being made up of above-mentioned alkaline excitation nano silicon dioxide self-curing powder body and distiller liquor; Wherein the distiller liquor volume is 1～3 with the ratio of alkaline excitation nano silicon dioxide self-curing powder quality: 1ml/g, form injectable plasticity slurry behind the mix, the plasticity slurry is repaired filling to bone/dental tissue is damaged, but plasticity slurry in-situ solidifying forms firming body.
Above-mentioned distiller liquor be in deionized water, simulated body fluid (SBF), inorganic salt solution or the organic solution any one.Carbonate, sulfate, chlorate or phosphate solution that preferred described inorganic salt solution is calcium perhaps are carbonate, sulfate, chlorate or the phosphate solution of sodium; Described organic solution is chitosan, polyvinyl alcohol, Weilan gum, gelatin or hyaluronic acid.
Above-mentioned inorganic salt solution concentration is (0.5～100) g/ml; The concentration of organic solution is (0.1～5) g/ml.
The present invention also provides the method for above-mentioned biological activity alkaline excitation nano silicon dioxide self-curing material, and its concrete steps are as follows:
(1) preparation of alkaline excitation nano silicon dioxide self-curing powder body:
Being raw material with analytical pure calcium hydroxide and nano silicon, is 1～4: 1 ratio batching with calcium hydroxide and nano silicon in molar ratio, after the mechanical mixture, namely obtains alkaline excitation silicon dioxide self-curing powder body;
(2) preparation of self-curing material
It is more even than the mixed for (1～3): 1ml/g to press distiller liquor volume and powder quality, the furnishing pasty state, the plasticity slurry, be the biologically active alkaline excitation nano silicon dioxide self-curing material.
Wherein distiller liquor be formulated as distiller liquor sterilization after, be enclosed in the sterilized bottle, standby.
The present invention also provides above-mentioned biological activity alkaline excitation nano silicon dioxide self-curing material to be used for the damaged filling reparation of human body bone/dental tissue and minimally-invasive treatment, but while carrying medicament in application.
Alkaline excitation nano silicon dioxide self-curing material of the present invention can be used for the filling reparation of damaged, the bone delay in healing of bone/dental tissue that a variety of causes causes; Union of fracture promoter in the trauma fracture; Accelerator is filled in the growth of osseous tissue in the extremity bone lengthening; The femur head necrosis repair materials; The damaged filling of bone or vertebral body strength reinforcing material in the compression fracture of spine; Vertebral body is orthopedic, the fusion embedded material; Vertebral body decompression bone-grafting material; The joint is overhauled and is used material; Steel plate, multiple screws are implanted bonding, are filled strengthening material; The skull bone impairment renovation material; Alveolar bone defect repair and alveolar ridge bed hedgehopping are with material etc.
According to foregoing, under the prerequisite that does not break away from the above-mentioned basic fundamental thought of the present invention, universal knowledege and technological means according to this area, add other biocompatibility and medicine component in alcaliotropism excitation nano silicon dioxide composite granule and the distiller liquor, all belong to modification, replacement and the change of the various ways of content of the present invention, all belong to scope of the present invention.
Beneficial effect:
1. nano silicon has huge specific surface area, and there is a large amount of silicon hydroxyls in the surface.Therefore, nano silicon has higher activity, generation and tricalcium silicate and the similar hydrated calcium silicate gel of dicalcium silicate hydrated product under the effect of water and alkali (as calcium hydroxide etc.).The self-curing powder body of nano silicon and calcium hydroxide, the pastel that adds the preparation of an amount of distiller liquor have any plasticity, characteristics such as curing voluntarily equally.When nano silicon under the effect of water and calcium hydroxide, the network structure depolymerization of nano silicon forms hydrated calcium silicate gel with calcium hydroxide, with the carrying out of reaction, the hydrated calcium silicate gel polymerizing curable forms the firming body with a large amount of micropores and intensity.It is similar with dicalcium silicate to tricalcium silicate, can induce the formation of osteoid apatite, can with the bone formation bonding, also have superior bioactive.The present invention changes calcium hydroxide and can realize the setting time of plasticity slurry and the regulation and control of injection performance with the ratio of alkaline excitation nano silicon dioxide self-curing powder quality with mol ratio and the distiller liquor volume of nano silicon; The plasticity slurry of mix has the good mobility energy, under the pressure of 100N, all has syringeability.
2. the curing physical ability of this material of proof was induced the formation of osteoid apatite during external activity was tested, and biologically active can be realized the bonding with osseous tissue; Can further improve biological activity and the bio-compatible performance of firming body as distiller liquor with inorganic salt solution; Can improve the anti-collapsibility performance of plasticity slurry with organic solution as distiller liquor, avoid washing away of body fluid to cause the failure of repairing and filling.Firming body has certain intensity, before new bone tissue generates healing, can play the supporting role of certain intensity, also can play the cementation to broken bone piece.
3. another characteristics of the present invention are carriers that alkaline excitation nano silicon dioxide self-curing material can be used as medicament slow release.Firming body is loose structure, and Kong Douwei nanoscale, and three-dimensional UNICOM from inside to outside can be introduced medicine in mediation, and the rate of release of control medicine is realized the controlled release to medicine.
Description of drawings
The XRD figure of Fig. 1 nano silicon, wherein ◆ be amorphous silica.
The injecting curve of Fig. 2 plasticity slurry.
Fig. 3 solidifies the XRD figure that the alkaline excitation nano silicon dioxide firming body soaks after 1 day in simulated body fluid (SBF), zero be calcium carbonate among the figure wherein; ● be apatite; ▲ be hydrated calcium silicate gel.
The stereoscan photograph on alkaline excitation nano silicon dioxide firming body inside (a) and surface (b) behind Fig. 4 medicine carrying.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiment is not limited in this, all technology that realizes based on foregoing of the present invention and the material of preparation all belong to protection scope of the present invention.
Embodiment 1
1) preparation of nano silicon
Be the feedstock production nano silicon with positive tetraethyl orthosilicate.At first, the positive tetraethyl orthosilicate of 0.2mol is added in the dehydrated alcohol of 200ml, hydrolysis is 2 hours in 80 ℃ water-bath; One-tenthization is after 2 days under the room temperature, inserts in 40 ℃ the vacuum drying oven dry 12 hours; Dried sample is removed all organic components 200 ℃ of following heat treatments 6 hours.After the sample cooling, namely obtaining mean diameter is the armorphous nano silicon-dioxide powdery of 150nm.Grinding 6 hours by vibromill, can prepare mean diameter is the armorphous nano silicon dioxide of 20nm, nano silicon is carried out XRD analysis (as Fig. 1), this method can be prepared unformed nano silicon more easily as can be seen from the results, and this nano silicon can have higher activity.
2) preparation of alkaline excitation nano silicon dioxide self-curing powder body
Be that the armorphous nano silicon dioxide of the step 1) preparation of 20nm is raw material with the particle diameter of analytical pure calcium hydroxide and preparation, be that 2 ratio takes by weighing a certain amount of raw material in the mol ratio of calcium hydroxide and silicon dioxide, after in agitator, stirring 30min, powder body is taken out, the sterilization back is standby, namely obtains the alkaline excitation nano silicon dioxide self-curing powder body.
3) preparation of distiller liquor
Adopt deionized water as distiller liquor, after the distiller liquor sterilization, be enclosed in the sterilized bottle, standby.
4) preparation of plasticity slurry
With deionized water distiller liquor and alkaline excitation nano silicon dioxide self-curing powder body in 1.3: the ratio of 1ml/g fully is in harmonious proportion 1～2min.
The plasticity slurry that will obtain that obtains fills with opening size to be in the syringe of 15ml of 2mm, to inject performance test (as Fig. 2) that as seen from the figure, under the situation of pressure position 100N, the plasticity slurry can all be injected, and has excellent injection performance; Solidify in the plasticity slurry 60min, solidify back comprcssive strength 9MPa greatly, this plasticity slurry can be used for bone and dental tissue defect repair and filling, also can be used for minimally-invasive treatment.
Embodiment 3
1) preparation of alkaline excitation nano silicon dioxide self-curing powder body
The mean diameter that adopts purchase is that the silicon dioxide of 30nm is raw material, will analyze the mol ratio of calcium hydroxide and silicon dioxide again and expand as 3, presses embodiment 2 operation preparation alkaline excitation nano silicon dioxide self-curing powder body.
2) preparation of distiller liquor
Take by weighing the 1.0g carboxymethyl chitosan with deionized water dissolving after, be settled to 100ml, obtain the carboxymethyl chitosan distiller liquor, the sterilization, be enclosed in the sterilized bottle, standby.
3) preparation of plasticity slurry
With carboxymethyl chitosan distiller liquor and alkaline excitation nano silicon dioxide self-curing powder body in 1: the ratio of 1ml/g fully is in harmonious proportion 1～2min.
Obtaining the plasticity slurry can use at the damaged place of the more bone of blood (body fluid), can prevent that blood to the infiltration of slurry inside, condensing in the 40min, has anti-collapsibility performance preferably.
Embodiment 4
1) preparation of alkaline excitation nano silicon dioxide self-curing powder body
With embodiment 1.
2) preparation of distiller liquor
Take by weighing the 20.0g sodium dihydrogen phosphate with deionized water dissolving after, be settled to 100ml, obtain the phosphate distiller liquor, the sterilization, be enclosed in the sterilized bottle, standby.
3) preparation of plasticity slurry
With phosphate distiller liquor and alkaline excitation nano silicon dioxide self-curing powder body in 1: the ratio of 1ml/g fully is in harmonious proportion 1～2min.
The plasticity slurry solidifies in 30min, and comprcssive strength can reach 20～30MPa in 1 day, can play the better supporting role to the damaged place of bone; The slurry that solidified 1 day soaks in simulated body fluid (SBF), and surface energy is induced the formation (as Fig. 3) of osteoid apatite, has good biological activity, can realize and being connected of osseous tissue.
1) preparation of alkaline excitation nano silicon dioxide self-curing powder body
With embodiment 1.
2) preparation of distiller liquor
Add a certain amount of gentamycin in deionized water, being configured to concentration is the gentamycin distiller liquor of 2mg/ml, and sterilization is enclosed in the sterilized bottle, and is standby.
3) preparation of plasticity slurry
With gentamycin (a kind of antibiosis anti-inflammatory drug) distiller liquor and alkaline excitation nano silicon dioxide powder body in 1.2: the ratio of 1ml/g fully is in harmonious proportion 1～2min, namely obtain the alkaline excitation nano silicon dioxide self-curing carrier material of gentamycin, the carrier that solidified 1 day is carried out scanning electron microscope analysis, gentamycin does not change the porous of firming body, firming body has the three-dimension hole (as Fig. 4) of UNICOM from inside to outside, is the stable carrier of medicament slow release excellence.
Embodiment 6
1) preparation of alkaline excitation nano silicon dioxide self-curing powder body
Be the feedstock production nano silicon with positive tetraethyl orthosilicate.At first, the positive tetraethyl orthosilicate of 0.5mol is added in the dehydrated alcohol of 200ml, hydrolysis is 3 hours in 70 ℃ water-bath; One-tenthization is after 4 days under the room temperature, inserts in 50 ℃ the vacuum drying oven dry 10 hours; Dried sample is removed all organic components 180 ℃ of following heat treatments 8 hours.After the sample cooling, namely obtaining mean diameter is the armorphous nano silicon-dioxide powdery of 200nm.Grinding 7 hours by vibromill, can prepare mean diameter is the armorphous nano silicon dioxide of 30nm.
2) preparation of distiller liquor
Adopt deionized water as distiller liquor, after the distiller liquor sterilization, be enclosed in the sterilized bottle, standby.
3) preparation of plasticity slurry
With distiller liquor and alkaline excitation nano silicon dioxide powder body in 1: the ratio of 1ml/g fully is in harmonious proportion 1～2min.
The plasticity slurry is injected diameter and the long rustless steel grinding tool that is respectively 3mm and 6mm, solidifies after 24 hours, firming body is implanted in the rabbit femoral bone cavitas medullaris, do not see suppuration or ooze out unusually, this material has better biocompatibility.6 weeks of postoperative, the deposition of the existing osteoid apatite of material surface, material has biological activity preferably, has formed newborn osseous tissue around the material, shows that this material has osteogenic ability preferably, can promote regeneration and the healing of osseous tissue.
Claims (6)
1. an alkaline excitation nano silicon dioxide self-curing powder body is characterized in that being made up of calcium hydroxide and nano silicon; Wherein, the mol ratio of calcium hydroxide and nano silicon is (1～4): 1; Described nano silicon be particle diameter at the armorphous nano silicon dioxide of 20～30nm, made by following steps:
Positive tetraethyl orthosilicate is joined in the dehydrated alcohol, and wherein the mole of positive tetraethyl orthosilicate and the volume ratio of dehydrated alcohol are 1-2.5mol/L, and hydrolysis is 1～3 hour in the water-bath of 70～80 ° of C; Ageing is after 1～7 day under the room temperature, inserts in the vacuum drying oven of 40～50 ° of C dry; Dried sample heat treatment 5～8 hours under 150～200 ° of C is removed all organic components; After the sample cooling, namely obtaining mean diameter is the armorphous nano silicon-dioxide powdery of 100～200nm; Ground 5～8 hours by vibromill, the preparation particle diameter is at the armorphous nano silicon dioxide of 20～30nm again.
2. a biologically active alkaline excitation nano silicon dioxide self-curing material is characterized in that the plasticity slurry of being made up of the described alkaline excitation nano silicon dioxide self-curing powder body of claim 1 and distiller liquor; Wherein the distiller liquor volume is 1～3:1ml/g with the ratio of alkaline excitation nano silicon dioxide self-curing powder quality.
3. self-curing material according to claim 2, it is characterized in that described distiller liquor be in deionized water, simulated body fluid, inorganic salt solution or the organic solution any one.
4. self-curing material according to claim 3 is characterized in that described inorganic salt solution is the chlorate solution of calcium, perhaps is carbonate, sulfate, chlorate or the phosphatic solution of sodium; Described organic solution is chitosan, polyvinyl alcohol, Weilan gum, gelatin or hyaluronic acid.
5. self-curing material according to claim 3, the concentration that it is characterized in that inorganic salt solution is 0.5～100g/ml; The concentration of organic solution is 0.1～5g/ml.
6. method for preparing biological activity alkaline excitation nano silicon dioxide self-curing material as claimed in claim 2, its concrete steps are as follows:
(1) preparation of alkaline excitation nano silicon dioxide self-curing powder body:
Being raw material with analytical pure calcium hydroxide and nano silicon, is the ratio batching of 1～4:1 with calcium hydroxide and nano silicon in molar ratio, after the mechanical mixture, namely obtains alkaline excitation silicon dioxide self-curing powder body;
(2) preparation of self-curing material
It is more even than the mixed for (1～3): 1ml/g to press distiller liquor volume and powder quality, the furnishing pasty state, the plasticity slurry, be the biologically active alkaline excitation nano silicon dioxide self-curing material.
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| 叶青 等.纳米SiO2与水泥硬化浆体中Ca(OH)2的反应.《硅酸盐学报》.2003,第31卷(第5期),517-522. * |
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