CN1621344A - Wollastonite nano-fiber and its preparing method and use - Google Patents
Wollastonite nano-fiber and its preparing method and use Download PDFInfo
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- CN1621344A CN1621344A CN 200410067214 CN200410067214A CN1621344A CN 1621344 A CN1621344 A CN 1621344A CN 200410067214 CN200410067214 CN 200410067214 CN 200410067214 A CN200410067214 A CN 200410067214A CN 1621344 A CN1621344 A CN 1621344A
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Abstract
The present invention is the preparation process of nanometer wollastonite fiber. Nanometer xonotlite fiber is first prepared with tetraehtoxysilane, soluble calcium salt and NaOH as material, with surfactant to provide template and under hydrothermal condition; and then calcined at high temperature to convert into wollastonite while maintaining the fiber shape and size. The nanometer wollastonite fiber thus prepared has dimmeter of 50-200 nm and maximum length of 20 microns, and is suitable for preparing high strength bioceramic material and composite material.
Description
Technical field
The present invention relates to Wollastonite nano-fiber and its production and use, belong to technical field of biological material.
Background technology
In recent years, because its particular performances, monodimension nanometer material (comprising nano wire, nanotube and nanometer rod etc.) and application thereof have caused people's extensive concern.Utilize cheap feedstock production monodimension nanometer material to cause gradually that also people more and more pay close attention to.Because its special mechanical properties, monodimension nanometer material has been widely used in preparing nano-device, high-strength ceramic, and the filler etc. that is used for nano structural material.
Wollastonite (CaSiO
3) be a kind of novel non-metallic minerals resource, because it has unique mineralogical characteristic and physical and chemical performance, so its Application Areas constantly enlarges.Wollastonite is mainly used in ceramic industry at present, and the filler that is used in polymkeric substance such as plastics, rubber.Wollastonite has also caused people's attention in recent years as the research of biomaterial.
Wollastonite comes from the A-W glass-ceramic of people's inventions such as T.Kokubo as the research of biomaterial, it is the best biological active ceramic material of present known mechanical property.Wollastonite is as one of two kinds of crystallite phases in the A-W glass-ceramic (another kind is a phosphatic rock), and not only the mechanical property to the A-W glass-ceramic has significant contribution, and also has very high biological activity simultaneously.T.Kokubo is studying CaO-SiO
2-P
2O
5Point out behind the system bioactivity glass: the various biological active materials of tool difference in functionality can be at CaO-SiO
2Develop on the basis of base bio-vitric.In view of this, technical field of biological material begin to abandon " phosphorus is requisite component in the biomaterial " this traditional view, then to wollastonite ceramics and CaO-SiO
2Be that biomaterials such as bio-vitric are studied.Existing so far many article and patents of invention about the wollastonite biological ceramics.Mechanical property and bioactive consideration based on improving composite biological material also have considerable research that wollastonite is used for the polymkeric substance packing material, and have obtained good result.
The research that inorganic fibers is used to strengthen pottery and macromolecular material has had many reports, has been widely used in the preparation of high-strength and high ductility material.In technical field of biological material, utilize the research of hydroxyapatite fiber and carbon fibre reinforced high-molecular and biological ceramics that many reports are also arranged, and reinforced effects is obvious.Yet up to the present Wollastonite nano-fiber yet there are no relevant report.
Summary of the invention
The purpose of this invention is to provide a kind of Wollastonite nano-fiber and its production and use.
Adopt the wollastonite purity height of hydrothermal method preparation, diameter is about about 50-200nm, and length is less than 20 μ m, generally at 8-20 μ m.
This preparation method of preparation method of Wollastonite nano-fiber provided by the invention is with Ca (NO
3)
2Be the calcium source, tetraethoxy (TEOS) is the silicon source, comprises two steps:
The one, with Hydrothermal Preparation xonotlite nanofiber; The 2nd, the xonotlite nanofiber is calcined under air atmosphere, make it dehydration and undergo phase transition the acquisition Wollastonite nano-fiber.
Concrete scheme is as follows: at first, configuration concentration is not higher than the soluble calcium salt of 3M (as Ca (NO respectively
3)
2) and concentration be not higher than the NaOH solution of 6M, the drips of solution of NaOH is added to Ca (NO
3)
2In the solution, generate (CaOH) of white
2Precipitation, and continue to drip NaOH solution and regulate pH to 9-14.Configuration concentration is higher than 0.3% tensio-active agent (as cetyl trimethyl ammonia bromine (CTAB), sodium laurylsulfonate (SDS)) solution, and adding and Ca (NO
3)
2The TEOS of equimolar amount, ultra-sonic dispersion is to emulsion.Mixed C a (OH)
2With TEOS emulsion, mixture is packed in the autoclave, 120-220 ℃ of insulation 20-50 hour down.The white precipitate that generates is used deionized water and absolute ethanol washing respectively, place in the 30-100 ℃ of baking oven and dried, obtain the xonotlite nanofiber through 24-108 hour.600-900 ℃ of calcining of xonotlite nanofiber after 1-5 hour, obtained Wollastonite nano-fiber.
The present invention provides the preparation method of Wollastonite nano-fiber first, and method is simple and convenient, cost is not high, and prepared nanofibers of dimensions is even.
The Wollastonite nano-fiber purity height of method preparation provided by the invention does not contain other elements except that Ca, Si, O, Ca/Si ratio is 0.85, near the theoretical chemistry proportioning 1.0 of wollastonite.
The Wollastonite nano-fiber purity of utilizing the present invention to prepare is higher, meets the medical use requirement.Prepared Wollastonite nano-fiber diameter is at Nano grade, and length-to-diameter ratio is bigger.
Based on the monodimension nanometer material special mechanical properties, Wollastonite nano-fiber will play an important role aspect raising biological ceramics and the composite materials property.Can be used for preparing high-intensity bioceramic material and matrix material.
Description of drawings
Fig. 1 and Fig. 2 are respectively the TEM photo and the XRD figure spectrum of prepared xonotlite nanofiber.By the tem analysis of Fig. 1 as can be known, prepared xonotlite nanofiber diameter 50-200nm, length 10-15 μ m.
Fig. 3 and Fig. 4 are respectively the TEM photo and the XRD figure spectrum of prepared Wollastonite nano-fiber, and wherein the illustration of Fig. 3 is that the SAD of nanofiber analyzes.Behind 800 ℃ of calcining 2h, by the XRD analysis of Fig. 4 as can be known, xonotlite changes wollastonite into, and the TEM image of Fig. 3 shows, the pattern of nanofiber remains unchanged.SAD collection of illustrative plates from Fig. 3 as can be known, the gained Wollastonite nano-fiber is a single crystal fibre.
Fig. 5 is that the EDS of prepared Wollastonite nano-fiber analyzes, and shows that nanofiber is mainly elementary composition by Ca, Si, three kinds of O.
Embodiment
The invention will be further described below in conjunction with example, but they are not that the present invention is imposed any restrictions.
Embodiment 1:
(1) 2.52g NaOH and 5.52g Ca (NO
3)
2Dissolve in 30ml H respectively
2Among the O, be stirred to the dissolving clarification.
(2) stir Ca (NO
3)
2Solution, and the NaOH drips of solution is added to wherein, Ca (OH) generated
2White precipitate.Be added dropwise to complete back suspension liquid pH and be about 12.75.
(3) 0.45g CTAB dissolves in 90ml H
2Among the O, add 6ml TEOS then, ultra-sonic dispersion is to forming emulsion.
(4) with emulsion and the Ca (OH) of TEOS
2Suspension liquid mixes, and in the autoclave of packing into after stirring, places 180 ℃ of hydro-thermal 30h in the baking oven.Mix back pH and be about 11.8.
(5) treat the autoclave naturally cooling after, open autoclave, suction filtration removes solution.Distinguish repeatedly cleaning reaction gained precipitation with deionized water and dehydrated alcohol, place 60 ℃ of baking oven inner drying 72h then.
(6) in High Temperature Furnaces Heating Apparatus, under the air atmosphere, 800 ℃ obtain Wollastonite nano-fiber through the 2h calcining.
The EDS analysis revealed shows that nanofiber is mainly elementary composition by Ca, Si, three kinds of O, and Ca/Si is 0.83.
Embodiment 2:
(1) 2.52g NaOH and 5.52g Ca (NO
3)
2Dissolve in 30ml H respectively
2Among the O, be stirred to the dissolving clarification.
(2) stir Ca (NO
3)
2Solution, and the NaOH drips of solution is added to wherein, Ca (OH) generated
2White precipitate.Be added dropwise to complete back suspension liquid pH and be about 12.75.
(3) 0.7g SDS dissolves in 90ml H
2Among the O, add 6ml TEOS then, ultra-sonic dispersion is to forming emulsion.
(4) with emulsion and the Ca (OH) of TEOS
2Suspension liquid mixes, and in the autoclave of packing into after stirring, places 180 ℃ of hydro-thermal 30h in the baking oven.Mix back pH and be about 11.8.
(5) treat the autoclave naturally cooling after, open autoclave, suction filtration removes solution.Distinguish repeatedly cleaning reaction gained precipitation with deionized water and dehydrated alcohol, place 60 ℃ of baking oven inner drying 72h then.
(6) in High Temperature Furnaces Heating Apparatus, under the air atmosphere, 800 ℃ obtain Wollastonite nano-fiber through the 2h calcining.
The EDS analysis revealed shows that nanofiber is mainly elementary composition by Ca, Si, three kinds of O, and Ca/Si is 0.85.
Embodiment 3:
(1) 2.52g NaOH and 2.59g CaCl
2Dissolve in 30ml H respectively
2Among the O, be stirred to the dissolving clarification.
(2) stir CaCl
2Solution, and the NaOH drips of solution is added to wherein, Ca (OH) generated
2White precipitate.Be added dropwise to complete back suspension liquid pH and be about 12.75.
(3) 0.45g CTAB dissolves in 90ml H
2Among the O, add 6ml TEOS then, ultra-sonic dispersion is to forming emulsion.
(4) with emulsion and the Ca (OH) of TEOS
2Suspension liquid mixes, and in the autoclave of packing into after stirring, places 180 ℃ of hydro-thermal 30h in the baking oven.Mix back pH and be about 11.8.
(5) treat the autoclave naturally cooling after, open autoclave, suction filtration removes solution.Distinguish repeatedly cleaning reaction gained precipitation with deionized water and dehydrated alcohol, place 60 ℃ of baking oven inner drying 72h then.
(6) in High Temperature Furnaces Heating Apparatus, under the air atmosphere, 800 ℃ obtain Wollastonite nano-fiber through the 2h calcining.
The EDS analysis revealed shows that nanofiber is mainly elementary composition by Ca, Si, three kinds of O, and Ca/Si is 0.84.
The chemical ingredients of the Wollastonite nano-fiber of table 1 the present invention three embodiment preparation,
| Component | Content | ||
| Example 1 | Example 2 | Example 3 | |
| ????CaO | ????45.33 | ????45.88 | ????45.59 |
| ????SiO 2 | ????54.67 | ????54.12 | ????54.41 |
| ????Ca/Si | ????0.83 | ????0.85 | ????0.84 |
Claims (6)
1, a kind of Wollastonite nano-fiber is characterized in that diameter is 50-200nm, and length is less than 20 μ m.
2, by the preparation method of the described a kind of Wollastonite nano-fiber of claim 1, it is characterized in that (NO with Ca
3)
2Be the calcium source, tetraethoxy (TEOS) is the silicon source, obtains Wollastonite nano-fiber with the xonotlite nanofiber being calcined under air atmosphere behind the Hydrothermal Preparation xonotlite nanofiber again.
3, by the preparation method of the described a kind of Wollastonite nano-fiber of claim 2, it is characterized in that described Hydrothermal Preparation xonotlite nanofiber comprises the steps:
(1) respectively the soluble calcium salt of configuration and NaOH solution, the solution of NaOH is added Ca (NO
3)
2In the solution, generate (CaOH)
2Precipitation, and regulate pH to 9-14;
(2) configuration concentration is higher than 0.3% tensio-active agent, and adding and Ca (NO
3)
2The tetraethoxy of equimolar amount (TEOS), ultra-sonic dispersion is to emulsion.Mixed C a (OH)
2And TEOS, mixture to be packed in the autoclave, the white precipitate that hydro-thermal reaction generates is dried through washing after, obtains the xonotlite nanofiber;
The step of described acquisition Wollastonite nano-fiber is that the xonotlite nanofiber after 1-5 hour, is obtained Wollastonite nano-fiber 600-900 ℃ of calcining.
4, by the preparation method of the described a kind of Wollastonite nano-fiber of claim 3, it is characterized in that described soluble calcium salt is Ca (NO
3)
2, concentration concentration is not higher than 3M, and the NaOH strength of solution is not higher than 6M.
5, by the preparation method of the described a kind of Wollastonite nano-fiber of claim 3, it is characterized in that described tensio-active agent is cetyl trimethyl ammonia bromine (CTAB) or sodium laurylsulfonate (SDS).
6, a kind of Wollastonite nano-fiber can be used for preparing high-intensity bioceramic material and matrix material.
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|---|---|---|---|
| CN 200410067214 CN1278934C (en) | 2004-10-15 | 2004-10-15 | Wollastonite nano-fiber and its preparing method and use |
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|---|---|---|---|
| CN 200410067214 CN1278934C (en) | 2004-10-15 | 2004-10-15 | Wollastonite nano-fiber and its preparing method and use |
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| Publication Number | Publication Date |
|---|---|
| CN1621344A true CN1621344A (en) | 2005-06-01 |
| CN1278934C CN1278934C (en) | 2006-10-11 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863654A (en) * | 2010-05-18 | 2010-10-20 | 武汉科技大学 | Bio-soluble ceramic fiber and preparation method thereof |
| CN102259876A (en) * | 2010-05-28 | 2011-11-30 | 延增国 | Preparation method of calcium silicate friction material |
| CN105905948A (en) * | 2016-02-19 | 2016-08-31 | 中国科学技术大学 | Preparation method of hematite submicron particles |
| CN115142116A (en) * | 2022-07-12 | 2022-10-04 | 郑州大学 | Preparation method of nano xonotlite fiber |
-
2004
- 2004-10-15 CN CN 200410067214 patent/CN1278934C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863654A (en) * | 2010-05-18 | 2010-10-20 | 武汉科技大学 | Bio-soluble ceramic fiber and preparation method thereof |
| CN101863654B (en) * | 2010-05-18 | 2012-08-29 | 武汉科技大学 | Bio-soluble ceramic fiber and preparation method thereof |
| CN102259876A (en) * | 2010-05-28 | 2011-11-30 | 延增国 | Preparation method of calcium silicate friction material |
| CN105905948A (en) * | 2016-02-19 | 2016-08-31 | 中国科学技术大学 | Preparation method of hematite submicron particles |
| CN105905948B (en) * | 2016-02-19 | 2017-07-25 | 中国科学技术大学 | A kind of preparation method of bloodstone submicron particles |
| CN115142116A (en) * | 2022-07-12 | 2022-10-04 | 郑州大学 | Preparation method of nano xonotlite fiber |
| CN115142116B (en) * | 2022-07-12 | 2023-10-20 | 郑州大学 | Preparation method of nano xonotlite fiber |
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| Publication number | Publication date |
|---|---|
| CN1278934C (en) | 2006-10-11 |
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Granted publication date: 20061011 Termination date: 20101015 |