CN104043151B - A kind of combined artificial ligament and preparation method thereof - Google Patents

A kind of combined artificial ligament and preparation method thereof Download PDF

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CN104043151B
CN104043151B CN201310082756.0A CN201310082756A CN104043151B CN 104043151 B CN104043151 B CN 104043151B CN 201310082756 A CN201310082756 A CN 201310082756A CN 104043151 B CN104043151 B CN 104043151B
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tow
line
artificial ligament
combined artificial
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CN104043151A (en
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谭荣伟
许孟强
魏欣苗
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SHENZHEN LANDO BIOMATERIALS CO Ltd
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SHENZHEN LANDO BIOMATERIALS CO Ltd
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Abstract

The present invention relates to a kind of combined artificial ligament and preparation method thereof, this combined artificial ligament has club shaped structure, and this club shaped structure is rolled by mesh grid to form; Described establishment net is the network structure be woven into by line, and the line in described club shaped structure tangles and obvolvent mutually, thus forms mesh cross structure; Described line is formed by several tow coilings with different degradation property, described several tow with different degradation property respectively by the component of different degradation property respectively by spinning or spin bundle and formed, thus make the described combined artificial ligament of acquisition have gradient degradation performance.Combined artificial ligament good mechanical properties of the present invention, can promote the attachment of surrounding tissue and the reparation of ligament tissue and normal growth, and constituent part can biodegradation gradually in vivo simultaneously, and does not cause the remarkable decline of ligament mechanical property during degraded.

Description

A kind of combined artificial ligament and preparation method thereof
Technical field
The present invention relates to Implantable Medical Device technical field, particularly relate to a kind of combined artificial ligament and preparation method thereof.
Background technology
The restriction of the blood supply of special due to the biological environment in knee joint in ligamentaum cruciatum, without the ability of normal healing after the fracture of ligamentaum cruciatum body, thus needs to carry out ligament reconstructive.Repair materials comprises autograft, allograft and artificial ligament.Autotransplantation exists not enough for district and supplies the problems such as district's complication, and heteroplastic transplantation exists ligament time delay, immunological rejection, even pathophorous danger.By contrast, artificial ligament has that operation technique is simple, and material source is reliably controlled, does not damage autologous tissue, and the advantage such as post surgery stabilization is good, have in ligament reconstructive reparation and apply widely.
Since occurring from artificial ligament, people once tried out multiple material, and the material being comparatively usually used in manufacturing artificial ligament at present has: the polymer, terylene, polypropylene etc. of the carbon fibre of synthesis, carbon template incorporating collagen or polyester, polytetrafluoroethylene fibre synthesis.But this type of material is often along with some defects: material non-degradable absorbs, the wearing and tearing bits of artificial ligament can cause iatrogenic arthrosis; Biocompatibility is bad, and ligament superficial cell and tissue cannot normal growths, easily cause foreign material repulsion to react; Artificial material hardness is high, aperiodicity relaxation, fatiguability and fractureing; With joint motion ligament in IA creep, artificial ligament can permanently be elongated, thus causes kneed instability.In addition, although part artificial ligament has mesh, peripheral cell and tissue can be grown into wherein, but before artificial ligament does not rupture, artificial ligament mesh of growing into organize the stimulation that can be subject to normal stress never, can not become normal ligament tissue, once artificial ligament fracture, will find, organizing of mesh of growing into is very soft, elasticity is too large, the function of anterior cruciate ligament can not be maintained.These defects result in artificial ligament can not the problem of life-time service.The artificial ligament that the invention of current artificial ligament provides mostly is banded or tubulose, although these two kinds of structure structures are simple, mechanical property and degradation property are often difficult to the requirement meeting ligament.
Summary of the invention
The technical problem to be solved in the present invention is: provide a kind of good mechanical properties, the attachment of surrounding tissue and the reparation of ligament tissue and normal growth can be promoted, simultaneously constituent part can biodegradation gradually in vivo, and does not cause the combined artificial ligament of the remarkable decline of ligament mechanical property during degraded.
The another technical problem that the present invention will solve is: the preparation method providing a kind of combined artificial ligament.
For solving the problems of the technologies described above, the technical scheme that the present invention takes is: a kind of combined artificial ligament, and it has club shaped structure, and this club shaped structure is rolled by mesh grid to form; Described establishment net is the network structure be woven into by line; Described line is formed by several tow coilings with different degradation property, described several tow with different degradation property respectively by the component of different degradation property respectively by spinning or spin bundle and formed, thus make the described combined artificial ligament of acquisition have gradient degradation performance.
Further, having described in several tow of different degradation property has at least a kind of tow relatively not degrade; And other tow degradation speed is different; Described tow of not degrading is positioned at the inner core of described line, and degradable tow cross winding is on described inner core.
Further, the line in described club shaped structure tangles and obvolvent mutually, thus forms mesh cross structure; The diameter range of described club shaped structure is 6 ~ 15mm; The mesh diameter scope of described mesh grid is 150 ~ 300 μm, and the thickness of net is 0.2 ~ 2mm; .
Further, the component of described different degradation property is three kinds of components; Wherein component one is selected from the one in collagen, polyglycolic acid, polylactide and its copolymer; Component two is selected from the one in poly-(6-caprolactone), poly-β-hybroxybutyric acid, chitin, fibroin albumen; Component three is selected from the one in polyethylene terephthalate, ultra-high molecular weight polyethylene.
Further, described three kinds of components are corresponding respectively forms tow one, tow two and tow three; Tow three is inner core silk, and tow one and tow two spiral are wrapped in the length direction of interior tow three across thus form described line.
Further, the number that described line comprises tow is 3 ~ 30; Number ratio between three kinds of tow that described three components is formed respectively is 1:1 ~ 1.5:1 ~ 2; Filament diameter in described tow is 1 ~ 20 μm; The intrafascicular silk number comprised of single synnema is 1 ~ 20.
Technical scheme of the present invention comprises further: a kind of method preparing described combined artificial ligament, comprises the following steps:
A, spinning: by the spinning or spin bundle and obtain the tow with different degradation property respectively of the component with different degradation property;
B, line processed: the tow with different degradation property is turned to line;
C, knitmesh: line is woven into network structure by lapper;
D, one-tenth rod: the network structure obtained by step c is rolled into the club shaped structure with certain diameter, adopt nonwoven needling technique that the line in club shaped structure is tangled and obvolvent mutually, form mesh cross structure.
Further, in described step a, be by the spinning or spin bundle respectively of degradable component one, component two and nondegradable component three; Degradable component adopts the preparation method of operation suture thread carry out spinning or spin bundle, and by nondegradable component by the method spinning of melt spinning or spin bundle.
Further, described component one is selected from the one in collagen, polyglycolic acid, polylactide and its copolymer; Component two is selected from the one in poly-(6-caprolactone), poly-β-hybroxybutyric acid, chitin, fibroin albumen; Component three is selected from the one in polyethylene terephthalate, ultra-high molecular weight polyethylene; Described step b is by the number ratio line of three kinds of component tow in 1:1 ~ 1.5:1 ~ 2; Described line is with component three tow for inner core, is mutually wrapped on inner core with component one and component two tow and forms line along the enterprising conduct in length of inner core direction to cross winding.
Further, the filament diameter that the component spinning described in step a obtains is 1 ~ 50 μm, and the silk number that single synnema bundle comprises is 1 ~ 20; The number range that line described in step b comprises tow is 3 ~ 30; The mesh diameter scope of the mesh grid obtained in step c is 150 ~ 300 μm, and the thickness of net is 0.2 ~ 2mm; In steps d, the diameter range of club shaped structure is 6 ~ 15mm.
Technical scheme of the present invention has the following advantages:
Combined artificial ligament of the present invention, its one-tenth having different degradation property by several is grouped into, and forms gradient degradation, solves artificial ligament non-degradable in the past and absorbs or too fast defect of degrading, promote the attachment of peripheral cell and the growth of ligament tissue; Gradient degradation can effectively prevent artificial ligament mechanical property in degradation process from significantly declining simultaneously, and its degraded opisthodetic ligament main component is newborn ligament tissue, and newborn ligament is subject to normal stress to stimulate and normal growth and growth, finally replaces artificial ligament;
Particularly, the performance of combined artificial ligament of the present invention mainly contains two aspects: (1) degradation property: show as gradient degradation, and the component one degradable time is 30 ~ 70 days, and the component two degradable time is 90 ~ 180 days, component three is not degraded, and concrete advantage sees above face; (2) mechanical property: can bear the pulling force limit is 2000 ~ 3000N.
In preparation method of the present invention, be by several components successively by spinning or spin bundle, be combined into line, be woven into net, net volume is become bar-shaped and with nonwoven needling technique reinforce form, even if like this in degradation process, the structure of product still keeps netted, mesh becomes large gradually, is more applicable to the attachment of surrounding tissue and the reparation of ligament tissue and growth.
Accompanying drawing explanation
Fig. 1 is the axonometric chart of embodiment of the present invention combined artificial ligament.
Fig. 2 is the expansion schematic diagram of mesh grid described in embodiment of the present invention combined artificial ligament.
Fig. 3 is the structural representation of line described in embodiment of the present invention combined artificial ligament.
Detailed description of the invention
The present invention is further illustrated for following specific embodiment, and following examples only for illustration of the present invention, and are not used in restriction scope of the present invention.
Combined artificial ligament of the present invention is a kind of combined artificial ligament of half degradability, its good mechanical properties, can promote the attachment of surrounding tissue and the reparation of ligament tissue and normal growth.The one-tenth that this combined artificial ligament has different degradation property by several is grouped into, thus forms gradient degradation, solves artificial ligament non-degradable in the past and absorbs or too fast defect of degrading, promote the attachment of peripheral cell and the growth of ligament tissue; Gradient degradation can effectively prevent artificial ligament mechanical property in degradation process from significantly declining simultaneously, and its degraded opisthodetic ligament main component is newborn ligament tissue, and newborn ligament is subject to normal stress to stimulate and normal growth and growth, finally replaces artificial ligament;
Please refer to Fig. 1-2, half degraded combined artificial ligament of the present invention is club shaped structure 100, and the diameter range of described club shaped structure is 6 ~ 15mm; It is rolled by a mesh grid 1 and forms, and described establishment net 1 is the network structure be woven into by line 10, and the line in described club shaped structure tangles and obvolvent mutually, forms mesh cross structure.
The mesh diameter scope of described mesh grid 1 is 150 ~ 300 μm, and the thickness of net is 0.2 ~ 2mm.
Described line 10 is formed by the tow coiling with different degradation property, thus give the gradient degradation performance of combined artificial ligament of the present invention.Preferably, wherein have at least a tow relatively not degrade, thus give half degradability of combined artificial ligament.
Please refer to Fig. 3, in the present embodiment, line 10 is wrapped in tow 11 on interior tow 13 and tow 12 with comprising interior tow 13 and cross-helicity.The length direction that described tow 11 and tow 12 radial direction are wrapped in interior tow 13 forms described line 10.The number that described line 10 comprises tow is 3 ~ 30, and the number ratio wherein between tow 11, tow 12, tow 13 is 1:1 ~ 1.5:1 ~ 2.
Described tow 11, tow 12, tow 13 are respectively by having the component one of different degradation property, component two and component three by spinning or spin bundle and formed.The filament diameter of the tow 11 that component one, component two and component three obtain, tow 12, tow 13 is 1 ~ 20 μm, and the silk number that Dan Shu comprises is 1 ~ 20.
Wherein said component one is selected from the one in collagen, polyglycolic acid, polylactide and its copolymer.Component two is selected from the one in poly-(6-caprolactone), poly-β-hybroxybutyric acid, chitin, fibroin albumen.Component three is selected from the one in polyethylene terephthalate, ultra-high molecular weight polyethylene.Three kinds of components have different degradation property, the degradation property of the combined artificial ligament therefore obtained shows as gradient degradation: the time that wherein component one is degradable is 30-70 days, component two degradable time is 90-180 days, and component three in vivo general non-degradable absorbs.The performance objective that combined artificial ligament of the present invention is intended reaching is: because the degradation property of each component is different, described artificial ligament is in human body, first showing as component one first degrades completely, the line of component two and component three almost keeps complete structure, on the one hand the degraded of component one forms the position that micropore is conducive to growing into of peripheral cell and ligament tissue and alternative compositions one, and the line of component two and component three still exists the mechanical property can maintaining artificial ligament on the other hand; In 90 ~ 180 days, also degraded is complete substantially for the line of component two, the continued growth of synkaingenesis ligament, now, the mechanics load-bearing of artificial ligament also stimulates normal growth along with newborn ligament is subject to normal stress and is maintained by newborn ligament, and the existence of component three line is also that newborn ligament is too early stressedly ruptures in order to prevent individual variation from causing.In addition, component three finally also can be sponged by macrophage because of fatigue fracture along with it gradually.
Further, the invention provides a kind of bar-shaped ligament, its stable mechanical property, can bear the pulling force limit is 2000-3000N, and the line forming this bar-shaped ligament is for inner core with component three, component one and component two cross winding, instead of take three conventional lines to mix side by side or mutually synthetic thread, its object is to: in the degraded of artificial ligament and the overall process generated gradually of newborn ligament, mainly stressed still component three, with the line of component three for inner core, it is the structure of artificial ligament structural relaxation in order to cause after preventing other two kinds of component degradations and prolongation, in addition, the degrading texture that such structure causes is degraded in pore-forming, and the hole of formation is increasing, is conducive to the surface adhesion of peripheral cell and tissue and penetrates into artificial ligament inside configuration.
In preparation method of the present invention, be by several components successively by spinning or spin bundle, be combined into line, be woven into net, net volume is become bar-shaped and with nonwoven needling technique reinforce form, even if like this in degradation process, the structure of product still keeps netted, mesh becomes large gradually, is more applicable to the attachment of surrounding tissue and the reparation of ligament tissue and growth.
Half degraded combined artificial ligament of the present invention is by spinning or spin bundle, be combined into line, be woven into net, net volume become bar-shaped and forms with the reinforcing of nonwoven needling technique by three kinds of components one with different degradation property, component two and components three.Combined artificial ligament of the present invention, its preparation method is specific as follows:
A, spinning: carry out Si Si with the component with different degradation property or spin bundle, can be retained to a rare component and not degrade;
B, line processed: the tow obtained by step a carries out turning to line, the tow of composition of keeping not degrading is positioned at inner core, and the tow cross winding of other component is on inner core;
C, knitmesh: line is woven into network structure by lapper;
D, one-tenth rod: the network structure obtained by step c is rolled into the club shaped structure with certain diameter, adopt nonwoven needling technique that the line in club shaped structure is tangled and obvolvent mutually, form mesh cross structure; Thus obtain the bar-shaped combined artificial ligament of partly degrading with gradient degradation performance and good mechanical property.
Wherein about step a, be that aforementioned for selection three components is carried out spinning in the present embodiment, wherein component one and component two adopt the preparation method of operation suture thread carry out spinning or spin bundle, and component threeway is crossed the method spinning of melt spinning or spun bundle.Specifically different according to three kinds of components functions, carrys out spinning by the preparation method of degradable component one and component dual-purpose operation suture thread or spins bundle, and non-degradable, the component three that is mainly used in meeting with stresses are adopted the mode spinning of melt spinning or spin bundle.Selecting mode spinning or the spinning of melt spinning, its objective is the tow in order to obtain high-tensile, mechanical property stable homogeneous.Spinning mode generally has dry spinning, wet spinning, electrostatic spinning and melt spinning etc., the principle of former three spinning process is all quantitatively extruded from spinneret orifice by polymer spinning solution, again through the process filamentation of desolventizing, the volatilization of solvent must cause a microstructure to be rendered as loose structure, thus causing the mechanical property spinning the silk each point come inconsistent, intensity is also not suitable for the requirement of artificial ligament.And the principle of melt spinning is after being extruded from spinneret orifice by polymer melt, cool filamentation in atmosphere, once just there is very strong tensile strength after solidification, meet the high-tensile requirement of artificial ligament.The filament diameter that described component one, component two and component three obtain is 1 ~ 50 μm, and the silk number that single synnema bundle comprises is 1 ~ 20.
By the number ratio line of three kinds of component tow in 1:1 ~ 1.5:1 ~ 2 in step b, described line is for inner core with component three tow.Preferably, be wound around with component one and component two tow along the enterprising conduct in length of inner core direction to cross-helicity thus be mutually wrapped on inner core and form line.The number range that described line comprises tow is 3 ~ 30.Certainly, other canoe also can be suitable for.
The mesh diameter scope of the mesh grid obtained in step c is 150 ~ 300 μm, and the thickness of net is 0.2 ~ 2mm.
In steps d, the diameter range of club shaped structure is 6 ~ 15mm.
Below enumerate concrete experiment so that combined artificial ligament of the present invention and preparation method thereof to be described, it is the present invention as an example only, and is not used in restriction scope of the present invention.
embodiment 1
Select collagen and poly-(6-caprolactone) two kinds of raw materials, the preparation method of operation suture thread is adopted to be spun into thread or pencil respectively, polyethylene terephthalate is selected to adopt the method for melt spinning to be spun into thread or pencil, wherein filament diameter is 1 ~ 50 μm, and the silk number that Dan Shu comprises is 1 ~ 20.
By the number ratio of three kinds of component tow in 1:1:1, prepare with component three tow for inner core, the line that component one and component two tow are mutually wound around on inner core, by lapper, line is woven into network structure, mesh diameter scope is 150 ~ 300 μm, finally network structure is rolled into the club shaped structure with 6mm, adopts nonwoven needling technique that the line in club shaped structure is tangled and obvolvent mutually, form mesh cross structure.
The artificial ligament initial tensile strength that said method obtains can reach 2000 ~ 3000N, external degradation experiment finds, first time is degradable is that component one is complete degraded in 30-50 days, second time is degradable is that component two is complete degraded in 100 ~ 130 days, after degraded completely, remaining component three hot strength still has about 1500N.
embodiment 2
Select polyglycolic acid and poly-β-hybroxybutyric acid two kinds of raw materials, the preparation method of operation suture thread is adopted to be spun into thread or pencil respectively, ultra-high molecular weight polyethylene is selected to adopt the method for melt spinning to be spun into thread or pencil, wherein filament diameter is 1 ~ 50 μm, and the silk number that Dan Shu comprises is 1 ~ 20.
By the number ratio of three kinds of component tow in 1:1:2, prepare with component three tow for inner core, the line that component one and component two tow are mutually wound around on inner core, by lapper, line is woven into network structure, mesh diameter scope is 150 ~ 300 μm, finally network structure is rolled into the club shaped structure with 10mm, adopts nonwoven needling technique that the line in club shaped structure is tangled and obvolvent mutually, form mesh cross structure.
The artificial ligament that said method obtains can possess with the similar effect of embodiment 1.
embodiment 3
Select polylactic acid and fibroin albumen two kinds of raw materials, the preparation method of operation suture thread is adopted to be spun into thread or pencil respectively, select polyethylene terephthalate to adopt the method for melt spinning to be spun into thread or pencil, wherein filament diameter is 1 ~ 50 μm, and the silk number that Dan Shu comprises is 1 ~ 20.
By the number ratio of three kinds of component tow in 1:1.5:2, prepare with component three tow for inner core, the line that component one and component two tow are mutually wound around on inner core, by lapper, line is woven into network structure, mesh diameter scope is 150 ~ 300 μm, finally network structure is rolled into the club shaped structure with 12mm, adopts nonwoven needling technique that the line in club shaped structure is tangled and obvolvent mutually, form mesh cross structure.
The artificial ligament that said method obtains can possess with the similar effect of embodiment 1.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is limited by claims and equivalency range thereof.

Claims (10)

1. a combined artificial ligament, is characterized in that: it has club shaped structure, and this club shaped structure is rolled by mesh grid to form; Described mesh grid is the network structure be woven into by line; Described line is formed by several tow coilings with different degradation property, described several tow with different degradation property respectively by the component of different degradation property respectively by spinning or spin bundle and formed, thus make the described combined artificial ligament of acquisition have gradient degradation performance; Described have in several tow of different degradation property have at least a kind of tow relatively not degrade; And other tow degradation speed is different; Tow of relatively not degrading is positioned at the inner core of described line, and degradable tow cross winding is on described inner core.
2. combined artificial ligament as claimed in claim 1, is characterized in that: described line is wrapped in tow one on the length direction of interior tow three and tow two with comprising interior tow three and cross-helicity; Described tow one, tow two, tow three are respectively by having the component one of different degradation property, component two and component three by spinning or spin bundle and formed; The time that wherein component one is degradable is 30-70 days, and component two degradable time is 90-180 days, and component three in vivo non-degradable absorbs.
3. combined artificial ligament as claimed in claim 2, is characterized in that: the line in described club shaped structure tangles and obvolvent mutually, thus forms mesh cross structure; The diameter range of described club shaped structure is 6 ~ 15mm; The mesh diameter scope of described mesh grid is 150 ~ 300 μm, and the thickness of net is 0.2 ~ 2mm.
4. combined artificial ligament as claimed in claim 2, is characterized in that: wherein component one is selected from the one in collagen, polyglycolic acid, polylactide and its copolymer; Component two is selected from the one in poly-(6-caprolactone), poly-β-hybroxybutyric acid, chitin, fibroin albumen; Component three is selected from the one in polyethylene terephthalate, ultra-high molecular weight polyethylene.
5. combined artificial ligament as claimed in claim 2, is characterized in that: it is 2000-3000N that described combined artificial ligament bears the pulling force limit; Artificial ligament component one in human body is first degraded and is fully formed micropore; In 90 ~ 180 days, completely, component three line exists in the line degraded of component two; The last fatigue fracture of described component three and being sponged by macrophage gradually; The degrading texture of described club shaped structure is degraded in pore-forming; Described net volume becomes bar-shaped and reinforces with nonwoven needling technique to form described combined artificial ligament, and the structure in described combined artificial ligament degradation process keeps netted, and mesh becomes large gradually.
6. combined artificial ligament as claimed in claim 4, is characterized in that: the number that described line comprises tow is 3 ~ 30; Number ratio between three kinds of tow that three kinds of components are formed respectively is 1:1 ~ 1.5:1 ~ 2; Filament diameter in described tow is 1 ~ 20 μm; The intrafascicular silk number comprised of single synnema is 1 ~ 20.
7. prepare a method for combined artificial ligament according to any one of claim 1 ~ 6, comprise the following steps:
A, spinning: by the spinning or spin bundle and obtain the tow with different degradation property respectively of the component with different degradation property;
B, line processed: the tow with different degradation property is turned to line;
C, knitmesh: line is woven into network structure by lapper;
D, one-tenth rod: the network structure obtained by step c is rolled into the club shaped structure with certain diameter, adopt nonwoven needling technique that the line in club shaped structure is tangled and obvolvent mutually, form mesh cross structure.
8. the preparation method of combined artificial ligament as claimed in claim 7, is characterized in that: in described step a, is by the spinning or spin bundle respectively of degradable component one, component two and nondegradable component three; Degradable component adopts the preparation method of operation suture thread carry out spinning or spin bundle, and by nondegradable component by the method spinning of melt spinning or spin bundle.
9. the preparation method of combined artificial ligament as claimed in claim 8, is characterized in that: described component one is selected from the one in collagen, polyglycolic acid, polylactide and its copolymer; Component two is selected from the one in poly-(6-caprolactone), poly-β-hybroxybutyric acid, chitin, fibroin albumen; Component three is selected from the one in polyethylene terephthalate, ultra-high molecular weight polyethylene; Described step b is by the number ratio line of three kinds of component tow in 1:1 ~ 1.5:1 ~ 2; Described line is with component three tow for inner core, is mutually wrapped on inner core with component one and component two tow and forms line along the enterprising conduct in length of inner core direction to cross winding.
10. the preparation method of combined artificial ligament as claimed in claim 7, it is characterized in that: the filament diameter that the component spinning described in step a obtains is 1 ~ 50 μm, the silk number that single synnema bundle comprises is 1 ~ 20; The number range that line described in step b comprises tow is 3 ~ 30; The mesh diameter scope of the mesh grid obtained in step c is 150 ~ 300 μm, and the thickness of net is 0.2 ~ 2mm; In steps d, the diameter range of club shaped structure is 6 ~ 15mm.
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