The invention relates to a structural element, especially a laminated panel that has a layer containing cells bordered by stiff lamellas with a fibre-reinforced polymerisable plastic composite cover plate at least on one side mechanically attached with adhesive to the edges of the lamellas, especially a laminated panel with a honeycomb. The invention also relates to a process for manufacturing such structural elements.
Laminated panels are widely used in vehicle industry—for the construction of land, water and air vehicles—, and they are also used in building industry. In the case of a large proportion of well-known laminated structures, on the two external surfaces of the core material with a low density, mass and solidity generally there is a thin load-bearing plate of high solidity fixed to the core material with adhesive of a solidity needed for the transmission of shearing forces. The structure constructed in this way is light, has a high bending stiffness and behaves as a homogenous material with respect to external forces.
Both the internal core and the external load-bearing plates can be made of different materials. For example the core can be made of plastic foam, inorganic foam such as foam glass, low-density wood, or a cell structure of different materials—generally a honeycomb structure—may form the core, while the external load-bearing plate is mostly a metal plate, wood plate, thermoplastic plate or fibre-reinforced thermosetting resin plate.
Generally the load-bearing plates are fixed to the surface of the homogenous core materials by adhesive bonding. Such homogenous cores can be made for example of plastic foams or inorganic foams, balsa wood, etc. A process is also known in the course of which the space between the plates forming the external surfaces is filled with foam, and this foam is bonded to the load-bearing plates directly. According to another solution reinforcing material impregnated with not yet cross-linked resin is applied to the surface of the core material, and it is moulded onto the surface of the core material by exerting pressure and heat.
Laminated panels having the most favourable characteristics from the aspect of solidity, that is panels ensuring the highest bending stiffness with the lowest weight, can be produced by using honeycomb core materials. The material of the honeycomb core can be paper, metal, especially aluminium, stainless steel or titanium, fibre-reinforced plastic, etc.
Laminated panels with honeycomb cores are manufactured by fixing the solid cover plates to the core material with an adhesive, in a way that the adhesive is applied either to the surface of the cover plate, or the edges of the honeycomb panels are dipped in the adhesive, then the cover plate and the honeycomb core are pressed together, and the adhesive is cured mostly by thermosetting. With this procedure laminated panels are mass-produced in vehicle industry; generally honeycomb cores are made of aluminium or stainless steel, and the external layers are made of 0.5-1.5 mm thick aluminium plate, which is fixed to the honeycomb core mostly with a resin-based adhesive. Instead of aluminium plate prefabricated, fibre-reinforced (glass, carbon, Kevlar, stb.) plastic plate—composite—is also used as cover plate, and it is also fixed to the honeycomb core with an adhesive. The used adhesive is almost exclusively some kind of synthetic resin polymer. Such laminated panels with a composite cover plate and a honeycomb core are lighter than panels made of aluminium plates, but their heat resistance is significantly lower, and the bond strength of the adhesive to the prefabricated and set composite plate is not as good as the strength of the adhesive bond between the honeycomb core and the aluminium plate.
U.S. Pat. No. 6,855,393 relates to a self-bearing fire-proof panel with aluminium honeycomb core, the fire-proof component of which is formed by a 3-12 mm inorganic thermo-expanding layer. The material of this layer is thermo-expanding graphite grain or fibre structure held together by a material that melts on the application of heat. On the external surface of the honeycomb core there is a solid glass-fibre reinforced plastic layer. The insulating layer is laminated, favourably fixed by an adhesive onto one surface of the honeycomb core panel with synthetic resin of the same material.
U.S. Pat. No. 6,982,020 describes a panel with a stretchable external surface and prefabricated tubular elements, and with an expandable and compressible honeycomb structure.
U.S. Pat. No. 6,149,971 relates to fire-proof laminated panel, the core material of which is practically aluminium honeycomb, and at least one side of the panel is made of glass-fibre plastic mixed with solvent-free phenol-formaldehyde, in some cases novolac powder. The proportion of synthetic resin and glass fibre is within the range of 5-6%-100%. The material is pre-compressed at a temperature of 80-100° C. with a pressure of 1.5-2.0 atm., then the resin is cross-linked at a temperature of 180-220° C. and at a pressure of 1.5-2.0 atm. The laminated panel with an aluminium honeycomb core is made by fixing the set plate to the honeycomb core fore example with polyurethane adhesive.
U.S. Pat. No. 4,859,517 describes a bendable laminated flat panel with honeycomb core, with cover plates made of perforated metal plate or a net woven from metal fibres. Bending is performed on a compression press.
U.S. Pat. No. 4,692,367 relates to the elements of stiff mirrors with a low thermal expansion coefficient used for high-energy laser technology, which elements are made of 50% glass and 50% graphite fibre. The elements fixed to each other with glass powder are honeycomb shaped.
U.S. Pat. No. 5,188,879 describes laminated panels with honeycomb core material the cavities of which are filled with polyamide foam. In the course of manufacturing the panel first a no completely polymerised polyamide-foam plate is made, the metal honeycomb core materials is pressed into it so that the foam fills each cell, and the foam is finally set in the course of subsequent heat treatment. Then a cover plate is fixed to the surfaces, or the metal surface of the honeycomb core is treated with polymer to which the foam will stick.
The common disadvantage of the honeycomb core construction described above is that the strength of the mechanical connection between the honeycomb core and the cover plates is determined exclusively by the adhesive capacity of the adhesive used. This adherence results in a secondary bonding strength. The adherence achieved with adhesives is generally not satisfactory for fibre-reinforced synthetic resin composite plates, the adhesives cannot be fixed to the already cross-linked solid synthetic surfaces satisfactorily, whether they have the same or a different molecule structure. It is known that the subsequent adhesive bonding of already cross-linked synthetic resins, e.g.: epoxy, polyester, phenol, etc., always represents a difficulty, it requires careful surface treatment and also a base coating in many cases. It is especially difficult to fix cover plates made of heat-resistant synthetic resins, such as phenol or furan resin, to the honeycomb core with an adhesive, because set plates made of these types of synthetic resin are even more difficult to fix with an adhesive than plates made of other types of resin. There are no known adhesives that cling well both to set phenol or furan resin surfaces and to the edges of honeycomb lamellas for example made of aluminium, and are also heat-resistant and flameproof.
The task to be solved with the invention is to provide a structural element, especially a laminated panel with a honeycomb structure core—or more generally a layer containing cells bordered by stiff lamellas—and load-bearing external or/and internal cover plates, which is lighter and more solid than the earlier known solutions of a similar nature; and may also be more heat resistant.
The invention is based on the recognition that if the mechanical connection between the cell layer, for example honeycomb core, and the cover plate(s) can be established by achieving higher solidity than in the case of simply fixing them together by an adhesive, the characteristics of the whole structure will significantly improve. We also realised that the above mechanical connection can be improved, if—with respect to the fact that no synthetic resin can be fixed with a chemical bond to already cross-linked synthetic resin, whether they are of the same type or not—instead of or beside the secondary or second-rate bonding strength of the achievable adhesion between the connecting surfaces a chemical bond is created too. The bond between the cell layer, for example honeycomb structure core, and the synthetic resin composite cover plate of high solidity is realised so that instead of a secondary bond the synthetic resin matrix of the plate and the molecules of the adhesive clinging to the core material are united by a chemical bond ensuring the strongest connection. According to our realisation it can be achieved by fixing the honeycomb core and the synthetic resin composite cover plates together in their so-called “B” status, that is before they are completely set, with a polymer-based adhesive clinging with a chemical bond to the material of the partially polymerised (pre-polymerised) resin matrix of the fibre-reinforced cover plates having a synthetic resin matrix.
The invention has a layer containing cells bordered by stiff lamellas and a cover plate fixed to the edges of the lamellas with some adhesive material, and this structural element is characterised by that the cover plate is a fibre-reinforced composite plate, and the edges of the lamellas extend into it keeping a certain distance, and they are connected to the cover plate via a chemical bond realised between its synthetic resin matrix and the adhesive material. Practically the structural element has a layer containing cells bordered by lamellas made of metal, favourably aluminium, but obviously the lamellas can also be made of a material other than metal. Generally the cover plate is made of textile woven or not woven from fibres, impregnated with polymerised plastic material.
In accordance with a further feature of the invention it is constructed as a laminated panel with a honeycomb structure core and with cover plates on two sides of the core connected to the edges of the lamellas with a chemical bond. Although this is expected to be the most common use of the invention, probably there will be other areas of use where there is a cover plate only on one side of the cells, that is the honeycomb core.
In the case of another construction example the structural element according to the invention is constructed as a body with several layers containing cells bordered by stiff lamellas, in which body the neighbouring cell layers are connected with a chemical bond to an intermediate plate functioning as a common internal cover plate. It means that two cell layers are held together by an intermediate plate as a common internal cover plate, and one or even both of the two external open cell surfaces can be sealed with an external cover plate, but a solution is also included in the sphere of protection of the invention in the case of which both free element surfaces remain open cell surfaces.
According to another construction example the fibre-reinforced plastic composite cover plate or/and intermediate plate and the matrix of the adhesive is epoxy, polyester, vinyl-ester, phenol or furan resin—containing a filler in a given case—or a mixture of them; and the fibres used in the favourably woven or not woven textile are glass, carbon, ceramic or Kevlar fibres.
It may also be favourable, if the cell layer is fixed to the cover plate with expanded adhesive.
The invention also relates to a process for manufacturing a structural element that has a layer containing cells bordered by stiff lamellas with a fibre-reinforced polymerisable plastic composite cover plate at least on one side mechanically attached with adhesive to the edges of the lamellas, especially a laminated panel with a honeycomb structure core, which is based on that the cover plate, while it is still in a partially polymerised, still soft condition, when it can already be handled, is connected to the layer containing cells after the polymer-based adhesive suitable for creating a chemical bond with the synthetic resin matrix of the cover plate has been applied to the connecting surfaces and the edges of said cells being pressed into the cover plate; and the cross-linking of the adhesive and the complete polymerisation of the synthetic resin matrix of the cover plate are realised simultaneously as a result of which a chemical bond is created between the cover plate and the layer containing cells, that is both the adhesive and the matrix of the synthetic resin are cross-linked at the same time until they are completely set. The fibre-reinforced plastic composite cover plate may be woven or not woven textile material impregnated with polymerised plastic bonded to the cell layer—or to the honeycomb structure core in the case of laminated panels—as a soft material that is not sticky any more and feels dry and can be handled, when its resin matrix is in a partially polymerised (pre-polymerised) condition.
According to a favourable realisation of the process the partial polymerisation of the cover plate is realised by tempering and/or by adding a catalytic agent. It is also favourable, if the cover plate and the cell layer, with adhesive applied to their connecting surfaces, are compressed practically in the course tempering for example with stiff, practically heated sheets, realising by this the complete polymerisation of the synthetic resin material of the cover plate and the adhesive at the same time.
In accordance with another feature of the invention the polymer-based adhesive is applied as a continuous layer onto the complete surface of one side of the pre-polymerised cover plate, but it may also be favourable, if the polymer-based adhesive is applied onto the area of the edges of the lamellas of the layer containing cells, practically by dipping the edges into the adhesive.
According to a further realisation of the process, if a laminated panel is made containing a honeycomb structure core with two cover plates, the two cover plates are pressed onto the core simultaneously, by exerting pressure on them, practically in the course of tempering; or, as described above, first one of the cover plates is attached to it, and then, after the complete polymerisation of the cover plate and the adhesive the second plate is attached to the core.
As it has been pointed out above, the cover plate used for manufacturing the structural element is made of textile woven or not woven from fibres, impregnated with polymerised plastic, still soft but not sticky, possible to handle and only partly polymerised. Generally glass, carbon, ceramic or Kevlar fibres are used as reinforcing fibres in the for example woven or not woven textile.
According to a different realisation of the process epoxy, polyester, vinylester, phenol or furan resin or a mixture of them is used as the polymer matrix of the cover plate, containing a filler in a given case and used with their catalytic agents known in themselves.
Generally it is favourable, if a material identical to the polymer matrix of the cover plate is used as an adhesive.
For the purpose of improving the heat-insulating ability of the structural element, for example laminated panel, it may be favourable, if the polymer adhesive is expanded by mixing an expanding agent to it during the period of cross-linking.
In accordance with the above the most important steps of the technology used in the majority of the cases are generally the following:
Below the invention is described in detail on the basis of the attached drawings showing the general construction of the laminated structure, the traditional connections between the honeycomb core and the cover plate and a few favourable constructions of the laminated structure according to the invention. In the drawings
As it can be seen in
The structural element according to the invention overcomes these deficiencies, as we significantly improved for example the mechanical connection between the honeycomb core and cover plates of a laminated panel, and made it possible to use cover plates of a composite material with a greater heat resistance than aluminium.
The manufacturing process of the laminated panel shown in
With the process according to the invention multilayer—multilevel—elements with cell layers, such as laminated panels, can also be manufactured as shown in
Below the invention is described in detail on the basis of examples.
A 22 mm thick laminated panel with a honeycomb core and cover plates surrounding it is manufactured with the procedure according to the invention. 330 g/m2 of glass cloth consisting of glass fibres with an approximate diameter of 12 microns (Typ. 5342055 Tolnatext) is impregnated with polyester resin (CRYSTIC 199, Scott Bader). As filler 1 weight percent of colloid silica thixotropic additive (HDK T 40, Wacker), as thickener 5 weight percent of magnesium dioxide (Bayer AG), and 10 weight percent of calcium carbonate (CALCITEC M/5, Sacile, Italy) is mixed in the resin.
Directly before impregnation 1.5 weight percent of methyl ethyl ketone peroxide catalytic agent (BUTANOX M50, Akzo Chemie) is added to the mixture. The weight proportion of the glass cloth and the resin mixture is 50-50%.
The glass cloth impregnated in this way is stored at a temperature of 25° C. for 48 hours, during which period the necessary pre-polymerisation takes place.
Adhesive is made from vinylester resin (DERAKANE 411-45, Dow Chemical), and 2 weight percent of colloid silica, 80 weight percent of kaolin (KAOLIN KKA, Lasselsberger a.s.) and 2 weight percent of methyl ethyl ketone peroxide is mixed to it.
The cover plates needed for the panel to be manufactured are cut out from the impregnated glass cloth, and a 1 mm thick adhesive layer is applied onto one side of them with ordinary tools used in synthetic resin industry (
The laminated panel prepared in this way are placed between heated pressing sheets. Silicone-treated separating paper (GRILLON 57, Ahltrom Spec) is placed on the pressing sheets. The temperature of the pressing sheets is set at 130° C. The press is sealed, and the plates coated with an adhesive layer are pressed onto both sides of the honeycomb core using pressure of 150.000 Pa. As a result of the heat and pressure perfect polymerisation takes place both in the plates and in the adhesive. The pressing time is 15 minutes.
The same procedure is followed as in example 1, but in this case for the purpose of improving the heat insulating ability of the laminated panel 4 weight percent of isocyanate-based expanding agent (ONGRONAT CR-30-20, Borsodchem Rt.) is mixed in the adhesive.
The same procedure is followed as in example 1 or 2, except for the method of applying the adhesive. In this case the adhesive is not applied onto the plates cut our from the impregnated glass cloth, but as described in connection with 6, with the help of a suitable applicator a 2 mm thick adhesive layer is applied onto the edges of the lamellas of the honeycomb core, or the honeycomb core is dipped into the adhesive, and the cover plates are pressed together with the core coated with adhesive in this way.
A laminated panel is manufactured using the honeycomb core described in example 1, but the cover plates are prepared as below:
330 g/m2 of glass cloth (Typ. 5342055, Tolnatext Bt, Hungary) is impregnated with 50 weight % of phenol resin (LENDAFEN 770, Nafta, Petrochem) filled with silica flour (SILBOND 600 EST, Quarzwerke GmbH), and 0.5 weight % of maleic anhydride is mixed to it. The resin and glass fibre proportion is 55%-45%.
Adhesive is made from the same resin as above, and 30 weight % of talcum (HAICHENG No. 1, Fu Yuan), 1 weight % of paratoluol sulphonic acid, 3 weight % of silica (HDK T 40, Wacker AG) and 15 weight % graphite powder (SPECIAL GRAFIT, Richard Anton KG) is mixed to it.
The impregnated glass cloth is dried at a temperature of 30° C. for 24 hours, while the water content of the resin is partly removed. Then it is stored at 15° C.
The plate pre-polymerised in this way can be handled and bent. From this point the procedure described in example 1 is followed with the only difference that pressing is performed at a temperature of 150° C.
A laminated panel of increased heat insulating capacity is manufactured in a way that the procedure described in examples 1 and 4 are followed, but in this case 1 weight % of glass microspheres (K25, 3M)—that is hollow microspheres with a diameter of 50 microns—is mixed to the adhesive, which results in a cellular structure in the resin.
The advantageous effects of the invention are the following:
the quality of the connection between the honeycomb core—the cell layer in general—and the cover plate, tearing strength is increased significantly, even by 30-120% due to the chemical bond. According to our laboratory measurements using the materials stated in example 1, in the case of a laminated panel made by fixing the aluminium honeycomb core to the cover plate completely cured in accordance with the traditional procedure the tearing strength is 20N/10 mm, while in the case of a panel made with the procedure according to the invention—a pre-polymerised cover plate polymerised together with the adhesive—this value is 45N/10 mm.
Due to this very significant increase of the tearing strength the invention makes it possible to use fibre-reinforced (e.g.: glass, carbon, Kevlar, ceramic fibres) plastic composite plates widely in the course of manufacturing high-strength laminated panels. It is known that composite plates have a higher tearing strength than aluminium, but they could not be fixed to the honeycomb core securely using an adhesive—in their completely cured condition as it is performed traditionally—, because completely cured synthetic resin is difficult to fix with an adhesive. The invention eliminates this problem perfectly.
At the same time the use of composite cover plates in the case of honeycomb structure laminated panels results in a significant weight reduction. The result of our concrete comparative measurements was that the weight difference between laminated panels made with 2×0.5 mm thick aluminium cover plates and 2×0.4 mm thick phenol resin composite cover plates—using the same amount of adhesive—was 900 g/m2, and despite the fact that the laminated panel made from synthetic resin composite was lighter, the bending strength of the two different laminated panels was the same.
A further advantage of the invention is that the heat resistance of the laminated panels made with our procedure can be increased. The heat resistance of laminated panels with a honeycomb core is determined by the cover plate and the adhesive used. We performed comparative measurements in this respect too on 200×200×20 mm laminated panels with a honeycomb core as described in example 1. In the first case the cover plates were made from aluminium, while in the second case they were made from phenol synthetic resin composite.
Both the first and the second panels were tested with jet flame of a temperature of 800° C. to determine their flame-resistance. In the case of the panel with an aluminium cover plate the flame-resistance was 0.5 minutes, while in the case of the panel prepared with the procedure according to the invention it was 8.0 minutes.
Obviously the invention is not restricted to the examples described above, but it can be realised in several other ways within the sphere of protection defined by the claims.
Number | Date | Country | Kind |
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P0500150 | Jan 2005 | HU | national |
P06600053 | Jan 2006 | HU | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
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PCT/HU2006/000008 | 1/27/2006 | WO | 00 | 5/13/2008 |