CN112775561A - Pyrolytic carbon mechanical valve leaflet with two-stage pattern on surface and preparation method thereof - Google Patents

Pyrolytic carbon mechanical valve leaflet with two-stage pattern on surface and preparation method thereof Download PDF

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Publication number
CN112775561A
CN112775561A CN202011629411.9A CN202011629411A CN112775561A CN 112775561 A CN112775561 A CN 112775561A CN 202011629411 A CN202011629411 A CN 202011629411A CN 112775561 A CN112775561 A CN 112775561A
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pattern
valve leaflet
pyrolytic carbon
leaflet
mechanical valve
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罗红林
阳正
周建业
王德
张全超
甘德强
荀晓伟
朱享波
万怡灶
王捷
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East China Jiaotong University
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East China Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/362—Laser etching
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/24—Heart valves ; Vascular valves, e.g. venous valves; Heart implants, e.g. passive devices for improving the function of the native valve or the heart muscle; Transmyocardial revascularisation [TMR] devices; Valves implantable in the body
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/60—Preliminary treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/70—Auxiliary operations or equipment
    • B23K26/702—Auxiliary equipment

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Mechanical Engineering (AREA)
  • Cardiology (AREA)
  • Transplantation (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Biomedical Technology (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Vascular Medicine (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Prostheses (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The invention discloses a pyrolytic carbon mechanical valve leaflet with a two-stage pattern on the surface and a preparation method thereof, wherein the surface of the leaflet comprises a primary pattern and a secondary pattern, the primary pattern is a grating-shaped pattern consisting of parallel and alternately arranged bulges and grooves, and the grating distance is 30-150 mu m; the secondary patterns on the surfaces of the convex parts of the primary patterns are in a cauliflower-shaped particle pattern with the particle size of 5-25 mu m, laser micromachining is carried out on the surface of the pyrolytic carbon by adopting laser wavelength of 1064nm, and the two-stage patterns are obtained on the surface of the valve leaflet through the mutual influence of laser spots under the condition of specific parameters; the surface of the valve leaf is covered with a low surface energy material layer. The pyrolytic carbon mechanical valve leaflet with the surface provided with the two-stage pattern has a surface static water contact angle larger than 150 degrees. The preparation of a secondary structure is realized on the surface of the pyrolytic carbon, the anticoagulation problem of the mechanical valve is improved, the surface has super-hydrophobic characteristics, the hemodynamic performance of the surface of the valve leaflet is obviously improved, and the thrombosis problem of the mechanical valve is solved.

Description

Pyrolytic carbon mechanical valve leaflet with two-stage pattern on surface and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of anticoagulant surfaces of medical implant materials, in particular to a pyrolytic carbon mechanical valve leaflet product with a two-stage pattern on the surface.
Background
Statistically, hundreds of thousands of patients worldwide need to receive valve replacement surgery each year. Currently, the most clinically used prosthetic heart valves are primarily biological and mechanical valves. Among them, the biovalve has good hemodynamic performance, but has the problems of easy calcification and performance degradation which cannot be solved so far, and cannot be used for a long time. Mechanical valves are well durable, have no risk of calcification, but have poor hemodynamic performance compared to biological valves. This is mainly due to the fact that the mechanical valve configuration is different from that of the natural heart valve, and turbulence occurs when the heart shoots blood, so that the high shear stress generated by the turbulence activates blood platelets, so that hemolysis and thrombus formation are caused. Therefore, how to solve the problem of thrombosis of the mechanical valve is a hot and difficult problem in the current mechanical valve research.
Long-term use of anticoagulants is a common means of reducing thrombosis on the surface of various implant materials, but these anticoagulants are only effective in the early stages. To this end, researchers have focused their attention on developing various mechanical valve surfaces with anticoagulant function. Surface modification by surface coating with polyethylene oxide, albumin, phosphorylcholine, or forming an anti-adhesive surface has been reported to reduce thrombosis. However, the effect of these modified surfaces is limited. More importantly, these surface coatings do not fundamentally improve the hemodynamic performance of mechanical valves, as their hemodynamic performance is primarily determined by their surface topology.
From the above, the existing technical means are difficult to solve the hemodynamic performance of the mechanical valve, and the problem of thrombosis cannot be solved fundamentally. In recent years, inspired by the two-stage structure pattern of the super-hydrophobic lotus leaf surface, the two-stage pattern constructed on the surface of the valve leaflet is expected to inhibit the adhesion of blood platelets on the surface, help to reduce the occurrence of turbulence, reduce the blood flow resistance and prevent the occurrence of thrombus.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a pyrolytic carbon mechanical valve leaflet with a two-stage pattern on the surface and a preparation method thereof. The method is characterized in that a cauliflower-shaped pattern and a grating-shaped pattern are creatively combined, and the pyrolytic carbon mechanical valve leaflet with a two-stage pattern on the surface is constructed by combining laser etching and low surface energy molecule self-assembly, so that the surface can fundamentally reduce the adhesion of blood on the surface of the leaflet and improve the hemodynamic performance of the surface of the leaflet, thereby solving the problem of thrombosis of the mechanical valve leaflet.
The invention provides a pyrolytic carbon mechanical valve leaflet with a two-stage pattern on the surface, the surface of the leaflet comprises a primary pattern and a secondary pattern, the primary pattern is a grating-shaped pattern consisting of parallel and alternately arranged bulges and grooves, and the secondary pattern on the surface of the bulge part of the primary pattern presents a cauliflower-shaped particle pattern; the surface of the valve leaf is covered with a low surface energy material layer.
Further, the pyrolytic carbon mechanical valve leaflet with the surface provided with the double-stage pattern comprises:
in the grating-shaped pattern, the grating pitch means the distance between the central lines of two adjacent grooves is C, and the value range of C is 30-150 μm as shown in FIG. 1. The thickness of the grating wall, i.e., the width of the raised portion, is A, A should be less than C, and is about 30-120 μm, and the depth of the grating groove (i.e., the height of the raised portion) is about 30-80 μm.
The particle size of the cauliflower-shaped particles of the secondary pattern is 5-25 microns, and preferably 5-15 microns.
After the surface of the valve leaflet is coated with the low-surface-energy material layer, the static water contact angle of the surface of the valve leaflet is larger than 150 degrees, so that the whole valve leaflet has low-adhesion super-hydrophobic characteristic, the detention time of blood on the surface of the valve leaflet is reduced, the occurrence of turbulence phenomenon is avoided, the activation of blood platelets is reduced, and the probability of thrombosis on the surface of the valve is reduced.
Meanwhile, the invention also provides a preparation method of the pyrolytic carbon mechanical valve leaflet with the surface provided with the two-stage pattern, which comprises the following steps:
step one, pretreatment of a mechanical valve leaflet: cutting a sample into a size required by a valve leaflet by using pyrolytic carbon as a base material and adopting a linear cutting technology, polishing the valve leaflet by using 800#, 2000#, 5000# and 7000# abrasive paper in sequence, then respectively ultrasonically cleaning the valve leaflet by using ethanol and deionized water for 10-20 min in sequence, and then drying the valve leaflet for later use;
step two, preparing a two-stage pattern on the surface of the valve leaf: carrying out laser etching on the surface of the pyrolytic carbon by adopting laser etching, and designing a laser etching pattern into a grating-shaped pattern with parallel stripes, wherein the grating interval is set to be 30-150 mu m; the laser etching parameters are as follows: the laser wavelength is 1064nm, the power is 24-30W, the linear scanning speed is 20-90 mm/s, and the frequency is 20 Hz;
step three, preparing a super-hydrophobic wetting surface: and (3) soaking the pyrolytic carbon mechanical valve leaflet with the surface double-stage pattern prepared in the step two in a low surface energy surfactant solution with the concentration of 0.01mol/L for 0.5-2 h, finally, putting the leaflet into a constant-temperature oven with the temperature of 60-120 ℃ for drying for 1-6 h, and cooling to room temperature to obtain the pyrolytic carbon mechanical valve leaflet with the surface double-stage pattern and the surface static water contact angle of more than 150 degrees.
In the second step, a region selection inclined light beam processing method is adopted in the laser etching process.
In step three, the low surface energy surfactant includes, but is not limited to, one of perfluorodecyltriethoxysilane, stearic acid, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltrimethoxysilane, and tridecafluorooctyltriethoxysilane.
The surface of the pyrolytic carbon mechanical valve leaflet prepared by the invention has special two-stage patterns, and after the pyrolytic carbon mechanical valve leaflet is treated by low-surface-energy substances, the surface has low-adhesion super-hydrophobic characteristics, so that the time of blood detention is shortened, the occurrence of turbulence phenomenon is avoided, the activation of platelets is reduced, and the incidence rate of valve-related complications is reduced.
Drawings
Fig. 1 is an SEM and contact angle photograph of the pyrolytic carbon mechanical valve leaflet having a bi-level pattern on the surface, prepared in example 1;
fig. 2 is an SEM and contact angle photograph of the pyrolytic carbon mechanical valve leaflet having a bi-level pattern on the surface, prepared in example 2;
fig. 3 is an SEM and contact angle photograph of the pyrolytic carbon mechanical valve leaflet having a bi-level pattern on the surface, prepared in example 3;
fig. 4 is an SEM and contact angle photograph of the pyrolytic carbon mechanical valve leaflet having a bi-level pattern on the surface, prepared in example 4;
fig. 5 is an SEM and contact angle photograph of the pyrolytic carbon mechanical valve leaflet having a bi-level pattern on the surface, prepared in example 5;
fig. 6 is an SEM and contact angle photograph of the pyrolytic carbon mechanical valve leaflet having a bi-level pattern on the surface prepared in example 6;
fig. 7 is an SEM and contact angle photograph of the pyrolytic carbon mechanical valve leaflet having a bi-level pattern on the surface prepared in example 7;
fig. 8 is an SEM and contact angle photograph of the pyrolytic carbon mechanical valve leaflet having a bi-level pattern on the surface prepared in example 8;
in fig. 1 to 8, the left SEM photographs are partially enlarged views showing the morphology of the cauliflower-like particles exhibited by the secondary patterns.
Fig. 9 is an SEM and contact angle photograph of the pyrolytic carbon mechanical valve leaflet having only a primary pattern on the surface, prepared in comparative example 1;
fig. 10 is an SEM and contact angle photograph of the pyrolytic carbon mechanical valve leaflet having only a primary pattern on the surface, prepared in comparative example 2;
in fig. 9 and 10, the left SEM photographs are enlarged views showing the grating-like morphology of the primary pattern.
Detailed Description
The following method uses pyrolytic carbon as a base material of the valve leaflet, and adopts a method combining laser etching and stearic acid molecule self-assembly to prepare the pyrolytic carbon mechanical valve leaflet with a two-stage pattern on the surface.
Example 1
Pre-treating a mechanical valve leaflet sample: cutting pyrolytic carbon into valve leaf shapes by adopting a linear cutting technology, grinding and polishing the valve leaves with rough surfaces by using serial abrasive paper from 800# to 7000#, sequentially ultrasonically cleaning the valve leaves by using absolute ethyl alcohol and deionized water for 15min, and drying and bagging the valve leaves for later use.
Preparing a bi-level pattern on the surface of the valve leaflet: designing a laser etching pattern into a grating-shaped pattern with parallel stripes, setting the grating interval to be 40 mu m, finishing laser spot focusing, setting the laser wavelength to be 1064nm, setting the laser output power to be 27W, setting the laser line scanning speed to be 50mm/s and setting the frequency to be 20 Hz; aligning the sample to an etching area, starting a marking program to etch the surface of the sample, obtaining a valve leaflet sample with a two-stage pattern on the surface after etching, and ultrasonically cleaning impurities on the surface of the valve leaflet sample by deionized water and then drying the valve leaflet sample for later use.
Preparing a super-hydrophobic wetting surface: and (2) dropwise adding 0.399g of perfluorodecyl triethoxysilane into 50ml of absolute ethanol in a glass beaker, uniformly stirring, sealing for 12 hours at normal temperature by using a preservative film, placing an etched sample into the solution after the hydrolysis is completed, soaking for 1 hour with the etched surface facing upwards, taking out, placing the sample into a constant-temperature oven at 60 ℃ for 5 hours, and cooling to room temperature to obtain the pyrolytic carbon mechanical valve leaflet with the surface provided with the two-stage pattern, wherein SEM and contact angle photographs of the surface are shown in figure 1.
The contact angle of the surface of the sample prepared in example 1 after laser treatment with water was 156.1 °, the obtained surface had a grating-like primary pattern arranged in parallel, the grating pitch (i.e., C) was 40 μm, the surface of the protruding portion (i.e., a) consisted of secondary cauliflower-like particles, and the size of the cauliflower-like particles varied from 5 to 15 μm.
Example 2
This example 2 was prepared substantially identically to example 1, except that: in the preparation step of the bi-level pattern on the surface of the valve leaf: the setting of the grating pitch in the laser etched pattern was changed from 40 μm to 70 μm. Example 2 the final pyrolyzate mechanical valve leaflet with a bi-level pattern on the surface is obtained, and the SEM and contact angle photographs of the surface are shown in fig. 2.
The contact angle between the surface of the sample prepared in example 2 after laser treatment and water was 153.9 °, the obtained surface had grating-like primary patterns arranged in parallel, the grating pitch was 70 μm, each grating consisted of secondary cauliflower-like particles, and the sizes of the cauliflower-like particles varied from 5 to 10 μm.
Example 3
This example 3 was prepared substantially identically to example 1, except that: in the preparation step of the bi-level pattern on the surface of the valve leaf: the setting of the grating spacing in the laser etching pattern is changed from 40 mu m to 30 mu m, and the scanning speed of the laser line is changed from 50mm/s to 80 mm/s. Example 3 the final pyrolyzation carbon mechanical valve leaflet with bi-level pattern on the surface is obtained, and the SEM and contact angle photographs of the surface are shown in fig. 3.
The contact angle of the surface of the sample prepared in example 3 after laser treatment with water was found to be 157.4 °, the obtained surface had grating-like primary patterns arranged in parallel, the grating pitch was 30 μm, the surface of each grating protrusion consisted of secondary cauliflower-like particles, and the sizes of the cauliflower-like particles varied from 5 to 10 μm.
Example 4
This example 4 was prepared substantially identically to example 1, except that: in the preparation step of the bi-level pattern on the surface of the valve leaf: the SEM and contact angle photographs of the surface of the mechanical valve leaflet having a bi-level pattern obtained in example 4 were shown in fig. 4, in which the setting of the grating pitch in the laser etching pattern was changed from 40 μm to 30 μm, the laser output power was changed from 27W to 24W, and the laser line scanning speed was changed from 50mm/s to 80 mm/s.
It was determined that the contact angle between the surface of the sample prepared in example 4 after laser treatment and water was 155.5 °, the obtained surface had grating-like primary patterns arranged in parallel, the grating pitch was 30 μm, the surface of each grating protrusion consisted of secondary cauliflower-like particles, and the size of the flower-like particles varied from 5 to 15 μm.
Example 5
This example 5 was prepared substantially identically to example 1, except that: in the preparation step of the bi-level pattern on the surface of the valve leaf: the setting of the grating spacing in the laser etching pattern is changed from 40 mu m to 150 mu m, and the laser output power is changed from 27W to 30W. Example 5 the final pyrolytic carbon mechanical valve leaflet with a bi-level pattern on the surface is obtained, and the SEM and contact angle photographs of the surface are shown in fig. 5.
The contact angle of the surface of the sample prepared in example 5 after laser treatment and water was measured to be 150.2 °, the obtained surface had grating-like primary patterns arranged in parallel, the grating pitch was 150 μm, the surface of each grating protrusion consisted of secondary cauliflower-like particles, and the sizes of the cauliflower-like particles varied from 5 to 9 μm.
Example 6
This example 6 was prepared substantially identically to example 1, except that: in the preparation step of the bi-level pattern on the surface of the valve leaf: the setting of the grating spacing in the laser etching pattern is changed from 40 mu m to 100 mu m, and the laser line scanning speed is changed from 50mm/s to 20 mm/s. Example 6 the final pyrolyzation carbon mechanical valve leaflet with bi-level pattern on the surface is obtained, and the SEM and contact angle photographs of the surface are shown in fig. 6.
It was determined that the contact angle between the surface of the sample prepared in example 6 after laser treatment and water was 151.1 °, the obtained surface had grating-like primary patterns arranged in parallel, the grating pitch was 100 μm, each grating consisted of secondary cauliflower-like particles, and the size of the cauliflower-like particles varied from 5 to 12 μm.
Example 7
The preparation process of this example 7 is substantially the same as that of example 1, except that: in the preparation step of the bi-level pattern on the surface of the valve leaf: the setting of the grating spacing in the laser etching pattern is changed from 40 mu m to 100 mu m, and the laser line scanning speed is changed from 50mm/s to 90 mm/s. Example 7 the final pyrolyzate mechanical valve leaflet with bi-level pattern on the surface is obtained, and the SEM and contact angle photographs of the surface are shown in fig. 7.
It was found that the contact angle between the surface of the sample prepared in example 7 after laser treatment and water was 151.6 °, the obtained surface had grating-like primary patterns arranged in parallel, the grating pitch was 100 μm, each grating consisted of secondary cauliflower-like particles, and the size of the cauliflower-like particles varied from 5 to 8 μm.
Example 8
This example 8 was prepared substantially identically to example 1, except that: in the preparation step of the bi-level pattern on the surface of the valve leaf: the setting of the grating spacing in the laser etching pattern is changed from 40 μm to 100 μm, and the laser output power is changed from 27W to 30W. Example 2 the final pyrolytic carbon mechanical valve leaflet with a bi-level pattern on the surface is obtained, and the SEM and contact angle photographs of the surface are shown in fig. 8.
It was determined that the contact angle between the surface of the sample prepared in example 8 after laser treatment and water was 152.3 °, the obtained surface had grating-like primary patterns arranged in parallel, the grating pitch was 100 μm, each grating consisted of secondary cauliflower-like particles, and the size of the cauliflower-like particles varied from 5 to 10 μm.
Comparative example 1
The pyrolytic carbon mechanical valve leaflet with the surface only provided with the primary grating-shaped pattern is prepared by taking pyrolytic carbon as a base material of the valve leaflet and adopting a method of combining laser etching and stearic acid molecule self-assembly. The procedure for the preparation of comparative example 1 is as follows:
sample pretreatment of mechanical valve leaflets, the procedure being as in example 1.
Preparing a primary grating pattern on the surface of the valve leaf: designing a laser etching pattern into a grating-shaped pattern with parallel stripes, setting the grating interval to be 170 mu m, finishing laser spot focusing, setting the laser output power to be 27W, the laser line scanning speed to be 50mm/s and the frequency to be 20 Hz; aligning the sample to an etching area, starting a marking program to etch the surface of the sample, obtaining a valve leaflet sample with a primary grating pattern on the surface after etching, ultrasonically cleaning impurities on the surface of the valve leaflet sample by deionized water, and drying the valve leaflet sample for later use.
Preparing a super-hydrophobic wetting surface: the procedure is as in example 1.
Comparative example 1 the finally obtained mechanical valve leaflet of pyrolytic carbon having a primary pattern on the surface thereof, whose SEM and contact angle photographs of the surface are shown in fig. 9.
The contact angle of the surface of the sample prepared in comparative example 1 after laser treatment with water was found to be 132.3 °, and the resulting surface had only a grating-like pattern in parallel arrangement, but no secondary cauliflower-like particle structure pattern.
Comparative example 2
The pyrolytic carbon mechanical valve leaflet with the surface only provided with the primary grating-shaped pattern is prepared by taking pyrolytic carbon as a base material of the valve leaflet and adopting a method of combining laser etching and stearic acid molecule self-assembly. Comparative example 2 was prepared as follows:
sample pretreatment of mechanical valve leaflets, the procedure being as in example 1.
Preparing a primary grating pattern on the surface of the valve leaf: designing a laser etching pattern into a grating-shaped pattern with parallel stripes, setting the grating interval to be 30 mu m, finishing laser spot focusing, setting the laser output power to be 27W, the laser line scanning speed to be 200mm/s and the frequency to be 20 Hz; aligning the sample to an etching area, starting a marking program to etch the surface of the sample, obtaining a valve leaflet sample with a primary grating pattern on the surface after etching, ultrasonically cleaning impurities on the surface of the valve leaflet sample by deionized water, and drying the valve leaflet sample for later use.
Preparing a super-hydrophobic wetting surface: the procedure is as in example 1.
Comparative example 2 the finally obtained mechanical valve leaflet of pyrolytic carbon having a primary pattern on the surface thereof, whose SEM and contact angle photographs of the surface are shown in fig. 10.
It was determined that the contact angle with water of the surface of the sample prepared in comparative example 2 after laser treatment was 147.8 °, the resulting surface had only a grating-like pattern in parallel arrangement, but no secondary cauliflower-like particle structure pattern.
In summary, the key technical point in the preparation method of the invention is to perform laser etching treatment on the surface of the valve leaflet which takes pyrolytic carbon as a base material to form the pyrolytic carbon mechanical valve leaflet with a two-stage pattern on the surface. The grating pitch, the laser output power and the line scanning speed are three core parameters for determining whether a double-stage pattern can be obtained, and the expected double-stage pattern can be obtained only if the three parameters are within the range defined by the invention. The pyrolytic carbon mechanical valve leaflet with the surface provided with the two-stage pattern obtained by the method has a surface static water contact angle larger than 150 degrees. The preparation of the secondary structure pattern on the surface of the pyrolytic carbon is expected to improve the anticoagulation problem of the mechanical valve. The surface has super-hydrophobic characteristics, and can remarkably improve the hemodynamic performance of the surface of the valve leaflet, thereby solving the thrombosis problem of a mechanical valve.
Although the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, which are only illustrative and not restrictive, and those skilled in the art can make many modifications without departing from the spirit of the present invention, which falls within the protection of the present invention.

Claims (8)

1. A pyrolytic carbon mechanical valve leaflet with a two-stage pattern on the surface is characterized in that the surface of the leaflet comprises a primary pattern and a secondary pattern, the primary pattern is a grating-shaped pattern consisting of parallel and alternately arranged bulges and grooves, and the secondary pattern on the surface of the bulge part of the primary pattern presents a cauliflower-shaped particle pattern; the surface of the valve leaf is covered with a low surface energy material layer.
2. The pyrolytic carbon mechanical valve leaflet with a bi-level pattern on the surface as claimed in claim 1, wherein in the grating-like pattern, the width of the protrusion is A, the centerline distance between two adjacent grooves is C, the value range of C is 30-150 μm, and A < C.
3. The pyrolytic carbon mechanical valve leaflet with the surface provided with the two-stage pattern according to claim 1, wherein the particle size of the cauliflower-shaped particles of the two-stage pattern is 5-25 μm.
4. The pyrolytic carbon mechanical valve leaflet with the surface provided with the two-stage pattern according to claim 3, wherein the particle size of the cauliflower-shaped particles of the two-stage pattern is 5-15 μm.
5. The pyrolytic carbon mechanical valve leaflet with a bi-level pattern on the surface as claimed in claim 1, wherein after a layer of low surface energy material is coated on the surface of the leaflet, the static water contact angle on the surface of the leaflet is more than 150 degrees, so that the whole leaflet has a low-adhesion super-hydrophobic characteristic, thereby reducing the detention time of blood on the surface of the leaflet, avoiding the occurrence of turbulence phenomenon, reducing the activation of blood platelets and reducing the probability of thrombosis on the surface of the valve.
6. The method for preparing the pyrolytic carbon mechanical valve leaflet with the surface having the double-stage pattern according to claim 1, comprising the following steps:
step one, pretreatment of a mechanical valve leaflet: cutting a sample into a size required by a valve leaflet by using pyrolytic carbon as a base material and adopting a linear cutting technology, polishing the valve leaflet by using 800#, 2000#, 5000# and 7000# abrasive paper in sequence, then respectively ultrasonically cleaning the valve leaflet by using ethanol and deionized water for 10-20 min in sequence, and then drying the valve leaflet for later use;
step two, preparing a two-stage pattern on the surface of the valve leaf: carrying out laser etching on the surface of the pyrolytic carbon by adopting laser etching, and designing a laser etching pattern into a grating-shaped pattern with parallel stripes, wherein the grating interval is set to be 30-150 mu m; the laser etching parameters are as follows: the laser wavelength is 1064nm, the power is 24-30W, the linear scanning speed is 20-90 mm/s, and the frequency is 20 Hz;
step three, preparing a super-hydrophobic wetting surface: and (3) soaking the pyrolytic carbon mechanical valve leaflet with the surface double-stage pattern prepared in the step two in a low surface energy surfactant solution with the concentration of 0.01mol/L for 0.5-2 h, finally, putting the leaflet into a constant-temperature oven with the temperature of 60-120 ℃ for drying for 1-6 h, and cooling to room temperature to obtain the pyrolytic carbon mechanical valve leaflet with the surface double-stage pattern and the surface static water contact angle of more than 150 degrees.
7. The method for preparing the pyrolytic carbon mechanical valve leaflet with the surface having the bi-level pattern as claimed in claim 6, wherein the laser etching process adopts a region-selective oblique beam processing method.
8. The method for preparing pyrolytic carbon mechanical valve leaflet having bi-level pattern on surface as claimed in claim 6, wherein the low surface energy surfactant comprises (but not limited to) one of perfluorodecyltriethoxysilane, stearic acid, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltrimethoxysilane and tridecafluorooctyltriethoxysilane.
CN202011629411.9A 2020-12-31 2020-12-31 Pyrolytic carbon mechanical valve leaflet with two-stage pattern on surface and preparation method thereof Pending CN112775561A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024140222A1 (en) * 2022-12-30 2024-07-04 深圳市健心医疗科技有限公司 Valve leaflet structure, preparation method for valve leaflet structure, and valve prosthesis

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