CN102020485B - 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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- CN102020485B CN102020485B CN201010520123A CN201010520123A CN102020485B CN 102020485 B CN102020485 B CN 102020485B CN 201010520123 A CN201010520123 A CN 201010520123A CN 201010520123 A CN201010520123 A CN 201010520123A CN 102020485 B CN102020485 B CN 102020485B
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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 research shows 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 through deposit (or assembling) biocompatibility preferred metal or organism at surface of crystalline silicon, like 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 receive very big restriction but the batch preparations cost is higher, sticking power is little and long-term biocompatibility is relatively poor etc.; Injecting H element technology through 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 high to equipment requirements, running cost is big, makes it be difficult to use the surface modification in batches with crystalline silicon, and is and should technology relatively poor to the surface-treated homogeneity of complex-shaped crystalline silicon; In addition, also have part Study to be employed in the surface biological consistency that method that surface of crystalline silicon directly prepares apatite coating improves 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 apatite coating and the crystalline silicon of these methods preparation, 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 HTHP 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 of plasma spraying [Liu Xuanyong, etc. silicate journal, 2002; 30 (1): 20]; Also have no work to relate to the surface biological modification that Calucium Silicate powder is applied to crystalline silicon, also do not prepare the report of Calucium Silicate powder coating, at the biological thin layer of surface of crystalline silicon in-situ preparing Calucium Silicate powder any similar or close research work is arranged under the HTHP that does not more have to adopt with the present invention at surface of crystalline silicon.What is worth mentioning is; 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, absolute ethyl alcohol and deionized water use ultrasonic cleaning, hyperacoustic cleaning frequency is 20～80kHz, preferred 40～75kHz; The ultrasonic cleaning time is 10～60 minutes, with deionized water rinsing, dry subsequent use;
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 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, said crystalline silicon successively carries out preferred 30～50 minutes of ultrasonic cleaning time in acetone, absolute ethyl alcohol and deionized water.
In the present invention, said calcium hydroxide is analytical pure or CP level reagent.
In the present invention, the preparation temperature of said calcium hydroxide saturated solution is preferred 20～30 ℃.
In the present invention, said 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, said 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, said 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 said crystalline silicon that from autoclave, takes out in electric furnace is preferred 350～500 ℃.
In the present invention, the annealing time of the said crystalline silicon that from autoclave, takes out 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 HTHP; 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 through 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 HTHP, 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; Silicate further combines to generate Calucium Silicate powder with the calcium ion that the ionization of oxidation calcium goes out; 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, and in addition, the high pressure conditions of autoclave also can effectively be controlled the hypertrophy of Calucium Silicate powder; Thereby favourable condition is provided 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 for bone shape phosphatic rock, cell and cambium adhering to and growth provides active place, be an effective way improving biologically inert surface of crystalline silicon biocompatibility, for research and development 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-treated crystalline silicon material, further expands the biomedical applications of above-mentioned device.
Beneficial effect:
The present invention adopts convenient controlled HTHP 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 random shape.
Embodiment
Be easy to understand and understand in order to make technique means of the present invention, creation characteristic, workflow, method of use reach purpose and effect,, 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, absolute ethyl alcohol and deionized water, at last with deionized water rinsing, dry subsequent use;
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; In 151 ℃, 0.5MPa high temperature and high pressure environment, handle after 10 hours crystalline silicon is taken out; Soak into and drip washing with deionized water repeatedly; Dry the back in electric furnace in 600 ℃ of annealing 0.5 hour, 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 made up of the calcium silicate nanowire shape crystal that is about 600nm, the about 30nm of diameter.
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, absolute ethyl alcohol and deionized water, at last with deionized water rinsing, dry subsequent use;
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; In 300 ℃, 5.0MPa high temperature and high pressure environment, handle after 0.5 hour crystalline silicon is taken out; Soak into and drip washing with deionized water repeatedly; Dry the back in electric furnace in 300 ℃ of annealing 5 hours, 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 made up of the calcium silicate nanowire pencil crystal that is about 1000nm, thick about 70nm.
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, absolute ethyl alcohol and deionized water, at last with deionized water rinsing, dry subsequent use;
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; In 160 ℃, 1.8MPa high temperature and high pressure environment, handle after 6 hours crystalline silicon is taken out; Soak into and drip washing with deionized water repeatedly; Dry the back in electric furnace in 350 ℃ of annealing 3 hours, 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 made up of the calcium silicate nanowire crystal that is about 720nm, the about 45nm of diameter.
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, absolute ethyl alcohol and deionized water, at last with deionized water rinsing, dry subsequent use;
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; In 220 ℃, 2.1MPa high temperature and high pressure environment, handle after 4.5 hours crystalline silicon is taken out; Soak into and drip washing with deionized water repeatedly; Dry the back in electric furnace in 450 ℃ of annealing 2 hours, 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 made up of the calcium silicate nanowire shape crystal that is about 810nm, the about 52nm of diameter.
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 explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be 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, absolute ethyl alcohol and deionized water use ultrasonic cleaning, hyperacoustic cleaning frequency is 20～80kHz; The ultrasonic cleaning time is 10～60 minutes, with deionized water rinsing, dry subsequent use;
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 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 in 0.5～5.0MPa environment; Handle and 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 said crystalline silicon successively carries out the ultrasonic cleaning time in acetone, absolute ethyl alcohol and deionized water be 30～50 minutes.
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 the preparation temperature of said calcium hydroxide saturated solution is 20～30 ℃.
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; Said treatment temp in the calcium hydroxide saturated solution of crystalline silicon in autoclave of surface cleaning is 160～260 ℃; Processing pressure is 1.0～3.0Mpa, and the treatment time is 3～6 hours.
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 the annealing temperature of the crystalline silicon that from autoclave, takes out in electric furnace is 350～500 ℃, and annealing time is 1～3 hour.
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| 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 |
| CN101787567A (en) * | 2009-01-22 | 2010-07-28 | 湖南大学 | New biological modification method of surface of crystalline silicon |
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| WO2011153544A1 (en) * | 2010-06-04 | 2011-12-08 | Neurologica Corp. | High resolution single photon emission computed tomography (spect) system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| JP特开平6-43280B2 1994.06.08 |
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