Low-modulus fatigue-resistant composite hydrogel, method of preparation and use

By combining low-modulus hydrogels with high-strength fabric layers and employing annealing and drying processes, the problems of fatigue resistance and interfacial failure in low-modulus applications of traditional hydrogels were solved, and a low-modulus fatigue-resistant composite hydrogel suitable for artificial heart valve prostheses was prepared.

CN119526843BActive Publication Date: 2026-04-24XI AN JIAOTONG UNIV
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Patent Information

Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
XI AN JIAOTONG UNIV
Filing Date
2024-12-06
Publication Date
2026-04-24

AI Technical Summary

Technical Problem

Existing technologies struggle to provide fatigue-resistant hydrogels for low-modulus applications, and traditional composite hydrogels are prone to interface failure during the swelling process.

Method used

A low-modulus fatigue-resistant composite hydrogel was prepared by combining a low-modulus hydrogel matrix with a high-strength stretchable fabric layer and controlling the interfacial properties through an annealing and drying process to form a strong interfacial synergistic deformation.

Benefits of technology

It achieves low modulus (<1MPa) and high fatigue threshold (>5000J/m2), maintaining integrity under high cycle fatigue, and is suitable for applications such as artificial heart valve prostheses.

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Abstract

The application discloses a kind of low modulus fatigue-resistant composite hydrogel, preparation method and application.The composite hydrogel uses low modulus hydrogel as soft matrix layer, and can be stretched fabric as reinforcing knitted fabric layer;Its preparation method includes, the stretchable fabric is placed in hydrogel pre-polymerization liquid, and is formed three-dimensional polymer network by cyclic freeze-thaw treatment method.Then again put into oven, after drying annealing treatment, form the composite hydrogel after annealing.Last, the composite hydrogel after annealing is immersed in deionized water, until completely swelled, form the composite hydrogel required;The application also discloses the application of the composite hydrogel as artificial heart valve prosthesis.The composite hydrogel of the application has the advantages such as biological tissue stress-strain behavior, low modulus, high fatigue threshold.
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Description

Technical Field

[0001] This invention relates to the field of polymer hydrogel technology, and in particular to a low-modulus anti-fatigue composite hydrogel, its preparation method, and its application. Background Technology

[0002] Hydrogels are high-molecular-weight polymer materials containing a large number of water molecules. With excellent stretchability and biocompatibility, hydrogels have been widely used in recent years in various fields such as flexible sensors, soft robots, bio-adhesives, wearable devices, and artificial tissues. The further development of smart healthcare, flexible electronics, and the robotics industry is inseparable from the development of high-performance hydrogels. The broad prospects of hydrogels in these fields have made the research of high-performance hydrogels a popular research direction in the interdisciplinary field of materials science, mechanics, and biomedicine.

[0003] Despite the development of numerous high-toughness, stretchable hydrogels, their practical application remains challenging. For instance, even with high toughness, hydrogels are prone to fatigue failure under long-term cyclic loading. In recent years, researchers have proposed several fatigue-resistant hydrogel strategies, such as annealing and drying, ice-templating assisted salting-out hydrogels, fiber-reinforced hydrogels, and phase-separated hydrogels. These hydrogels disperse stress concentration at crack tips by introducing hard phase crystals, hard phase fibers, and hard phase separation, thereby increasing the fatigue threshold. However, the introduction of such high-content hard phases leads to an increase in the hydrogel's modulus, making it unsuitable for applications requiring low modulus. Therefore, obtaining a low-modulus fatigue-resistant hydrogel remains a pressing problem. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the purpose of this invention is to provide a low-modulus, fatigue-resistant composite hydrogel, solving the problem that using reinforcing phases in previous methods would simultaneously increase the hydrogel modulus. Another technical problem this invention aims to solve is to provide a method for preparing a low-modulus, fatigue-resistant composite hydrogel, which allows for the control of the fabric-hydrogel matrix interface to form a strong interface, thereby promoting synergistic deformation and ensuring that the composite hydrogel retains both low modulus and a high fatigue threshold value even after swelling equilibrium. A further technical problem this invention aims to solve is to provide applications for the aforementioned low-modulus, fatigue-resistant composite hydrogel.

[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0006] A low-modulus fatigue-resistant composite hydrogel includes a hydrogel-based soft matrix layer and a reinforcing knitted fabric layer covering the hydrogel-based soft matrix layer; the hydrogel-based soft matrix layer is made of low-modulus hydrogel; the reinforcing knitted fabric layer is made of a stretchable fabric woven from high-strength fibers with a curved fiber structure, which can form bridging fibers under cyclic loading to resist fatigue crack propagation.

[0007] The hydrogel-based soft matrix layer has a modulus of less than 1 MPa and a tensile ratio of greater than 2; the reinforcing knitted fabric layer has a strength of greater than 10 MPa and a basis weight of greater than 80 g / cm³. 2 The incomplete filling coefficient is greater than 10; a strong interface is formed between the soft matrix and the knitted fabric, enabling synergistic deformation of the soft matrix and the knitted fabric, effectively improving the fatigue resistance of the hydrogel. The fatigue threshold value of the composite hydrogel is greater than 5000 J / m. 2 Meanwhile, the low initial modulus of the knitted fabric allows the composite hydrogel to maintain a low modulus of less than 1 MPa.

[0008] The method for preparing a low-modulus anti-fatigue composite hydrogel includes the following steps:

[0009] (1) Lay a single or multiple layers of stretchable fabric in the mold;

[0010] (2) Pour the hydrogel precursor liquid into the mold in step (1) and perform freeze-thaw cycle treatment on the entire mold to demold and form a pre-made composite hydrogel.

[0011] (3) Place the pre-made composite hydrogel obtained in step (2) into an oven for annealing and drying to obtain the annealed composite hydrogel;

[0012] (4) Immerse the annealed composite hydrogel obtained in step (3) in the solution until it is fully swollen and balanced; to obtain a low-modulus anti-fatigue composite hydrogel.

[0013] The mold described in step (1) includes two glass plates and a layer of perforated silicone pad, wherein the perforated silicone pad is located between the two glass plates.

[0014] The fibers used in the stretchable fabric in step (1) include any one or more of the following: metal, polyurethane, nylon, Kevlar, polyester, polytetrafluoroethylene, ultra-high molecular weight polyethylene, polyetheretherketone, polysulfone, polyether, polyamide, and polyetherimide; the stretchable fabric structure is any one or more of the following: warp-knitted or weft-knitted plain knit, rib, double rib, and double-sided structure; the diameter of any fiber in the stretchable fabric in step (1) is 10 to 100 micrometers; the laying angle θ between the multiple layers of stretchable fabric laid in the mold in step (1) is 1-360°; the stretchable fabric can be pre-stretched and tensioned to a maximum deformation of 200%.

[0015] The precursor in the hydrogel precursor solution in step (2) includes any one or a combination of at least two of the following compounds: polyvinyl alcohol, polyethylene glycol, acrylamide, acrylic acid, hyaluronic acid, cellulose, sodium alginate, and chitosan; the solvent of the hydrogel precursor solution is any one or more of water, tetrahydrofuran, dimethyl sulfoxide, ethanol, and acetone; and the mass percentage of the precursor in the precursor solution is 1-20%.

[0016] The temperature of the cold source used in the freeze-thaw cycle in step (2) is -80 to -20°C; the freezing time is 6 to 24 hours.

[0017] The temperature for annealing and drying in step (3) is 30-110℃, and the temperature control time is 1-1440 min.

[0018] Step (4) The solution used for swelling is any one or a combination of at least two of the following: deionized water, dimethyl sulfoxide, ethanol, and ionic liquid. The swelling time is 1 to 2880 min, and the temperature of immersion in the solution is 0 to 80 °C.

[0019] The application of the low-modulus fatigue-resistant composite hydrogel involves cutting the composite hydrogel into artificial heart valve leaflets, suturing them onto a metal stent, and assembling them into an artificial heart valve prosthesis. This artificial heart valve prosthesis can smoothly open and close under pulsating flow and withstand 25,000,000 cyclic loads without damage.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] (1) A low-modulus anti-fatigue composite hydrogel of the present invention has a low modulus (<1MPa) and a high fatigue threshold (>5000J / m). 2 The fatigue threshold value is higher than that of hydrogels with the same modulus in the past;

[0022] (2) The method for preparing low-modulus anti-fatigue composite hydrogel of the present invention uses annealing and drying process to regulate the interfacial properties of fiber and matrix, so that the prepared hydrogel has strong interfacial and anti-swelling properties, and the soft matrix and knitted fabric can deform in synergy. The method of the present invention is simple and effective, and solves the problem of interfacial failure under swelling of traditional composite hydrogel.

[0023] (3) The composite hydrogel was used to prepare an artificial heart valve prosthesis, which can open and close well and has a high-cycle fatigue life of more than 25,000,000 cycles, which is not achievable under the existing high-cycle fatigue test of hydrogel. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the mold in Example 1.

[0025] Figure 2 This is a schematic diagram of the multi-layer fabric laying angle in Example 6.

[0026] Figure 3 This is a macroscopic morphology diagram of the composite hydrogel in Example 1.

[0027] Figure 4 This is a microscopic morphology diagram of the composite hydrogel in Example 1.

[0028] Figure 5 This is the uniaxial tensile strain-stress curve of the composite hydrogel in Example 1.

[0029] Figure 6 This is the strain-stress curve diagram of the fracture toughness measurement of the composite hydrogel in Example 1.

[0030] Figure 7 This is a fatigue threshold value diagram of the composite hydrogel in Example 1.

[0031] Figure 8 This is the uniaxial tensile strain-stress curve of the composite hydrogel in Example 2.

[0032] Figure 9 This is the strain-stress curve diagram of the fracture toughness measurement of the composite hydrogel in Example 2.

[0033] Figure 10 This is a fatigue threshold value diagram of the composite hydrogel in Example 2.

[0034] Figure 11 This is an image of the artificial heart valve prosthesis prepared from the composite hydrogel in Example 2.

[0035] Figure 12 This is an image showing the open and closed state of the artificial heart valve prosthesis prepared from the composite hydrogel in Example 2.

[0036] Figure 13 This is a morphological image of the artificial heart valve prosthesis prepared by the composite hydrogel in Example 2 after high-cycle fatigue testing. Detailed Implementation

[0037] The present invention will now be further described with reference to the accompanying drawings. The following examples are for illustrative purposes only and do not limit the scope of protection of the present invention.

[0038] Example 1: A method for preparing a low-modulus anti-fatigue composite hydrogel

[0039] First, a mold was prepared using two glass plates and a 0.2mm perforated silicone pad. A 0.15mm thick plain weave fabric was soaked overnight in a mixed solution containing 90wt% alcohol and 10wt% acetone to remove oil and wax from the fabric surface, and then placed into the mold. A 10% polyvinyl alcohol aqueous solution was poured into the mold containing the fabric. The mixture and mold were placed in a freezer at -20°C for 12 hours, followed by thawing at room temperature for 3 hours. Next, the composite hydrogel was removed from the mold and annealed in a 40°C oven for 2 hours. Finally, the annealed composite material was immersed in deionized water for 24 hours.

[0040] The macroscopic morphology of the fabric provided in Example 1 was characterized using an optical microscope. The structure is as follows: Figure 3 As shown. By Figure 3 It can be seen that it has two main directions.

[0041] The microstructure of the cross-section of the composite hydrogel prepared in Example 1 was characterized using scanning electron microscopy. The results are as follows: Figure 4 As shown. By Figure 4 It can be seen that both interfaces are well-designed.

[0042] The composite hydrogel prepared in Example 1 was subjected to tensile mechanical testing using an electronic universal testing machine. The strain-stress curve is shown below. Figure 5 As shown, by Figure 5 It can be seen that the composite hydrogel has a J-shaped stress-strain curve and anisotropy similar to biological tissue. The testing conditions of the electronic universal testing machine were: room temperature, a mechanical sensor of 100 N, and a tensile speed of 50 mm / min.

[0043] The fracture toughness of the composite hydrogel prepared in Example 1 was tested using an electronic universal testing machine, and its stress-strain curve is shown in the figure. Figure 6 As shown, by Figure 6 It can be seen that the fracture toughness of the composite hydrogel under latitudinal loading is 53 kJ / m. 2 The fracture toughness along the meridional loading direction is 52 kJ / m. 2 The testing conditions for the electronic universal testing machine were as follows: at room temperature, the mechanical sensor was 100N, and the tensile speed was 50mm / min. The fracture toughness test method was as follows: the test specimen was cut into a rectangle 50mm wide and 30mm high. For specimens with pre-cracks, a 20mm pre-crack was introduced into the middle plane. The edges of the specimen were fixed to an acrylic plate, ensuring a gauge height of 10mm. The thickness of each specimen was measured using a micrometer screw before the test. Based on the pre-cracked specimen, the critical fracture tensile ratio λc was determined from the crack propagation initiation point. The fracture toughness G was calculated as follows: Γ=W(λc)×H.

[0044] Where W(λc) is the integral area of ​​the stress-strain curve of the unnotched specimen from 1 to the critical fracture tensile ratio. H is the initial height of the specimen.

[0045] The fatigue resistance of the composite hydrogel provided in Example 1 was tested using an electronic universal testing machine along the two principal directions. The test results are as follows: Figure 7 As shown, by Figure 7 It can be seen that the fatigue threshold value of the composite hydrogel under latitudinal loading is 5173 J / m. 2 The fatigue threshold value along the radial loading direction is 4880 J / m. 2 The testing conditions for the electronic universal testing machine were as follows: room temperature, 100N mechanical sensor, and tensile speed of 50mm / min. The fatigue threshold test method involved cutting the test specimen into rectangles 50mm wide and 30mm high. For specimens with pre-existing cracks, a 20mm pre-crack was introduced into the center plane. The specimen edges were fixed to an acrylic plate, ensuring a gauge height of 10mm. The thickness of each specimen was measured using a micrometer screw before the test. The specimens were immersed in deionized water for testing. During the test, both unnotched specimens and specimens with pre-existing cracks were subjected to cyclic loading at a fixed maximum strain at a loading rate of 10mm / s. For specimens with pre-existing cracks, the loading process was recorded using a video recorder to obtain the relationship between the number of cycles and the crack propagation length. The energy release rate was calculated using the following method:

[0046] G = W(λ) × H,

[0047] Where W(λ) is the integral area of ​​the stress-strain curve of the unnotched specimen from week 1 to the maximum strain λ under loading at week N. H is the initial gauge height of the specimen. If the fiber breaks, N is taken as the week before the breakage. If the fiber does not break and the crack stops, N is taken as the stress-strain curve under loading at week 30,000. The fatigue threshold value of this composite hydrogel exhibits two limits: one is the fatigue threshold value at which the crack does not propagate at all, and the other is the fatigue threshold value at which the crack stops after the fiber has played its role.

[0048] Example 2: A method for preparing a low-modulus anti-fatigue composite hydrogel

[0049] This embodiment provides an anti-fatigue polyvinyl alcohol hydrogel and its preparation method. The only difference between this embodiment and Example 1 is that the polyvinyl alcohol aqueous solution poured into the mold containing the fabric has a mass fraction of 5%.

[0050] Example 3: A method for preparing a low-modulus fatigue-resistant composite hydrogel

[0051] This embodiment provides an anti-fatigue polyvinyl alcohol hydrogel and its preparation method. The only difference between this embodiment and Example 1 is that the polyvinyl alcohol aqueous solution poured into the mold containing the fabric has a mass fraction of 20%.

[0052] Example 4: A method for preparing a low-modulus anti-fatigue composite hydrogel

[0053] This embodiment provides an anti-fatigue polyvinyl alcohol hydrogel and its preparation method. The only difference between this embodiment and Example 1 is that the annealing time in a constant temperature oven at 40°C is 24 hours.

[0054] Example 5: A method for preparing a low-modulus, fatigue-resistant composite hydrogel

[0055] This embodiment provides an anti-fatigue polyvinyl alcohol hydrogel and its preparation method. The only difference between this embodiment and Example 1 is that the annealing temperature in the constant temperature oven is 110°C.

[0056] Example 6: A low-modulus anti-fatigue composite hydrogel, its preparation method, and 6

[0057] First, a mold is prepared using two glass plates and a 0.5mm layer of perforated silicone. Two 0.15mm thick plain weave fabrics are then soaked overnight in a mixed solution containing 90wt% alcohol and 10wt% acetone to remove oil and wax from the fabric surface. The fabrics are then stacked 90° together and placed into the mold. Figure 2 (Diagram showing the angle of multi-layer fabric laying). Then, a 10% (w / w) polyvinyl alcohol aqueous solution is poured into the mold containing the fabric. The mixture and mold are placed in a refrigerator and frozen at -20°C for 12 hours, followed by thawing at room temperature for 3 hours. Next, the composite hydrogel is removed from the mold and annealed in a 40°C oven for 2 hours. Finally, the annealed composite material is immersed in deionized water for 24 hours.

[0058] The composite hydrogel provided in Example 1 was subjected to tensile mechanical testing using an electronic universal testing machine, and its strain-stress curve is shown below. Figure 8 As shown, by Figure 8 It can be seen that the composite hydrogel has a J-shaped stress-strain curve similar to that of biological tissue. The testing conditions of the electronic universal testing machine were: room temperature, a mechanical sensor of 100 N, and a tensile speed of 50 mm / min.

[0059] The fracture toughness of the composite hydrogel provided in Example 1 was tested using an electronic universal testing machine, and its strain-stress curve is shown below. Figure 9 As shown, by Figure 9 It can be seen that the fracture toughness of the composite hydrogel is 50 kJ / m. 2The testing conditions for the electronic universal testing machine were as follows: room temperature, 100N mechanical sensor, and tensile speed of 50mm / min. The fracture toughness test method involved cutting the test specimen into a rectangle 50mm wide and 30mm high. For specimens with pre-existing cracks, a 20mm pre-crack was introduced into the center plane. The specimen edges were fixed to an acrylic plate, ensuring a height of 10mm. The thickness of each specimen was measured using a micrometer screw before the test. Based on the pre-existing crack specimen and the crack propagation initiation point, the critical fracture tensile ratio λc was determined. The fracture toughness G was calculated as follows.

[0060] Γ=W(λc)×H,

[0061] Where W(λc) is the integral area of ​​the stress-strain curve of the unnotched specimen from 1 to the critical fracture tensile ratio. H is the initial height of the specimen.

[0062] The fatigue resistance of the composite hydrogel provided in Example 1 was tested using an electronic universal testing machine. The test results are as follows: Figure 10 As shown, by Figure 10 It can be seen that the fatigue threshold value of the composite hydrogel is 5440 J / m. 2 The testing conditions for the electronic universal testing machine were as follows: room temperature, 100N mechanical sensor, and tensile speed of 50mm / min. The fatigue threshold test method involved cutting the test specimen into rectangles 50mm wide and 30mm high. For specimens with pre-existing cracks, a 20mm pre-crack was introduced into the center plane. The specimen edges were fixed to an acrylic plate, ensuring a gauge height of 10mm. The thickness of each specimen was measured using a micrometer screw before the test. The specimens were immersed in deionized water for testing. During the test, both unnotched specimens and specimens with pre-existing cracks were subjected to cyclic loading at a fixed maximum strain at a loading rate of 10mm / s. For specimens with pre-existing cracks, the loading process was recorded using a video recorder to obtain the relationship between the number of cycles and the crack propagation length. The energy release rate was calculated using the following method:

[0063] G = W(λ) × H,

[0064] Where W(λ) is the integral area of ​​the stress-strain curve of the unnotched specimen from week 1 to the maximum strain λ under loading at week N. H is the initial gauge height of the specimen. If the fiber breaks, N is taken as the week before the breakage. If the fiber does not break and the crack stops, N is taken as the stress-strain curve under loading at week 30,000. The fatigue threshold value of this composite hydrogel exhibits two limits: one is the fatigue threshold value at which the crack does not propagate at all, and the other is the fatigue threshold value at which the crack stops after the fiber has played its role.

[0065] Example 7: A method for preparing a low-modulus anti-fatigue composite hydrogel 7

[0066] This embodiment provides an anti-fatigue polyvinyl alcohol hydrogel and its preparation method. The only difference between this embodiment and Embodiment 1 is that the number of fabric layers laid in the mold is 12, the laying angle is 30°, and other conditions are the same as in Embodiment 1.

[0067] Example 8: A method for preparing a low-modulus anti-fatigue composite hydrogel for in vitro fatigue testing of artificial heart valve prostheses.

[0068] The composite hydrogel was sutured onto a stainless steel scaffold, resulting in... Figure 11 The artificial heart valve prosthesis shown. Figure 12 This image shows the opening and closing state of the composite hydrogel under pulsating flow. Its low modulus properties allow the artificial heart valve prosthesis made from the composite hydrogel to exhibit excellent opening and closing morphology. The artificial heart valve prosthesis, composed of the composite hydrogel and a metal stent, was mounted on an accelerated wear testing machine and subjected to pulsating flow cycling at a frequency of 15 Hz for in vitro high-cycle fatigue testing. Even after 25,000,000 cycles, the artificial heart valve prosthesis made from the composite hydrogel remained intact. Figure 13 These are scanning electron microscope images after high-cycle fatigue testing. They show that the composite hydrogel did not develop any cracks after ultra-high cycle loading, demonstrating that this low-modulus, fatigue-resistant composite hydrogel has the potential for use in artificial heart valve prostheses.

[0069] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A low-modulus fatigue-resistant composite hydrogel, characterized in that, It includes a hydrogel-based soft matrix layer and a reinforced knitted fabric layer covering the hydrogel-based soft matrix layer; the hydrogel-based soft matrix layer is made of low-modulus hydrogel; the reinforced knitted fabric layer is made of stretchable fabric woven from high-strength fibers with a curved fiber structure, which can form bridging fibers under cyclic loads to resist fatigue crack propagation. The hydrogel-based soft matrix layer has a modulus of less than 1 MPa and a tensile ratio of greater than 2; the reinforcing knitted fabric layer has a strength of greater than 10 MPa and a basis weight of greater than 80 g / cm³. 2 The unfilled coefficient is greater than 10; The soft substrate and knitted fabric form a strong interface, enabling synergistic deformation between them, which effectively improves the fatigue resistance of the hydrogel. The fatigue threshold value of the composite hydrogel is greater than 5000 J / m. 2 Meanwhile, the low initial modulus of the knitted fabric allows the composite hydrogel to maintain a low modulus of less than 1 MPa.

2. The method for preparing a low-modulus anti-fatigue composite hydrogel according to claim 1, characterized in that, Includes the following steps: (1) Lay a single or multiple layers of stretchable fabric in the mold; (2) Pour the hydrogel precursor liquid into the mold in step (1) and perform freeze-thaw cycle treatment on the entire mold to demold and form a pre-made composite hydrogel; (3) Place the pre-made composite hydrogel obtained in step (2) into an oven for annealing and drying to obtain the annealed composite hydrogel; (4) Immerse the annealed composite hydrogel obtained in step (3) in the solution until it is fully swollen and balanced; to obtain a low-modulus anti-fatigue composite hydrogel.

3. The method for preparing a low-modulus anti-fatigue composite hydrogel as described in claim 2, characterized in that... The mold described in step (1) includes two glass plates and a layer of hollow silicone pad, wherein the hollow silicone pad is located between the two glass plates.

4. The method for preparing a low-modulus anti-fatigue composite hydrogel as described in claim 2, characterized in that... The fibers used in the stretchable fabric described in step (1) include any one or more of the following: metal, polyurethane, nylon, Kevlar, polyester, polytetrafluoroethylene, ultra-high molecular weight polyethylene, polyetheretherketone, polysulfone, polyether, polyamide, and polyetherimide; the weave structure of the stretchable fabric is any one or more of the following: warp-knitted or weft-knitted plain knit, rib, double rib, and double-sided weave; the diameter of any fiber in the stretchable fabric described in step (1) is 10-100 micrometers; the laying angle between the multiple layers of stretchable fabric laid in the mold in step (1) is... θ It has a range of 1-360°; stretchable fabrics can be pre-stretched and tensioned to a maximum of 200% deformation.

5. A method for preparing a low-modulus anti-fatigue composite hydrogel as described in claim 2, characterized in that... In step (2), the precursor in the hydrogel precursor solution includes any one or a combination of at least two of polyvinyl alcohol, polyethylene glycol, acrylamide, acrylic acid, hyaluronic acid, cellulose, sodium alginate, and chitosan; the solvent of the hydrogel precursor solution is any one or more of water, tetrahydrofuran, dimethyl sulfoxide, ethanol, and acetone; and the mass percentage of the precursor in the precursor solution is 1-20%.

6. A method for preparing a low-modulus anti-fatigue composite hydrogel as described in claim 2, characterized in that... In step (2), the temperature of the cold source used in the freeze-thaw cycle is -80 to -20°C; the freezing time is 6 to 24 hours.

7. A method for preparing a low-modulus anti-fatigue composite hydrogel as described in claim 2, characterized in that... In step (3), the temperature for annealing and drying is 30~110℃ and the time is 1~1440min.

8. A method for preparing a low-modulus anti-fatigue composite hydrogel as described in claim 2, characterized in that... Step (4) The solution used for swelling is any one or a combination of at least two of the following: deionized water, dimethyl sulfoxide, ethanol, and ionic liquid. The swelling time is 1 to 2880 min, and the temperature of immersion in the solution is 0 to 80°C.

9. The application of the low-modulus anti-fatigue composite hydrogel according to claim 1, characterized in that: The composite hydrogel is cut into artificial heart valve leaflets and sutured onto a metal stent to assemble an artificial heart valve prosthesis. This artificial heart valve prosthesis can open and close smoothly under pulsating flow and withstand 25,000,000 cycles of load without damage.

Citation Information

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