High-thermal-conductivity anti-sticking coating as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of coating preparation, and particularly relates to a high-thermal-conductivity anti-sticking coating and a preparation method and application thereof.The high-thermal-conductivity anti-sticking coating is prepared by using gallium-based liquid metal as a binding material of a carbon nanotube array, modifying the surface of a to-be-coated object with a gallium-based liquid metal layer, and growing the carbon nanotube array perpendicular to the gallium-based liquid metal layer; by means of good heat conduction and cooling performance of the gallium-based liquid metal layer and good hydrophobicity of the vertical carbon nano tube array layer, the synergistic effect of the double coatings is achieved, and then the heat conduction performance and the anti-adhesion capacity of the bipolar electric coagulation forceps are improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of coating preparation, and particularly relates to a high thermal conductivity anti-adhesion coating, a preparation method thereof, and an application thereof. Background Art

[0002] Electrocoagulation forceps are widely used in the field of surgical operations and have the advantages of high cutting efficiency, simple operation, and less blood oozing. Its working principle is: under the action of high-frequency current, the tip of the electrocoagulation forceps releases to the human tissue and generates a thermal effect, so that the blood vessel wall is dehydrated and the blood coagulates to achieve the purpose of hemostasis and cutting. However, during the operation, when the electrocoagulation forceps are used at too high a temperature and the heat conduction effect is poor, tissue crusting is caused, and it is easy to cause problems such as blood and tissue adhesion at the tip of the forceps. It is more difficult to remove the adhered tissue during the operation, resulting in problems such as a decrease in surgical accuracy and an extension of the operation time.

[0003] To solve the problem of tissue adhesion during the use of electrocoagulation forceps, the existing measures mainly include: designing a dripping device for cooling and heat dissipation, using materials with excellent anti-adhesion performance, coating an anti-adhesion coating, etc. Among them, the design of the dripping device is relatively complex and it should maintain vertical dripping during use, which brings inconvenience to the operator. And the research on anti-adhesion materials and coatings is mostly on one kind of material. For example, when directly depositing an independent carbon nanotube array on the tip of the electrocoagulation forceps, due to the poor contact and binding between the array and the solid surface, the thermal conductivity is poor and there are certain safety hazards. Summary of the Invention

[0004] To solve the problems raised in the background art, the present invention provides a high thermal conductivity anti-adhesion coating, a preparation method thereof, and an application thereof.

[0005] The technical solution of the present invention is as follows:

[0006] The present invention provides a high thermal conductivity anti-adhesion coating, including:

[0007] The surface of the object to be coated is modified with a gallium-based liquid metal layer, and carbon nanotubes are deposited on the outer surface of the gallium-based liquid metal layer;

[0008] The carbon nanotubes are a carbon nanotube array growing perpendicular to the gallium-based liquid metal layer;

[0009] The thickness of the carbon nanotubes is 4 - 11 μm, and the diameter is 19 - 27 nm;

[0010] The thermal conductivity is 36.9 - 38.1 W / mK, and the water contact angle is 127.1 - 136.8°.

[0011] The present invention also provides a preparation method of the high thermal conductivity anti-adhesion coating as described above, including the following steps:

[0012] (1) After the object to be coated is cleaned, it is vertically immersed in the gallium-based liquid metal, and then dried to obtain a gallium-based liquid metal layer;

[0013] (2) After the gallium-based liquid metal layer undergoes chemical vapor deposition to grow carbon nanotubes, a carbon nanotube array growing perpendicular to the gallium-based liquid metal layer is obtained.

[0014] In the step (1), the gallium-based liquid metal is Ga-In, Ga-Sn, Ga-Ag, Ga-Zn or Ga-In-Sn, and the content of Ga is 60%-95%.

[0015] In the step (1), the immersion time is 3-10 h.

[0016] In the step (2), the growth temperature is 740-760 °C, and the growth time is 10-20 min.

[0017] The present invention also provides an application of the high thermal conductivity anti-adhesion coating described above or the high thermal conductivity anti-adhesion coating prepared by the preparation method described above in surgical medical instruments.

[0018] Furthermore, the application of the high thermal conductivity anti-adhesion coating as described above in surgical medical instruments for improving thermal conductivity, enhancing hydrophobicity and anti-tissue adhesion ability.

[0019] Furthermore, the application of the high thermal conductivity anti-adhesion coating as described above in bipolar coagulation forceps.

[0020] Beneficial effects

[0021] The present invention uses gallium-based liquid metal as the binding material for the carbon nanotube array. After the surface of the object to be coated is modified with a gallium-based liquid metal layer, a carbon nanotube array grows perpendicular to the gallium-based liquid metal layer. By utilizing the good thermal conductivity and cooling performance of the gallium-based liquid metal layer and the good hydrophobicity of the vertical carbon nanotube array layer, the synergistic effect of the double coating is realized, thereby improving the thermal conductivity and anti-adhesion ability of the bipolar coagulation forceps. Description of the drawings

[0022] Figure 1 It is a schematic structural diagram of the coagulation forceps of the present invention. The description of the reference numerals: 1, forceps tip; 2, forceps body; 3, insulating seat.

[0023] Figure 2 It is a scanning electron microscope image of the coating prepared in Example 1 of the present invention.

[0024] Figure 3 It is a transmission electron microscope image of the coating prepared in Example 1 of the present invention.

[0025] Figure 4 It is a comparison chart of the thermal conductivities of the coatings prepared in Examples 1-3 and Comparative Examples 1-4 of the present invention.

[0026] Figure 5 Water contact angle diagrams of the coatings prepared according to the present invention, where (a) is Example 1, (b) is Example 2, (c) is Example 3, (d) is Comparative Example 1, (e) is Comparative Example 2, (f) is Comparative Example 3, and (g) is Comparative Example 4.

[0027] Figure 6 Comparison diagram of the anti-tissue adhesion results of the coatings prepared in Examples 1-3 and Comparative Examples 1-4 of the present invention applied to electrocoagulation forceps. Detailed implementation manners

[0028] The following examples are intended to illustrate the present invention, rather than further limiting the present invention.

[0029] The present invention provides a high thermal conductivity anti-sticking coating, which is composed of a surface-modified gallium-based liquid metal layer on the surface of the object to be coated, and carbon nanotubes deposited on the outer surface of the gallium-based liquid metal layer. For example, when the object to be coated is the tip of an electrocoagulation forceps, the coating is applied to the tip of the electrocoagulation forceps, and the metal tip substrate material is stainless steel, copper alloy, titanium alloy, or tungsten. In addition, the electrocoagulation forceps further includes a forceps body and an insulating seat, and the forceps body is coated with an insulating paint layer or sleeved with a plastic insulating sleeve, specifically as Figure 1 shown.

[0030] Furthermore, the carbon nanotubes are a carbon nanotube array perpendicular to the gallium-based liquid metal layer.

[0031] The gallium-based liquid metal layer has good thermal conductivity and temperature reduction performance, and the vertical carbon nanotube array layer has good hydrophobicity. The double coating acts synergistically to solve the problems of tissue adhesion during surgery and the abnormal use of electrocoagulation forceps.

[0032] To improve the thermal conductivity of the coating, preferably, the thickness of the carbon nanotubes is 4-11 μm, and the diameter is 19-27 nm; the thermal conductivity of the coating is 36.9-38.1 W / mK, and the water contact angle is 127.1-136.8°, having good thermal conductivity and hydrophobicity. Most preferably, the thickness of the carbon nanotubes is 7±1 μm, the diameter is 25±2 nm, and the water contact angle is 134.5±2.3°.

[0033] In view of the problem that when the carbon nanotube array is directly deposited on the tip of the electrocoagulation forceps alone, the thermal conductivity is poor because the array does not form good contact and bonding with the solid surface, the present invention uses gallium-based liquid metal as the bonding material for the carbon nanotube array. After the surface of the forceps tip is modified with a gallium-based liquid metal layer, a carbon nanotube array is grown perpendicular to the gallium-based liquid metal layer to obtain a coating material with high thermal conductivity, strong electrical conductivity, good hydrophobicity, and good biocompatibility.

[0034] The present invention also provides a preparation method of the high thermal conductivity anti-sticking coating, including the following steps:

[0035] (1) After the object to be coated is cleaned, it is vertically immersed in the gallium-based liquid metal, and then dried to obtain a gallium-based liquid metal layer.

[0036] To ensure the cleanliness of the deposition surface, for the cleaning treatment of the object to be coated, such as the cleaning of the forceps tip, it specifically includes:

[0037] The forceps tip of the electrocoagulation forceps is successively placed in ethanol (>99.8%), acetone, and deionized water, and ultrasonically cleaned (1000W) for 20 minutes each, and then dried and placed in a clean and sealed container for standby.

[0038] Regarding the selection of the modification material, as an emerging material, liquid metal is in a liquid state at room temperature, showing low toxicity and good biocompatibility. Different from traditional metal materials, liquid metal has high thermal conductivity and electrical conductivity.

[0039] Preferably, the gallium-based liquid metal is Ga-In, Ga-Sn, Ga-Ag, Ga-Zn or Ga-In-Sn, and the content of Ga is 60%-95%.

[0040] In addition, since the growth parameters of the modification layer will affect the performance, in order to reasonably control the thickness of the gallium-based liquid metal layer, it can be achieved by repeated impregnation, and the impregnation time is 3-10 hours. The most preferred impregnation time is 6 hours.

[0041] After the forceps tip of the electrocoagulation forceps is impregnated with the gallium-based liquid metal, a wetting interface is formed by reaction. After taking it out, it is rinsed with deionized water and left to stand and dry for more than 12 hours to obtain the forceps tip with a modified gallium-based liquid metal layer. Modifying the gallium-based liquid metal layer on the forceps tip can improve the thermal conductivity and cooling ability of the electrocoagulation forceps.

[0042] (2) After the gallium-based liquid metal layer undergoes chemical vapor deposition to grow carbon nanotubes, a carbon nanotube array perpendicular to the gallium-based liquid metal layer is obtained.

[0043] Before depositing the carbon nanotubes, the forceps tip with the modified gallium-based liquid metal layer is pretreated, and 10 nm Al 2 O 3 (buffer layer) and 1.2 nm Fe (catalyst) are deposited by electron beam evaporation method. Then, carbon nanotubes are grown by chemical vapor deposition method, where the carbon source is ethylene (99.999%, 200 sccm).

[0044] To control the growth of the carbon nanotubes, preferably, the growth temperature is 740-760 °C, and the atmosphere and flow rate are respectively He (99.9999%, 100 sccm), H 2 (99.9999%, 400 sccm), Ar / O 2(99.9999% Ar / 1% O 2 , 250 sccm), with a growth time of 10 - 20 min to control the thickness of the carbon nanotube coating. The most preferred growth temperature is 750 °C and the growth time is 15 min.

[0045] After growth, it is cooled to room temperature under He protection, and a carbon nanotube array perpendicular to the gallium-based liquid metal layer is obtained. The array is closely arranged, has a consistent aspect ratio, good orientation, high purity, and good hydrophobicity, thereby enabling the electrocoagulation forceps to have better anti-tissue adhesion performance.

[0046] Finally, the tweezer tip and the tweezer body are welded together, and an insulating paint layer is coated on the processed tweezer body or a plastic insulating sleeve is sleeved to obtain the electrocoagulation forceps.

[0047] The present invention also provides an application of the high thermal conductivity anti-adhesion coating in surgical medical devices, such as bipolar electrocoagulation forceps.

[0048] Specifically, it is an application of the high thermal conductivity anti-adhesion coating in surgical medical devices that improve thermal conductivity, enhance hydrophobicity, and anti-tissue adhesion ability.

[0049] The present invention uses gallium-based liquid metal as the binding material for the carbon nanotube array. After modifying the surface of the tweezer tip with a gallium-based liquid metal layer, a carbon nanotube array is grown perpendicular to the gallium-based liquid metal layer. By utilizing the better thermal conductivity and cooling performance of the gallium-based liquid metal layer and the good hydrophobicity of the perpendicular carbon nanotube array layer, the synergistic effect of the double coatings is realized, thereby improving the thermal conductivity and anti-adhesion ability of the bipolar electrocoagulation forceps.

[0050] The following examples all use tweezer tips made of 316L stainless steel. The tweezer tips are successively placed in ethanol (>99.8%), acetone, and deionized water, and ultrasonically cleaned (1000 W) for 20 min each, then dried and placed in a clean and sealed container for standby.

[0051] Example 1

[0052] (1) The cleaned tweezer tip is used as the substrate. At room temperature and in an argon protection environment, it is vertically immersed in the gallium-based liquid metal Ga-In (Ga 75 In 25 ) for 6 h, taken out, rinsed with deionized water, and left to stand and dry for more than 12 h to obtain a tweezer tip with a modified gallium-based liquid metal layer.

[0053] (2) The tweezer tip with the modified gallium-based liquid metal layer is pretreated, and 10 nm of Al is deposited by electron beam evaporation 2 O 3(Buffer layer) and 1.2 nm Fe (catalyst), and then, by chemical vapor deposition method, carbon nanotubes are grown. Among them, the carbon source is ethylene (99.999%, 200 sccm), the growth temperature is 750 °C, and the atmosphere and flow rate are He (99.9999%, 100 sccm), H 2 (99.9999%, 400 sccm), Ar / O 2 (99.9999% Ar / 1% O 2 , 250 sccm), the growth time is 15 min, and after growth, it is cooled to room temperature under the protection of He to obtain the tweezer tip with a carbon nanotube array growing perpendicular to the gallium-based liquid metal layer.

[0054] Example 2

[0055] (1) The cleaned tweezer tip is used as the substrate, and at room temperature and under the protection of argon atmosphere, it is vertically immersed in the gallium-based liquid metal Ga-Ag (Ga 95 Ag 5 ) for 3 h, taken out and rinsed with deionized water, and left to dry for more than 12 h to obtain the tweezer tip modified with a gallium-based liquid metal layer.

[0056] (2) The tweezer tip modified with a gallium-based liquid metal layer is pretreated, and 10 nm Al is deposited by electron beam evaporation 2 O 3 (Buffer layer) and 1.2 nm Fe (catalyst), and then, by chemical vapor deposition method, carbon nanotubes are grown. Among them, the carbon source is ethylene (99.999%, 200 sccm), the growth temperature is 740 °C, and the atmosphere and flow rate are He (99.9999%, 100 sccm), H 2 (99.9999%, 400 sccm), Ar / O 2 (99.9999% Ar / 1% O 2 , 250 sccm), the growth time is 20 min, and after growth, it is cooled to room temperature under the protection of He to obtain the tweezer tip with a carbon nanotube array growing perpendicular to the gallium-based liquid metal layer.

[0057] Example 3

[0058] (1) The cleaned tweezer tip is used as the substrate, and at room temperature and under the protection of argon atmosphere, it is vertically immersed in the gallium-based liquid metal Ga-Sn (Ga 60 Sn 40 ) for 10 h, taken out and rinsed with deionized water, and left to dry for more than 12 h to obtain the tweezer tip modified with a gallium-based liquid metal layer.

[0059] (2) The tweezer tip modified with a gallium-based liquid metal layer is pretreated, and 10 nm Al is deposited by electron beam evaporation2 O 3 (Buffer layer) and 1.2 nm Fe (catalyst), then, carbon nanotubes are grown by chemical vapor deposition method, where the carbon source is ethylene (99.999%, 200 sccm), the growth temperature is 760 °C, and the atmosphere and flow rate are He (99.9999%, 100 sccm), H 2 (99.9999%, 400 sccm), Ar / O 2 (99.9999% Ar / 1% O 2 , 250 sccm), the growth time is 10 min, and after growth, it is cooled to room temperature under He protection to obtain the tweezer tip with carbon nanotube array grown perpendicular to the gallium-based liquid metal layer.

[0060] Comparative Example 1

[0061] Compared with Example 1, the impregnation time in step (1) is 1 h, the growth time in step (2) is 5 min, and other operations and process parameters are the same as those in Example 1.

[0062] Comparative Example 2

[0063] Compared with Example 1, the impregnation time in step (1) is 15 h, the growth time in step (2) is 30 min, and other operations and process parameters are the same as those in Example 1.

[0064] Comparative Example 3

[0065] The cleaned tweezer tip is used as the substrate for pretreatment, and 10 nm Al 2 O 3 (Buffer layer) and 1.2 nm Fe (catalyst) are deposited by electron beam evaporation method, then, carbon nanotubes are grown by chemical vapor deposition method, where the carbon source is ethylene (99.999%, 200 sccm), the growth temperature is 750 °C, and the atmosphere and flow rate are He (99.9999%, 100 sccm), H 2 (99.9999%, 400 sccm), Ar / O 2 (99.9999% Ar / 1% O 2 , 250 sccm), the growth time is 15 min, and after growth, it is cooled to room temperature under He protection to obtain the tweezer tip coated with a carbon nanotube layer.

[0066] Comparative Example 4

[0067] The cleaned tweezer tip is not modified.

[0068] Experimental Results

[0069] 1. Morphology Analysis

[0070] Perform morphological analysis on Example 1. It can be seen from Figure 2 that the vertically aligned carbon nanotube coating is uniformly deposited on the gallium-based liquid metal layer, with a thickness of 7 ± 1 μm, consistent orientation and close arrangement. In addition, it can be seen from Figure 3 that the vertically grown carbon nanotube arrays are multi-walled carbon nanotubes with 13 - 14 layers, and the diameter is about 25 ± 2 nm.

[0071] 2. Performance analysis

[0072] To analyze the thermal conductivity, hydrophobicity and anti-tissue adhesion properties of the electrocoagulation forceps, relevant tests are carried out on the obtained coatings. Among them, Examples 1 - 3 are coatings obtained by using the preparation method of the present application, Comparative Example 1 is a coating obtained by reducing the impregnation time of gallium-based liquid metal and the growth time of carbon nanotubes, Comparative Example 2 is a coating obtained by increasing the impregnation time of gallium-based liquid metal and the growth time of carbon nanotubes, Comparative Example 3 is a coating only coated with a carbon nanotube layer, and Comparative Example 4 is a tweezer tip without any modification.

[0073] 2.1 Thermal conductivity

[0074] To verify the thermal conductivity of the electrocoagulation forceps, the thermal conductivities of the coatings of Examples 1 - 3 and Comparative Examples 1 - 4 at 100 °C are detected, as Figure 4 shown.

[0075] Compared with Comparative Examples 1 - 4, the coatings of Examples 1 - 3 have higher thermal conductivities. Among them, compared with Comparative Examples 1 - 4, the thermal conductivities of the coating of Example 1 are increased by 16.5%, 20.8%, 33.3%, and 77.8% respectively, indicating that the coating obtained by using the preparation method of the present application has high thermal conductivity, good thermal conductivity performance, and is easy to cool and dissipate heat.

[0076] 2.2 Hydrophobicity

[0077] To verify the hydrophobicity of the electrocoagulation forceps, the water contact angles of the coatings of Examples 1 - 3 and Comparative Examples 1 - 4 are detected, as Figure 5 shown. Among them, the water contact angles of the coatings of Examples 1 - 3 are as shown in (a) - (c) in Figure 5 , which are 134.5 ± 2.3°, 132.2 ± 2.1°, and 129.5 ± 2.4° respectively; the water contact angles of Comparative Examples 1 - 4 are as shown in (d) - (g) in Figure 5 , which are 123.5 ± 2.1°, 121.8 ± 2°, 110.2 ± 1.8°, and 39.9 ± 0.9° respectively. Moreover, compared with Comparative Examples 3 and 4, the water contact angles of the electrocoagulation forceps modified with the double coatings of gallium-based liquid metal and carbon nanotubes are significantly increased, indicating that the coating obtained by using the preparation method of the present application has better hydrophobicity.

[0078] 2.3 Anti-tissue adhesion property

[0079] The tips of forceps coated with the coatings of Examples 1-3 and Comparative Examples 1-4 were respectively assembled into electrocoagulation forceps. Using a high-frequency electrosurgical system, fresh pig livers were cut at 60 W in the electrocoagulation mode for 5 seconds, 10 seconds, and 20 seconds. The quality of the tissue adhered to the electrode surface after cutting was compared to detect the anti-tissue adhesion performance of the electrocoagulation forceps. The results are as Figure 6 shown.

[0080] It can be seen from the comparison results that compared with Comparative Examples 1-4, the quality of the tissue adhered to the coated electrocoagulation forceps of Examples 1-3 was significantly reduced, and the anti-tissue adhesion effect was good, indicating that the coating obtained by the preparation method of the present application has good anti-adhesion performance when used for electrocoagulation forceps.

Claims

1. A high thermal conductivity anti-stick coating, characterized in that: include: The surface of the object to be coated is modified with a gallium-based liquid metal layer, and carbon nanotubes are deposited on the outer surface of the gallium-based liquid metal layer; The carbon nanotubes are carbon nanotube arrays grown vertically on the gallium-based liquid metal layer; The carbon nanotubes have a thickness of 4-11 μm and a diameter of 19-27 nm; The thermal conductivity is 36.9-38.1 W / mK and the water contact angle is 127.1-136.8°.

2. A method for preparing a high thermal conductive anti-stick coating according to claim 1, characterized in that: The following steps are involved: (1) After cleaning the object to be coated, immersing it in a gallium-based liquid metal perpendicular to the liquid surface, and drying it to obtain a gallium-based liquid metal layer; (2) The gallium-based liquid metal layer is subjected to chemical vapor deposition to grow carbon nanotubes, thereby obtaining a carbon nanotube array that grows perpendicular to the gallium-based liquid metal layer.

3. The method for preparing a high thermal conductive anti-stick coating according to claim 2, characterized in that: In the step (1), the gallium-based liquid metal is Ga-In, Ga-Sn, Ga-Ag, Ga-Zn or Ga-In-Sn, and the Ga content is 60%-95%.

4. The method for preparing a high thermal conductive anti-stick coating according to claim 2, characterized in that: In the step (1), the immersion time is 3-10 hours.

5. The method for preparing a high thermal conductive anti-stick coating according to claim 2, characterized in that: In the step (2), the growth temperature is 740-760° C. and the growth time is 10-20 min.

6. Use of the high thermal conductivity anti-stick coating according to claim 1 or the high thermal conductivity anti-stick coating prepared by the preparation method according to any one of claims 2 to 5 in surgical medical devices.

7. The use according to claim 6, characterized in that: The high thermal conductivity anti-stick coating is used in surgical medical devices to improve thermal conductivity, hydrophobicity and anti-tissue adhesion capabilities.

8. The use according to claim 6, characterized in that: Application of the high thermal conductivity anti-stick coating in bipolar electrocoagulation forceps.

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