EP3483321A1 - Mailles de fibres à tailles de pores contrôlées - Google Patents

Mailles de fibres à tailles de pores contrôlées Download PDF

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Publication number
EP3483321A1
EP3483321A1 EP17201061.3A EP17201061A EP3483321A1 EP 3483321 A1 EP3483321 A1 EP 3483321A1 EP 17201061 A EP17201061 A EP 17201061A EP 3483321 A1 EP3483321 A1 EP 3483321A1
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EP
European Patent Office
Prior art keywords
fibre
fibres
network
segments
mat
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Withdrawn
Application number
EP17201061.3A
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German (de)
English (en)
Inventor
Sebastian DOMASCHKE
Alexander Ehret
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Eidgenoessische Materialpruefungs und Forschungsanstalt
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Eidgenoessische Materialpruefungs und Forschungsanstalt
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Priority to EP17201061.3A priority Critical patent/EP3483321A1/fr
Priority to PCT/EP2018/080724 priority patent/WO2019092166A1/fr
Priority to EP18800155.6A priority patent/EP3707301A1/fr
Publication of EP3483321A1 publication Critical patent/EP3483321A1/fr
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/4291—Olefin series
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4358—Polyurethanes

Definitions

  • the present invention describes a method for controlling stable pore size, pore shape, overall porosity, mat thickness or mat volume of a random fibre network, comprising a stack of layers of randomly distributed fibres in form of a non-woven mat, with fibre thicknesses distributed around a mean fibre diameter, with a variety of fibre segments between cross-links along the fibres with fibre segment length between cross-links, at which different fibres are fixed, a fibre network, comprising a stack of layers of randomly distributed fibres in form of a non-woven mat, with fibre thickness distributed around a mean fibre diameter, with a multiplicity of fibre segments between cross-links along the fibres with average fibre segment length along the fibre between cross-links, at which different fibres are fixed and the use of such fibre networks.
  • Fibre meshes and related applications are known, e.g., produced by electrospinning, wherein volume, pore size and porosity can be changed.
  • the retention rate, as well as the air and water permeability, as main filter properties, are influenced by the size and distribution of pores within the network of the fibre mesh.
  • the here interesting meshes comprise multiple layers of fibres, stacked in a z-direction.
  • the elastic or elastoplastic fibres are connected at multiple bonding points in a perpendicular x-y plane, building a grid structure in 3D.
  • the fibre-thickness varies in particular between 10nm and 10 ⁇ m, especially if the meshes are produced by electrospinning.
  • Electrospinning presents one preferred manufacturing technique, since it allows creating fibre meshes with fibres and pores of length-scales relevant for a variety of technical applications. Electrospinning is a simple, cost-efficient and versatile method to produce advanced materials consisting of ultrathin fibres from a range of materials. The total thicknesses of the final as-spun (i.e. without further treatment) mats are in the range of 10 ⁇ m to 1 mm. Large scale electrospinning is possible on the meter range as in-plane dimension, however, the in-plane dimension for the proposed applications is in the mm to cm range.
  • Controlled porosity is also an important property of breathable textiles, as larger pore size leads to increased breathability.
  • the quality and success of scaffold structures in tissue engineering are assessed by the cell seeding efficiency and subsequent cell spreading and proliferation in the scaffold. Cell infiltration is facilitated by high and interconnected porosity, and one of the main challenges for electrospun materials in biomedical applications is, indeed, the lack of colonialization due to small pore dimensions.
  • One strategy to obtain larger pores is based on modified, usually noncontinuous collectors.
  • patterned collectors were used by Vaquette & Copper-White and metal wire meshes were applied as collectors.
  • the obtained pore-size is increased with larger space between the steel wires.
  • Coburn et al. [ Coburn, J., et al., Biomimetics of the extracellular matrix: an integrated three-dimensional fiber-hydrogel composite for cartilage tissue engineering. Smart Structures and Systems, 2011. 7(3): p. 213-222 ] spun onto a 9:1 ethanol/water solution, froze and vacuum dried fibres to obtain scaffolds with high porosity.
  • Lee et al. Lee, J.B., et al., Highly porous electrospun nanofibers enhanced by ultrasonication for improved cellular infiltration. Tissue Eng Part A, 2011. 17(21-22): p. 2695-702 ], for example, applied ultrasonication to fibre meshes that were pre-wetted with ethanol and immersed in distilled water.
  • Shim et al. Shim, I.K., et al., Novel three-dimensional scaffolds of poly((L)-lactic acid) microfibers using electrospinning and mechanical expansion: fabrication and bone regeneration. Journal of Biomedical Materials Research Part B-Applied Biomaterials, 2010. 95b(1): p. 150-160 ] applied a metal comb to brush flat PLLA networks into three-dimensional mats with high porosity.
  • sacrificial material Another common possibility to modify the pore size is to add sacrificial material during the spinning process which can be removed afterwards to generate void spaces.
  • NaCl sodium chloride
  • Sacrificial fibres can be added by use of multi-jet electrospinning, which has been studied intensively. Ice as a sacrificial material is used in low-temperature or cryogenic electrospinning techniques. During electrospinning under humidity control onto a cooled mandrel ice crystals form between the depositing fibres, which leave large pores when removed. Simonet et al.
  • Ki et al. [ Ki, C.S., et al., Development of 3-D nanofibrous fibroin scaffold with high porosity by electrospinning: implications for bone regeneration. Biotechnology Letters, 2008. 30(3): p. 405-410 ] combined the use of NaCl as porogen with a dispersion of fibre obtained by spinning into a liquid bath, which was then stabilised and lyophilised to obtain nanofibrous fibroin foams with large pores.
  • Kerr-Phillips et al. Kerr-Phillips, T.E., et al., Electrospun rubber fibre mats with electrochemically controllable pore sizes. Journal of Materials Chemistry B, 2015. 3(20): p. 4249-4258 ] proposed electroactive fibre mats by swelling of rubbery electrospun fibre networks in EDOT, which was polymerized to PEDOT by oxidation. By immersion of the electroactive mats in an electrolyte, the pore size could be modified reversibly by control of the electrical field. Pore size variations of 5% in phosphate buffered saline and 25% in lithium bis-trifluoromethanesulfonimide were shown. The restriction of that method is that the material has to be immersed in an electrolyte and an electric field needs to be applied which complicates its use in most applications.
  • Another method that allows changing the microstructure and, with this, pore size and porosity, is based on the use of shape memory polymers to produce fibres.
  • shape memory polymers to produce fibres.
  • Such networks were suggested as supporting sleeves to stabilize bone-defects for example in WO2014205306 A1 ; the bone defects in these applications were filled by shape memory foams that expand to their programmed shape after heating.
  • the object of the present invention is to create a simplified, cost-efficient method for controlling stable pore size, pore shape, overall porosity, mat thickness or mat volume of a random fibre network, without use of toxic chemicals, ultrasound, brush technique, application of external electric fields, and methods with high energy consumption.
  • the aim was in particular to avoid cost or time-expensive secondary processing techniques.
  • Another problem to be solved was to reach fibre networks with reproducible volume and pore shape, adaptable to different uses, characterized by the features of claims 8 to 11.
  • the disclosed method is based on stretch-expansion of fibrous networks to increase their volume, porosity and pore-size, to adapt the fibrous networks to related applications.
  • the method and related applications apply to a variety of non-woven meshes and fibrous mats produced in various processes, but especially produced by electrospinning.
  • the method proposed here mainly makes use of an auxetic effect that astonishingly occurs in electrospun networks and other fibrous materials with similar aspect ratios between fibre diameter and length of the fibre segments, as length between bonding points of the fibres.
  • auxetic effects as an intrinsic property of such networks has not been reported before.
  • Auxetic behaviour i.e. an expansion of material in a direction perpendicular to the axis of elongation, can be elicited by structuring sheets or layers of a material, including electrospun mats, on a larger scale.
  • scaffolds for tissue engineering and drug release devices could improve or replace other solutions in several applications.
  • the increased volume taken by the stretch-expanded mesh here can be used to occlude a lumen or provide a filter within the lumen to collect solid particles.
  • these operations are performed by occlusion devices and embolic filters, respectively.
  • the former are typically realized by a deployable frame, unfolded by a mechanism, and covered by some sort of thin material layer that acts as an occluding membrane.
  • electrospun meshes are used to provide this function. Embolic filters need to be permeable for blood while retaining particles such as emboli.
  • Fibre meshes and related applications are disclosed that can, e.g., be produced by electrospinning, and for which astonishingly thickness, volume, pore size and porosity can be changed on demand by simple mechanical stimulus.
  • a cross-link is understood as a point where one fibre interacts with one or several other fibres in a way that at least some of the displacement and rotation degrees of freedom of the first fibre are partly or entirely coupled to the degrees of freedom of the other fibres.
  • the fixation may be permanent or temporary for the time at which stretch expansion occurs.
  • the length of the fibre segments between two cross-links is defined by l s .
  • Extension is understood as an increase of length by application of an external loading, such as an applied force or prescribed displacement at the boundaries.
  • Expansion (of the fibre mat) is understood as an increase of thickness and overall volume.
  • the stretch of a fibre mat is defined as the ratio between new and original length of an original fibre mat and an expanded fibre mat, wherein the tensile stretch occurs in direction of elongation.
  • Pore size, volume, porosity and thickness of fibrous networks and non-wovens, made of different materials, can be adapted, wherein the most critical parameter, that characterises stretch expandable fibre networks is the ratio (aspect ratio) between fibre segment length l s , i.e. the length of the fibre segments between two cross-links, and the fibre diameter d.
  • the network In order to obtain a significant increase in total volume of the network, and thereby pore volume and porosity, the network needs to contain fibre segments with an aspect ratio of l s / d ⁇ 5. Due to the fact, that the networks are statistical, there will always be segments with lower ratios, but here the majority of segments have to have a ratio l s / d ⁇ 5.
  • Fig. 1a shows a fibre mesh in original shape, unexpanded shape in a top view in z-direction and two cross-sections. After a stretch-expansion the fibre mat is shaped as depicted in Fig. 1b ) view in z-direction and cross-sections. A network stretched in x-direction is depicted.
  • the thickness d of the fibres is homogeneous, but fibres may also have a distribution in diameter d and change their diameter d slightly, at least when extended.
  • the achievable increase in thickness and volume of an expanded fibre mesh depends on the aspect ratio ls/d.
  • a thickness increase (in z-direction) of at least 40% and a volume increase by at least 50% can be achieved for 10% extension.
  • Fig.1c shows a few example fibres in y-z and x-z cross-sectional views.
  • the buckling of fibres respectively fibre segments in z-direction can be seen, leading to a special distribution of the buckled fibres. Due to the stretch expansion, all fibres stay damagefree. Stretch expansion leaves the network integrity and all fibres undamaged, avoids disruption of crosslinks, breakage of fibres and elicits only marginal changes in fibre diameter and cross section. Due to the buckling of the fibre segments of different fibre layers, the fibre density decreases from a fibrous network core in -z and +z direction, which is visible for the outermost regions.
  • fibres of an electrospun network are depicted, wherein between two cross-links along a fibre, a fibre segment s is depicted, showing the fibre segment length Is.
  • This fibre segment s lies substantially in the x-y-plane, while the angle ⁇ , between the later extension direction x and fibre segment direction is shown.
  • the buckling leading to a buckled fibre segment bs is shown, while the elongation of the former fibre segment is shown in dotted lines. Therefore it seems clear, that networks with long fibre segments s display substantial volume increase already for remarkably small longitudinal extensions.
  • Fig. 2 shows simulated values of angle ⁇ versus the normalised out-of-plane dimension of the fibres.
  • thermoplastics in general, for example thermoplastic polyolefins, polyurethane or aliphatic polyamides like Nylon.
  • the thickness of the mats before and after stretching differed by a factor of 3-4, as depicted in Figures 4a and 4b .
  • an electrospun PLLA sample was measured.
  • tests on denser types of mats with much lower porosity and consequently lower mean segment lengths Is showed no change in thickness visible by eye.
  • Stretch expandable fibrous materials such as electrospun networks, can be used to fill gaps and longish cavities by placing the unexpanded strip in place and expand it by longitudinal extension ( Fig. 5 ).
  • the strip can either be placed entirely within the lumen of the cavity ( Fig. 5a ) or protrude, so that after expansion, the material is locked within the gap ( Fig. 5b ).
  • Potential biomedical applications are self-locking wound covers or swabs, e.g. to be placed between teeth in dental medicine.
  • the expanded material When placed into a stream and deployed by axial extension, the expanded material might provide a barrier for particles but provides fluid flow through the porous structure (5c). This could be used for embolic filters that collect particles from the blood stream within artery, e.g., during an up-stream surgery.
  • hydrophobicity/-philicity of the fibre material may be used to affect liquid penetration in the latter case, in order to realise occlusion of a vessel in case of a vascular accident.
  • such devices consist of multi-part structures comprising coils, threads and tubes, cf. e.g., EP2575637 , US2015257763 .
  • the porosity increases, and entails an increase of permeability. At a given constant fluid pressure, this leads to higher fluid flux through the fibre mesh ( Fig. 6a ).
  • the fluid has to travel a longer distance to pass the expanded material; this may affect the effective dwell time of the fluid within the network material and may thus be used to control interactions, e.g., if the network material carries catalysts.
  • the increase of porosity and pore size with expansion will affect filter properties.
  • the material's filter efficiency for particles of a certain size can thus be changed by expansion.
  • the filter can be activated/deactivated for all particles ( Fig. 6b ), or its cut-off value can be changed to larger particles ( Fig. 6c ).
  • the possibility to increase porosity on demand might be beneficial for back washing of filters: Temporarily increasing pore size and raising the fluid flux during flow reversal will not only disrupt the filter cake but the higher fluid velocities generally lead to higher pressures and increased shear stress on material clogging the filter.
  • the retention of liquid in a liquid/gas mixture could be controlled by the applied mechanical load, e.g. for applications to breathable textiles.
  • the increase of porosity and pore size with extension will affect the rate by which particles or microcapsules entrapped in the pores will be released.
  • the higher porosity will affect the hydrodynamic conditions in a liquid environment and thus additionally favour the release of particles by hydrodynamic forces.
  • Increased flux through the porous network would also affect the rate by which drugs embedded into the electrospun fibres will be released.
  • volume expansion effect can be made for scaffolds in tissue engineering applications, where low porosity and small pore sizes are a main restriction for cellular infiltration and propagation into electrospun networks.
  • this method allows to transform standard electrospun mats (with segment-to-diameter ratios in an appropriate range) into more three-dimensional structures with larger pores.
  • the increase of porosity may lead to a higher uptake of liquid.
  • the on-demand activation of this property by expansion allows a dense packing of the absorbent material, e.g. for transport purposes.
  • the proposed method to change pore size, pore shape and overall volume of fibrous meshes on demand requires an extension of the fibre mesh in one direction that leads to a decrease of the lateral in-plane dimension and thus causes buckling of fibre segments.
  • Preferred materials of the fibres are biodegradable and bioactive thermoplastic aliphatic polyester like Poly-L-Lactid (PLLA), Poly-D-Lactid (PDLA) or Poly-(L-co-D/L-Lactid) (PLDLLA).
  • PLLA Poly-L-Lactid
  • PDLA Poly-D-Lactid
  • PLDLLA Poly-(L-co-D/L-Lactid)
  • Spinning is a manufacturing process for creating polymer fibres. It is a specialized form of extrusion that uses a spinneret to form multiple continuous filaments. There are many types of spinning: wet, dry, dry jet-wet, melt, gel, and electrospinning. Electrospinning uses an electrical charge to draw very fine (typically on the micro or nano scale) fibres from a liquid - either a polymer solution or a polymer melt. Electrospinning shares characteristics of both electrospraying and conventional solution dry spinning of fibres. The process does not require the use of coagulation chemistry or high temperatures to produce solid threads from solution. This makes the process particularly suited to the production of fibres using large and complex molecules. Melt electrospinning is also practiced; this method ensures that no solvent can be carried over into the final product.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonwoven Fabrics (AREA)
  • Materials For Medical Uses (AREA)
EP17201061.3A 2017-11-10 2017-11-10 Mailles de fibres à tailles de pores contrôlées Withdrawn EP3483321A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP17201061.3A EP3483321A1 (fr) 2017-11-10 2017-11-10 Mailles de fibres à tailles de pores contrôlées
PCT/EP2018/080724 WO2019092166A1 (fr) 2017-11-10 2018-11-09 Mailles de fibres ayant des tailles de pores contrôlées
EP18800155.6A EP3707301A1 (fr) 2017-11-10 2018-11-09 Mailles de fibres ayant des tailles de pores contrôlées

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP17201061.3A EP3483321A1 (fr) 2017-11-10 2017-11-10 Mailles de fibres à tailles de pores contrôlées

Publications (1)

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EP3483321A1 true EP3483321A1 (fr) 2019-05-15

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EP18800155.6A Withdrawn EP3707301A1 (fr) 2017-11-10 2018-11-09 Mailles de fibres ayant des tailles de pores contrôlées

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WO (1) WO2019092166A1 (fr)

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CN113333750B (zh) * 2021-05-31 2022-08-02 西北有色金属研究院 一种具有三维负泊松比的金属纤维多孔材料的制备工艺
DE102021208606B4 (de) 2021-08-06 2025-02-06 Friedrich-Alexander Universität Erlangen-Nürnberg, Körperschaft des öffentlichen Rechts Verfahren zur Herstellung eines Polymer-Vliesstoffs

Citations (13)

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US20040153118A1 (en) 2003-01-30 2004-08-05 Clubb Thomas L. Embolic filters having multiple layers and controlled pore size
US20040153119A1 (en) 2003-01-30 2004-08-05 Kusleika Richard S. Embolic filters with a distal loop or no loop
US20040153117A1 (en) 2003-01-30 2004-08-05 Clubb Thomas L. Embolic filters with controlled pore size
US20050142331A1 (en) * 2003-12-31 2005-06-30 Kimberly-Clark Worldwide, Inc. Nonwovens having reduced poisson ratio
WO2011153304A1 (fr) 2010-06-02 2011-12-08 Cook Medical Technologies, LLC Dispositif d'occlusion
US20140114266A1 (en) * 2012-10-22 2014-04-24 Ams Research Corporation Ostomy Implant System and Method
GB2514074A (en) * 2011-09-06 2014-11-19 Univ Malta Stents with zero poisson's ratio cells
WO2014205306A1 (fr) 2013-06-20 2014-12-24 Syracuse University Matériaux actionnés à mémoire de forme pour cicatrisation accélérée de blessures orthopédiques
US20150073324A1 (en) * 2013-09-10 2015-03-12 The Procter & Gamble Company Cell forming structures
US20150257763A1 (en) 2014-03-12 2015-09-17 Cook Medical Technologies Llc Occlusion device
AU2015201164B2 (en) * 2009-11-23 2016-06-30 Boston Scientific Scimed, Inc. Patterned implant and method
CN107217390A (zh) * 2017-06-09 2017-09-29 东华大学 一种利用高温熔融静电纺丝法制备拉胀长丝纤维的装置、方法及用途
CN107268185A (zh) * 2017-06-09 2017-10-20 东华大学 一种混合纺丝制备稳定结构柔性拉胀材料的方法

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040153119A1 (en) 2003-01-30 2004-08-05 Kusleika Richard S. Embolic filters with a distal loop or no loop
US20040153117A1 (en) 2003-01-30 2004-08-05 Clubb Thomas L. Embolic filters with controlled pore size
US20040153118A1 (en) 2003-01-30 2004-08-05 Clubb Thomas L. Embolic filters having multiple layers and controlled pore size
US20050142331A1 (en) * 2003-12-31 2005-06-30 Kimberly-Clark Worldwide, Inc. Nonwovens having reduced poisson ratio
AU2015201164B2 (en) * 2009-11-23 2016-06-30 Boston Scientific Scimed, Inc. Patterned implant and method
WO2011153304A1 (fr) 2010-06-02 2011-12-08 Cook Medical Technologies, LLC Dispositif d'occlusion
EP2575637A1 (fr) 2010-06-02 2013-04-10 Cook Medical Technologies LLC Dispositif d'occlusion
GB2514074A (en) * 2011-09-06 2014-11-19 Univ Malta Stents with zero poisson's ratio cells
US20140114266A1 (en) * 2012-10-22 2014-04-24 Ams Research Corporation Ostomy Implant System and Method
WO2014205306A1 (fr) 2013-06-20 2014-12-24 Syracuse University Matériaux actionnés à mémoire de forme pour cicatrisation accélérée de blessures orthopédiques
US20150073324A1 (en) * 2013-09-10 2015-03-12 The Procter & Gamble Company Cell forming structures
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