CN102020485A - Method for preparing calcium silicate biofilm on surface of crystalline silicon in situ - Google Patents
Method for preparing calcium silicate biofilm on surface of crystalline silicon in situ Download PDFInfo
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- CN102020485A CN102020485A CN201010520123XA CN201010520123A CN102020485A CN 102020485 A CN102020485 A CN 102020485A CN 201010520123X A CN201010520123X A CN 201010520123XA CN 201010520123 A CN201010520123 A CN 201010520123A CN 102020485 A CN102020485 A CN 102020485A
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Abstract
The invention discloses a method for preparing a calcium silicate biofilm on the surface of crystalline silicon in situ, which comprises the following steps: i) carrying out surface cleaning on crystalline silicon; ii) preparing a saturated calcium hydroxide solution; and iii) forming a calcium silicate biofilm on the surface of the crystalline silicon in situ: taking the liquid supernatant of the calcium hydroxide solution obtained in step ii, and pouring the liquid supernatant into a high pressure autoclave, then soaking the crystalline silicon subjected to surface cleaning into the saturated calcium hydroxide solution, after the obtained mixture is processed in a high temperature and high pressure environment, taking out the crystalline silicon, and repeatedly soaking and rinsing the crystalline silicon by the deionized water, after the crystalline silicon is dried, carrying out annealing on the crystalline silicon in an electric furnace so as to prepare a calcium silicate biofilm on the surface of crystalline silicon in situ. The method disclosed by the invention is suitable to be used in the preparation of the calcium silicate biofilm on the surface of a crystalline silicon material with any shape in situ.
Description
Technical field
The invention belongs to surface of crystalline silicon modification field, be specifically related to the preparation method of surface of crystalline silicon coating, particularly relate to method at the biological thin layer of surface of crystalline silicon in-situ preparing Calucium Silicate powder.
Background technology
The crystalline silicon of good biocompatibility is the crucial starting material of research and development based on the reliable new bio chip of the long-term safety of using in the body (Biochips), micro sensor (Micro-sensors), microelectromechanical systems microdevices such as (MEMS), particularly along with the development of biomedical engineering, Application and Development is even more important in the above-mentioned highly sensitive of biomedical sector and the microdevice of tolerance range and Biosafety, and this will provide important support for original position inline diagnosis and the treatment that promotes cause of disease.But present studies show that, the biocompatibility of crystalline silicon self is relatively poor, causes bad physiological responses such as local inflammation, repulsion when implanting easily.
At present, correlative study work is mainly by deposit (or assembling) biocompatibility preferred metal or organism at surface of crystalline silicon, as nanometer gold and [Suet P L, et al.Biomaterials, 2006, the 27:4538 such as non-toxic organic molecule that contain amino; Bharat B, et al.Acta Biomaterialia, 2005,1:327], reason also causes its application to be very restricted but the batch preparations cost is higher, sticking power is little and long-term biocompatibility is relatively poor etc.; Injecting H element technology by surface ion can make surface of crystalline silicon possess the sedimentary ability of the phosphatic rock of inducing [Liu X Y et al.Biomaterials, 2004,25 (6): 5575], but it is big to equipment requirements height, running cost, make it be difficult to use surface modification in batches with crystalline silicon, and this technology is relatively poor to the surface modification homogeneity of complex-shaped crystalline silicon; In addition, also have part Study to adopt the method that directly prepares apatite coating at surface of crystalline silicon to improve the surface biological consistency of crystalline silicon, comprise and adopt electroless plating [Chung R, et al.Surface and Coatings Technology, 2003:194], sol-gel (sol-gel) method [Miguel M, et al.International Journal of Inorganic Materials, 2001:1153], laser melting coating [Guillot N O et al.J.Appl.Phys, 1996,80 (6): 1803], bionical deposition [Seala S, et al.AppliedSurface Science, 2001,137:339] etc. several method, have sharp interface but adopt between the apatite coating of these methods preparation and the crystalline silicon, relatively poor associativity causes the apatite coating inefficacy that comes off easily.
Based on the deficiency of above-mentioned surface of crystalline silicon biological modification method, be necessary very much to develop new coating that can conveniently be applied to bio-medical surface of crystalline silicon biological modification and preparation method thereof.Maximum innovative point of the present invention is to adopt first calcium hydroxide and crystalline silicon top layer atom direct reaction under the High Temperature High Pressure to generate the new technology of Calucium Silicate powder, the Calucium Silicate powder thin layer that goes out to have nanostructure in the surface of crystalline silicon in-situ preparing.The proposition of the new modification thinking that this invention relates to is mainly based on the controllable reaction that can realize crystalline silicon simple substance and calcium hydroxide in (1) high temperature and high pressure environment; (2) Calucium Silicate powder thin layer original position is created on surface of crystalline silicon, can form good bonding interface with crystalline silicon; (3) the nanometer Calucium Silicate powder has the ability of inducing osteolith forming core and growth, and has the excellent biocompatibility with cell and tissue.The calsil that comprises Calucium Silicate powder and wollastonite etc. promote the osteolith deposition with and excellent biocompatibility confirmed [Hench L.J Am Ceram Soc, 1991,74 (7): 1487 by correlative study work; Nakamura T.J Biomed MaterRes, 1985,19:685]; At present, the main preparation of Calucium Silicate powder salt biomaterial and application form comprise that sol-gel method or chemical deposition or solid reaction process prepare physiologically acceptable ceramic powder or vesicular structure biological ceramics implant [Zhu Hongyang, Deng. biomedical engineering research, 2008,27 (1): 9; Wan Xianghui, etc. Materials Science and Engineering journal, 2005,23 (2): 230; Lin Kaili, etc. Journal of Inorganic Materials, 2005,20 (3): 692; Lin Kaili, Deng. Chinese invention patent CN1403414, CN1439618], the medical metal-based biocompatible coating [Liu Xuanyong of plasma spraying, Deng. silicate journal, 2002,30 (1): 20], also relate to the surface biological modification that Calucium Silicate powder is applied to crystalline silicon without any work, the report that does not also prepare the Calucium Silicate powder coating at surface of crystalline silicon has any similar or close research work at the biological thin layer of surface of crystalline silicon in-situ preparing Calucium Silicate powder under the High Temperature High Pressure that does not more have to adopt to the present invention.What is particularly worth mentioning is that, with the existing method contrast that is used for preparing Calucium Silicate powder salt biological ceramic powder body, coating and body material, the high temperature and high pressure method that the present invention proposes all has remarkable advantages at the aspects such as controllability of modification cost, modification flow process and processing parameter, is to having multiple appearance structure, being applied to the ideal new way that the crystalline silicon of biomedical sector carries out surface biological modification.
Summary of the invention
Main purpose of the present invention provide a kind of can be in the novel method of variform surface of crystalline silicon in-situ preparing nano coatings such as sheet, wire and tubulose, specifically provide a kind of method at the biological thin layer of surface of crystalline silicon in-situ preparing Calucium Silicate powder, mortise is avoided the problem that comes off of external coating between biological thin layer of the Calucium Silicate powder that the expectation original position forms and crystalline silicon base material, expects that simultaneously the biological thin layer of Calucium Silicate powder of good biocompatibility can improve the surface biological consistency of biologically inert crystalline silicon.
The novel method of the biological thin layer of surface of crystalline silicon in-situ preparing Calucium Silicate powder disclosed by the invention is characterized in that, may further comprise the steps:
I) surface cleaning of crystalline silicon: sheet or wire or tubular crystal silicon are successively put into acetone, dehydrated alcohol and deionized water ultrasonic cleaning, and hyperacoustic cleaning frequency is 20～80kHz, preferred 40～75kHz; The ultrasonic cleaning time is 10～60 minutes, with deionized water rinsing, dry standby;
The ii) preparation of saturated aqua calcis: be 15～35 ℃ in temperature excessive calcium hydroxide poured in the deionized water that the sealing bottleneck leaves standstill after stirring a little;
The iii) formation of the biological thin layer of surface of crystalline silicon original position Calucium Silicate powder: the supernatant liquor of calcium hydroxide saturated solution is poured in the autoclave in getting ii), with i) in immerse saturated aqua calcis through the crystalline silicon of surface cleaning, 151～300 ℃ of temperature.Pressure is 0.5～5.0MPa, handle in the environment after 0.5～10 hour crystalline silicon is taken out, soak into and drip washing with deionized water repeatedly, in electric furnace, be 300～600 ℃ after drying and annealed 0.5～5 hour, promptly make the biological thin layer of Calucium Silicate powder in the surface of crystalline silicon original position in temperature.
In the present invention, described crystalline silicon successively carries out preferred 30～50 minutes of ultrasonic cleaning time in acetone, dehydrated alcohol and deionized water.
In the present invention, described calcium hydroxide is analytical pure or chemical pure level reagent.
In the present invention, the preparation temperature of described calcium hydroxide saturated solution is preferred 20～30 ℃.
In the present invention, described through preferred 160～260 ℃ of the treatment temp in the calcium hydroxide saturated solution of crystalline silicon in autoclave of surface cleaning.
In the present invention, described through the preferred 1.0～3.0MPa of processing pressure in the calcium hydroxide saturated solution of crystalline silicon in autoclave of surface cleaning.
In the present invention, described through preferred 3～6 hours of the treatment time in the calcium hydroxide saturated solution of crystalline silicon in autoclave of surface cleaning.
In the present invention, the annealing temperature of the described crystalline silicon that takes out from autoclave in electric furnace is preferred 350～500 ℃.
In the present invention, the annealing time of the described crystalline silicon that takes out from autoclave in electric furnace is preferred 1～3 hour.
The crystalline silicon of variforms such as sheet, wire, tubulose is handled in the calcium hydroxide saturated solution of High Temperature High Pressure, utilize the calcium hydroxide alkaline reaction of the medium tenacity under elementary silicon and the high temperature to generate Calucium Silicate powder, and be grown to nano shape and combine closely with the crystalline silicon base material by the high pressure control Calucium Silicate powder, at last by middle The high temperature anneal, thereby form the biological thin layer of Calucium Silicate powder in variform surface of crystalline silicon original position, realization has the preparation of the silica-based biological thin layer of crystal of excellent combination interface and biocompatibility.
The method that adopts calcium hydroxide saturated solution of the present invention and crystalline silicon under High Temperature High Pressure, to react, can be at the biological thin layer of surface of crystalline silicon in-situ preparing Calucium Silicate powder, its ultimate principle is to utilize elementary silicon under the high temperature to dissolve the hydroxide ion reaction that ionization goes out with calcium hydroxide to generate silicate ion and water, the calcium ion that silicate and the ionization of oxidation calcium go out is further combined with generating Calucium Silicate powder, owing to raising, reduces the solubility with temperature of calcium hydroxide, the crystalline silicon agent structure that can avoid too much hydroxide ion at high temperature the violent corrosion of elementary silicon to be caused is damaged, and lower ionization calcium ion concn can suppress the quick forming core of Calucium Silicate powder crystalline and grow up, in addition, the high pressure conditions of autoclave also can effectively be controlled the hypertrophy of Calucium Silicate powder, thereby provide favourable condition for forming the biological thin layer of the Calucium Silicate powder of combining closely with the crystal silicon-base in situ, the biological thin layer of the Calucium Silicate powder of good biocompatibility also is a bone shape phosphatic rock, cell and cambium adhere to and growth provides active place, it is an effective way improving biologically inert surface of crystalline silicon biocompatibility, for researching and developing based on the new bio chip of using in the body (Biochips), micro sensor (Micro-sensors), microelectromechanical systems (Micro-electro-mechanical System, MEMS) etc. the miniature organism medical devices provides Biosafety reliable surface modification crystalline silicon material, further expands the biomedical applications of above-mentioned device.
Beneficial effect:
The present invention adopts convenient controlled High Temperature High Pressure calcium hydroxide saturated solution thermal reaction method to carry out coating modified to surface of crystalline silicon, promptly at the biological thin layer of surface of crystalline silicon in-situ preparing Calucium Silicate powder, required modifying agent cheaply is easy to get, the equipment input is little, technological operation is convenient to implement, and this method is applicable to the preparation of the biological thin layer of crystalline silicon material surface in situ Calucium Silicate powder of arbitrary shape.
Embodiment
In order to make technique means of the present invention, creation characteristic, workflow, using method reach purpose and effect is easy to understand,, further set forth the present invention below in conjunction with specific embodiment.
Embodiment 1
I) surface cleaning of crystalline silicon: the tabular crystal silicon that will grow with the wide 3cm of being respectively and 2cm, thick 0.5mm successively respectively cleaned in the 20kHz ultrasonic cleaner 60 minutes with acetone, dehydrated alcohol and deionized water, at last with deionized water rinsing, dry standby;
The ii) preparation of saturated aqua calcis: under 15 ℃, 5g analytical pure calcium hydroxide is poured in the plastic beaker that fills the 300mL deionized water, sealed bottleneck, leave standstill after the magnetic agitation a little with preservative film;
The iii) formation of the biological thin layer of surface of crystalline silicon original position Calucium Silicate powder: the 120mL of preparation calcium hydroxide saturated solution pours in the autoclave that capacity is 150mL in getting ii), with i) in immerse saturated aqua calcis through the crystalline silicon of surface cleaning, at 151 ℃, 0.5MPa handle after 10 hours in the high temperature and high pressure environment crystalline silicon is taken out, soak into and drip washing with deionized water repeatedly, drying the back annealed 0.5 hour in 600 ℃ in electric furnace, promptly make the biological thin layer of Calucium Silicate powder in the surface of crystalline silicon original position, the biological thin layer of Calucium Silicate powder is by being about 600nm, the calcium silicate nanowire shape crystal of the about 30nm of diameter constitutes.
Embodiment 2
I) surface cleaning of crystalline silicon: the about 3mm wire of diameter crystalline silicon was successively respectively cleaned in the 80kHz ultrasonic cleaner 10 minutes with acetone, dehydrated alcohol and deionized water, at last with deionized water rinsing, dry standby;
The ii) preparation of saturated aqua calcis: under 35 ℃, 3g analytical pure calcium hydroxide is poured in the plastic beaker that fills the 200mL deionized water, sealed bottleneck, leave standstill after the magnetic agitation a little with preservative film;
The iii) formation of the biological thin layer of surface of crystalline silicon original position Calucium Silicate powder: the 135mL of preparation calcium hydroxide saturated solution pours in the autoclave that capacity is 150mL in getting ii), with i) in immerse saturated aqua calcis through the crystalline silicon of surface cleaning, at 300 ℃, 5.0MPa handle after 0.5 hour in the high temperature and high pressure environment crystalline silicon is taken out, soak into and drip washing with deionized water repeatedly, drying the back annealed 5 hours in 300 ℃ in electric furnace, promptly make the biological thin layer of Calucium Silicate powder in the surface of crystalline silicon original position, the biological thin layer of Calucium Silicate powder is by being about 1000nm, the calcium silicate nanowire pencil crystal of thick about 70nm constitutes.
Embodiment 3
I) surface cleaning of crystalline silicon: the about 3mm wire of diameter crystalline silicon was successively respectively cleaned in the 40kHz ultrasonic cleaner 30 minutes with acetone, dehydrated alcohol and deionized water, at last with deionized water rinsing, dry standby;
The ii) preparation of saturated aqua calcis: under 20 ℃, 5g analytical pure calcium hydroxide is poured in the plastic beaker that fills the 350mL deionized water, sealed bottleneck, leave standstill after the magnetic agitation a little with preservative film;
The iii) formation of the biological thin layer of surface of crystalline silicon original position Calucium Silicate powder: the 130mL of preparation calcium hydroxide saturated solution pours in the autoclave that capacity is 150mL in getting ii), with i) in immerse saturated aqua calcis through the crystalline silicon of surface cleaning, at 160 ℃, 1.8MPa handle after 6 hours in the high temperature and high pressure environment crystalline silicon is taken out, soak into and drip washing with deionized water repeatedly, drying the back annealed 3 hours in 350 ℃ in electric furnace, promptly make the biological thin layer of Calucium Silicate powder in the surface of crystalline silicon original position, the biological thin layer of Calucium Silicate powder is by being about 720nm, the calcium silicate nanowire crystal of the about 45nm of diameter constitutes.
Embodiment 4
I) surface cleaning of crystalline silicon: the tabular crystal silicon that will grow with the wide 5cm of being respectively and 3cm, thick 0.5mm successively respectively cleaned in the 60kHz ultrasonic cleaner 20 minutes with acetone, dehydrated alcohol and deionized water, at last with deionized water rinsing, dry standby;
The ii) preparation of saturated aqua calcis: under 28 ℃, 6g analytical pure calcium hydroxide is poured in the plastic beaker that fills the 500mL deionized water, sealed bottleneck, leave standstill after the magnetic agitation a little with preservative film;
The iii) formation of the biological thin layer of surface of crystalline silicon original position Calucium Silicate powder: the 100mL of preparation calcium hydroxide saturated solution pours in the autoclave that capacity is 150mL in getting ii), with i) in immerse saturated aqua calcis through the crystalline silicon of surface cleaning, at 220 ℃, 2.1MPa handle after 4.5 hours in the high temperature and high pressure environment crystalline silicon is taken out, soak into and drip washing with deionized water repeatedly, drying the back annealed 2 hours in 450 ℃ in electric furnace, promptly make the biological thin layer of Calucium Silicate powder in the surface of crystalline silicon original position, the biological thin layer of Calucium Silicate powder is by being about 810nm, the calcium silicate nanowire shape crystal of the about 52nm of diameter constitutes.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that describes in the foregoing description and the specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (5)
1. the method for the biological thin layer of surface of crystalline silicon in-situ preparing Calucium Silicate powder is characterized in that, may further comprise the steps:
I) surface cleaning of crystalline silicon: sheet or wire or tubular crystal silicon are successively put into acetone, dehydrated alcohol and deionized water ultrasonic cleaning, and hyperacoustic cleaning frequency is 20～80kHz, preferred 40～75kHz; The ultrasonic cleaning time is 10～60 minutes, with deionized water rinsing, dry standby;
The ii) preparation of saturated aqua calcis: be 15～35 ℃ in temperature excessive calcium hydroxide poured in the deionized water that the sealing bottleneck leaves standstill after stirring a little;
The iii) formation of the biological thin layer of surface of crystalline silicon original position Calucium Silicate powder: the supernatant liquor of calcium hydroxide saturated solution is poured in the autoclave in getting ii), with i) in immerse saturated aqua calcis through the crystalline silicon of surface cleaning, 151～300 ℃ of temperature.Pressure is 0.5～5.0MPa, handle in the environment after 0.5～10 hour crystalline silicon is taken out, soak into and drip washing with deionized water repeatedly, in electric furnace, be 300～600 ℃ after drying and annealed 0.5～5 hour, promptly make the biological thin layer of Calucium Silicate powder in the surface of crystalline silicon original position in temperature.
2. the method for the biological thin layer of a kind of surface of crystalline silicon in-situ preparing Calucium Silicate powder according to claim 1 is characterized in that described crystalline silicon successively carries out preferred 30～50 minutes of ultrasonic cleaning time in acetone, dehydrated alcohol and deionized water.
3. the method for the biological thin layer of a kind of surface of crystalline silicon in-situ preparing Calucium Silicate powder according to claim 1 is characterized in that preferred 20～30 ℃ of the preparation temperature of described calcium hydroxide saturated solution.
4. the method for the biological thin layer of a kind of surface of crystalline silicon in-situ preparing Calucium Silicate powder according to claim 1, it is characterized in that, described through preferred 160～260 ℃ of the treatment temp in the calcium hydroxide saturated solution of crystalline silicon in autoclave of surface cleaning, preferred 1.0～the 3.0Mpa of processing pressure, preferred 3～6 hours of treatment time.
5. the method for the biological thin layer of a kind of surface of crystalline silicon in-situ preparing Calucium Silicate powder according to claim 1 is characterized in that preferred 350～500 ℃ of the annealing temperature of the described crystalline silicon that takes out in electric furnace, preferred 1～3 hour of annealing time from autoclave.
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| CN101673785A (en) * | 2009-09-25 | 2010-03-17 | 上海大学 | Method for preparing reflection reduction film with surface embedded type porous silicon structure of silicon base solar battery |
| CN101787567A (en) * | 2009-01-22 | 2010-07-28 | 湖南大学 | New biological modification method of surface of crystalline silicon |
| JP6043280B2 (en) * | 2010-06-04 | 2016-12-14 | ニューロロジカ・コーポレーション | High resolution single photon emission computed tomography (SPECT) system |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6562127B1 (en) * | 2002-01-16 | 2003-05-13 | The United States Of America As Represented By The Secretary Of The Navy | Method of making mosaic array of thin semiconductor material of large substrates |
| CN101498053A (en) * | 2009-01-22 | 2009-08-05 | 湖南大学 | Electrochemical modification method for silicon face biology performance |
| CN101787567A (en) * | 2009-01-22 | 2010-07-28 | 湖南大学 | New biological modification method of surface of crystalline silicon |
| CN101660210A (en) * | 2009-09-03 | 2010-03-03 | 无锡中彩科技有限公司 | Silicon core cleaning technique |
| CN101673785A (en) * | 2009-09-25 | 2010-03-17 | 上海大学 | Method for preparing reflection reduction film with surface embedded type porous silicon structure of silicon base solar battery |
| JP6043280B2 (en) * | 2010-06-04 | 2016-12-14 | ニューロロジカ・コーポレーション | High resolution single photon emission computed tomography (SPECT) system |
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