CN109972116B - Diamond tube and preparation method thereof - Google Patents
Diamond tube and preparation method thereof Download PDFInfo
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- CN109972116B CN109972116B CN201711466838.XA CN201711466838A CN109972116B CN 109972116 B CN109972116 B CN 109972116B CN 201711466838 A CN201711466838 A CN 201711466838A CN 109972116 B CN109972116 B CN 109972116B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
Abstract
The invention provides a diamond tube and a preparation method thereof, and relates to the field of diamond tubes. When the diamond tube obtained by the preparation method is used as a hollow microneedle, the technical problems that the hollow microneedle in the prior art is poor in biocompatibility with organisms and low in strength, and broken needles are easy to stay can be solved, and the technical effects of avoiding broken needles and causing adverse reactions are achieved.
Description
Technical Field
The invention relates to the technical field of diamond tubes, in particular to a diamond tube and a preparation method thereof.
Background
The traditional administration methods are mainly oral administration and injection administration, but the traditional administration methods have respective defects. Oral administration is not particularly suitable for protein and DNA drugs because the drug needs to pass through the gastrointestinal digestive tract and is subject to metabolism, so that the drug effect is reduced; the injection administration needs the operation of professional personnel, can cause pain to the human body, and also limits the application range of the injection administration. To avoid the above disadvantages and to efficiently and conveniently deliver drugs to the circulatory system of the human body, researchers have proposed the concept of transdermal drug delivery. The micro-needle array transdermal drug delivery technology developed based on the bio-micro-electro-mechanical technology in recent years is a great technical breakthrough in the field of drug release. Because the micro-needle is small in size and less than 1mm in length, the micro-needle can penetrate through the stratum corneum of the skin and can not enter the dermis, so that the micro-needle can be prevented from contacting pain nerves in the dermis and can not cause pain.
At present, microneedles are mainly classified into 4 types: (1) the solid micro-needle is generally made of monocrystalline silicon or metal, and has the action mode that the micro-needle is removed after the skin is pretreated, and then the external medicine is coated; (2) coating the micro-needle with medicine, wrapping the micro-needle body with medicine, applying the medicine on the skin, and then releasing the medicine; (3) the polymer micro-needle is prepared by mixing the drug and the polymer matrix and then used for the skin, and the drug is released along with the dissolution or swelling of the polymer; (4) hollow microneedles, like a collection of many micro-syringes, inject a drug solution into the skin by applying pressure. The hollow microneedle has the characteristics of higher bioavailability, quicker response and the like compared with other microneedles for administration, and in addition, the liquid preparation can quickly reach a wider area through the microneedle of the type.
The existing hollow micro-needle is mainly a metal hollow micro-needle or a silicon-based hollow micro-needle, which has poor compatibility with organisms and is easy to cause other diseases. In addition, most of the existing hollow microneedles are made of materials with high brittleness, and the problem of broken needles and retention is easily caused due to low strength of the hollow microneedles.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a diamond tube, and when the diamond tube prepared by the method is used as a hollow microneedle, the technical problems that the hollow microneedle has poor biocompatibility and low strength, and the broken microneedle is easy to stay in the prior art can be solved.
The second purpose of the invention is to provide a diamond tube obtained by the preparation method, which has high strength, good compactness and easy operation of the process.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a preparation method of a diamond tube comprises the steps of adsorbing diamond particles on a growth substrate, growing a diamond film by taking the diamond particles as seed crystals, and removing the growth substrate to obtain the diamond tube.
Further, the preparation method of the diamond tube comprises the following steps: adsorbing nano diamond particles on a growth substrate, growing a nano diamond film by taking the nano diamond particles as seed crystals, and removing the growth substrate to obtain a nano diamond tube;
preferably, the nanodiamond particles comprise detonation nanodiamond particles.
Further, the nano-diamond particles are modified firstly, and then are adsorbed on the growth substrate;
preferably, the nano diamond particles and a dispersing agent are ultrasonically mixed for modification treatment to obtain a nano diamond particle suspension;
preferably, in the nano-diamond particle suspension, the mass concentration of the nano-diamond is 0.005-0.5%;
preferably, the dispersant comprises a sodium p-methoxyfatty amidobenzenesulfonate solution;
preferably, the concentration of the dispersant is 10-7～10-4mol/L；
Preferably, the pH value of the dispersing agent is 2-8;
preferably, the suspension of nano-diamond particles is centrifuged to obtain a dispersion of nano-diamond particles having a particle size of less than 10 nm.
Further, the adsorbing comprises immersing the growth substrate in a nano-diamond particle dispersion liquid for adsorbing;
preferably, the adsorption is ultrasonic adsorption, the adsorption time is 25-35 min, and the ultrasonic power is 3000-4000W;
preferably, after the adsorption is completed, the growth substrate is subjected to a washing and drying process.
Further, the growth substrate is a metal substrate, preferably a nano copper wire, and further preferably a copper microneedle;
preferably, the growth substrate is pretreated and then adsorbed with the nano-diamond particles;
preferably, the pretreatment process comprises washing and hydrotreating;
preferably, the hydrogenation treatment comprises hydrogenation treatment by chemical vapor deposition, and the process parameters are as follows: and introducing hydrogen, wherein the heating power of the filament is 6000-800W, the filament sample distance is 12-16 mm, the pressure is 3500-4500 Pa, and the time is 25-35 min.
Further, the method for growing the diamond film by taking the nano diamond particles as the seed crystal comprises a hot wire chemical vapor deposition method;
preferably, the growth process of the hot wire chemical vapor deposition method is as follows: the flow rate of methane is 30-35 sccm, the flow rate of hydrogen is 770-830 sccm, the power of a hot wire is 6000-7000W, the distance of a wire sample is 10-15 mm, the pressure is 2000-2500 Pa, and the time is 8-12 min.
Further, the method for removing the growth substrate includes an etching method;
preferably, the etching solution used in the etching method comprises an acid solution, preferably a hydrochloric acid solution;
preferably, the concentration of the hydrochloric acid solution is 30% -40%, and the corrosion time is 3-7 min.
Further, the inner surface of the diamond tube is gradient modified so that the hydrophilicity of the inner surface of the diamond tube is gradually increased from the administration port to the injection port.
Further, the gradient modification comprises gradient corrosion treatment on the inner surface of the diamond tube;
preferably, the gradient corrosion treatment comprises the following steps: vertically placing the diamond tube in corrosive liquid steam for steam corrosion, wherein a drug feeding port of the diamond tube is arranged above, and an injection port of the nano diamond tube is arranged below;
preferably, the corrosive liquid is a mixed solution mainly composed of sulfuric acid, potassium nitrate, potassium hydroxide and hydrogen peroxide;
preferably, the concentration of the sulfuric acid is 95-98%;
preferably, the ratio of the volume of the sulfuric acid to the mass of the potassium nitrate is (9-12): 1, the ratio of the volume of the sulfuric acid to the mass of the potassium hydroxide is (9-12): 1, the volume ratio of the sulfuric acid to the hydrogen peroxide is (9-12): 4;
preferably, the temperature in the steam corrosion is 150-200 ℃, and the steam corrosion time is 10-20 min.
A diamond tube obtained according to the above preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the diamond tube provided by the invention is that the diamond film grows on the growth substrate, and then the growth substrate is corroded to obtain the diamond tube. The preparation method has strong operability, and the diamond tubes with different sizes, different compactabilities and strengths can be obtained by controlling the growth conditions.
When the diamond tube obtained by the preparation method provided by the invention is used as a needle body of a hollow microneedle, the hardness and the strength are very high, the phenomenon of needle breakage can not occur in the administration process, and the diamond tube has excellent biocompatibility with organisms, so that various adverse reactions are avoided.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
One aspect of the invention provides a method for preparing a diamond tube, which comprises the steps of adsorbing diamond particles on a growth substrate, growing a diamond film by taking the diamond particles as seed crystals, and removing the growth substrate to obtain the diamond tube.
The preparation method of the diamond tube provided by the invention is that the diamond film grows on the growth substrate, and then the growth substrate is corroded to obtain the diamond tube. The preparation method has strong operability, and the diamond tubes with different sizes, different compactabilities and strengths can be obtained by controlling the growth conditions.
When the diamond tube obtained by the preparation method provided by the invention is used as a needle body of a hollow microneedle, the hardness and the strength are very high, the phenomenon of needle breakage can not occur in the administration process, and the diamond tube has excellent biocompatibility with organisms, so that various adverse reactions are avoided.
In one embodiment of the present invention, a method for manufacturing a diamond tube includes the steps of: firstly, dispersing and adsorbing nano diamond particles on a growth substrate, then growing a nano diamond film by taking the nano diamond particles as seed crystals, and then removing the growth substrate to obtain the nano diamond tube.
The nano-diamond tube is prepared by a method of firstly planting crystals on a growth substrate, then growing the crystals, and finally removing the growth substrate, the nano-diamond tube prepared by the method has good compactness, few surface defects and no pore residue, has very high hardness and strength when used as a hollow microneedle, and can not break a needle in the drug delivery process, and the preparation method has the advantages of simple process and low cost.
In one embodiment of the present invention, the nanodiamond particles comprise detonation nanodiamond particles. The detonation nano-diamond particles are uniform in particle size distribution and smaller in particle size, and the compactness of the nano-diamond film can be improved.
In one embodiment of the present invention, the nano-diamond particles are modified and then dispersed and adsorbed on the growth substrate.
Through modification, the electrification of the nano-diamond particles can be changed to be opposite to the electric property of the surface of the growth substrate, so that the adsorption strength between the nano-diamond particles and the growth substrate is improved.
In one embodiment of the present invention, the nano-diamond particles and a dispersant are ultrasonically mixed to perform a modification treatment, so as to obtain a nano-diamond particle suspension, wherein the nano-diamond concentration in the nano-diamond particle suspension is preferably 0.005 to 0.5% by mass.
By optimizing the mixing mode of the nano-diamond particles and the dispersing agent and combining the specific dispersing agent, the problem of agglomeration of the nano-diamond particles in water can be better solved, so that the nano-diamond particles are in a dispersed state, and meanwhile, the electrical property of the nano-diamond particles can be changed, so that the dispersion uniformity of the nano-diamond particles on a growth substrate is higher, the growth quality of a subsequently grown nano-diamond film is further improved, the internal defect of the nano-diamond film is reduced, and the compactness of the nano-diamond film is improved.
In the nanodiamond particle suspension of the above embodiment, the mass concentration of nanodiamond is 0.005%, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, or 0.5%.
In one embodiment of the invention, the dispersant comprises a sodium p-methoxyfatty amidobenzenesulfonate solution; optionally, the concentration of the dispersant is 10-7～10-4mol/L; optionally, the pH value of the dispersing agent is 2-8.
By optimizing the type of dispersant, the amount of dispersant used can be reduced. In the embodiment, the dispersion effect of the nano-diamond particles can be realized only by using a trace amount of the dispersing agent, the nano-diamond particles are prevented from agglomerating, the effect of adjusting the positive and negative charges on the surfaces of the nano-diamond particles can be achieved only by adjusting the pH value of the dispersing agent and the concentration of the dispersing agent, and the adsorption strength between the nano-diamond particles and a growth substrate is improved.
In the above embodiments, the concentration of the dispersant may be, for example, but not limited to: 10-7mol/L、10-6mol/L、10-5mol/L or 10-4mol/L; the pH of the dispersant may be, for example, without limitation, 2, 3, 4, 5, 6, 7, or 8.
In one embodiment of the present invention, the suspension of nano-diamond particles is centrifuged to obtain a dispersion of nano-diamond particles having a particle size of less than 10 nm. Optionally, in the centrifugal operation, the centrifugal speed is 4500-5500 r/min, and the time is 5-15 min.
The nano-diamond particle dispersion liquid with smaller particle size is obtained through centrifugal operation, the growth substrate is placed in the nano-diamond particle dispersion liquid, the diamond particles with smaller particle size can be adsorbed, the adsorption compactness of the nano-diamond particles is improved, and therefore the nano-diamond film with higher strength and better density can be grown.
In one embodiment of the present invention, the adsorbing comprises immersing the growth substrate in a nanodiamond particle dispersion for adsorption; optionally, the adsorption is ultrasonic adsorption, the adsorption time is 25-35 min, and the ultrasonic power is 3000-4000W; optionally, after adsorption is complete, the growth substrate is washed and dried.
By optimizing the adsorption process, the adsorption strength between the nano-diamond particles and the growth matrix is further improved, and the compactness between the adsorbed nano-diamond particles is improved.
In one embodiment of the present invention, the growth substrate is a metal substrate, preferably a nano copper wire, and more preferably a copper microneedle; the copper micro-needle is used as a growth substrate, so that the high-density adsorption of the nano-diamond particles can be realized.
In one embodiment of the invention, the growth substrate is pretreated and then adsorbed with the nano-diamond particles; optionally, the pretreatment process comprises washing and hydrotreating. Through pretreatment, the surface of the growth substrate is decontaminated, the electrical property of the surface of the growth substrate is improved, and the adsorption strength and the adsorption density of the surface of the growth substrate and the nano diamond particles are improved.
In one embodiment of the present invention, the cleaning comprises the steps of first ultrasonic cleaning with deionized water, then ultrasonic cleaning with acetone, and then drying.
In one embodiment of the present invention, the hydrogenation treatment comprises hydrogenation treatment by chemical vapor deposition, and the process parameters are as follows: and introducing hydrogen, wherein the heating power of the filament is 6000-800W, the filament sample distance is 12-16 mm, the pressure is 3500-4500 Pa, and the time is 25-35 min.
In one embodiment of the present invention, the method of growing a diamond film using the nano-diamond particles as a seed comprises a hot filament chemical vapor deposition method; optionally, the growth process of the hot wire chemical vapor deposition method is as follows: the flow rate of methane is 30-35 sccm, the flow rate of hydrogen is 770-830 sccm, the power of a hot wire is 6000-7000W, the distance of a wire sample is 10-15 mm, the pressure is 2000-2500 Pa, and the time is 8-12 min. The method for growing the diamond film by using the hot wire chemical vapor deposition method has the advantages of simple operation and mature process, and is suitable for industrial batch production.
It is understood that the method of removing the growth substrate includes, but is not limited to, etching; alternatively, the etching solution used in the etching method includes, but is not limited to, an acid solution.
In one embodiment of the invention, the etching solution is a hydrochloric acid solution; optionally, the concentration of the hydrochloric acid is 30% -40%, and the corrosion time is 3-7 min. The method can rapidly dissolve the copper micro-needle without causing any damage to the nano-diamond tube.
In one embodiment of the invention, the inner surface of the diamond tube is gradient modified to gradually increase the hydrophilicity of the inner surface of the diamond tube from the administration port to the injection port.
By adopting the modification method, the hydrophobicity of the inner surface of the diamond tube is changed into hydrophilicity through modification treatment, so that the water-soluble injection medicine can be more easily transmitted in the diamond tube; meanwhile, the modification method enables the hydrophilicity of the inner surface of the diamond tube to be gradually enhanced from the drug administration port to the injection port, so that the acting force between the injected drug from the drug administration port to the injection port and the inner surface of the diamond tube is gradually increased, the diamond tube has a self-suction effect on the injected drug and automatically flows from the drug administration port to the injection port, and therefore self-driven drug administration can be achieved, and extra pressurizing equipment is avoided.
Wherein the administration end is the end connected to the administration member and the injection end is the end in contact with the human or other animal body.
It is understood that the gradient modification includes, but is not limited to, subjecting the inner surface of the diamond tube to a gradient erosion process; optionally, the gradient corrosion treatment comprises the following steps: and vertically placing the diamond tube in corrosive liquid steam for steam corrosion, wherein the administration port of the diamond tube is arranged above, and the injection port of the nano diamond tube is arranged below.
Will the diamond tube is vertical to be placed and carries out steam corrosion in the corrosive liquid steam, and the steam that corrodes this moment condenses for the corrosive liquid after at the diamond intraduct, and the corrosive liquid flows from last to down, forms the gradient corrosion from last to down in the diamond intraduct, piles up gradually along with the corrosive liquid downwards promptly, and the diamond intraduct is from last to corrosion degree progressively increasing down, makes the intraduct hydrophilicity of diamond from last to progressively reinforcing down. The diamond tube obtained by the gradient corrosion mode can ensure that the medicine can easily flow to the human body from the medicine feeding port end in a directional way, so that the aim of self-driven directional medicine feeding is fulfilled, an external pressure device can be omitted, the equipment is simplified, and the carrying is convenient.
In one embodiment of the invention, the corrosive liquid is a mixed solution mainly composed of sulfuric acid, potassium nitrate, potassium hydroxide and hydrogen peroxide; optionally, the concentration of the sulfuric acid is 95-98%; optionally, the ratio of the volume of the sulfuric acid to the mass of the potassium nitrate is (9-12): 1, the ratio of the volume of the sulfuric acid to the mass of the potassium hydroxide is (9-12): 1, the volume ratio of the sulfuric acid to the hydrogen peroxide is (9-12): 4; optionally, the temperature in the steam corrosion is 150-200 ℃, and the steam corrosion time is 10-20 min.
By optimizing the composition and the corrosion conditions of the corrosive liquid, the corrosion effect can be further improved, the differentiation degree of the step corrosion is more obvious, and the driving force of the self-driven directional dosing of the nano-diamond tube is further improved.
The present invention will be described in further detail with reference to examples and comparative examples.
Example 1
The embodiment is a preparation method of a nano-diamond tube, which comprises the following steps:
step a) growth matrix pretreatment: selecting copper microneedles or nano copper wires as a growth substrate, firstly carrying out ultrasonic cleaning in deionized water for 2min, then carrying out ultrasonic cleaning in acetone for 5min, and then standing and drying in the air; then putting the cleaned growth substrate in a CVD furnace for hydrogenation treatment, wherein the power of a hot wire is 7000W, the distance of a wire sample is 15mm, introducing hydrogen, setting the pressure to be 4000Pa, and setting the time to be 30 minutes;
step b) preparing a nano diamond suspension: adopts sodium p-methoxy fatty amide benzene sulfonate as a dispersant, deionized water as a solvent, and the concentration of the dispersant is 10-7mol/L, pH is 2, then detonation nano-diamond powder is added into the dispersant solution, the mass concentration of the nano-diamond is 0.005 wt%, and ultrasonic mixing is carried out for 15min, so as to obtain nano-diamond powder suspension;
step c) preparing a nano-diamond dispersion: centrifuging the obtained nano-diamond suspension to obtain nano-diamond dispersion liquid with the particle size of less than 10 nm; in the centrifugal operation, the rotating speed is 5000r/min, and the time is 10 min;
step d) adsorption treatment: putting the growth substrate into the nano-diamond dispersion liquid for ultrasonic treatment to enable nano-diamond particles to be adsorbed on the surface of the growth substrate, wherein the ultrasonic time is 30min and the power is 3500W; after adsorption, taking out the growth substrate adsorbed with the nano diamond particles, sequentially soaking the growth substrate in deionized water and alcohol for cleaning, and then drying in air;
step e) growing a nano-diamond film: the growth substrate absorbed with the nano-diamond particles is placed in hot wire chemical vapor deposition equipment to grow the nano-diamond film, and the growth process comprises the following steps: 32sccm of methane, 800sccm of hydrogen, 6500W of hot wire power, 12mm of wire sample distance, 2200Pa of pressure and 10 minutes of time;
step f) etching the growth substrate: and after the growth is finished, taking out the union of the nano-diamond film and the growth substrate, placing the union in hydrochloric acid, wherein the concentration of the hydrochloric acid is 37 percent, and the time is 5 minutes, and corroding the growth substrate to obtain the nano-diamond tube.
Example 2
The embodiment is a method for preparing a nano-diamond tube, and is different from the embodiment 1 in the process of preparing a nano-diamond suspension.
The preparation process of the nano-diamond suspension in the embodiment is as follows: adopts sodium p-methoxy fatty amide benzene sulfonate as a dispersant, deionized water as a solvent, and the concentration of the dispersant is 10-5And (3) mol/L, wherein the pH value is 4, then detonation nano-diamond powder is added into the dispersant solution, the mass concentration of the nano-diamond is 0.02%, and the nano-diamond powder is ultrasonically mixed for 15min to obtain a nano-diamond powder suspension.
The preparation was the same as in example 1 except for the above differences.
Example 3
The embodiment is a method for preparing a nano-diamond tube, and is different from the embodiment 1 in the process of preparing a nano-diamond suspension.
The preparation process of the nano-diamond suspension in the embodiment is as follows: adopts sodium p-methoxy fatty amide benzene sulfonate as a dispersant, deionized water as a solvent, and the concentration of the dispersant is 10-4And (3) mol/L, wherein the pH value is 7, then, adding detonation nano-diamond powder into the dispersant solution, wherein the mass concentration of the nano-diamond is 0.3 wt%, and ultrasonically mixing for 15min to obtain a nano-diamond powder suspension.
The preparation was the same as in example 1 except for the above differences.
Example 4
The embodiment is a preparation method of a nano-diamond tube, which comprises the following steps:
step a) growth matrix pretreatment: selecting copper microneedles or nano copper wires as a growth substrate, firstly carrying out ultrasonic cleaning in deionized water for 2min, then carrying out ultrasonic cleaning in acetone for 5min, and then standing and drying in the air; then putting the cleaned growth substrate in a CVD furnace for hydrogenation treatment, wherein the power of a hot wire is 7000W, the distance of a wire sample is 15mm, introducing hydrogen, setting the pressure to be 4000Pa, and setting the time to be 30 minutes;
step b) preparing a nano diamond suspension: adopts sodium p-methoxy fatty amide benzene sulfonate as a dispersant, deionized water as a solvent, and the concentration of the dispersant is 10-7mol/L, pH 2, then detonation nano-goldAdding diamond powder into the dispersant solution, wherein the mass concentration of the nano-diamond is 0.005 wt%, and ultrasonically mixing for 15min to obtain a nano-diamond powder suspension;
step c) preparing a nano-diamond dispersion: centrifuging the obtained nano-diamond suspension to obtain nano-diamond dispersion liquid with the particle size of less than 10 nm; in the centrifugal operation, the rotating speed is 5000r/min, and the time is 10 min;
step d) adsorption treatment: putting the growth substrate into the nano-diamond dispersion liquid for ultrasonic treatment to enable nano-diamond particles to be adsorbed on the surface of the growth substrate, wherein the ultrasonic time is 30min and the power is 3500W; after adsorption, taking out the growth substrate adsorbed with the nano diamond particles, sequentially soaking the growth substrate in deionized water and alcohol for cleaning, and then drying in air;
step e) growing a nano-diamond film: the growth substrate absorbed with the nano-diamond particles is placed in hot wire chemical vapor deposition equipment to grow the nano-diamond film, and the growth process comprises the following steps: 32sccm of methane, 800sccm of hydrogen, 6500W of hot wire power, 12mm of wire sample distance, 2200Pa of pressure and 10 minutes of time;
step f) etching the growth substrate: after the growth is finished, taking out the union of the nano-diamond film and the growth substrate, placing the union in hydrochloric acid, wherein the concentration of the hydrochloric acid is 37 percent, and the time is 5 minutes, and corroding the growth substrate to obtain a nano-diamond tube;
step g) carrying out gradient corrosion treatment on the nano diamond tube: vertically placing the nano-diamond tube above a corrosive solution, wherein the corrosive solution is a mixed solution of 50ml of 98% concentrated sulfuric acid, 5 g of potassium nitrate, 5 g of potassium hydroxide and 20ml of hydrogen peroxide, and steaming at 180 ℃ for 15min to obtain the gradient modified nano-diamond tube.
Example 5
The present embodiment is a method for manufacturing a nano-diamond tube, and is different from embodiment 4 in that the process of performing gradient etching treatment on the nano-diamond tube is different.
The gradient corrosion treatment process for the nano-diamond tube in the embodiment is as follows: vertically placing the nano-diamond tube above a corrosive solution, wherein the corrosive solution is a mixed solution of 45ml of 98% concentrated sulfuric acid, 4 g of potassium nitrate, 5 g of potassium hydroxide and 18ml of hydrogen peroxide, and steaming at 160 ℃ for 20min to obtain the gradient modified nano-diamond tube.
The preparation was the same as in example 4 except for the above differences.
Example 6
The embodiment is a method for preparing a nano-diamond tube, and is different from the embodiment 4 in the process of performing gradient corrosion treatment on the nano-diamond tube.
The gradient corrosion treatment process for the nano-diamond tube in the embodiment is as follows: vertically placing the nano-diamond tube above a corrosive solution, wherein the corrosive solution is a mixed solution of 98% concentrated sulfuric acid 60ml, potassium nitrate 5 g, potassium hydroxide 5 g and hydrogen peroxide 20ml, and steaming at the temperature of 200 ℃ for 12min to obtain the gradient modified nano-diamond tube.
The preparation was the same as in example 4 except for the above differences.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
Claims (8)
1. The preparation method of the diamond tube is characterized in that diamond particles are adsorbed on a growth substrate, then a diamond film is grown by taking the diamond particles as seed crystals, and then the growth substrate is removed to obtain the diamond tube;
performing gradient modification on the inner surface of the diamond tube so that the hydrophilicity of the inner surface of the diamond tube is gradually increased from a dosing port to an injection port;
the gradient modification comprises gradient corrosion treatment on the inner surface of the diamond tube;
the gradient corrosion treatment comprises the following steps: vertically placing the diamond tube in corrosive liquid steam for steam corrosion, wherein a drug feeding port of the diamond tube is arranged above, and an injection port of the diamond tube is arranged below;
the corrosive liquid is a mixed solution mainly composed of sulfuric acid, potassium nitrate, potassium hydroxide and hydrogen peroxide;
the concentration of the sulfuric acid is 95-98%;
the ratio of the volume of the sulfuric acid to the mass of the potassium nitrate is (9-12): 1, the ratio of the volume of the sulfuric acid to the mass of the potassium hydroxide is (9-12): 1, the volume ratio of the sulfuric acid to the hydrogen peroxide is (9-12): 4;
the temperature in the steam corrosion is 150-200 ℃, and the steam corrosion time is 10-20 min.
2. The method for preparing the diamond tube according to claim 1, wherein the nano-diamond particles are adsorbed on a growth substrate, then a nano-diamond film is grown by taking the nano-diamond particles as seed crystals, and then the growth substrate is removed to obtain the nano-diamond tube;
the nanodiamond particles include detonation nanodiamond particles.
3. The method of manufacturing a diamond tube according to claim 2, wherein the nano-diamond particles are modified and then adsorbed on the growth substrate;
ultrasonically mixing the nano diamond particles with a dispersing agent for modification treatment to obtain a nano diamond particle suspension;
in the nano-diamond particle suspension, the mass concentration of nano-diamond is 0.005-0.5%;
the dispersing agent comprises a sodium p-methoxy fatty amido benzene sulfonate solution;
the concentration of the dispersant is 10-7～10-4mol/L；
The pH value of the dispersing agent is 2-8;
and carrying out centrifugal operation on the nano-diamond particle suspension to obtain the nano-diamond particle dispersion liquid with the particle size of less than 10 nm.
4. The method of manufacturing a diamond tube according to claim 3, wherein the adsorption comprises immersing the growth substrate in a dispersion of nanodiamond particles for adsorption;
the adsorption is ultrasonic adsorption, the adsorption time is 25-35 min, and the ultrasonic power is 3000-4000W;
after adsorption is completed, the growth substrate is cleaned and dried.
5. The method of manufacturing a diamond tube according to claim 1 or 2, wherein the growth substrate is a metal substrate;
pretreating the growth substrate and then adsorbing the nano diamond particles;
the pretreatment process comprises cleaning and hydrogenation treatment;
the hydrogenation treatment comprises the step of carrying out hydrogenation treatment by using a chemical vapor deposition method, wherein the process parameters are as follows: and introducing hydrogen, wherein the heating power of the filament is 6000-800W, the filament sample distance is 12-16 mm, the pressure is 3500-4500 Pa, and the time is 25-35 min.
6. The method of manufacturing a diamond tube according to claim 2, wherein the method of growing a diamond film using the nano-diamond particles as the seed crystal comprises a hot filament chemical vapor deposition method;
the growth process of the hot wire chemical vapor deposition method comprises the following steps: the flow rate of methane is 30-35 sccm, the flow rate of hydrogen is 770-830 sccm, the power of a hot wire is 6000-7000W, the distance of a wire sample is 10-15 mm, the pressure is 2000-2500 Pa, and the time is 8-12 min.
7. The method of manufacturing a diamond tube according to claim 1 or 2, wherein the method of removing the growth substrate includes an etching method;
the corrosive liquid used in the corrosion method is hydrochloric acid solution;
the concentration of the hydrochloric acid solution is 30% -40%, and the corrosion time is 3-7 min.
8. A diamond tube obtained by the production method according to any one of claims 1 to 7.
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| CN112779516B (en) * | 2020-12-22 | 2024-03-08 | 苏州恒之清生物科技有限公司 | Crystal silicon microneedle with hard coating protection and preparation method thereof |
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