WO2000037241A1 - Procede de production de pieces moulees par rotation comprenant des nanoparticules de renforcement - Google Patents

Procede de production de pieces moulees par rotation comprenant des nanoparticules de renforcement Download PDF

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Publication number
WO2000037241A1
WO2000037241A1 PCT/US1999/029986 US9929986W WO0037241A1 WO 2000037241 A1 WO2000037241 A1 WO 2000037241A1 US 9929986 W US9929986 W US 9929986W WO 0037241 A1 WO0037241 A1 WO 0037241A1
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WO
WIPO (PCT)
Prior art keywords
reinforcing particles
particles
thermoplastic
powder
molten material
Prior art date
Application number
PCT/US1999/029986
Other languages
English (en)
Other versions
WO2000037241A9 (fr
Inventor
Phillip S. Wilson
Original Assignee
Magna International Of America, Inc.
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 Magna International Of America, Inc. filed Critical Magna International Of America, Inc.
Priority to CA002356221A priority Critical patent/CA2356221A1/fr
Priority to AU23656/00A priority patent/AU2365600A/en
Publication of WO2000037241A1 publication Critical patent/WO2000037241A1/fr
Publication of WO2000037241A9 publication Critical patent/WO2000037241A9/fr

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Classifications

    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
    • 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
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/04—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould
    • B29C41/042—Rotational or centrifugal casting, i.e. coating the inside of a mould by rotating the mould by rotating a mould around its axis of symmetry
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts

Definitions

  • Rotational molding of polymers offers an economical approach to producing hollow articles for various applications.
  • injection molding has been used to produce complex, higher cost molded items at high production rates, whereas blow molding is employed for items such as one-piece closed vessels.
  • Rotational molding is ideally suited for producing hollow, closed, relatively thick- walled items at reasonably low per unit cost.
  • Advantages of rotational molding include uniform wall thickness of the molded articles, as well as close control of the weight of molded products.
  • thermoplastic resin powder of relatively low viscosity is placed inside an aluminum mold and the mold is heated in an oven. The mold is rotated during heating, thereby forcing the resin against the mold surface. The resin then sinters and fuses, coating the inside of the mold. The melt is then cooled and solidifies to assume the shape of the mold. Articles of uniform wall thickness, zero orientation and good physical properties may be generated via this process.
  • Certain automobile parts may be efficiently produced by rotational molding methods. Such parts historically have included air ducts, fuel tanks, glove boxes and fender liners. Solid removable convertible tops, such as removable hard tops for sport utility vehicles, may also be rotationally molded. In an attempt to reduce automobile unit weight, the automotive industry has sought techniques with which to reduce wall thickness of molded automobile parts without compromising impact resistance and dimensional strength. Additionally, greater wall thickness of such molded articles requires more raw materials per molded part, thereby increasing the cost of production. Cycle times may be high for rotational molding due to the heating and cooling periods required, which depend upon the wall thickness of the article being formed.
  • U.S. Patent number 4,363,687 to Anderson discloses a method of producing large, fiber reinforced storage tanks.
  • the reinforced resin articles of Anderson '687 contain glass reinforcement fiber, resin, and catalyst which are applied to the inner surface of a revolving mold.
  • this traditional approach to reinforced rotational molding causes resin rich regions to form on the surface of the mold due to uneven dispersion of the glass fibers during rotation.
  • Filament winding around or within molded articles are additional techniques used to reinforced rotationally molded products.
  • U.S. patent number 4,123,307 to Lemelson is directed to a method of reinforcing a molded article whereby filamentary material is wound around the article, thus strengthening the outer stratum thereof.
  • patent number 4,002,715 to Usui et al. discloses a synthetic resin pipe which is reinforced by winding belt-like or thread-like glass fiber around a tapered core bar, inserting the arrangement into a tapered mold, and thereafter removing the core bar such that the wound glass fiber remains. Thermosetting liquid resin is then introduced into the mold, which is rotated at an inclined angle. Rotation of the mold causes the resin material to permeate the reinforcing material, which then hardens into the form of a pipe.
  • the cited techniques using external and preformed fibers do not permit even reinforcement throughout the entire molded article. Therefore, a need exists for improved reinforcement of hollow rotationally molded resin articles.
  • an object of the present invention is to overcome the problems delineated hereinabove.
  • the present invention provides a rotationally molded article.
  • Such articles are suitable for use as automobile components.
  • the articles are formed by a method comprising (a) preparing a powder composition of at least one thermoplastic and about 2% to about 15% by volume reinforcing particles.
  • the reinforcing particles are substantially uniformly dispersed in the thermoplastic.
  • At least 50% of the reinforcing particles are less than about 20 layers thick, and at least 99% of the reinforcing particles are less than about 30 layers thick, the layers of the reinforcement particles have a unit thickness of between about 0.7 nm - 1.2 nm; (b) heating the powder into a molten material; (c) rotating the molten material in a mold cavity so that the molten material conforms to the surfaces of the mold cavity, the molten material having substantially the same uniformity of dispersion of the reinforcing particles therein in comparison with the uniformity of dispersion of the reinforcing particles in the thermoplastic powder; and (d) cooling the molten material to form a reinforced article.
  • the parts manufactured according to the invention are constructed to be both lightweight and strong, exhibiting good impact resistance and dimensional stability.
  • reinforcing nanoparticle fillers are added in levels of only a few percent by volume to polymer resin compositions prior to rotational molding into an article.
  • the impact resistance and dimensional stability of thin-walled molded articles made of resins, such as polyolefins is improved.
  • large, hollow rotationally molded articles can be reinforced according to the invention, thereby imparting good dimensional stability.
  • FIG. 1 illustrates a conventional rotational molding apparatus, generally indicated at 10, that can be employed in the method of the present invention.
  • the apparatus 10 includes a mold structure 12 defining a mold cavity 14.
  • the mold structure 12 is mounted for rotation around an axis extending through a feeding tube 16. More specifically, the opposite ends of the mold structure 12 are mounted on bearing carrying supports 18.
  • One end of the mold structure is connected by linkage 20 that connects the structure 12 to a motor 22 that drives the mold structure 12 for rotation about said axis.
  • the motor 22 and supports 18 are mounted on a mounting structure 24.
  • the mounting structure 24 is mounted on a movable mechanism 26 that can tilt the mounting structure 24 to ensure that powder introduced into the cavity 14 is uniformly distributed along the longitudinal axis.
  • the aforementioned tube 16 is hollow and provided with a plurality of openings 30.
  • a powder material to be described in greater detail below, is introduced through a feeding tube 32 into the interior of tube 16. The powder can then be distributed into the cavity 14 through the openings 30.
  • the present invention contemplates that the mold structure 12 can be provided with two mold halves (or parts) or be provided with a door that can be opened in order to deposit a pre-measured amount of powder into the cavity 14. In this alternate construction, tube 16 would not be provided.
  • the die structure 12 is rotated by motor 22 about the axis.
  • the die structure is provided with a spiral passageway, as indicated at 44, or otherwise jacketed to enable hot oil or other hot liquid to be used to heat the die structure.
  • the passageway 44 can be omitted, and the entire structure 12 placed in an oven.
  • the powder is heated so that it is in molten form.
  • the molten material is then evenly dispersed over the interior surface 46 of the mold structure 12.
  • cooling fluid such as water
  • the powder used preferably comprises at least one thermoplastic and about 2% to about 15% by volume reinforcing particles.
  • the said reinforcing particles are substantially uniformly dispersed in the thermoplastic, at least 50% of the reinforcing particles being less than about 20 layers thick, the layers of the reinforcing particles having a thickness of between about 0.7 nm - 1.2 nm.
  • the powder introduced into the mold cavity is formed by grinding of pellets, the pellets preferably formed in an extruding process. More specifically, the nanoparticles and the thermoplastic material are preferably extruded together to form the pellets. The pellets are then ground in a mechanical grinder to form the powder. The nanoparticles are substantially uniformly dispersed in the pellets and hence also in the particles forming the powder. Because the nanoparticles are very small, there is no possibility of such reinforcing particles becoming damaged in the grinding operation. This is unlike a methodology that would use larger reinforcements, such as glass fibers, which reinforcements would have their reinforcing characteristics damaged by a grinding operation.
  • thermoplastic is originally formed as a powder and the nanoparticles are later added to the powder in a powder blending device.
  • the parts manufactured in accordance with the present invention comprise a composite material of a polymer having dispersed therein reinforcement fillers in the form of very small mineral reinforcement particles.
  • the reinforcement filler particles also referred to as "nanoparticles" due to the magnitude of their dimensions, each comprise one or more essentially flat platelets.
  • each platelet has a thickness of between about 0.7-1.2 nanometers. The average platelet thickness is approximately 1 nanometer.
  • the preferred aspect ratio of the reinforcement particles which is the largest dimension of a particle divided by the thickness of the particle, is about 50 to about
  • the particle reinforcements will not provide the desired reinforcement characteristics. More preferably, the aspect ratio for each particle is between 100-200. Most preferably at least 90% of the particles have an aspect ratio within the 100-200 range.
  • the platelet particles or nanoparticles are derivable from larger layered mineral particles. Any layered mineral capable of being intercalated may be employed in the present invention. Layered silicate minerals are preferred. The layered silicate minerals that may be employed include natural and artificial minerals.
  • Non-limiting examples of more preferred minerals include montmorillonite, vermiculite, hectorite, saponite, hydrotalcites, kanemite, sodium octosilicate, magadite, and kenyaite.
  • Mixed Mg and Al hydroxides may also be used.
  • Various other clays can be used, such as claytone H.Y.
  • montmorillonite is a group consisting of montmorillonite.
  • swellable layered minerals such as montmorillonite and saponite are known to intercalate water to expand the inter layer distance of the layered mineral, thereby facilitating exfoliation and dispersion of the layers uniformly in water. Dispersion of layers in water is aided by mixing with high shear.
  • the mineral particles may also be exfoliated by a shearing process in which the mineral particles are impregnated with water, then frozen, and then dried. The freeze dried particles are then mixed into molten polymeric material and subjected to a high sheer mixing operation so as to peel individual platelets from multi-platelet particles and thereby reduce the particle sizes to the desired range.
  • the polymer composites of the present invention are prepared by combining the platelet mineral with the desired polymer in the desired ratios.
  • the components can be blended by general techniques known to those skilled in the art. For example, the components can be blended and then melted in mixers. Thereafter, solidified polymer/nanoparticle mixtures may be ground into powders for rotational molding. The extremely small size of the nanoparticles permits such grinding without loss of reinforcing capabilities.
  • the ratios will be determined based on, for example, desired dimensional stabilization and/or desired mechanical properties of the final molded article. Additional specific preferred methods, for the purposes of the present invention, for forming a polymer composite having dispersed therein exfoliated layered particles are disclosed in U.S. Patent Nos. 5,717,000, 5,747,560, 5,698,624, and WO 93/11 190, each of which is hereby incorporated by reference. For additional background, the following are also incorporated by reference: U.S.
  • Typical resins used in rotational molding include vinyl plastisols and powdered low viscosity polyolefins.
  • Liquid vinyl dispersions may be used to rotationally cast automotive parts, such as arm rests.
  • Other automobile components may be molded of polyolefins.
  • Powdered polyolefins are available in a variety of melt indexes, densities and particle sizes.
  • polyethylenes having low melt indexes provide for articles having good impact strength as well as resistance to low-temperature brittleness.
  • High density resins impart high rigidity to rotationally molded products, permitting reduction of wall thicknesses of the products. Increasing the density of the polyolefin resin also raises the melting point of the polymer, permitting higher service temperatures to be used.
  • the thermoplastic of the present invention is a powdered polyolefin or a homogenous or copolymer blend of polyolefins.
  • the preferred polyolefin is at least one member selected from the group consisting of polypropylene, ethylene-propylene copolymers, thermoplastic olefins (TPOs), and thermoplastic polyolefin elastomers (TPEs).
  • TPOs thermoplastic olefins
  • TPEs thermoplastic polyolefin elastomers
  • the process permits use of recycled materials, such as scrap polyolefins or post consumer polyolefins. For high performance applications, engineering thermoplastics are most preferred.
  • Such engineering thermoplastic resins may include polycarbonate (PC), acrylonitrile butadiene styrene (ABS), a PC/ABS blend, polyethylene terephthalates (PET), polybutylene terephthalates (PBT), polyphenylene oxide (PPO), or the like.
  • PC polycarbonate
  • ABS acrylonitrile butadiene styrene
  • PC/ABS blend polyethylene terephthalates
  • PET polyethylene terephthalates
  • PBT polybutylene terephthalates
  • PPO polyphenylene oxide
  • the exfoliation of layered mineral particles into constituent layers need not be complete in order to achieve the objects of the present invention.
  • the present invention contemplates that at least 50% of the particles should be less than about 20 nanometers in thickness. Otherwise stated, more than about 50% of the particles should be less than about 20 platelets (20 layers) stacked upon one another in the thickness direction.
  • at least 99% of the reinforcement particles should be less than about 30 layers (i.e., 30 nanometers) in thickness.
  • at least 90 % of the particles should have a thickness of less than 5 layers. It is most preferable to have as many particles as possible to be as small as possible, ideally including only a single platelet. Particles having more than 30 layers may behave as stress concentrators and are preferably avoided.
  • each of the automotive parts that can be manufactured in accordance with the principles of the present invention should contain nanoparticle reinforcement in amounts less than 15% by volume of the total volume of the part.
  • the balance of the part is to comprise an appropriate thermoplastic material and optionally, suitable additives. If greater than 15% by volume of reinforcement filler is used, the viscosity of the composition becomes too high and thus difficult to mold.
  • the amount of reinforcing nanoparticles is greater than 2% by volume (as lower amounts would not achieve the desired increase in strength) and less than 15%.
  • rotationally molded automobile components comprise reinforcement particles of the type described herein at about 2-15% of the total volume of the part, with the balance comprising the thermoplastic substrate. It is even more preferable for these reinforced components to have reinforcement particles of the type contemplated herein comprising about 3%-8% of the total volume of the part. For some applications, inclusion of about 3%-5% reinforcing nanoparticles is optimal.
  • additives may optionally be included in the polymer resin composition to improve processability.
  • aging modifiers such as glycerol monostearate
  • Aging modifiers are useful additives in polymer compositions for molding. Aging modifiers are typically present in an amount from about 0.5% to about 5% polyolefin resin.
  • Other additives include pigments, heat stabilizers, antioxidants, flame retardants, ultraviolet absorbing agents and the like. Reinforced articles of the invention exhibit improved properties over non- reinforced articles.
  • polyethylene articles having 5% nanoparticles by volume wherein 90% of the particles have 5 or fewer layers, increased flexural modulus by 2.5 to about 3 times over compositions lacking reinforcing nanoparticles, as measured under ASTM D790 test conditions.
  • This 5% nanoparticle polyethylene article exhibited > 200% elongation to rupture.
  • about 25% glass fiber reinforcement is required in such articles to achieve an equivalent modulus.
  • Polypropylene articles according to the invention showed about a 60% improvement in flexural modulus over articles lacking reinforcement nanoparticles.
  • the use of reinforcing nanoparticles according to the invention provides articles having good flexural stiffness.
  • producing reinforced articles comprises preparing a powder composition of at least one thermoplastic powder and about 2% to about 15% by volume reinforcing particles.
  • the reinforcing particles are substantially uniformly dispersed in the thermoplastic powder. At least 50% of the reinforcing particles are less than about 20 layers thick, with the layers comprising platelets which have a thickness of between about 0.7 nm to 1.2nm.
  • the method of producing reinforced articles further comprises heating the powder into a molten material, rotating the powder in a mold cavity so that the molten material conforms to surfaces of the mold cavity, and cooling the molten material to form a reinforced article.
  • the molten material has substantially the same uniformity of dispersion of the reinforcing particles therein in comparison with the uniformity of dispersion of the reinforcing particles in the thermoplastic powder.
  • the relatively small size of the nanoparticles enables the reinforcement particles to be dispersed uniformly in the molded article, irrespective of the centrifugal force applied in rotational molding.
  • the uniformity of dispersion in the molten powder is essentially the same as the uniformity of dispersion of the nanoparticles in the thermoplastic powder.

Abstract

L'invention concerne un procédé de production d'articles renforcés, qui consiste à: a) préparer une composition en poudre d'au moins un matériau thermoplastique et d'environ 2 à 15 % en volume de particules de renforcement. Ces particules de renforcement sont dispersées de manière sensiblement uniforme dans le matériau thermoplastique. Au moins 50 % des particules de renforcement ont une épaisseur inférieure à environ 20 couches, et les couches de particules de renforcement présentent une épaisseur des unités comprise entre environ 0,7 et 1,2 nm; b) chauffer la poudre pour la transformer en une matière fondue; c) imprimer des rotations à la matière fondue dans une cavité du moule pour amener cette dernière à épouser les forme des surfaces de la cavité du moule, la matière fondue ayant une uniformité de dispersion sensiblement identique à celle des particules de renforcement qu'elle renferme, par comparaison avec l'uniformité de dispersion des particules de renforcement renfermées dans la poudre thermoplastique; et d) refroidir la matière fondue pour former un article renforcé.
PCT/US1999/029986 1998-12-21 1999-12-17 Procede de production de pieces moulees par rotation comprenant des nanoparticules de renforcement WO2000037241A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002356221A CA2356221A1 (fr) 1998-12-21 1999-12-17 Methode de fabrication de pieces moulees par rotation comprenant des nanoparticules de renforcement
AU23656/00A AU2365600A (en) 1998-12-21 1999-12-17 Method of making rotationally moulded parts having nano-particle reinforcement

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11313298P 1998-12-21 1998-12-21
US60/113,132 1998-12-21

Publications (2)

Publication Number Publication Date
WO2000037241A1 true WO2000037241A1 (fr) 2000-06-29
WO2000037241A9 WO2000037241A9 (fr) 2000-12-07

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AU (1) AU2365600A (fr)
CA (1) CA2356221A1 (fr)
WO (1) WO2000037241A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7144441B2 (en) * 2003-07-03 2006-12-05 General Electric Company Process for producing materials reinforced with nanoparticles and articles formed thereby
US9018280B2 (en) 2005-05-13 2015-04-28 Continental Structural Plastics, Inc. Low-density molding compound
EP3103624A1 (fr) * 2015-06-09 2016-12-14 Hobas Engineering GmbH Procédé de fabrication d'un tuyau multicouche comprenant des microfibres, et tuyau correspondant
US9868829B2 (en) 2014-06-27 2018-01-16 Continental Structure Plastics, Inc. Low-density molding compound containing surface derivatized microspheres

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986005436A1 (fr) * 1985-03-23 1986-09-25 Dow Chemical Gmbh Tuyau en plastique renforce par des fibres et son procede de fabrication par coulee centrifuge
DE3510625A1 (de) * 1985-03-23 1986-10-02 Dow Chemical GmbH, 2160 Stade Faserverstaerktes kunststoffrohr und schleudergussverfahren zu seiner herstellung
US4739007A (en) * 1985-09-30 1988-04-19 Kabushiki Kaisha Toyota Chou Kenkyusho Composite material and process for manufacturing same
US5747560A (en) * 1991-08-12 1998-05-05 Alliedsignal Inc. Melt process formation of polymer nanocomposite of exfoliated layered material
WO1999061287A1 (fr) * 1998-05-22 1999-12-02 Magna International Of America, Inc. Carenage frontal a faible epaisseur de paroi destine a un vehicule motorise
WO1999061236A1 (fr) * 1998-05-22 1999-12-02 Magna International Of America, Inc. Elements de garniture interieure pour vehicule a moteur
WO1999061281A1 (fr) * 1998-05-22 1999-12-02 Magna International Of America, Inc. Panneaux exterieurs destines a des vehicules a moteur
WO1999061237A1 (fr) * 1998-05-22 1999-12-02 Magna International Of America, Inc. Vitre pour vehicule a moteur

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1986005436A1 (fr) * 1985-03-23 1986-09-25 Dow Chemical Gmbh Tuyau en plastique renforce par des fibres et son procede de fabrication par coulee centrifuge
DE3510625A1 (de) * 1985-03-23 1986-10-02 Dow Chemical GmbH, 2160 Stade Faserverstaerktes kunststoffrohr und schleudergussverfahren zu seiner herstellung
US4739007A (en) * 1985-09-30 1988-04-19 Kabushiki Kaisha Toyota Chou Kenkyusho Composite material and process for manufacturing same
US5747560A (en) * 1991-08-12 1998-05-05 Alliedsignal Inc. Melt process formation of polymer nanocomposite of exfoliated layered material
WO1999061287A1 (fr) * 1998-05-22 1999-12-02 Magna International Of America, Inc. Carenage frontal a faible epaisseur de paroi destine a un vehicule motorise
WO1999061236A1 (fr) * 1998-05-22 1999-12-02 Magna International Of America, Inc. Elements de garniture interieure pour vehicule a moteur
WO1999061281A1 (fr) * 1998-05-22 1999-12-02 Magna International Of America, Inc. Panneaux exterieurs destines a des vehicules a moteur
WO1999061237A1 (fr) * 1998-05-22 1999-12-02 Magna International Of America, Inc. Vitre pour vehicule a moteur

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7144441B2 (en) * 2003-07-03 2006-12-05 General Electric Company Process for producing materials reinforced with nanoparticles and articles formed thereby
US9018280B2 (en) 2005-05-13 2015-04-28 Continental Structural Plastics, Inc. Low-density molding compound
US9663608B2 (en) 2005-05-13 2017-05-30 Continental Structural Plastics, Inc. Low-density molding compound
US9868829B2 (en) 2014-06-27 2018-01-16 Continental Structure Plastics, Inc. Low-density molding compound containing surface derivatized microspheres
EP3103624A1 (fr) * 2015-06-09 2016-12-14 Hobas Engineering GmbH Procédé de fabrication d'un tuyau multicouche comprenant des microfibres, et tuyau correspondant
WO2016198172A1 (fr) * 2015-06-09 2016-12-15 Hobas Engineering Gmbh Procédé pour la fabrication d'un tuyau multicouche contenant des microfibres, ainsi que tuyau de ce type

Also Published As

Publication number Publication date
WO2000037241A9 (fr) 2000-12-07
AU2365600A (en) 2000-07-12
CA2356221A1 (fr) 2000-06-29

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