EP0520058A1 - Materiau composite sans matrice - Google Patents

Materiau composite sans matrice

Info

Publication number
EP0520058A1
EP0520058A1 EP92902391A EP92902391A EP0520058A1 EP 0520058 A1 EP0520058 A1 EP 0520058A1 EP 92902391 A EP92902391 A EP 92902391A EP 92902391 A EP92902391 A EP 92902391A EP 0520058 A1 EP0520058 A1 EP 0520058A1
Authority
EP
European Patent Office
Prior art keywords
composite material
fibers
material according
temperature
plastic
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP92902391A
Other languages
German (de)
English (en)
Inventor
Uwe Koser
Kuno Stellbrink
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Deutsches Zentrum fuer Luft und Raumfahrt eV
Original Assignee
Deutsches Zentrum fuer Luft und Raumfahrt eV
Deutsche Forschungs und Versuchsanstalt fuer Luft und Raumfahrt eV DFVLR
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 Deutsches Zentrum fuer Luft und Raumfahrt eV, Deutsche Forschungs und Versuchsanstalt fuer Luft und Raumfahrt eV DFVLR filed Critical Deutsches Zentrum fuer Luft und Raumfahrt eV
Publication of EP0520058A1 publication Critical patent/EP0520058A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/08—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer the fibres or filaments of a layer being of different substances, e.g. conjugate fibres, mixture of different fibres
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • 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
    • D04H1/54—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 by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/559—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 by welding together the fibres, e.g. by partially melting or dissolving the fibres being within layered webs
    • 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
    • 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
    • D04H1/74—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 orientated, e.g. in parallel (anisotropic fleeces)
    • 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
    • D04H13/00—Other non-woven fabrics
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • 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
    • B32B2605/00—Vehicles
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft

Definitions

  • the invention relates to a novel matrixless composite material.
  • Fiber-plastic composites have been used for some time in the manufacture of specifically light and strong components and can be produced using a wide range of processing methods such as laminating, spraying or winding.
  • the previously known composite materials consist, on the one hand, of a matrix made of thermoplastic or thermosetting plastic, which is reinforced by embedded fibers, fiber bundles, mats, fabrics, nonwovens, etc.
  • the matrix is mainly responsible for the shape retention, the embedded fibers mainly for the improvement of the mechanical properties.
  • the fiber-plastic composites form a so-called composite of at least two chemically or physically different materials.
  • a one-component material is to be imprinted with anisotropic properties, e.g. for thermoplastics processes such as injection molding, extrusion or fiber spinning, in which the orientation of the macromolecules of the plastic, and thus the generation of anisotropy, are generated from the melt by shear or stretching currents during the processing operation.
  • thermoplastics processes such as injection molding, extrusion or fiber spinning, in which the orientation of the macromolecules of the plastic, and thus the generation of anisotropy, are generated from the melt by shear or stretching currents during the processing operation.
  • the object of the invention is to propose a material with which components or molded parts with precisely specifiable mechanical properties can be produced from a single material.
  • a matrix-free composite material with at least one layer of highly oriented plastic fibers, which are arranged in multiple layers and in a predetermined angular position to one another and are connected to one another by sintering using pressure and temperature.
  • novel material to be characterized here forms the middle between fiber-plastic composites (FRP), reinforcing fibers and unreinforced plastic matrices, without being a fiber-plastic composite in the usual sense.
  • FRP fiber-plastic composites
  • matrixless composite material was therefore chosen for him.
  • a basic prerequisite for the success of the proposed method is the following properties of the material to be processed: First of all, a high pre-orientation of the macromolecules, and thus a high anisotropy of the mechanical and other physical properties, must be present in the starting material. Here are highly oriented fibers. Furthermore, the material must be combined into one component without further additives, but the anisotropy of the properties must not decrease significantly during this time. This condition is ideally met, for example, by liquid-crystalline, thermoplastic polymers in fiber form, the TLCP fibers. The thermoplasticity enables the macromolecules to be connected to one another, while the orientation of the macromolecules is largely retained due to the special molecular structure.
  • the directional dependence of the mechanical properties of highly oriented, liquid-crystalline polymers in fiber form is analogous to that of conventional fiber-plastic composites, resulting from the molecular structure of the material.
  • the oriented stiff-chain macromolecules correspond to the reinforcing fibers, the main bond strengths their tensile strength and the secondary bond strengths to the strength of the previous matrix and the boundary layer. It is thus possible to find fields of use for components made of matrix-free composite materials similar to those for conventional high-performance composites. Calculation methods which are already known for fiber-plastic composites can likewise be adopted analogously.
  • the strength values of the preferred direction are obtained in the longitudinal direction of the fiber and strength properties in the transverse direction, as would roughly correspond to a normal unreinforced synthetic resin.
  • the new matrix-free composite material is also a single-component, single-grade material that can be easily recycled.
  • High-strength Trevira fibers are suitable as highly oriented fibers for producing the composite material according to the invention. Care must be taken here during processing that the temperature does not rise to the melting point of the Treviva plastic, since otherwise the degree of orientation would be lost.
  • Liquid crystal fibers which are particularly suitable because of their favorable fire behavior, are used as plastic fibers with a high degree of orientation, for use in composite materials which are used, for example, in aircraft interior construction. In addition, these materials generally have very good chemical resistance and weather resistance. The low toxicity should also be mentioned. In contrast to other highly oriented materials, in the case of liquid crystal fibers, the processing temperature can reach the melting point without any significant loss in the degree of orientation and thus in the anisotropy of the specific properties.
  • the fibers made of TLCP which are used as examples, can be combined by sintering using pressure and temperature in such a way that, on the one hand, their specific properties, in particular also in their anisotropy, are retained and, on the other hand, a composite material is formed which remains unchanged Properties can be processed to a variety of molded parts.
  • all of the methods customary in fiber-plastic composites are available for this purpose, with the restriction that matrix material is not used.
  • interaction forces are understood not only as Van der Waals forces, but also hydrogen bonds, chemical bonds and ionic and dipole-dipole interaction forces.
  • a matrix-free composite material differs fundamentally from conventional fiber-plastic composites or, for example, injection molded plastics.
  • the arrangement of the starting material in the matrix-free composite material is of course not restricted to certain, for example linear, geometries. Rather, there is the possibility, for example, of adapting looped fibers to the flow of force, integrated in the component, in a targeted manner, particularly to the introduction of force. If the individual fibers are combined to form fiber strands and textile structures are formed therefrom, such as two-dimensional fabrics, fleece or three-dimensional knitted fabrics, a distribution of properties corresponding to the structure of the fiber network is already achieved within one layer. Combinations of fiber networks and unidirectional layers are possible.
  • the loose starting material is consolidated into a rigid component.
  • the variation of the parameters pressure and temperature influences its flow via the viscosity of the plastic.
  • the variation of the cycle time and the temperature control influences relaxation and recrystallization processes. This means that a component made of a matrix-free composite material can be adapted to technical conditions almost without restriction.
  • the composite material is preferably produced in such a way that the individual plastic fibers are connected to one another by interaction forces which are essentially comparable to the forces which bring about the cohesion of the molecular chains in the individual fibers.
  • the degree of orientation disruption is extremely low, i.e. a maximum of advantageous properties of the fibers are found in the composite material.
  • the highly oriented plastic fiber is the degree of orientation.
  • the composite materials are preferably produced in such a way that the temperature when the fibers are connected is selected in the region of the melting point of the plastic fibers or below. This temperature is also only used for a short time, so that this ensures that the degree of orientation is retained to the maximum.
  • the pressure used in the connection of the fibers preferably ensures that the material is essentially free of voids, which means that the composite material is obtained compactly and without greater porosity.
  • Preferred uses for the matrix-free composite materials are in particular fire-retardant molded parts.
  • Figure 1 inventive matrix-free composite material in sheet form
  • FIG. 2 enlarged section A from FIG. 1 in a schematic representation
  • FIG. 3 multilayer composite material according to the present invention
  • FIGS. 4a, b, c composite materials according to the invention made from differently structured starting materials
  • FIG. 5 temperature and pressure curve in a typical manufacturing process of a composite material according to the invention.
  • FIG. 1 shows a material plate made of the matrix-free composite material according to the invention, provided with the reference number 10, the structure of which can be seen better in FIG. 2, which shows an enlarged section A of the plate 10 in FIG. 1 in a schematic illustration.
  • the plate 10 consists of a dense, multilayered layering of liquid-crystalline polymers in fiber form.
  • FIG. 2 shows the individual fibers 12 in the upper right half in a schematic representation and also an area 14 in which the fibers 12 are arranged close to one another. If pressure and temperature are used to connect and compress the layered individual fibers, a matrixless composite structure is obtained, as is the case in the area 16 of plate 10 is shown in section A.
  • the temperature during pressing is preferably kept as low as possible, ie it moves in the region of the melting point of the liquid-crystalline fibers or below, so that the degree of orientation of the fibers is retained.
  • the area 16 in FIG. 2 indicates that the individual fibers 12 adjoin one another directly and are connected to one another without a matrix. This means that the fibers are brought so close to one another by the action of pressure and temperature that interaction forces can form between the fibers as they develop themselves within the fibers for connecting the macromolecules (not shown) arranged there to have.
  • interaction forces are understood not only to be Van der Waals forces, but also hydrogen bonds, chemical bonds and ionic and dipole-dipole interaction forces.
  • the material plate made of the matrixless composite material according to the invention shown in FIGS. 1 and 2 has a grain 20 on its upper side 18, as well as on the non-visible underside, which gives the user information about the preferred direction of the composite material, i.e. the direction of the maximum resilience.
  • FIG. 3 shows an alternative construction of a material plate made of the matrixless composite material according to the invention, layers 22 and 23 and the remaining layers belonging to plate 24 alternately having running directions which form an angle of 90 ° to the running direction of the neighboring layer.
  • the plate 24 according to FIG. 3 has equally good strength values which correspond to the strength values of the highly oriented plastic fibers, proportionally related, as they have strength values as expected from an unoriented, essentially isotropic plastic material .
  • a similar effect can be achieved with textile surface structures, e.g. with a kind of weave structure, in a single fiber layer, as shown in the fiber layer 26 according to FIG.
  • textile surface structures e.g. with a kind of weave structure
  • the matrixless composite material representing only one or a few of these layers.
  • Combinations of layers such as the layer with the pronounced weave structure in FIG. 26, FIG. 4, are combined with others, e.g. the layers 22 or 23 of Figure 3, or with layers in which the fibers are freely arranged according to the stress, e.g. in layer 25 in FIG. 4a, or with highly oriented foils, as shown schematically in FIGS. 4b and c by 26, 27, in any way possible.
  • x and y are in the ratio of approximately 60:40, the molecular weight is approximately 20,000.
  • the size-free fibers When delivered, the size-free fibers were wound in multiple layers around a plate-shaped core in parallel orientation.
  • the plate-shaped core and the counter plates of the press mold were treated with a temperature-stable, common release agent in order to facilitate the detachment of the material from the core or the counter plates at the end of the production cycle.
  • the roll was manufactured with a thickness of approx. 1 mm; the number of turns to achieve the mentioned thickness was calculated from the thread volume.
  • the fibers were subjected to drying at a drying temperature of 150 ° C. for one hour in a forced air oven.
  • the temperature-time curve of FIG. 5 shows the corresponding process, the temperature profile being the same in both examples.
  • the fiber layer on the plate-shaped core was heated to the drying temperature of 150 ° C.
  • the drying temperature is reached at time t- ⁇ WO 92/12005 PCT / EP92 / 00043
  • the drying temperature was maintained at 150 ° C for one hour ( ⁇ ⁇ - ⁇ ).
  • the fiber layer was placed in a hot press heated on both sides immediately after the drying process.
  • the heating press was already at the sintering temperature of 302 ° C selected in this case and was pressurized immediately after insertion, corresponding to a compression pressure of 3 MPa (30 bar) (cf. pressure increase in the pressure-time diagram in FIG 5 from time t2) •
  • the holding time after reaching the sintering temperature of 302 ° C. (t 4 - t 3 ) was 14 minutes.
  • cooling of the hot press was initiated at time t *, the pressing process only being ended after the drying temperature of 150 ° C. had been reached (time tc), and cooling was continued without pressure until room temperature (time tg) .
  • the wrapped plate-shaped core was placed on a hot table at room temperature.
  • the wrapped form was covered with aluminum foil and sealed and insulated against heat loss to the environment with an approximately 5 cm thick layer of glass wool.
  • time t that is, at the beginning of the heating phase for drying to 150 ° C.
  • the pressure was reduced to 0.001 MPa.
  • time t3 After the drying temperature of 150 ° C. had been reached, a drying time of one hour was also observed.
  • time t3 was kept constant for 15 minutes (until time ⁇ ).
  • cooling was initiated and at time tg, in which the fiber layer on the plate-shaped core had reached room temperature, the vacuum was released and the sintered material plate was removed from the mold.
  • the temperature control during the sintering process or during the heating period can be found in the temperature-time diagram in FIG. 5 and the corresponding pressure conditions in the pressure-time diagram in FIG. 5.
  • the time period within which the maximum press temperature did not change by more than ⁇ 1 C was defined as the holding time for the sintering temperature.
  • the longitudinal strength is significantly higher in the production method according to the invention with a processing temperature below the melting temperature than in processing methods with a processing temperature above the melting point.
  • the transverse strength and transverse stiffness assume practically the same values as in a production process in which work is carried out above the melting temperature, since the use of fibers means that a large number of contact surfaces in the transverse direction is present, which are to be connected to one another in order to obtain good transverse strength and transverse rigidity values.
  • the method according to the invention for the production of matrix-free composite materials thus opens up the possibility, with virtually unchanged transverse strength and transverse rigidity of the molded parts, of achieving a longitudinal rigidity or longitudinal strength in the molded parts which is incomparably greater than what could be achieved in the usual injection molding process with the same materials and what was possible can be achieved at a processing temperature above the melting point of the liquid-crystalline polymers.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Il est proposé un nouveau matériau composite sans matrice comportant au moins une couche de fibres synthétiques fortement orientées, lesquelles sont disposées en plusieurs plis et en position angulaire prédéterminée les unes par rapport aux autres et liées entre elles par frittage sous l'effet de la pression et de la chaleur.
EP92902391A 1991-01-10 1992-01-10 Materiau composite sans matrice Withdrawn EP0520058A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4100488 1991-01-10
DE4100488 1991-01-10

Publications (1)

Publication Number Publication Date
EP0520058A1 true EP0520058A1 (fr) 1992-12-30

Family

ID=6422756

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92902391A Withdrawn EP0520058A1 (fr) 1991-01-10 1992-01-10 Materiau composite sans matrice

Country Status (2)

Country Link
EP (1) EP0520058A1 (fr)
WO (1) WO1992012005A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2752970A1 (fr) * 1996-09-02 1998-03-06 Goreta Lucas Dispositif electronique et acoustique au format carte de credit integre dans un substrat de type fibre cristal liquide

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4440819A (en) * 1982-12-27 1984-04-03 Hughes Aircraft Company Interconnection of unidirectional fiber arrays with random fiber networks
US4943472A (en) * 1988-03-03 1990-07-24 Basf Aktiengesellschaft Improved preimpregnated material comprising a particulate thermosetting resin suitable for use in the formation of a substantially void-free fiber-reinforced composite article
EP0330960A3 (fr) * 1988-03-04 1990-07-11 General Electric Company Procédé de formation d'articles thermoplastiques renforcés avec des fibres

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9212005A1 *

Also Published As

Publication number Publication date
WO1992012005A1 (fr) 1992-07-23

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