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WO1991001210A1 - Materiaux polymeres - Google Patents

Materiaux polymeres Download PDF

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Publication number
WO1991001210A1
WO1991001210A1 PCT/GB1990/001081 GB9001081W WO9101210A1 WO 1991001210 A1 WO1991001210 A1 WO 1991001210A1 GB 9001081 W GB9001081 W GB 9001081W WO 9101210 A1 WO9101210 A1 WO 9101210A1
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WO
WIPO (PCT)
Prior art keywords
polymer
process according
microstructure
mass
materials
Prior art date
Application number
PCT/GB1990/001081
Other languages
English (en)
Inventor
Kenneth Ernest Evans
Kim Lesley Ainsworth
Original Assignee
National Research Development Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Research Development Corporation filed Critical National Research Development Corporation
Publication of WO1991001210A1 publication Critical patent/WO1991001210A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D99/00—Subject matter not provided for in other groups of this subclass
    • B29D99/0089—Producing honeycomb structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B31—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER; WORKING PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER
    • B31D—MAKING ARTICLES OF PAPER, CARDBOARD OR MATERIAL WORKED IN A MANNER ANALOGOUS TO PAPER, NOT PROVIDED FOR IN SUBCLASSES B31B OR B31C
    • B31D3/00—Making articles of cellular structure, e.g. insulating board
    • B31D3/002—Methods for making cellular structures; Cellular structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/28—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer comprising a deformed thin sheet, i.e. the layer having its entire thickness deformed out of the plane, e.g. corrugated, crumpled

Definitions

  • This invention relates to novel polymeric materials, to processes for their production and to devices incorporating said materials.
  • This class comprises materials having a microstructure comprising finite sized particles which are conventionally termed nodes connected by fibrils wherein the microstructure is such that the application of a tension 1n one direction causes the nodes to be displaced in the transverse direction. This displacement produces the expansion in the transverse direction which 1s the characteristic of materials having a negative Poisson ratio.
  • the discovery enables a variety of polymers to be produced in a form which exhibits a negative Poisson ratio and in consequence exhibit a large shear modulus relative to their bulk modulus. Appropriate selection of the polymer enables materials to be produced which combine this with superior mechanical properties such as the Youngs modulus. This combination of properties can be exploited 1n a variety of useful devices.
  • our invention provides polymeric materials having a microstructure comprising nodes Interconnected by fibrils which are characterised in that they exhibit a negative Poisson ratio and have a Youngs modulus of at least 0.2 GPa.
  • the materials of this invention may be formed from any polymer which is capable of being produced 1n a form having a microstructure comprising nodes and fibrils.
  • the polymer must be sufficiently ductile to form fibrils when expanded, e.g. by drawing and yet must retain the particulate microstructure which provides the nodes. Not all mlcrostructures comprising nodes and fibrils provide a material having a negative Poisson ratio and the conditions necessary to produce any particular polymer in a form having the desired microstructure may need to be determined by experiment.
  • the materials comprise a microstructure comprising finite sized particles (nodes ) connected by fibrils wherein the length of the fibrils is greater than the shortest distance between the nodes which they connect and wherein the distance between adjacent nodes which are not connected by fibrils is less than maximum distance between fibrils connected to a particular node.
  • This first type of microstructure is illustrated in Figure 1 which is a cross sectional sketch of such a microstructure. The nodes are represented as cross hatched spheres and the fibrils by the solid lines. Figure 1 illustrates the microstructure prior to the application of a tension in the direction of the x axis.
  • Figure 2 represents the same cross section after the application of a tension along the x axis (not drawn to scale).
  • the fibrils are now taut and the nodes have been displaced In the direction of the y axis. It Is this displacement which gives rise to the negative Poisson ratio.
  • a second class of microstructure which can give rise to a material having a negative Poisson ratio is one in which the nodes are anisotropic.
  • the useful microstructures are those in which the nodes are aligned in such a way that their longer dimension lies in the direction of the axis of the material and wherein the nodes are connected by fibrils which are longer than the distance between the nodes which they connect.
  • FIG. 3 is a cross-sectional sketch of such a microstructure.
  • the nodes are shown as cross-hatched discoid areas connected by fibrils which are represented by solid lines.
  • Figure 3(a) shows a structure in which the nodes are close together and aligned so that their longest dimension lies along the x axis.
  • Figure 3(b) shows that following the application of a tension along the x axis, the distance between the nodes measured along the x axis has Increased. At the same time there has been some expansion along the y axis by virtue of an Interaction between the nodes and fibrils of the type described in relation to Figures 1 and 2.
  • Figure 3(c) shows how the continued application of the tension has caused the nodes to rotate so that their longest dimension 1s displaced toward the y axis. This rotation produces the negative Poisson ratio as each "layer" of nodes displaces the adjacent "layer” along the y axis.
  • Figure 3(d) represents the limiting case 1n which the nodes have rotated so that their longest dimension Is now aligned with the y axis.
  • sketches 1 to 3 are two dimensional representations which illustrate possible mechanisms whereby the polymers of this invention may exhibit a negative Poisson ratio. In practice the polymers are three dimensional and may well exhibit a microstructure which is not uniform. It 1s characteristic of the materials of this invention that they exhibit a negative Poisson ratio, i.e.
  • the materials of this invention may be isotroplc or anisotropic.
  • isotroplc materials the minimum Poisson ration which can be achieved is minus 1.
  • anisotropic materials the minimum Poisson ratio may be much smaller (at least in one direction).
  • the materials may exhibit a ratio which is close to the theoretical limit of minus the square root of the ratio of the maximum Youngs modulus of the material divided by its minimum Youngs modulus and such materials may be preferred In particular applications.
  • the materials of this invention preferably exhibit a Poisson ratio of less than minus 0.25 and preferably one which 1s less then minus 0.75 although for the anisotropic materials ratios of as low as minus 10 or minus 12 are attainable and may be preferred.
  • the materials of this invention may be formed from any suitable polymer which can be processed to a form having a suitable microstructure.
  • a particulate thermofor able polymer as the starting material and to deform a compacted polymer material under controlled conditions.
  • the polymer should be sufficiently ductile so as to enable it to be deformed under conditions which result 1n the formation of fibrils and yet retain the particulate microstructure which forms the nodes.
  • suitable materials include poly- tetrafluoroethylene and copolymers thereof, polyolefins and copolymers thereof especially polyethylene and copolymers thereof and particularly high molecular weight polyethylene, polypropylene and copolymers thereof, polystyrene and poly(meth)- acrylates.
  • the size of the nodes in the microstructure may vary through a wide range say a maximum dimension of from 0.1 ⁇ m to 0.1 mm.
  • the ratio of the fibril length to the length of the maximum dimension of the node should preferably be greater than 1 and more usually will be within the range 1.1:1 to 2.0:1.
  • the polymer from which the materials of this invention are formed will be selected so as to provide the desired properties.
  • the polymer selected will result in the formation of a material having a Youngs Modulus of at least 1.0 GPa.
  • the materials also preferably have a density of at least 150Kgm ⁇ 3 and more preferably at least 500 gm ⁇ 3 .
  • the polymeric materials of this invention may incorporate a filler such as asbestos, carbon black, mica, silica or titanium dioxide.
  • a filler 1s preferably incorporated Into the material by mixing with the polymer particles prior to the processing step which is required in order to produce the appropriate microstructure.
  • Impregnating 1t with a liquid phase comprising a monomer or prepolymer for example methyl methacr late and subsequently polymerising that monomer or prepolymer. This impregnation may be carried out before or after the processing step.
  • microstructure of the materials and hence their properties may also be Influenced by the form of the polymer from which they are produced.
  • the materials are produced from particulate polymer granules the general shape of the particles tends to be retained by the nodes 1n the microstructure.
  • the use of spherical polymer particles tends to result in a microstructure having broadly spherical nodes.
  • the materials may be formed by a process which comprises compacting the polymer particles at elevated temperatures and pressures and deforming the compacted polymer.
  • this invention provides a process for the production of a polymeric material having a microstructure comprising nodes interconnected by fibrils which exhibits a negative Poisson ration which comprises compacting a particulate polymeric material and de f orming the polymer so as to cause it to expand in at least one direction.
  • the compaction step preferably comprises heating a mass of polymer particles to a temperature of at least 50°C and more usually at least 90 ⁇ C.
  • Polymers which have a melting point above these temperatures are preferred for present use.
  • the temperature shcild be within 50°C and more preferably within 20 ⁇ C of the melting point of the polymer.
  • the force applied may vary through a wide range, say from 1.0 to 100 MPa.
  • the polymer should preferably be subjected to these conditions for a period which Is sufficiently long to allow the entire mass to attain a thermal equilibrium.
  • the polymers are deformed by expansion in at least one direction until the desired microstructure is obtained.
  • the deformation may be carried out using techniques known in the polymer art such as extrusion drawing or draw assisted extrusion.
  • the deformation is preferably carried out at elevated temperatures say of at least 50°C and more usually of at least 100°C.
  • the polymers may conveniently be produced using conventional polymer extrusion equipment.
  • the polymer powder or granules may be introduced Into the barrel of the extruder. They are then conveniently formed into a compacted rod by compression preferably at elevated temperature. Thereafter the polymer may be extruded through a die.
  • the diameter of the die, the temperature at which the polymer is extruded and the speed at which the polymer is extruded may all Influence the microstructure of the polymer.
  • the rate of deformation of the polymer should be sufficient to result in the production of the desired microstructure. Too low a rate may not be useful and typically for polyethylene an extrusion rate of greater than 250 or more preferably 500 mm/min may be utilised.
  • the optimum conditions for each polymer may be established by experiment. In general the temperature of the polymer during the extrusion will be at least as high as that used in the compaction step and preferably the temperature may be increased before extrusion commences. Thereafter the extruded material is allowed to cool to ambient temperature.
  • the microstructure of the polymer may be examined using conventional techniques such as scanning electron microscopy. If the polymer does not exhibit the desired microstructure the polymer may be subjected to a further processing step which comprises compressing the polymer in a direction which is perpendicular to the original draw direction. Such cor--resslc is preferably carried out whilst the drawn polymer is maintained at an elevated temperature generally at least 50 ⁇ C and preferably at least 90 ⁇ C. Where particular materials do not exhibit the desired microstructure the parameters of the drawing process may need to be adjusted.
  • the microstructure of the drawn material may not be uniform. It may comprise regions where the Poisson ratio 1s higher or even takes a positive value. Nevertheless such materials may be useful on various applications provided that they exhibit a negative Poisson ratio in at least one direction.
  • the materials produced by the process may already be fully drawn out in that direction. Such materials will not exhibit a negative Poisson ratio but may do so following a compression step as described above.
  • Partially drawn materials may also be compressed 1f desired. The compression may remove all traces of the microstructure from the material but 1t is characteristic of the materials of this invention that the changes brought about by compression are at least partially reversible and the microstructure may be at least partially restored by extension in the original draw direction.
  • the materials of this invention find potential use 1n a variety of applications. They can for example be used to seal a cavity since a plug formed from a material having a negative Poisson ratio will expand laterally when stretched. They also find use in applications wherein compliance of dimension under stress is desirable, e.g. as the interior filler for structural sandwich panels and for shock and vibration absorption. The materials may also find use in a variety of medical applications.
  • Example 1 The barrel of a laboratory manufactured compacted powder extruder was filled with an ultra high molecular weight polyethylene powder sold under the Trademark Hostalen GUR 415 by Hoechst (UK) Ltd. of Salisbury Road, Middlesex. The extruder was fitted with a blank die and preheated to a temperature of 110 ⁇ C. The barrel, internal diameter 1 cm and length 8 cm, and contents were allowed to equilibriate for 10 minutes. The plunger was then driven into the barrel by a Schenk mechanical testing machine at a rate of 20 mm/min until a force of 7.31 kN was reached. These conditions were maintained for 20 minutes. The result was a compacted polyethylene rod.
  • the extruder was then fitted with a die having a diameter of 5 mm and an entry angle of 45°. The temperature was maintained at 160°C for a further 20 minutes. The plunger was then driven into the barrel at a rate of 500 mm/min.
  • the extrudate comprised a rod having the appearance shown in Figure 4.
  • the Poisson ratio of the extrudate was determined by applying compressive strains in the directions indicated in Figure 4.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cosmetics (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)

Abstract

Des polymères ayant une microstructure comprenant des noeuds et des fibriles peuvent présenter un coefficient de Poisson négatif. On peut les produire par compactage d'un polymère particulaire, par exemple du polyéthylène UHW, et par la déformation par extrusion du produit compacté. Les polymères trouvent une utilisation dans une variété d'applications dans lesquelles ils sont soumis à une charge.
PCT/GB1990/001081 1989-07-14 1990-07-13 Materiaux polymeres WO1991001210A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898916231A GB8916231D0 (en) 1989-07-14 1989-07-14 Polymeric materials
GB8916231.7 1989-07-14

Publications (1)

Publication Number Publication Date
WO1991001210A1 true WO1991001210A1 (fr) 1991-02-07

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PCT/GB1990/001081 WO1991001210A1 (fr) 1989-07-14 1990-07-13 Materiaux polymeres

Country Status (5)

Country Link
EP (1) EP0482058A1 (fr)
JP (1) JPH04506638A (fr)
CA (1) CA2063396A1 (fr)
GB (3) GB8916231D0 (fr)
WO (1) WO1991001210A1 (fr)

Cited By (37)

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WO2000018564A1 (fr) * 1998-09-30 2000-04-06 Toray Industries, Inc. Film polymere a stabilite dimensionnelle elevee et support d'enregistrement magnetique dans lequel ledit film est utilise
WO2001045766A1 (fr) 1999-12-22 2001-06-28 Advanced Cardiovascular Systems, Inc. Dispositif medical en polyolefine de poids moleculaire tres eleve
US6428506B1 (en) 1999-12-22 2002-08-06 Advanced Cardiovascular Systems, Inc. Medical device formed of ultrahigh molecular weight polyethylene
WO2004012785A1 (fr) 2002-08-02 2004-02-12 Auxetica Limited Doublures tubulaires auxetiques
US6743388B2 (en) 2001-12-31 2004-06-01 Advanced Cardiovascular Systems, Inc. Process of making polymer articles
US6793960B1 (en) 2001-04-06 2004-09-21 Advanced Cardiovascular Systems, Inc. Medical device having surface modification with superoxide dismutase mimic
US6841029B2 (en) 2003-03-27 2005-01-11 Advanced Cardiovascular Systems, Inc. Surface modification of expanded ultra high molecular weight polyethylene (eUHMWPE) for improved bondability
US6878320B1 (en) 1999-03-06 2005-04-12 The University Of Bolton, Higher Education Corporation A Uk Corporation Auxetic materials
DE102005012906B3 (de) * 2005-03-21 2006-12-14 Corovin Gmbh Flächiges Bahnenmaterial, Verfahren und Vorrichtung zur Herstellung desselben sowie dessen Verwendung
US7247265B2 (en) 2000-03-06 2007-07-24 Auxetic Technologies Ltd. Auxetic filamentary materials
RU2338820C2 (ru) * 2003-03-29 2008-11-20 Дау Корнинг Лимитед Усовершенствования в композиционных материалах и структурах, а также усовершенствования, имеющие отношение к композиционным материалам и структурам
US7455567B2 (en) 2006-08-02 2008-11-25 Hanesbrands Inc. Garments having auxetic foam layers
WO2009142836A3 (fr) * 2008-05-23 2010-01-14 Schlumberger Canada Limited Système et procédé d’amélioration des caractéristiques fonctionnelles de dispositifs utilisés dans un puits
EP2157121A1 (fr) 2006-05-24 2010-02-24 Auxetic Technologies Ltd. Matériau composite
KR100990023B1 (ko) * 2008-02-29 2010-10-26 서강대학교산학협력단 음의 프와송비를 갖는 질점 회전 구조체 튜브 및 그제조방법
WO2011090588A2 (fr) 2009-12-30 2011-07-28 3M Innovative Properties Company Procédé une fabrication d'une maille auxétique
WO2011090587A2 (fr) 2009-12-30 2011-07-28 3M Innovative Properties Company Treillis auxétique moulé
US8129293B2 (en) 2006-03-08 2012-03-06 Dow Corning Corporation Impregnated flexible sheet material
WO2012171911A1 (fr) 2011-06-14 2012-12-20 Dow Corning Corporation Matériau de pression
US8343404B2 (en) 2008-03-07 2013-01-01 Giuseppe Meli Method for the production of cellular materials
US8728372B2 (en) 2005-04-13 2014-05-20 Trivascular, Inc. PTFE layers and methods of manufacturing
US8840824B2 (en) 2005-04-13 2014-09-23 Trivascular, Inc. PTFE layers and methods of manufacturing
US8967147B2 (en) 2009-12-30 2015-03-03 3M Innovative Properties Company Filtering face-piece respirator having an auxetic mesh in the mask body
WO2015038455A1 (fr) * 2013-09-10 2015-03-19 The Procter & Gamble Company Structures de formation de cellules
US9926416B2 (en) 2013-01-30 2018-03-27 W. L. Gore & Associates, Inc. Method for producing porous articles from ultra high molecular weight polyethylene
CN110524960A (zh) * 2019-08-07 2019-12-03 东华大学 一种非对称性高缓冲柔性功能拉胀复合材料及其制备方法
USD869889S1 (en) 2017-12-05 2019-12-17 Steelcase Inc. Chairback
USD869872S1 (en) 2017-12-05 2019-12-17 Steelcase Inc. Chair
USD869890S1 (en) 2017-12-05 2019-12-17 Steelcase Inc. Chairback
USD870479S1 (en) 2017-12-05 2019-12-24 Steelcase Inc. Chair
US10813463B2 (en) 2017-12-05 2020-10-27 Steelcase Inc. Compliant backrest
USD907383S1 (en) 2019-05-31 2021-01-12 Steelcase Inc. Chair with upholstered back
USD907935S1 (en) 2019-05-31 2021-01-19 Steelcase Inc. Chair
EP3673007A4 (fr) * 2017-08-25 2021-03-24 Honeywell International Inc. Matériau composite résistant aux chocs
US11291305B2 (en) 2017-12-05 2022-04-05 Steelcase Inc. Compliant backrest
CN116535724A (zh) * 2023-05-06 2023-08-04 西南大学 一种宽温域高灵敏度负泊松比生物基应力传感材料的制备方法及其产品和应用
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CN100503703C (zh) * 2005-12-21 2009-06-24 中国科学院化学研究所 负泊松比材料及其制备方法和用途
US8016549B2 (en) 2006-07-13 2011-09-13 United Technologies Corporation Turbine engine alloys and crystalline orientations
EP2995289A1 (fr) * 2014-09-10 2016-03-16 The Procter and Gamble Company Structures de formation de cellules multiniveau et leur utilisation dans des produits de consommation jetables
EP2995288A1 (fr) * 2014-09-10 2016-03-16 The Procter and Gamble Company Structures de formation de cellules et leur utilisation dans des produits de consommation jetables
WO2016112366A1 (fr) 2015-01-09 2016-07-14 President And Fellows Of Harvard College Structures gaufrées à coefficient de poisson négatif

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Cited By (68)

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Publication number Priority date Publication date Assignee Title
US6797381B1 (en) 1998-09-30 2004-09-28 Toray Industries, Inc. Highly size-stabilized polymer film and magnetic recording medium using the film
WO2000018564A1 (fr) * 1998-09-30 2000-04-06 Toray Industries, Inc. Film polymere a stabilite dimensionnelle elevee et support d'enregistrement magnetique dans lequel ledit film est utilise
US6878320B1 (en) 1999-03-06 2005-04-12 The University Of Bolton, Higher Education Corporation A Uk Corporation Auxetic materials
WO2001045766A1 (fr) 1999-12-22 2001-06-28 Advanced Cardiovascular Systems, Inc. Dispositif medical en polyolefine de poids moleculaire tres eleve
US6428506B1 (en) 1999-12-22 2002-08-06 Advanced Cardiovascular Systems, Inc. Medical device formed of ultrahigh molecular weight polyethylene
US6602224B1 (en) 1999-12-22 2003-08-05 Advanced Cardiovascular Systems, Inc. Medical device formed of ultrahigh molecular weight polyolefin
US6890395B2 (en) 1999-12-22 2005-05-10 Advanced Cardiovascular Systems, Inc. Medical device formed of ultrahigh molecular weight polyolefin
US6761786B2 (en) * 1999-12-22 2004-07-13 Advanced Cardiovascular Systems, Inc. Process of making a balloon for an intraluminal catheter
US7247265B2 (en) 2000-03-06 2007-07-24 Auxetic Technologies Ltd. Auxetic filamentary materials
US7311970B2 (en) 2001-04-06 2007-12-25 Abbott Cardiovascular Systems Inc. Medical device having surface modification with superoxide dismutase mimic
US6793960B1 (en) 2001-04-06 2004-09-21 Advanced Cardiovascular Systems, Inc. Medical device having surface modification with superoxide dismutase mimic
US7396582B2 (en) 2001-04-06 2008-07-08 Advanced Cardiovascular Systems, Inc. Medical device chemically modified by plasma polymerization
US7470469B1 (en) 2001-04-06 2008-12-30 Advanced Cardiovascular Systems Inc. Medical device having surface modification with superoxide dismutase mimic
US6780361B1 (en) 2001-12-31 2004-08-24 Advanced Cardiovascular Systems, Inc. Process of making polymer articles
US6743388B2 (en) 2001-12-31 2004-06-01 Advanced Cardiovascular Systems, Inc. Process of making polymer articles
GB2393657A (en) * 2002-08-02 2004-04-07 Rudy Hengelmolen Auxetic tubular liners
WO2004012785A1 (fr) 2002-08-02 2004-02-12 Auxetica Limited Doublures tubulaires auxetiques
US6841029B2 (en) 2003-03-27 2005-01-11 Advanced Cardiovascular Systems, Inc. Surface modification of expanded ultra high molecular weight polyethylene (eUHMWPE) for improved bondability
US7425357B2 (en) 2003-03-27 2008-09-16 Advanced Cardiovascular Systems, Inc. Surface modification of expanded ultra high molecular weight polyethylene(eUHMWPE) for improved bondability
RU2338820C2 (ru) * 2003-03-29 2008-11-20 Дау Корнинг Лимитед Усовершенствования в композиционных материалах и структурах, а также усовершенствования, имеющие отношение к композиционным материалам и структурам
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GB2235200B (en) 1993-02-10
GB8916231D0 (en) 1989-08-31
GB9015466D0 (en) 1990-08-29
GB2235200A (en) 1991-02-27
CA2063396A1 (fr) 1991-01-15
GB9014006D0 (en) 1990-08-15
JPH04506638A (ja) 1992-11-19

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