CN115054410B

CN115054410B - Super-ductility plastic titanium mesh and processing method and application thereof

Info

Publication number: CN115054410B
Application number: CN202210649741.7A
Authority: CN
Inventors: 张学慧; 邓旭亮; 白云洋; 袁慎坡; 王逸君; 孙晓雯
Original assignee: Peking University School of Stomatology
Current assignee: Peking University School of Stomatology
Priority date: 2022-06-09
Filing date: 2022-06-09
Publication date: 2023-03-28
Anticipated expiration: 2042-06-09
Also published as: CN115054410A

Abstract

The invention discloses a super-ductility shapeable titanium mesh and a processing method and application thereof. The super-ductile malleable ductile titanium mesh includes ductile structural units and connecting structural units. Wherein the ductile structural unit comprises a central hole formed by the bracket, a first outer circumferential hole and a second outer circumferential hole, the first outer circumferential hole has a connecting arm, and the connecting arms of the plurality of first outer circumferential holes are closed around the central hole; the connection structure unit includes connection holes formed by the bracket, through which the ductile structure unit is spaced. The ductility of the titanium net is enhanced by regulating and controlling the structural units and the gap patterns of the titanium net, and the super ductility and the plasticity are organically unified. In addition, the super-ductility plastic titanium mesh has good performances in both macroscopic performance and microstructure, provides a suitable three-dimensional space for bone filling material osteogenesis in the bone repair process, and has wide application prospects in the field of implantation repair materials for orthopedics and oral surgery.

Description

Super-ductility plastic titanium mesh and processing method and application thereof

Technical Field

The invention relates to the technical field of implant repair materials for orthopedics and oral surgery, in particular to a super-ductility plastic titanium mesh and a processing method and application thereof.

Background

In oral clinics, a plurality of patients have horizontal or vertical jaw bone defects, especially patients with severe alveolar bone atrophy and absorption caused by long-term tooth loss, trauma, periodontal disease or congenital tooth loss. For implant repair of large-area jaw defects, especially horizontal implant repair with simultaneous vertical bone loss, how to effectively reconstruct alveolar bone height and bone width is a major challenge facing current oral medicine.

Guided Bone Regeneration (GBR) is the most used bone augmentation technique in modern implant surgery. The basic principle is that the barrier membrane is utilized to effectively prevent the soft tissue fiber cells from entering a bone defect area, maintain the defect space and promote the bone defect repair. However, the conventional materials (such as absorbable collagen membrane or non-absorbable PTFE membrane) used as barrier membrane lack self-forming ability and are difficult to provide effective osteogenic space, and may be folded and fall off due to the movement of the labial and buccal muscles after operation, so that the bone grafting material is displaced and absorbed, and the osteogenic effect is affected. The traditional titanium mesh is adopted to repair large-area bone defects clinically at home and abroad, and the titanium mesh has good biocompatibility, certain strength and plasticity and can provide stable osteogenic space. Meanwhile, the titanium mesh can shape the outline of the new bone. As a space support for bone increment, the titanium mesh has good strength, can effectively organize the soft tissue to sink, can bear certain external pressure, and provides space support for the increase of the height and the width of the alveolar bone.

However, the titanium mesh which is commonly used clinically at present is complex in clinical operation, lacks ductility, is not attached to the anatomical morphology of alveolar bone, influences the stability of bone graft and further reduces the effect of guiding bone regeneration. Therefore, the improvement of the ductility and plasticity of the titanium mesh is an important way for solving the problems that the existing titanium mesh is poor in form fit with the jaw bone and cannot ensure good bone regeneration support, and the like, and is also an urgent need for clinically meeting the GBR of the large-range bone defects in the oral cavity at present.

At present, a technology for designing and preparing a personalized titanium mesh by using a three-dimensional printing technology is available, although the technology can accurately print the outline of a titanium mesh main body according to the optimal repairing effect after alveolar bone reconstruction, the technology has bone defect form dependence, does not have universality, has high requirements on titanium mesh preparation, is complex and tedious in process, and is difficult to ensure the predictability in the bone regeneration process by taking the optimal effect after repairing reconstruction as outline support, so that the difficulty in retaining and stabilizing an internal bone filling material is caused.

The information in this background is only for the purpose of illustrating the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art that is already known to a person skilled in the art.

Disclosure of Invention

The super-ductility plastic titanium mesh can be suitable for complex large-area bone defects, can be more attached to anatomical forms of jawbones (such as alveolar bones), and can be fixed on buccal sides, lingual sides, near centers and far centers, and can resist larger lateral force and vertical force. Specifically, the present invention includes the following.

In a first aspect of the present invention, there is provided a super-ductile titanium mesh comprising a ductile structural unit and a connection structural unit, wherein:

the ductile structural unit comprises a central hole formed by a bracket, at least one first peripheral hole and at least one second peripheral hole, wherein the first peripheral hole is internally provided with a connecting arm so as to divide the first peripheral hole into two small holes, the second peripheral hole is not provided with the connecting arm, the first peripheral hole and the second peripheral hole are arranged on the periphery of the central hole in a spaced mode, and the connecting arms are closed around the central hole;

the connection structure unit includes at least one connection hole formed by a stent, and a plurality of the ductile structure units are spaced apart by the connection structure unit.

According to the super-ductility malleable ductile titanium mesh of the present invention, preferably, the ductile structural units and the connection structural units are integrally formed.

According to the super-ductility malleable ductile titanium mesh of the present invention, preferably, the ductile structural units form a fractal self-similar structure, wherein the self-similar structure comprises a biomimetic structural unit comprising a profile having a biomimetic structure derived from any animal or plant, wherein the biomimetic structural unit comprises a fish-type structure.

Also preferably, the ductile structural units form one selected from the group consisting of a triangle, a quadrangle, and an ellipse, or a substantially triangle, quadrangle, and ellipse.

According to the super-ductility malleable ductile titanium mesh of the present invention, preferably, the central hole, the first peripheral hole, the second peripheral hole, and the connection hole have the same or different shapes; or the central hole, the first outer circumferential hole, the second outer circumferential hole and the connecting hole have the same or different sizes.

According to the super-ductility malleable ductile titanium mesh of the present invention, preferably, the central hole, the first outer circumferential hole, the second outer circumferential hole, and the connection hole are each a quadrangle, and the central hole is larger than the first outer circumferential hole, the second outer circumferential hole, or the connection hole.

The super-ductility malleable ductile titanium mesh according to the present invention, preferably, comprises the ductile structural units and the connection structural units arranged at linear intervals in a horizontal direction; or the ductile structural units and the connection structural units are arranged at intervals in the horizontal direction and the vertical direction.

According to the super-malleable ductile titanium mesh of the present invention, preferably, the connection structural unit and the adjacent two ductile structural units constitute a plurality of connection arms to form a radial shape around the center of the connection unit.

According to the super-ductility malleable ductile titanium mesh of the present invention, preferably, when the edge of the super-ductility ductile titanium mesh is the second peripheral hole and/or the connection hole, the second peripheral hole and/or the connection hole are/is an open hole and/or a closed hole, respectively.

In a second aspect of the present invention, a method for processing a malleable ductile titanium mesh is provided, comprising the steps of:

(1) Providing a titanium plate, wherein the titanium plate comprises a pure titanium plate and/or a titanium-based material with good biocompatibility;

(2) Cutting the titanium plate to obtain the super-ductility plastic titanium mesh; and

(3) And cleaning the super-ductility shapeable titanium mesh.

In a third aspect of the present invention, there is provided an electroactive titanium stent composite membrane, preferably comprising the malleable ductile titanium mesh of the first aspect and a membrane material covering the malleable ductile titanium mesh.

In a fourth aspect of the invention, the use of the super-malleable ductile titanium mesh of the first aspect or the composite film of the third aspect in the field of implant repair materials for orthopaedics and oral surgery is provided.

The beneficial effects of the invention include but are not limited to:

(1) The ductility is greatly enhanced by regulating and controlling the structural units and the gap patterns of the titanium mesh, and meanwhile, the exposure risk is reduced.

(2) According to the invention, by regulating and controlling the structural units and the gap patterns of the titanium mesh, the thickness of the titanium mesh is reduced on the basis of ensuring the mechanical strength, and the organic unification of super-ductility and plasticity is realized. The titanium mesh comprises closed cells (C-shaped cells) and radial cells (R-shaped cells), wherein the four corners of the C-shaped cells are closed, so that the parts with large curvature change or the surface curvature changes positively and negatively (namely, the concave-convex change) is facilitated; the four corners of the R-shaped unit are radial, so that the surface stretching or compressing area is favorably attached.

(3) The super-ductility shapeable titanium mesh provided by the invention has good performances on both macroscopic performance and microstructure, and provides a proper three-dimensional space for osteogenesis of a bone filling material in the bone repair process; adopting three-dimensional finite element analysis, wherein the pressure of the titanium mesh is 100kPa-500kPa, and the thickness is 50 μm-200 μm; the maximum displacement of the titanium mesh is 0.1-2.93mm and the average displacement of the surface is 0.1-1.61mm by adopting three-dimensional finite element analysis. In addition, the processing or preparation method of the invention can lead the bone repair material to have good plasticity and the potential for repairing and treating large-scale bone defects.

Drawings

FIG. 1 is a schematic diagram of an exemplary super-ductile malleable ductile titanium mesh construction.

Fig. 2 is a schematic diagram of another exemplary super-ductile titanium mesh structure.

Fig. 3 is a schematic view of another exemplary super-ductile titanium mesh structure.

Fig. 4 is a schematic view of another exemplary super-ductile titanium mesh structure.

Fig. 5 is a schematic illustration of the anisotropic pitch (in mm) of the ductile titanium web.

FIG. 6 shows a repeating array structure formed of ductile structural units and connecting structural units of the present invention.

Fig. 7 is a model of the structural unit design of the ductile ultra-ductile titanium mesh.

Fig. 8 is a graph comparing the stress distribution of the ductile titanium mesh of the present invention with a control (round hole titanium mesh).

Fig. 9 is a comparison of the degree of post-shear deformation of the ductile titanium mesh of the present invention and a control (round-bore titanium mesh).

Fig. 10 shows the results of ductility analysis of the ductile ultra-ductile titanium mesh.

Fig. 11 shows the plasticity results of the super-ductile, ductile titanium mesh in different states of use.

Description of reference numerals:

1-center hole, 2-first peripheral hole, 3-second peripheral hole, 4-connecting arm, 5-connecting hole.

Detailed Description

Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.

It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that the upper and lower limits of the range, and each intervening value therebetween, is specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control. Unless otherwise indicated, "%" is percent by weight.

In the present invention, the titanium stent is composed of a titanium plate of a titanium-based material, and the titanium-based material is not particularly limited as long as it can achieve a desired elastic modulus and a desired bending strength under an ultra-thin thickness condition, but it is preferable to use a pure titanium plate or a titanium plate of a titanium-based material having good biocompatibility. The purity of titanium in the pure titanium plate is generally 99.90% or more, preferably 99.95% or more, and more preferably 99.99% or more. Examples of such pure titanium plates include, but are not limited to, quaternary pure titanium plates, quinary pure titanium plates. Examples of titanium-based plates with good biocompatibility include, but are not limited to, titanium-based alloy materials such as titanium hexa-aluminum tetra-vanadium, titanium zinc alloy, and the like.

In the invention, the term "super-extension" means that the titanium mesh can be deformed to a large extent without damaging the structure under the condition of stretching the plastic titanium mesh.

In the present invention, the term "fractal self-similar structure" means that the geometric shape can be divided into several parts, and each part is (at least approximately) an overall reduced shape, which has self-similar properties. In other words, the smaller part can be enlarged by a suitable ratio to obtain a structure that is almost completely identical to the whole.

In the present invention, the term "biomimetic building block" comprises any animal or plant biomimetic structure, preferably similar or substantially similar to the structure of a part derived from an animal or plant, including any animal and plant occurring in nature. In certain embodiments, the biomimetic structural unit comprises a fish-type (shape) structure. In certain embodiments, the biomimetic structural unit comprises a leaf-shaped structure. It will be appreciated that the malleable structural elements of the invention need not be identical in structure to the parts of animals and plants, and that substantially similar profiles will accomplish the objectives of the invention. Thus, in certain embodiments, the ductile structural units of the present invention form one selected from the group consisting of a triangle, a quadrilateral and an oval, or a substantially triangle, quadrilateral and oval.

As used herein, the term "desired modulus of elasticity" refers to the modulus of elasticity that is effective to bend during bone repair. The modulus is generally in the range of 0.02 to 0.5GPa, preferably 0.05 to 0.4GPa, more preferably 0.05 to 0.35GPa. Here, the elastic modulus was measured by using a universal tester. If the elastic modulus is too small, the repair of the bone defect is not facilitated due to the maintenance of the defect space during tooth implantation repair, and even the postoperative folding collapse is likely to occur, so that the bone regeneration is affected. If the modulus is too high, too high stress is created on the repair part and it is not easy to suture shut.

Herein, the term "desired bending strength" refers to a strength capable of being effectively bent without breaking when bone is repaired. The strength is generally in the range from 10 to 100MPa, preferably from 12 to 80MPa, more preferably from 15 to 50MPa. The bending strength range can provide powerful support and maintain stable space.

As used herein, the term "malleable titanium mesh" refers to an implant material for fixation at a site of a bone defect to repair the same. The thickness of the titanium mesh is generally 50 to 200 μm. The shape of the whole moldable titanium mesh is not particularly limited, and can be any shape, such as a shape which is individually designed according to a specific space to be repaired. In an exemplary embodiment, the malleable titanium mesh has a generally quadrilateral profile including ductile structural elements and connective structural elements, as described in detail below.

Ductile structural unit

In the present invention, the ductile structural unit includes a center hole formed by a stent, at least one first outer circumferential hole having a connecting arm therein to divide the first outer circumferential hole into two small holes, and at least one second outer circumferential hole not having a connecting arm provided therein, and the first outer circumferential hole and the second outer circumferential hole are provided at an outer circumference of the center hole in a spaced manner such that the plurality of connecting arms are closed around the center hole. In some embodiments, the first and second peripheral apertures are each 4 in number, thereby forming a quadrilateral or substantially quadrilateral configuration about the central aperture.

In the present invention, the center hole, the first outer circumferential hole, and the second outer circumferential hole have the same or different shapes, or the center hole, the first outer circumferential hole, and the second outer circumferential hole have the same or different sizes. Preferably, the central aperture has a square configuration with sides of 8-15mm, more preferably 9-14mm, even more preferably 9-13 mm. The first peripheral apertures have a square configuration with a side length of 2 to 8mm, preferably also 3 to 7 mm. In the present invention, the pitch between the holes is 0.1 to 3mm, preferably 0.5 to 2.5mm, still preferably 0.8 to 2mm, and further preferably 0.8 to 1.2mm.

It is understood that the square configuration of the present invention is merely exemplary and that one skilled in the art may modify or deform the shape based on the above design to provide ductile structural units having other shapes, including, but not limited to, for example, triangular, quadrilateral, and elliptical, or substantially one of triangular, quadrilateral, and elliptical.

In some embodiments, the central aperture is larger than the first peripheral aperture, the second peripheral aperture, or the connecting aperture.

Connection structure unit

In the present invention, the connection structural unit includes at least one connection hole formed by the stent, and a plurality of the ductile structural units are connected at intervals through the at least one connection hole, thereby forming a repeating array based on the ductile structural units and the connection structural units. Preferably, the malleable structural element and the connecting structural element are integrally formed.

In the present invention, the connection hole may have the same or different shape as the center hole, the first outer circumferential hole, and the second outer circumferential hole, or the same or different size as the center hole, the first outer circumferential hole, and the second outer circumferential hole. Preferably, the connecting hole is quadrangular or substantially quadrangular.

Super-ductility shapeable titanium mesh

In the present invention, the arrangement of the ductile structural units and the linking structural units is not particularly limited. In some embodiments, the ductile structural units and the connection structural units are linearly spaced in a horizontal direction to form a single column or row of the super ductile malleable ductile titanium mesh, which may have an up-down symmetrical structure and/or a left-right symmetrical structure.

In some embodiments, the ductile structural units and the connection structural units constitute repeating units, and the ductile structural units and the connection structural units are arranged at intervals in the horizontal direction and the vertical direction, thereby forming an array structure. The number of repeating units is not particularly limited, and for example, an array structure may be formed by more than 2 to 80 repeating units, such as 4, 6, 8, 10, 20, 30, 40, 50, 60, 70, 80 repeating units.

In some embodiments, the malleable ductile titanium mesh of the present invention has at least one C-shaped unit in which the plurality of connecting arms of the first plurality of peripheral holes are closed around the central hole and at least one R-shaped unit. In the R-shaped unit, the linking structural unit and the adjacent two ductile structural units constitute a plurality of linking arms to form a radial shape around the center of the linking unit. And the C-shaped unit and the R-shaped unit share at least 2 connecting arms to be closed or radial around the central hole.

In the present invention, when the edges of the ductile titanium mesh are the second peripheral holes and/or the connection holes, the second peripheral holes and/or the connection holes are respectively open holes and/or closed holes. The open holes are that when the holes are positioned at the side of the outline of the whole structure of the super-ductility malleable ductile titanium mesh, the outer sides of the holes are not provided with a support structure, so that an open structure is formed. By closed pore is meant that the pore forms a closed structure.

In addition, the structure of the super-ductility plastic titanium mesh has an inclined supporting structure with a fish-shaped structure, so that the super-ductility plastic titanium mesh is ensured to have higher bending strength. In some embodiments, for example where the first peripheral aperture is square, the connecting arm divides the first peripheral aperture into two apertures, wherein the two perpendicular sides of the apertures extend to form a structure comprising at least a central aperture and the apertures or the first peripheral aperture form a substantially fish-shaped configuration. Analysis shows that the shapeable titanium mesh based on the structure can bear load uniformly and very well, local stress concentration is reduced, and the risk of local damage is solved. The panels and intermediate slashes (connecting arms) support the structure during the repetitive stretching process, providing the necessary strength for the structure, achieving good ductility.

In some embodiments, the titanium stent is optionally surface treated or surface modified, such as dopamine surface modification or titanium mesh surface roughening, and the like. Further preferably, the dopamine surface modification can adopt dopamine to form a dopamine film polymerized on the surface of the titanium mesh by methods such as chemical oxidative polymerization, enzymatic oxidative polymerization, electrochemical polymerization or photopolymerization, so as to improve biocompatibility of the titanium mesh and promote bone formation. And the bonding effect of the titanium mesh and the high polymer material layer is enhanced. As a non-limiting example, the dopamine-treated titanium mesh can be obtained by adding the titanium mesh into 0.01-0.1mol/L dopamine aqueous solution, stirring for 6-12 h at 40-80 ℃, then ultrasonically shaking for 1-15 min, centrifugally washing for 3-5 times, and then ultrasonically treating for 1-10min under the condition that the power is 180W.

In some embodiments, preferably, the surface roughening treatment may be treated using a sand blasting-acid etching method. For example, a titanium mesh is first treated with SiO ₂ The particles were grit blasted under a pressure of 0.4mPa and then treated with 10% H ₂ SO ₄ Acid etching with 10% HCl mixed solution at 60 deg.C for 30min.

Processing method

In a second aspect of the present application, a method of processing a super-ductile titanium mesh is provided, comprising:

(1) Providing a titanium plate, wherein the titanium plate comprises a pure titanium plate and/or a titanium plate with good titanium base biocompatibility;

(3) And cleaning the super-ductility shapeable titanium mesh.

In the present invention, the method of cutting is not particularly limited, and examples thereof include, but are not limited to, at least one of laser cutting, ultraviolet cutting, 3D printing, stamping, water cutting, etching, or precision machining. Laser cutting is preferably used, and the apparatus for laser cutting is not particularly limited, and a laser micro-cutting machine known in the art may be used.

In some embodiments, the titanium plate substrate surface is degreased and dusted, the titanium plate substrate surface is kept smooth, and the titanium plate substrate surface is placed on a sample table to be cut. And then a three-dimensional model file of the ductility structural units and the connecting structural units according to the design. And setting a walking route of the cutting process according to the three-dimensional model file, wherein the walking route forms a specific grid structure formed by the ductility structure units and the connecting structure units, so that the mechanical arm cuts along the edge of the set grid structure. The process parameters during cutting are not particularly limited, such as cutting speed, laser power, gas pressure, defocus amount, working distance, cutting gas, etc., and can be adjusted by those skilled in the art as needed.

In some embodiments, the titanium mesh is ultrasonically cleaned in deionized water, and then placed in an alcohol solvent for cleaning, such as ultrasonically cleaned using absolute ethanol, and dried to obtain the malleable ductile titanium mesh of the present invention.

Use of

In a third aspect of the invention, the use of a super-malleable ductile titanium mesh in the field of orthopedic and oral surgical implant repair materials is provided.

The invention also provides application of the super-ductility plastic titanium mesh in an electroactive titanium stent composite membrane, and preferably, the composite membrane comprises a membrane material coating the super-ductility plastic titanium mesh. The shape of the composite membrane is not particularly limited, and any shape may be designed according to clinical use. In an exemplary embodiment, the composite membrane has a strip shape, and fixing site retention fixing regions are provided corresponding to or near four corners of the strip shape. The composite membrane comprises a titanium support and a membrane material for coating the titanium support.

The film material used in the present invention is a polymer material layer, wherein the polymer material comprises PVDF and its derivatives, collagen or chitosan, preferably PVDF and its derivatives, examples of which include, but are not limited to, polyesters, polyvinylidene fluoride PVDF, polyvinylidene fluoride trifluoroethylene P (VDF-TrFE), polymethyl methacrylate PMMA and polydimethylsiloxane. The high polymer material layers on the two sides of the super-ductility shapeable titanium mesh can be made of the same component or different components. In certain embodiments, the layer of polymeric material may be dense, thereby preventing the passage or migration of bacteria through or from connective tissue cells and epithelial cells. In another embodiment, the layer of polymeric material contains pores that allow oxygen or blood to pass through, but at the same time prevent the passage of bacteria or the migration of connective tissue cells and epithelial cells therethrough. Preferably, the membrane material forms a tight bond with the malleable ductile titanium mesh of the present invention.

The invention further provides a process for the preparation of an electroactive reinforced composite membrane, comprising at least:

(1) Compounding the super-ductility shapeable titanium mesh inside the high polymer material layer so as to form a film structure;

(2) Heating to 105-145 deg.C, preferably 110-130 deg.C, more preferably 120-130 deg.C at a rate of 2.5-4 deg.C/min, maintaining for 30-80 min, preferably 40-70 min, more preferably 60min, and cooling, preferably naturally cooling to room temperature;

(3) And (3) carrying out polarization treatment in a polarization mode, wherein the polarization treatment parameters comprise the polarization field intensity of 0.1-10kV/mm and the polarization time of 10-60min, and thus the electroactive reinforced composite membrane can be obtained.

In step (1), the malleable ductile titanium mesh may be cut into the titanium substrate in a known manner, for example, by a cutting device such as a laser micro-cutting machine. The thickness of the cut titanium substrate is generally 20 to 500. Mu.m, for example 20 to 400. Mu.m, preferably 20 to 200. Mu.m. When using a titanium substrate of higher thickness, the substrate is preferably first subjected to a thinning treatment, such as an etching treatment. The etching process is generally preferred because it roughens the surface of the titanium stent, thereby enhancing the follow-up force on the polymer material layer.

The annealing treatment is carried out in the step (2), and the composite film material is uniformly and stably electrified through the polarization of the annealing auxiliary electrode. The temperature rise of the surface of the composite film material can generate a pyroelectric effect, and the electrode polarization can enable the charge in the material to generate polarization deflection along a certain direction. The reason may be that after heating and cooling, the crystal generates surface charges in a certain direction due to temperature changes, and the polarization dipole moment can change with the direction of the applied electric field.

And (3) polarizing by a high-voltage electric field to enable the surface of the composite membrane to have a bionic potential, and constructing a bionic electrical microenvironment in the damaged area. The polarization conditions include a polarization field strength of 0.1 to 10kV/mm, preferably 1 to 5kV/mm, for example 2V/mm, 3V/mm, 4V/mm; the polarization time is 5-60min, preferably 10-50min, more preferably 15-40min, e.g., 20, 25, 30, 35min, etc.

In a specific embodiment, firstly, oil stains and dust are removed from the surface of the titanium sheet base material, the surface of the titanium sheet base material is kept smooth, and the titanium sheet base material is placed on a sample platform to be cut. A three-dimensional model file of at least the aforementioned ductile building blocks and/or the connecting building block structure is then designed. And setting a traveling route of the cutting process according to the three-dimensional model file, so that the manipulator cuts along the edge of the pre-related structural contour of the dumbbell type, the Chinese character 'mi' type or the glider type. The process parameters for laser cutting are not particularly limited, and may be adjusted by those skilled in the art as needed, for example, cutting speed, laser power, gas pressure, defocus amount, working distance, cutting gas, etc.

The process of forming the film structure is preferably achieved by: weighing a ferroelectric high molecular polymer, adding the ferroelectric high molecular polymer into an organic solvent DMF, and stirring for 3-6 h until the ferroelectric high molecular polymer is completely dissolved to obtain a polymer solution; the concentration of the obtained solution is 1-5g/ml; the ferroelectric high molecular polymer is polyvinylidene fluoride or polyvinylidene fluoride-trifluoroethylene; removing bubbles from the polymer solution in vacuum, pouring the polymer solution on a quartz plate, and drying to obtain a polymer film with the thickness of 10-500 mu m after the organic solvent is completely volatilized; and (3) placing the super-ductility shapeable titanium mesh between two polymer films, dissolving surface layer polymers by using DMF (dimethyl formamide) for example to bond the upper film and the lower film, and performing hot pressing treatment until the two films are fully combined to obtain the composite film material.

Example 1

This embodiment is an exemplary super-ductile malleable ductile titanium mesh that includes two ductile structural units and one connecting unit in between. The ductile structural elements comprise a central hole 1, a first peripheral hole 2 and a second peripheral hole 3 formed by the stent. Each first peripheral hole 2 has a connecting arm 4 therein so as to divide the first peripheral hole 2 into two small holes.

The second peripheral holes 3 are located at the outermost edge of the malleable ductile titanium mesh, which is not provided with the connecting arms 4, thus forming open holes. In the present embodiment, the number of the first outer circumferential holes 2 and the second outer circumferential holes 3 is 4, respectively, and the first outer circumferential holes 2 and the second outer circumferential holes 3 are provided at intervals in the outer periphery of the

center hole

1, and 4 of the 4 first outer circumferential holes are made to be closed around the center hole 1. In a single ductile structural element, the number of first peripheral holes 2 and second peripheral holes 3 is 4 each.

In the present embodiment, the center hole 1, the first outer peripheral hole 2, and the second outer peripheral hole 3 have the same shape, and the center hole 1, the first outer peripheral hole 2, and the second outer peripheral hole 3 have the same size. Preferably, the central hole 1, the first peripheral holes 2 and the second peripheral holes 3 have a square structure with a side length of 1 to 15mm, preferably 2 to 13mm, further preferably 2 to 8 mm. The spacing between the holes (the width of the stent between the holes) is 0.1 to 3mm, preferably 0.5 to 2.5mm, still preferably 0.8 to 2mm, and further preferably 0.8 to 1.2mm.

It is understood that the square configurations described in the embodiments are exemplary only, and one skilled in the art can modify or deform the shapes based on the above designs to obtain ductile structural units having other shapes, including, but not limited to, for example, triangular, quadrilateral, and elliptical, or at least one of substantially triangular, quadrilateral, and elliptical shapes.

The connection structural unit includes a connection hole 5 formed by the bracket. The number of the connecting holes is 3 in the embodiment, the ductility structure units on two sides are connected at intervals through the 3 connecting holes 5 connected in series, and the ductility structure units and the connecting structure units are integrally formed.

The connection hole 5 has the same shape as the center hole 1, the first outer circumferential hole 2, and the second outer circumferential hole 3, and has the same size as the center hole 1, the first outer circumferential hole 2, and the second outer circumferential hole 3. Preferably, the connecting hole 5 is quadrangular or substantially quadrangular, such as square.

The ductility structure unit and the connecting structure unit are linearly arranged at intervals in the horizontal direction, so that the super-ductility malleable titanium mesh extending in the horizontal direction has a structure which is symmetrical left and right in the vertical direction of the connecting structure unit.

In fig. 1, the ductile ultra-ductile titanium mesh has 2C-shaped cells at the left and right sides and an R-shaped cell at the center, and the C-shaped cell and the R-shaped cell at the center share a plurality of connecting arms 4 distributed in a radial shape at the center. In the C-shaped unit, the plurality of connecting arms 4 of the plurality of first peripheral holes 2 are closed around the central hole 1. In the R-shaped unit, a connection structural unit formed of at least one connection hole 5 and two adjacent ductile structural units constitute a plurality of connection arms 4 to take a radial shape around the center of the connection structural unit. In addition, fig. 7 also illustrates a C-type cell having a left side and an R-type cell having a right side. And the left C-shaped cell and the right R-shaped cell share two connecting arms 4 located at one side of the ductile structural unit.

When the edge of the super-ductility ductile titanium mesh is the second peripheral holes 2 and/or the connecting holes 5, the second peripheral holes 2 are open holes and/or closed holes, and the connecting holes 5 are open holes and/or closed holes. The open holes are the holes without a support structure when the connecting holes 5 are positioned at the side of the outline of the whole structure of the super-ductility malleable titanium mesh, thereby forming an open structure. The closed hole is formed by the bracket to form a closed structure.

Example 2

Fig. 2 is another exemplary super-ductile titanium mesh comprising one ductile structural unit and two connection structural units and a portion of the ductile unit connected to the other side of the connection unit (including a partial structure formed by 2 first

peripheral holes

2 and 1 second peripheral hole 3 from the ductile unit side by side).

As shown in fig. 2, the ductile structural unit includes a center hole 1 formed by a bracket, a first outer circumferential hole 2, and a second outer circumferential hole 3, and the first outer circumferential hole 2 has a connection arm 4 therein, thereby dividing the first outer circumferential hole 2 into two small holes.

The second outer circumferential holes 3 are not provided with the link arms 4, and the first outer circumferential holes 2 and the second outer circumferential holes 3 are provided at the outer periphery of the center hole 1 in a spaced manner, and the plurality of link arms 4 are made to be closed around the center hole 1. In a single ductile structural unit, the number of first peripheral holes 2 and second peripheral holes 3 is 4 each, thereby forming a quadrangular or substantially quadrangular structure around the central hole 1.

The connecting structure unit comprises a connecting hole 5 formed by a bracket, the ductile structure units on two sides or parts of the ductile structure units are connected at intervals through the connecting hole 5, and the ductile structure units and the connecting structure units are integrally molded.

In fig. 2, the ductile ultra-ductile titanium mesh has 2C-type cells and 2R-type cells, and the C-type cells and the R-type cells share a plurality of connection arms 4 at the central portion. In the C-shaped unit, the plurality of connecting arms 4 of the plurality of first peripheral holes 2 are closed around the central hole 1. In the R-shaped unit, a connection structural unit formed of at least one connection hole 5 and an adjacent ductile structural unit and a partial structure thereof form a plurality of connection arms 4 to take a radial shape around the center of the connection structural unit.

When the edge of the super-ductility malleable ductile titanium mesh is the second peripheral hole 2 and/or the connection hole 5, the second peripheral hole 2 is an open hole and/or a closed hole, and the connection hole 5 is an open hole and/or a closed hole.

Example 3

Fig. 3 and 4 show an example of a super-ductile titanium mesh. The center hole 1, the first peripheral hole 2, the second peripheral hole 3 and the connecting hole 5 are respectively quadrilateral, and the center hole 1 is larger than the first peripheral hole 2 and the second peripheral hole 3. The super-ductile malleable titanium mesh of fig. 3 includes ductile structural units and connecting structural units arranged at linear intervals in a vertical direction. In fig. 4, the ductile ultra-ductile titanium mesh includes ductile structural units and connection structural units arranged at intervals in the horizontal direction and the vertical direction.

The center hole 1, the first outer circumferential hole 2, and the second outer circumferential hole 3 have different shapes, and the center hole 1, the first outer circumferential hole 2, and the second outer circumferential hole 3 have different sizes. Wherein, the central hole 1 has a square structure with the side length of 8-15mm, preferably 9-14mm, and more preferably 9-13 mm. The first peripheral aperture has a square configuration with sides of 2 to 8mm, preferably also 3 to 7 mm.

The fish-type configuration of the diagonal support structure in the super-ductile titanium mesh structure of the present invention will be more apparent in fig. 3-5. Taking fig. 5 as an example, the first peripheral hole 2 or the small hole located below divided by the connecting arm 4 together with at least the central hole 1 constitutes a fish-shaped structure. The fish-shaped inclined supporting structure ensures that the super-ductility plastic titanium mesh has higher bending strength. Analysis finds that the plastic titanium mesh based on the configuration can bear load uniformly and very well, reduces local stress concentration and solves the risk of local damage. The panels and intermediate slash support structures provide the necessary strength to the structure during the repetitive stretching process, achieving good ductility.

Example 4

Fig. 6 is another exemplary malleable ductile titanium mesh comprising an array of repeating units, wherein the ductile structural units and the connective structural units form repeating units. As shown in fig. 6, the ductile structural units and the connection structural units are arranged at intervals in the horizontal direction and the vertical direction, thereby forming an array structure.

Example 5

This example illustrates the machining method of a ductile super-ductile titanium mesh.

The titanium net is manufactured by adopting an ultraviolet cutting machine or a stamping method, a laser cutting machine or a metal 3D printing technology, a pure titanium plate is flatly fixed on a clamp, cutting is carried out according to a designed three-dimensional grid model file, and as shown in figure 5, the size of a cut pore is as follows: the center hole 1 (C in the figure) is 11mm × 11mm, the first outer peripheral hole 2 (A in the figure) is 5mm × 5mm, the second outer peripheral hole 3 (B in the figure) is 11mm × 5mm, the hole pitch (E in the figure) is 1mm, and the connection hole 5 is 11mm × 11mm.

Ultrasonically cleaning the obtained titanium mesh in deionized water for 3 times, and 5min each time; then putting into absolute ethyl alcohol for ultrasonic cleaning for 3 times, 5min each time. Drying to obtain the super-ductility plastic titanium mesh.

Test example 1

The test example uses a three-dimensional finite element analysis to analyze the titanium mesh uniform distribution pressure, and the result is shown in fig. 8, wherein the titanium mesh uniform distribution pressure is 100kPa, and the thickness is 100 μm. The super-ductility plastic titanium mesh material has good plasticity and ductility. The C-shaped units in the design structure are closed in the form of four-corner units, which is beneficial to the parts with large curvature change or the surface curvature changes positively and negatively (namely concave-convex change). The R-shaped units in the design structure are units with four corners in a radial shape, and the attachment of a surface stretching or compressing area is facilitated. As shown in FIG. 8, the diagonal bracing structure has higher bending strength, the maximum displacement of the round hole design of the comparative titanium mesh is 4.79mm and the average displacement of the plane is 2.45mm under the uniform pressure of 100kPa and the thickness of 100 μm, while the maximum displacement of the super-ductile titanium mesh material of the present invention is 2.93mm and the average displacement of the plane is 1.61mm. Under the condition of the same thickness and stress, the displacement of the super-ductility plastic titanium mesh structure is reduced by 38 percent. The normal displacement caused by the same normal stress, namely the stress vertical to the titanium mesh, namely the vertical movement of the super-ductility titanium mesh is smaller, and the maximum displacement point is the center of the titanium mesh. Under the same stress, the displacement is small, which indicates that the space maintenance capability is strong, and the mucosa can be supported, thereby effectively preventing the soft tissue from collapsing to a certain extent and providing a space for the regeneration of new bones.

Test example 2

The test example tests the plasticity of the super-ductility plastic titanium mesh under complex conditions.

As shown in fig. 9, the fish-based diagonal bracing structure has a self-similar structure, where self-similarity means that the features of a certain structure or process are similar from different spatial or temporal scales, or the local nature or the resident structure of a certain system or structure is similar to the whole, thereby adapting to the use of complex surfaces. After shearing (fracture in the figure), the bending strength does not change significantly. Compared with the round hole structure, the bending strength is greatly reduced because the closed part is changed into the open hole part after being sheared. It can be seen that the deformation of the round hole member exceeds 3mm under the same stress and thickness.

As shown in FIG. 10, the self-similar structure based on the diagonal bracing structure and the R/C units can bear loads uniformly and well, reduce local stress concentration and eliminate the risk of local damage. The panels and intermediate slash support structures provide the necessary strength to the structure during the repetitive stretching process, achieving good ductility. At present, the titanium net/titanium plate for clinical use is mainly used for supporting and fixing, is lack of ductility and plasticity, has large shape difference of bone defects in clinical application, and needs to be shaped according to the bone shape, so that the ductility is favorable for shaping the titanium net. Meanwhile, when the amount of bone regeneration exceeds the expected three-dimensional space, the malleable titanium mesh has less restriction on bone augmentation.

As shown in fig. 11, the super-ductile titanium mesh of the present invention has excellent ductility in its ability to maintain its formed shape when external force is removed after being deformed by external force, and thus can be applied to various clinical repair scenarios including, but not limited to: stomatology, orthopedics, spinal surgery, arthrology, alveolar bone, skull, jaw bone, long bone.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Many modifications and variations may be made to the exemplary embodiments of the present description without departing from the scope or spirit of the present invention. The scope of the claims is to be accorded the broadest interpretation so as to encompass all modifications and equivalent structures and functions.

Claims

1. The utility model provides a super ductility malleable shapeable titanium net, its characterized in that includes ductility constitutional unit and connection constitutional unit, wherein:

2. The malleable ductile titanium mesh according to claim 1, wherein the ductile structural units and the connecting structural units are integrally formed.

3. The malleable ductile titanium mesh according to claim 1, wherein the ductile structural units form a fractal self-similar structure, wherein the self-similar structure comprises a biomimetic structural unit comprising a profile with a biomimetic structure derived from any animal or plant, wherein the biomimetic structural unit comprises a fish-type structure.

4. The malleable ductile titanium mesh according to claim 1, wherein the central hole, the first peripheral hole, the second peripheral hole, and the connection hole have the same or different shapes; or the central hole, the first peripheral hole, the second peripheral hole and the connecting hole have the same or different sizes;

the center hole, the first peripheral hole, the second peripheral hole and the connecting hole are respectively quadrilateral, and the size of the center hole is larger than that of the first peripheral hole, the second peripheral hole or the connecting hole.

5. The super ductile malleable titanium mesh according to claim 1, comprising said ductile structural units and said connection structural units arranged at linear intervals in a horizontal direction; or the ductile structural units and the connection structural units are arranged at intervals in the horizontal direction and the vertical direction.

6. The super ductile malleable titanium mesh according to claim 1, wherein said connecting structure unit and two adjacent ductile structure units constitute a plurality of connecting arms to form a radial shape around the center of the connecting unit.

7. The super-ductile titanium mesh according to claim 1, wherein when the edges of the super-ductile titanium mesh are second peripheral holes and/or connection holes, the second peripheral holes and/or connection holes are each open holes and/or closed holes, respectively.

8. The method of machining a super ductile malleable ductile titanium mesh according to any of claims 1-7, comprising the steps of:

(3) And cleaning the super-ductility shapeable titanium mesh.

9. An electroactive titanium stent composite membrane comprising the ductile ultra-ductile titanium mesh of any one of claims 1 to 7 and a membrane material covering the ductile ultra-ductile titanium mesh.

10. Use of the super-ductile malleable ductile titanium mesh according to any one of claims 1-7 for the preparation of implant repair materials for orthopaedics and oral surgery.