CN113663138A - External bone fixing instrument with functional structure on surface of skin penetrating part and processing method thereof - Google Patents
External bone fixing instrument with functional structure on surface of skin penetrating part and processing method thereof Download PDFInfo
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/02—Inorganic materials
- A61L31/022—Metals or alloys
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
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- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- 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
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
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- 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
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
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Abstract
The invention provides an external bone fixing instrument with a functional structure on the surface of a skin penetrating part and a processing method thereof, wherein the surface of the skin penetrating part of the external bone fixing instrument is provided with TiO with a three-level micro-nano composite structure2The surface of the layer has higher biological activity and bacteriostatic property. The three-level micro-nano composite structure can effectively inhibit the adhesion growth of staphylococcus aureus and candida mucocutaneous, further prevent the staphylococcus aureus and candida mucocutaneous from entering skin tissues through gaps of an instrument-skin interface in the early stage of implantation of a fixed instrument, and meanwhile, the structure and the coating can promote the growth of epithelial cells and skin stem cells to accelerate the integration of the skin and the instrument interface, so that the skin tissues are separated from external bacteria.
Description
Technical Field
The invention belongs to the field of orthopedic external fixation instruments, relates to a metal surface modification technology and a laser processing technology, and particularly relates to an external bone fixation instrument with a skin-penetrating part surface having a structure with functions of inhibiting bacterial adhesion growth and promoting cell adhesion proliferation and a processing method thereof.
Background
External bone fixation devices are increasingly applied to the fields of bone trauma treatment, deformity correction and the like, for example, in the field of fracture repair, the application of the external bone fixation devices to fix fracture parts is an important step in fracture repair, and the external bone fixation devices can ensure that fracture points can be accurately butted within a period of time, and can apply certain pressure to the fracture parts to accelerate bone healing. With the deepening of clinical practice, the attention on endowing the surface of the skin penetrating part of the orthopedic external fixation instrument with the functions of promoting tissue integration and resisting bacterial infection is more and more extensive. After the fixation device is implanted, bacteria and fungi can easily enter skin tissues through the junction of the skin and the device to cause infection and even cause implantation failure. Therefore, there is an urgent clinical need to develop an external bone fixation device with dual functions of accelerating skin-device interface integration and resisting infection. However, the existing technology for endowing the surface of the instrument with bacteriostatic ability has obvious disadvantages, for example, the chemical grafting method can improve the bacteriostatic property of the surface of the instrument, but the related technology can not meet the requirements of quality control, sterilization, long-term storage and the like in the production of medical instruments, the grafted chemical coating can not maintain the efficacy for a long time, and the supervision and approval of the current medical instrument registration certificate are difficult to pass. And no orthopaedics fixing instrument with anti-infection and skin-instrument interface integration acceleration functions at the skin penetrating part is approved to be sold in the market at present.
Disclosure of Invention
The invention aims to solve the problem of infection of a skin penetrating part of an external bone fixing instrument, and provides an external bone fixing instrument with a skin penetrating part surface having a structure with functions of inhibiting bacteria and promoting endothelial cells and a processing method thereof.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a skin-penetrating part of external bone fixer with antibacterial effect is prepared through preparing TiO layer on the surface of skin-penetrating part2Coating the TiO with a layer of a coating2And manufacturing a three-level micro-nano composite structure on the coating.
The surface of the skin penetrating part of the orthopedic fixing instrument is provided with TiO with the thickness of 1-2 mu m2A coating, the coating being prepared by a sol-gel process. TiO22The defects on the surface can adsorb active groups such as hydroxyl and the like, so that the surface activity is effectively improved, the biological activity of the surface can be effectively improved, the adhesion and proliferation of epithelial cells and skin stem cells on the surface are promoted, and the interface integration between skin tissues and the surface of a fixing device is accelerated.
TiO2The surface still lacks the antibacterial function, and the coating has the problem of falling off caused by insufficient binding force, so that the surface is subjected to pulse laser processing, and a three-level micro-nano composite structure is prepared on the surface. The surface is remelted in the process of pulse laser processing, so that TiO can be effectively improved2The bonding force between the coating and the substrate of the fixed device. Meanwhile, the surface component after laser processing is still TiO2And laser processing causes more defects on the surface, so that the surface activity is further improved. The micro-nano structure prepared by the pulse laser processing is formed by superposing structures with three levels of sizes, the first level structure is a micron-scale groove structure with the sizes of epithelial cells and skin stem cells, the second level structure is a submicron-scale stripe structure or an array protrusion structure, and the third level structure is a nanometer-scale protrusion structure. The first level structure consists of trenches 60-120 μm wide and about 1 μm deep. The second-level structure can be composed of stripes with the width of 100-400nm and the height of 10-40nm, and the second-level structure is distributed on the surface of the first-level structure. The third-level structure is a nano-scale protrusion structure and is composed of nano-particles with the size of 5-100nm, and the third-level structure is distributed on the surface of the second-level structure.
Due to the size effect, the primary structure effectively increases the surface area of the material, and the width and the depth of the primary structure are similar to those of the epithelial cells and the skin stem cells, so that the adhesion and the growth of the epithelial cells on the primary structure are facilitated. The secondary structures provide increased surface roughness and provide adhesion sites for epithelial cell adhesion, while these structures effectively reduce bacterial adhesion. The tertiary structure can further inhibit the adhesion of bacteria without affecting cell growth. The comprehensive effect of the three structures enables the surface of the skin penetrating part of the external fixing instrument to have the function of inhibiting bacteria adhesion, so that bacteria are prevented from entering skin tissues through the gap between the instrument and the skin interface in the early stage of implantation of the instrument, and meanwhile, the physical structure can promote the growth of epithelial cells to accelerate the integration of the skin and the interface of the fixing instrument, so that the skin tissues are separated from external bacteria.
Does not prepare TiO2The layer, only prepare the tertiary micro-nano structure on the external bone fixation apparatus surface of position of wearing the skin, can make it have Staphylococcus aureus of inhibiting, skin mucosa candida adhesion growth, promote epithelial cell, adhesion proliferation of the skin stem cell at the same time.
The invention has the advantages and beneficial effects that:
the invention prepares TiO with a three-level micro-nano composite structure on the surface of the skin penetrating part of the external bone fixing instrument2The preparation method of the surface does not conflict with the existing production process of the orthopedic fixation instrument, and can also reduce the difficulty of registration and approval of related orthopedic fixation instrument products.
Description of the drawings:
FIG. 1 is a surface topography map for example 1;
FIG. 2 shows the results of surface composition measurements in example 1, wherein a, b, and c are respectively 316L stainless steel with TiO after polishing2The stainless steel of the coating and the surface components of the stainless steel after femtosecond laser processing, d and e are respectively TiO before and after the femtosecond laser processing2High resolution spectrogram of coating Ti element;
FIG. 3 is a graph comparing the adhesion of surface epithelial cells and skin stem cells in comparative example 2;
FIG. 4 is a graph comparing the adhesion of Staphylococcus aureus on the surface and Candida on the skin mucosa in comparative example 2;
FIG. 5 is a graph comparing the adhesion of surface epithelial cells and skin stem cells in comparative example 3;
FIG. 6 is a graph comparing the adhesion of Staphylococcus aureus on the surface and Candida on the skin mucosa in comparative example 3;
FIG. 7 is a surface topography map for example 2.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
Example 1
In the embodiment, TiO with a micro-nano composite structure is prepared on the surface of the skin penetrating part of the 316L stainless steel bone external fixation instrument2And simultaneously, femtosecond laser processing is carried out to prepare a physical antibacterial structure on the surface of the skin penetrating part of the external bone fixing instrument.
Firstly, a mechanical grinding method is applied to treat the surface of 316L stainless steel, and then TiO with the thickness of about 1.5 mu m is prepared on the surface of the 316L stainless steel by a sol-gel method2And (4) coating. The method comprises the following specific steps: preparing a mixed solution of absolute ethyl alcohol and butyl phthalate according to a volume ratio of 4:1, preparing a mixed solution of deionized water, absolute ethyl alcohol and nitric acid according to a volume ratio of 5:5:1, dripping the mixed solution of the absolute ethyl alcohol and the butyl phthalate into the mixed solution of the absolute ethyl alcohol, the nitric acid and the deionized water, stirring for 3 hours to form light yellow sol, soaking 316L stainless steel in the sol and drying to obtain smooth TiO2The surface of the coating is smoother.
Subsequent application of femtosecond laser processing method to TiO2And preparing a micro-nano composite structure on the surface of the coating, and adjusting the position of a light spot to enable the laser light spot to irradiate at the initial position. The processing technology comprises the steps of processing the surface of a sample at the laser frequency of 1kHz, the wavelength of 800nm, the pulse width of 150fs, the pulse energy of 600uJ, the spot diameter of 150 microns, the line spacing of 100 microns and the scanning speed of 2mm/s, and simultaneously moving the moving platform along the defocusing direction to ensure that the distance from the laser focus to the surface of the sample is unchanged and scanning the whole surface of the sample. The obtained structure is a three-level micro-nano composite structure, wherein the first-level structure consists of a groove with the width of about 95 mu m and the depth of about 1 mu m. The second-level structure is composed of periodic stripes with the width of 400-600nm and the height of about 45nm, the second-level structure is distributed on the surface of the first-level structure, and the third-level structure is distributed on the surface of the second-level structure.
The laser machining affected layer has a thickness of about 1.8 μm, enhancing the bond between the coating and the substrate. FIG. 1 shows the surface morphology of the machined part, FIG. 2 shows the component detection results of XPS on the surface of stainless steel, where a, b, and c are respectively the surface after polishing316L stainless steel with TiO2The stainless steel of the coating and the surface components of the stainless steel after femtosecond laser processing, d and e are respectively TiO before and after the femtosecond laser processing2The high resolution spectrogram of the coating Ti element does not change the coating composition by femtosecond laser processing.
Comparative example 1
In order to test the TiO with the micro-nano structure surface prepared by the method2The coating bioactivity, this control example, was polished 316L stainless steel with smooth TiO 2316L stainless steel with coating and TiO with micro-nano structure2Simulated body fluid immersion experiments of coated 316L stainless steel surfaces. Wherein the polished 316L stainless steel surface is prepared by mechanically polishing 316L stainless steel to smooth TiO2The 316L stainless steel surface of the coating is prepared by a sol-gel method and is provided with TiO with a micro-nano structure2A coated 316L stainless steel surface was prepared by the method in example 1.
The three surfaces were immersed in 1.5 times of simulated body fluid for 14 days, respectively, and surface components were detected and analyzed using EDS. The following table shows the element components of three samples after the surfaces are soaked for 7 days, and the result shows that the three surfaces have Ca and P deposition and have TiO with a micro-nano structure2The relative atomic weight of Ca and P on the surface of 316L stainless steel of the coating is the highest, the calcium-phosphorus ratio is about 1.46, the deposition amount of Ca and P elements on the surface is the largest, the components are closest to hydroxyapatite, and compared with TiO with a micro-nano structure2The Ca and P contents of the other two surfaces of the 316L stainless steel surface of the coating are lower, and the calcium and phosphorus contents are lower. TiO, surface of 316L stainless steel lack of biological activity2The defect is that the surface of the material has a large number of active groups such as hydroxyl groups, so that the TiO2The coating can effectively improve the surface bioactivity of the stainless steel and is TiO with a micro-nano structure2The coating has higher specific surface area and more surface defects, so the surface bioactivity is highest.
Comparative example 2
The cell adhesion experiment and the bacterial adhesion experiment were performed in this comparative example, and it was verified that 316L stainless steel with smooth TiO was polished2316L stainless steel with coating and TiO with micro-nano structure2Effect of coated 316L stainless steel surface on cell, bacterial adhesion. The preparation method of the three surfaces was the same as that in comparative example 1.
Cell experiments adhesion experiments of epithelial cells and skin stem cells were performed, the experimental method was: mixing 40. mu.l, 5X 104The cell suspension/ml is dropped on the surface of each of the three samples, and after 24 hours of incubation, the surface is washed with PBS, and the number of the three surface-adherent cells is compared by the CCK-8 method. FIG. 3 shows the OD 24 hours after the two cells were seeded, which was measured by the CCK-8 method. The result shows that the TiO with the micro-nano structure2The OD value of the 316L stainless steel surface of the coating is obviously higher than that of the other two surfaces, which shows that the TiO with the micro-nano structure2The stainless steel surface of the coating has the largest cell adhesion number, which proves that the surface has the strongest biological activity and has the most obvious promotion effect on the adhesion of epithelial cells and skin stem cells.
The common inflammatory bacteria staphylococcus aureus and skin mucosa candida in the field of orthopedic fixation instruments are selected for carrying out a bacterial adhesion experiment, and the experimental method comprises the following steps: mixing 40 μ l of 10%6And respectively dripping each/ml bacterial solution on the surfaces of the three samples, culturing for 6h, washing the surface bacterial solution by PBS, carrying out fluorescent staining, observing by a laser confocal microscope, and counting the fluorescence intensity of any 10 positions on each surface. Polishing 316L stainless Steel surface and with smooth TiO as shown in FIG. 42The coated stainless steel surface had a high level of adhesion of both Staphylococcus aureus and Candida dermalis as the two surfaces had no bacteriostatic capacity with smooth TiO2The coated stainless steel surface had a higher amount of bacteria adhesion than the polished 316L stainless steel surface due to the increased bioactivity. TiO with micro-nano composite structure2The adhesion of two kinds of bacteria on the surface of the stainless steel of the coating is small although TiO2The coating improves the surface biological activity, but the second and third level structures in the micro-nano structure effectively block the adhesion of bacteria on the coating, so that the surface has the function of inhibiting the adhesion of bacteria.
Comparative example 3
The comparative example compares the influence of the 316L stainless steel surface with the TiO2 coating with the micro-nano composite structure and the 316L stainless steel surface with the micro-nano composite structure on the adhesion of bacteria and cells.
Wherein, the TiO with the micro-nano composite structure2A coated 316L stainless steel surface was prepared using the method of example 1. The preparation method of the 316L stainless steel surface with the micro-nano composite structure comprises the following steps: firstly, preparing and polishing the surface of 316L stainless steel by using a mechanical polishing method, and then treating the surface by using a femtosecond laser processing method, wherein the laser processing technology comprises the following steps: the laser frequency is 1kHz, the wavelength is 800nm, the pulse energy is 800uJ, the pulse width is 150fs, the spot diameter is 150 mu m, the line spacing is 100 mu m, the scanning speed is 5mm/s, the surface of the sample is processed, meanwhile, the moving platform moves along the defocusing direction to ensure that the distance from the laser focus to the surface of the sample is not changed, and the whole surface of the sample is scanned. The surface structure of which substantially corresponds to the structure of the surface in example 1.
The effect of both surfaces on both cell adhesion was compared by epithelial cell and skin stem cell adhesion experiments, which were identical to those of comparative example 2. FIG. 5 shows the OD values of two surfaces with micro-nano composite structure TiO measured by CCK-8 method2The two cells adhered more to the surface of the coated 316L stainless steel due to TiO2The coating activity is higher than that of 316L stainless steel.
The bacteriostatic ability of both surfaces was compared by staphylococcus aureus and candida mucocutaneous adhesion experiments, the experimental method being identical to that in comparative example 2. FIG. 6 is a statistical result of the adhesion fluorescence intensity of two bacteria on two surfaces, wherein the adhesion amount of Staphylococcus aureus and Candida mucosae on the two surfaces is similar.
Example 2
The nanosecond laser has higher average power and higher processing efficiency, and the sol-gel method and the nanosecond laser processing are sequentially applied to prepare the TiO with the micro-nano composite structure on the surface of the NiTi alloy in the embodiment2And (4) coating.
In the processing method, the laser processing technology comprises the following steps: the laser frequency is 100kHz, the pulse energy is 8000uJ, the wavelength is 1030nm, the pulse width is 50ns, the spot diameter is 80 microns, the line spacing is 60 microns, the scanning speed is 30mm/s, the stainless steel surface is machined, and meanwhile, the X axis moves to ensure that the distance from the laser focus to the sample surface is constant, so that the whole sample surface is covered. The others are the same as in example 1. Fig. 7 shows the surface morphology of the obtained sample, and the surface micro-nano structure is also a three-level composite structure.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept, and these changes and modifications are all within the scope of the present invention.
Claims (7)
1. An external bone fixation device, comprising: the surface of the skin penetrating part is provided with an antibacterial functional structure which is a three-level micro-nano composite structure, the first-level structure is composed of grooves with the width of 60-120 mu m and the depth of about 1 mu m, the second-level structure is composed of stripes with the width of 100-400nm and the height of 10-40nm, and the second-level structure is distributed on the surface of the first-level structure; the third-level structure is composed of nano-particles with nano-scale, and the third-level structure is distributed on the surface of the second-level structure.
2. The external fixation device of claim 1, wherein: the width and depth of the primary structure are similar to those of epithelial cells or skin stem cells.
3. A method for processing the external bone fixation device as claimed in claim 1 or 2, wherein: the three-level micro-nano composite structure is prepared by a pulse laser processing method.
4. The processing method according to claim 3, characterized in that: firstly, TiO is manufactured on the surface of the skin penetrating part of the percutaneous metal orthopedic implantation instrument2Coating on the TiO subsequently2And preparing a three-level micro-nano composite structure on the coating.
5. The processing method according to claim 4, characterized in that: the TiO is2Thickness of coatingThe degree is 1-2 um.
6. The processing method according to claim 4, characterized in that: the TiO is2The coating is prepared by a sol-gel method.
7. The processing method according to claim 3 or 4, characterized in that: the parameters of the pulse laser processing are as follows: the laser frequency is 1-100 kHz, the wavelength is 800-1500 nm, the pulse width is 50-150 fs, the pulse energy is 600-8000 uJ, the spot diameter is 80-150 μm, the line spacing is 60-100 μm, and the scanning speed is 2-30 mm/s.
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| PCT/CN2022/097106 WO2022262604A1 (en) | 2021-06-17 | 2022-06-06 | External bone fixation instrument having functional structure on surface of skin-penetrating part, and processing method therefor |
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| WO2022262604A1 (en) * | 2021-06-17 | 2022-12-22 | 北京万嘉高科医药科技有限公司 | External bone fixation instrument having functional structure on surface of skin-penetrating part, and processing method therefor |
| WO2022262600A1 (en) * | 2021-06-17 | 2022-12-22 | 河北工业大学 | Medical material for promoting cell growth and inhibiting bacterial adhesion and processing method |
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