DD242194A1 - METHOD FOR THE PRODUCTION OF HOMOGENEOUS FIBER AMPLY ARTICLES - Google Patents

Abstract

The invention relates to a manufacturing method for glasfaserverstaerkte articles with outer or intermediate layer. The aim is to produce homogeneous articles such as plates, profiles, tubes, containers or the like of glass fibers and sensitized resin, to lower the lamination and polymerization times below 10%, to increase the layer thickness at a homogeneous crosslinking density, to cause the resin to disappear from the fibers to avoid and to achieve higher strength while saving material. The task is to produce glass fiber / resin laminates with invisible made fibers homogeneous and solidify homogeneously. The essence of the invention is to provide sensitized resin coated Verstaerkungsmaterialien by esp. From below and perpendicular to the fiber direction arranged mechanical vibrations in relative movements to the occurrence of a homogeneous composite structure between fibers and resin and also a homogeneous bond between the outer or intermediate layer, then To irradiate the composite structure, esp. The layer in several stages by light emitters and thereby adjust the wavelength and dose rate of the starting materials and the layer thickness. Fields of application include cladding for houses and machines, bodies, containers, profiles, plates or the like. Design elements.

Description

Field of application of the invention

The invention relates to a process for the preparation of homogeneous fiber-reinforced articles made of unsaturated polyester or epoxy resin and blended solidification initiators blasenarm coated or impregnated thread, rope, strand or strip-shaped glass fiber reinforcing materials, preferably with at least one outer or intermediate layer of other materials or semi-finished products ,

Characteristic of the known technical solutions

There is no known method for producing homogeneous fiber reinforced articles, neither without, nor with outer or intermediate layers of other materials or semi-finished products.

Object of the invention

The object of the invention is to provide a process for the discontinuous or continuous production of homogeneous fiber-reinforced articles from esp. Glass fiber reinforced unsaturated polyester or epoxy resin, preferably with at least one outer or intermediate layer of other materials or semi-finished products, with it in a single operation on the one hand Using only a sensitizer or Sensibilisatorgemisches and electromagnetic waves esp. In the light wave range at high reinforcing material content and complete impregnation and wetting is simultaneously possible to make the glass fibers or other radiopaque fibers invisible, the lamination and polymerization or solidification time at layer thicknesses below 3 mm to lower to less than 10 minutes under layer thicknesses of less than 12 mm and under layer thicknesses of less than 12 mm, to be able to irradiate layer thicknesses of up to approximately 15 to 20 mm, and thereby require structures which are required for strength To achieve crosslinking density, to avoid internal stresses, to increase the strength between fibers and resin, to save up to 50% material at about twice the tensile / shear and flexural strength, the curing conditions esp. To reduce the volume contraction of the resin to the starting materials, the layer thickness and in continuous production, also to adapt the transport speed and, on the other hand, in the production with at least one outer or intermediate layer of other materials or semi-finished products to homogeneously and firmly bond this layer or layers or semi-finished products during production of the homogeneous fiber-reinforced article, and preferably use-related properties to create.

Explanation of the essence of the invention

The invention is based on the object, a method for producing homogeneous fiber-reinforced articles made with unsaturated polyester or epoxy resin and blended solidification initiators low-bubble coated or impregnated filament, rope, strand or ribbon-shaped radiopaque, esp. Glass fiber reinforcement materials, preferably with at least one outer or intermediate layer of other solidifiable materials or semi-finished products can be produced by the one or more laminates in particular. Homogeneously made with invisible fibers and homogeneously solidified and in which, if necessary, the applied in the meantime and applied to at least one homogenized fiber-reinforced layer other materials and / or semi-finished homogeneous with each other preferably to generate use-related properties are connected, whereby by appropriate mechanical use and summary of several process steps de r workload is reduced, the production time in total and esp. The polymerization or processing time is significantly shortened, the materials or layers vented, esp. Of bubbles and hollow bodies (voids) freed, brought together to the intimate bond and the required quality and strength properties are produced by different chemical composition of the materials and by multiple identical or different, exerted on the outside of the materials or layers and / or induced in the interior and acting in these physical and chemical reactions.

By scientific analysis of the penetration and wetting and the formation of phase boundary layers, in particular between organic resins and inorganic fiber reinforcements, their properties and hardening possibilities, and by inventive ideas, it has been possible to provide a process for the production of homogeneous fiber-reinforced articles in which these materials are used required composition, shape, amount and time unit supplied to the individual production stages or devices and there be-or. be processed, esp. The reinforcing materials with the plastics, preferably impregnated with unsaturated polyester or epoxy resins automatically wetted and then polymerized or solidified to layers or objects alone or with the other materials or semi-finished products.

The above object is achieved in that initiators, esp. Sensitisers containing resins and thus coated or impregnated reinforcing materials, esp. Also other serving as outer or intermediate layer solidifiable materials or semi-finished by preferably from below and perpendicular to the fiber direction exerted mechanical vibrations in the Up to the occurrence of a homogeneous composite structure between fibers and resin and esp. Of a homogeneous composite between the other materials or semi-finished products are added that the coated or impregnated reinforcing materials, esp. The composite structure preferably also the other materials or Semi-finished products preferably in several stages with electromagnetic waves esp. Ini light wave range is irradiated to the formation of semi-finished or finished product and that the intermittently emitted waves in W ellenlänge and dose rate depending on the starting materials, layer thickness and transport speed are adapted to the initiator or sensitizer. The liquid plastics mentioned above or the resins are preferably mixed with activating additives or sensitizers, especially those which absorb in the light wave range outside the UV range, before they are processed.

These additives or sensitizers are preferably made of polyvalent metal oxides or carbonyls or their compounds, for. As iron pentacarbonyl, and / or organic amines, eg. As triethanolamine, or their compounds and are added in amounts of less than 1 to 10 wt .-%, preferably of two weight percent, the resin. Thereafter, these sensitized resins are optionally mixed with thixotropic agents and / or fillers which can be influenced by the abovementioned vibrations and then brought into contact with the reinforcing materials with little bubbles.

In particular, in a continuous process, the resins before and / or during the vibration treatment or during the supply and / or immediately after the application to the said surfaces for polymerization by irradiation excited and polymerized or solidified after the vibration treatment in a controlled reaction course.

embodiment

The production of an article in the batch process is carried out in the following manner:

First of all, the preparation of the material adapted to the manufacture of the article in shape and size is prepared. This happens because a release agent is applied to the preferably heated surface of this stationary or stationary production form. If the article is not to be transparent, a color layer or a so-called gelcoat layer is applied to this layer. This gelcoat consists z. B. from a mixture of said polyester and dyes or color pigments and / or from polyesters and MetaIlpulvern and / or corresponding feed, preferably from esp. Anodized Aluminiumflittern or the like. And thereby produces special effects.

Depending on the required layer thickness, initiators, especially resins containing sensitizers, and reinforcing materials are applied to this layer. After application, these materials are added to the substrate or the production form in the above-mentioned vibrations and thereby and / or exposed by said electromagnetic waves suitable and esp. The initiator or sensitizer adapted wavelength and dose rate, whereby the resins, esp sensitized unsaturated polyester or epoxy resins are polymerized or solidified.

If the object to be discontinuously manufactured, with or without a gelcoat layer, should also have at least one outer or intermediate layer made of said other materials or semi-finished products, this layer or semi-finished product is applied before or preferably between two vibrational treatments.

The preparation of an article in a continuous process is as follows, wherein the shape and surface shape of the object to be generated, for. B. a flat or profiled plate, a profile, z. B. a double-T-beam, a mast or hollow mast, a pipe or container or the like. Is to be considered.

Here, the materials are moved, z. As rotating surfaces of manufacturing forms such as cores, esp.

Winding cores simultaneously or sequentially as turn next to winding next turn and / or stratified or long way fed, brought to this, possibly there or formed by the corresponding surface and during the supply and / or after or after applying the said vibrations and / or exposed to electromagnetic waves. Esp. in the case of continuous production, the thickness of the layer or layers is varied as a function of the application rate applied simultaneously or successively per unit of time. Thus, the production time of the article or, the cycle time of the production form, esp. Of the winding core or in the profile production is affected or can be significantly shortened.

If the object to be continuously produced is to have at least one outer or intermediate layer of said other materials or semi-finished products, this is also applied here before or preferably between two vibratory treatments for intimate bond formation.

Furthermore, since vibrations of different frequencies, of vibration, vibration and / or ultrasonic frequency can be applied in one or more stages, this has a favorable effect on the reduction of the production time.

It is advantageous if the materials after the single or multilayer application to tape-like structures, documents or films of transparent plastics or the like. And / or after application to the surface of an open or sealable manufacturing mold, a core, a balloon or hose or the like are exposed to said vibrations and / or waves and / or heating and / or cooling and / or subcooling zones.

In this way, the materials can be better transported and treated by the aforementioned vibrations and waves and can after their compression or the generation of a homogeneous composite structure and the radiation or by the additional heating zone first cured faster and then rapidly cooled and demolded by the cooling zone become.

If an open-mold is used, the formation of solvent vapors, e.g. B. of Styroldämpfen, quickly prevented by the waves. When using a closable production form, said vapors can no longer escape into the atmosphere after closing the mold. In addition, then the mold can be evacuated.

If a balloon or tube is used as the manufacturing mold, core or hub, the layers are created on its surface.

Irradiation with said waves may be continuous or continuous, intermittent or interrupted at intervals, and may occur at standstill (eg in the batch process) or during transport of the materials to be solidified or those to be produced or produced or already formed solidifying objects and the radiator are performed. In this way, the resins of the individual layers or layers are uniformly polymerized or solidified during production from the inside to the outside, whereby in connection with the regulation esp. The dose rate of radiation, the solidification is integrated into the production and cured exactly after production Objects can be removed from the mold. This significantly reduces the cycle time of the molds or cores and increases labor productivity.

By the above vibrations, z. As the vibration or vibration vibrations are still contained in the materials contained bubbles up and out of these and thereby destroyed and filled the hollow areas by the resins and / or the reinforcing materials. As a result, in addition to a quick and intimate impregnation and wetting of the reinforcing materials with the resins, a homogeneous composite structure between fibers and resin or in the laminate is achieved.

This homogeneous composite structure only occurs or arises from the fact that the mechanical oscillations between the resin and the reinforcing materials, which are exerted in particular by the bottom and perpendicular to the fiber direction on the coated or impregnated and at least unilaterally freely movable reinforcing materials, cause a multiple relative movement of alternating direction and rapid succession is generated, which still shortly before gelation of the initiator or

Sensitizer is homogeneously mixed with the resin and can no longer settle and the viscosity of the resin is reduced and adapts to the respective capillary structure of the reinforcing materials, the fibers located on the fibers and air bubbles are driven upwards in the direction of their natural buoyancy, the friction between Reduced fibers and resin and the surface tensions are positively affected, flaccid reinforcing fibers stretched and tightened and thereby the reinforcing materials are homogenized under certain orientation, a complete impregnation and wetting takes place and due to the latter, a phase boundary layer between the inorganic fibers and the organic resin is formed whereby a homogeneous transition between the fibers and the resin is formed, the phase boundary layer acts as an anti-reflection layer, the fibers esp. Due to the boundary layer and interference conditions not are more visible and the phase boundary layer is colored by its residual reflection in the complementary color, e.g. Violet, appears and thus additionally sensitizing.

If now this homogeneous composite structure or the laminate with the invisible made reinforcing materials irradiated by electromagnetic waves in esp. Light wave range, preferably both sides in one or more stages in adaptation of the wavelength and dose rate to the sensitizer taking into account starting materials, thickness of the composite structure and transport speed ( in continuous production), so not only a very rapid solidification or curing can be achieved, but it can be due to the made by the invisible fibers greatly reduced extinction much thicker and homogeneous and crosslinked with high crosslink density required or solidified items in yet to produce unachieved quality.

Is used as an outer or intermediate layer, a solidifiable, but by the applied electromagnetic waves undurchstrahlbarer material, eg. B. in light waves, for example, a cement-mortar mixture or mixed with solidified Barem binder crushed metallic material used, which preferably contains components that react with said resin, it can only be irradiated on one side. The intimate production of compounds then takes place depending on the vibration, in particular by the aforementioned radiation-initiated polymerization of the resin and also by the components reacting with the resin. "

If the outer or intermediate layer can be irradiated, it can be irradiated on both sides. If this layer still contains initiators or sensitizers, the bond becomes more intimate.

The present invention provides advantages for the first time, because the polyvalent metal oxides or carbonyl compounds used as light sensitizers (non-UV sensitizers), in particular iron pentacarbonyl (which decomposes into free radicals, such as iron tetra- and tricarbonyl upon irradiation, and thereby the solidification or Polymerization reaction triggers) or preferably also said carbonyl / amine compounds can mix well in the resin and hardly settle, have a high dark storage stability and esp. Through these sensitizers of the absorption in the long-wave UV range and out of this out in the visible Is shifted light wave range, so that on the one hand a much broader emission spectrum is absorbed by the sensitizer and on the other hand said (total) absorption in the UV range significantly reduced and even almost eliminated, in addition to reducing the Extink tion in this wavelength range, and on the other hand adaptation of the sensitizer to the radiator (or vice versa) and the production conditions become much easier than in said single UV polymerization, from which the short cure times also result.

Due to this shift in the absorption range by the sensitizer, an unforeseen unexpected effect is created by the fact that the reinforcing materials transmit the said light waves significantly better, in particular in the visible wave range, or absorb less than in the UV range.

For example, the organic amines, e.g. For example, triethylamine, allylamine or the like. In alcoholic solvents, optionally with the addition of catalysts used. In this way, the viscosity and reaction of the resins can be influenced. Furthermore, an amine or a diethylenetriamine in which a versamine is dissolved can also be used as a hardener or sensitizer.

Esp. For the production of articles with layer thicknesses of more than 12 mm, it is advantageous, in the case of one-sided irradiation, to add small amounts of conventional initiators (hardener and / or accelerator) to the resin, because in this way the extinction effect present in particular at such layer thicknesses can be compensated.

If the resin suitable, esp. Active fillers and / or thixotropic agents of different density, for example in the order of 7 to 25% added, although usually increases the curing time according to the type and proportion of filler and / or thixotropic agent, but are due to the defined Vibration treatment Objects with the respective load case adapted strength and density produced. When using suitable active fillers and / or thixotropic agents, i. H. those which swell or react with the resin in the resin and in particular lead to an increase in the molecular weight, the oscillations in this case (not only in the phase boundary layer) a combined physical / chemical effect, esp. in the resin between the fibers and in Oxides and / or carbonates of, in particular, polyvalent metals, eg silica gel (silica gel, silica gel, silica xerogel) or zinc oxide, titanium dioxide or the like, are preferably used as thixotropic agents, ie when using these fillers and / or thixotropic agents the viscosity and the chemistry of the resins are positively influenced, for example, the viscosity and the molecular weight are increased in order to prevent the resins of surfaces or hubs from leaking on the one hand and significantly higher strengths in the cross-linked state (especially in connection with one-pentaparbonyl higher flexural strength and impact resistance).

In addition, the resins are reduced by the vibrations in their viscosity and with said fillers and / or thixotropic agents by the Thixotropiereffekt occurring much more, so that the resins adapt in this way quickly and safely the respective capillary structure of the reinforcing materials.

After the vibration treatment occurs esp. In thixotropierten resins immediately the viscosity-increasing effect. Is then irradiated, is cured or polymerized very rapidly, whereby the increase in molecular weight on the one hand and by the composite structure produced on the other hand very high-strength objects. For this reason, it is unfavorable in the production of fiber-reinforced articles to use low-viscosity, ie low-viscosity resins, which has hitherto always been done and was unavoidable.

If ultrasonic vibrations are used, unpredictable effects, which have a positive effect on the production, are produced, which at the moment are only partially physically and / or chemically interpretable. Not only that the said bubbles and voids are removed much faster and the impregnation and wetting of the reinforcing materials with the resin is much faster, but the composite structure is additionally positively influenced.

If the resin contains thixotropic agent, it becomes more viscous or significantly less viscous in the case of ultrasound action in particular, adapts to the respective capillarity of the reinforcing materials and soaks and wets them in a matter of seconds, and the aforementioned positive effects are enhanced. After completion of the ultrasound exposure, the thus treated resin cures very rapidly when said irradiation. Whether a depolymerization and / or polymerization and / or special capillary effect additionally occurs in this case is assumed. As reinforcing materials come out of the threads or ropes strands or band-shaped structures of short fibers, corrugated, webs, fabrics, knits, or chips from said structures, or powder, preferably all of glass or minerals, even in combination with each other, for use , The corresponding variation or combination depends on the particular application. The additional use of short fibers, even when corrugated, creates a three-dimensional bond within the layers by causing these short fibers to move downwardly as a result of the vibrations that act on them, perpendicular (with appropriate fiber-reinforced material thickness and oscillation time) put.

Thus, by virtue of the oscillations exerted according to the invention, said composite structure is produced and the fibers are rendered invisible, and the sensitizer according to the invention makes it possible to use such light waves for polymerization or solidification, which penetrates the composite structure or laminate substantially better and without interference in much shorter times, much thicker and, for the first time, homogeneous fiber-reinforced articles can be produced.

By the polymerization in at least two stages or stages of preferably different wavelengths, the degree of cross-linking becomes much higher and another advantage arises from the fact that the composite structure produced and the homogeneously controlled solidification prevent any shrinkage (volume contraction) of the resin from the reinforcing fibers, thereby adding strength increases, especially since the light waves little heat enters the laminate. Furthermore, the above-mentioned polymerization improves the health and occupational safety by the styrene evaporation, which is reduced to about 20%, compared to conventional lamination and almost completely prevents air inhibition. In addition, by the vibrations no air can be incorporated into the laminate, that-laminating requires no more physical work and that by the vibrations, especially the impregnation and wetting time regardless of the size of the surface to be produced and almost independent of the layer thickness is because the entire laminate at once z. B. can be added for 2 to 4 minutes in the vibrations and then already the composite structure is produced, that the resin / reinforcing material ratio can be precisely adjusted and kept constant and that by the achievable high work productivity, which are up to about 1000% compared to the hand lamination The set up can be amortized very quickly.

The invention thus became the previously impossible, an object, d. H. Fiberglass reinforcing materials also in the resin for the eye, invisible for X-rays, hard to detect for X-rays and smoothly penetrable for the mentioned light waves, achieved for the first time and it was also the first time a homogeneous fiber-reinforced object produced in perfect quality and at a thickness of about 3 mm in about One minute and a layer thickness of 12 mm solidifies under about ten minutes.

If the objects consist of said fiber-reinforced and other materials, esp. For generating purpose-related properties, this is at least one outer and / or intermediate layer, a mixture of said material components, materials and / or layers, in particular the fiber-reinforced plastics and solid, made of liquid or pasty other materials, at least some of which are partially or completely chemically react with the plastics. The solid materials used are very finely ground to finely comminuted and / or present in free-flowing or pourable form. As liquid materials is preferably a suspension of these, and as pasty materials, a paste or a slurry is produced.

As materials for the solid, liquid or pasty layers or mixtures esp. Metals, also polyvalent metals, .Metalloxide and / or carbonates and / or polyoxides and / or polycarbonates z. As the iron and / or at least one other metal, and building materials such. B sand, gravel, Portland cement, also in the form of mortar or mortar.

The production of an article from the aforementioned layers or materials, for example, depending on the intended application as follows:

First, a layer of fiber-reinforced materials is applied to the surface of the stationary or moving or rotated production form except the release agent and treated accordingly. Thereafter, another layer of fiber-reinforced plastics (eg with short fibers), which are intimately mixed with the solid and / or pasty materials applied, and also with said vibrations and / or electromagnetic waves, but in a suitable for this polymerization Wavefront treated. If it is necessary, as a further intermediate layer or as an outer layer, a fiber-reinforced plastic layer, for example consisting of said glass fiber mats or fabrics and unsaturated polyester resins or the like, which are then treated again as the first layer applied. By chemical reaction z. B. of some metal oxides with the plastics, the composite of the materials and / or the layers is improved together, for example, in that they diffuse into one another.

Are as other materials metal powder or building materials, eg. B. used as an intermediate layer, high weight objects with special properties are required, which do not have, for example, conventional objects made of concrete or sintered metals, for. B. insensitivity to certain aggressive media and / or impact and shock and the like.

Of course, an article of a cover layer of fiber-reinforced materials with gelcoat layer and of building materials as a wall element for houses or the like. Be used. In this way, the gelcoat and fiber-reinforced plastic layer used as the outer layer is at the same time façade with a long service life over years and at the same time has surface effects with appropriate color design.

As further materials can therefore metal oxides and / or carbonates and / or polyoxides and / or polycarbonates such as the chemical composition

a · MO · Fe ₂ O ₃

where M is iron (Fe) and / or another, especially bivalent, metal, for example of cubic or hexagonal crystal structure, and a and b are a numerical factor equal to or preferably greater than 1. These or a part of these materials enter into chemical compounds with the named plastics and / or the other materials and thus have a positive influence on the properties of the objects to be produced. As the formula component M or MO, e.g. Elements of the I. group of the periodic system, e.g. Sodium or corresponding salts or the II. Group, eg. As alkaline earth metals, such as calcium or magnesium (crystallize hexagonal), or the III. Group ζ. As aluminum or gadolinium (which crystallize with the garnets) or the IV. Group, z. Lead or the V. group, e.g. B. phosphorus, or the subgroups, z. As titanium, iron or cobalt, even in mixtures or compounds with each other.

For example, magnesium oxide enters into chemical reactions with said plastics, in particular with unsaturated polyesters, which increase the bond between them.

Corresponding experiments have confirmed that the above-mentioned solid, liquid or pasty further materials depending on the purpose depending on the order of between 5 and 75%, based on said plastic and / or reinforcing material shares and reacting with the plastics shares in the order of zero (tracks) up to 10% can be used. Larger shares are esp. For strength reasons not useful. For the production of articles with support core or with sandwich construction, for. As for the cold and / or heat protection, for example, for refrigerated trucks, bodies, walls, houses, pipes, aircraft fuselages, floats or the like. As at least one outer and / or intermediate layer, a porous expectant layer, for. Example, a foam layer, one of foamable materials, in particular made of rigid foam raw materials or produced layer or a material that forms cavities or cavities forming agent, eg. B. salts (NaCl) or gases (CO ₂ ), which optionally reacts under irradiation with the plastic. In this way, for. As tubes with an inner layer of fiber reinforced materials, an intermediate layer of foamable materials and an outer layer made of fiber-reinforced materials that not only have high strength, but are also relatively cheap, because the layers of fiber-reinforced materials can be made quite thin and on this way material is saved. If said objects have a higher strength or the internal composite are increased, the foamable materials reinforcing materials, eg. As glass short or metal fibers or various chips added. The or at least one foam layer, for example of hard foam, can also be produced from a plurality of layers of different cell size and / or from foam segments of different hardness.

Furthermore, apart from the fiber-reinforced layers, the porous or porous layers, in particular the foam layers, can also have reinforcements, hollow profile bodies and / or spacing and / or fastening elements made of steel, plastics or fiber-reinforced plastics.

The reinforcements, hollow profile bodies and / or the spacing and / or fastening elements can be co-produced during manufacture, fastened on or in the corresponding layers or merely applied to the materials or the layers. In this way, the objects with other objects, such. As walls, ceilings, body parts, parts of refrigerated vehicles or the like. Are connected. Also, the connection can be made by gluing and / or with the help of special nails or screws. In this way, structures, refrigerator cars, aircraft or ship hulls or the like. Can be produced.

Since the fields of application of the articles are very different, it is possible that the layer thickness of the foam, the support core layer relative to the layer thickness of the fiber reinforced layer has a ratio between 3: 1 and 30: 1 or higher. As a result, very lightweight and high-strength objects with high thermal insulation can be generated. To the production rate and the movement of the manufacturing devices, eg. B. the winding core or the transport devices, the multi-component units and the radiator and the like. Match exactly with each other, the above-mentioned thread, rope or tape-shaped reinforcing materials or the structures mentioned or even with plastics, esp. With synthetic resins glued or verbackbaren Layers or the like stretched in the respective feeding direction. In this way, for example, serve the band-shaped reinforcing materials and / or said structures simultaneously for the transport of the binder or resins or the like placed on them.

For the production of hollow bodies or containers, a corresponding, for example, zigzag or helical mesh cylinder of the mentioned reinforcing materials in the required shape and size can preferably be produced on a winding core and impregnated with the liquid binders. Also, after this impregnation, further materials or layers, for example foamable materials, can be applied to them, for example on or between band-shaped structures (liners) or substrates.

It is also possible to apply to the surfaces to be coated as outer and / or intermediate layer fiber-reinforced materials and then materials of lower (eg foam starting materials) and higher density, for example the mentioned free-flowing materials, in particular of metal or construction materials, such as sand or the like ., With a high injection rate, esp. With the help of said multicomponent units, can be applied. Due to the high injection rate esp. The materials of higher density penetrate these already partially in the pregelled or by irradiation to the polymerization excited fiber reinforced materials and increase in this way the composite effect.

For example, for the purpose of generating use-related properties of the article to be produced on the said moving or stationary surfaces, preferably on the inner surface of a particular twisted manufacturing mold or a spinner mold said materials components, materials and materials of higher density, for example, said pourable or pulpy materials such as metals and / or building materials, including magnetizable or magnetic materials brought and exposed to the said oscillations and / or electromagnetic waves or fields and / or the pressure of said media and / or shaping elements, penetrate the materials of higher density depending on the speed of the mold the said fiber-reinforced materials and are wrapped or wrapped by these partially or completely depending on the dosage. In this way, it is possible to produce articles whose production is relatively simple, but which, after being treated with said oscillations and the electromagnetic waves or fields, are so high-strength and high-density that they can be used instead of steel pipes, but they are aggressive because of their immunity Far surpassing the media. Another advantage is that this except the relatively expensive fiber-reinforced materials very cheap and abundant waste products of the rolling or metal-working industry and / or even cheaper building materials can be used.

The shaping and / or surface shaping of the objects to be produced is carried out either by the above-mentioned oscillations, because thereby the fiber-reinforced materials or corresponding layers are quickly applied to the surface of the production mold or the corresponding base due to their own weight. However, said shaping can also be effected by the pressure of preferably extensible and resilient support and / or shaping elements on the material components, the materials and / or the layers or the band-shaped structures, documents or films or by gaseous and / or liquid Media. This happens z. B. in that z. B. a closable production form is used, which is evacuated after introduction of said materials, etc. or by supplying gaseous or liquid media, such as activating gases or liquids or foamable materials on the material components already contained on the mold surface or in the form , Materials etc. exert a pressure which, depending on the applied vacuum or overpressure, forms the named materials etc.

For the production of profiles or carriers or the said double-T-carriers or the like. Preferably, the said shaping elements are used.

The shaping of the objects can also take place in that the material components, the materials and / or the layers or the structures mentioned, etc., are deformed after treatment with said vibrations and / or after their irradiation excitation. This can also be done with the interposition of a cooling and subcooling zone. In this way, preforms or so-called prepregs are produced, which are then deformed later. For further deformation and / or further densification, solidification or polymerizate and / or the sintering treatment, the preforms or articles produced are removed from said surfaces and at other locations, if necessary between punches and dies or m Spritzgieß- or Kerngieß- or other processing machines deformed andjiier solidified or polymerized using heat and pressure and / or said electromagnetic waves, in particular a radioactive radiation or an activated gas or the like.

As an outer or intermediate layer and / or in particular as or instead of a foam layer, the following mixture may be used:

a) consisting, for example, of 100 parts by weight of an acrylate powder with redox systems or hardener, from about 7 to 25, esp. 14 parts by weight of a filler mixture, from about 20 to 40 parts by weight of aqueous liquids, esp. Water or for example a saline solution, about 60 to 130 parts by weight an acrylate monomer mixture, and / or

b) a phenol or formaldehyde resin, for example consisting of 80 to 90% phenol, concentrated preferably 27% formalin and calcium oxide and hardener (in particular from p-toluenesulfonic acid in aqueous or alcoholic solution), the foaming agent possibly known for foaming in the Order of 20 to 150% of the previous amount can be added.

Such a layer has a much higher hardness than the previously mentioned rigid foams, has a porosity similar to an integral foam (becoming smaller toward a closed surface in the direction of the outer surfaces) and, owing to its higher density, diffuses well into the surface region of the fiber reinforced materials and thus creates an excellent bond with these.

For the production of exterior and / or interior trim and / or housing for people and animals such as houses, workshops, offices, apartments, stables, walls, wall elements, refrigerator cars, bodies or the like. It is advantageous if in the production of the corresponding objects or Elements, windows or panes placed in designated places and / or injected with or embedded or glued, in this way, for. B.

Wall panels are produced with windows in the continuous manufacturing process.

It is also possible for transparent plastics to be brought to the abovementioned sites and / or solidified or polymerized during production.

Furthermore, from two identical half-shells or from a plurality of objects, the aforementioned dwellings or other objects of greater extent can be created and, as mentioned, connected to one another.

In a further refinement, the layers and / or the structures or parts of the object to be produced, for example also the half-shells, can be connected to one another by the mentioned liquid plastics and / or by adhesively bonded and / or caked layers and plastics or the like.

As adhesive layers such materials can be used, which are the aforementioned layers, for example polypropylene fiber layers with other layers, for. B. connect from curable plastics together. As a coatable layers z. B. layers of softenable by heat materials, such as thermoplastics such as polyvinyl chloride or polyvinyl acetate, in question, which are baked together in this way and, for example, gas-impermeable layers that form so-called vapor barriers.

The layers can also be produced from the materials mentioned in powder, pasty or liquid form.

The venting and compression of the material components, the materials and / or the layers and the like can be carried out by the intumescent materials via open at normal pressure and pressure-dependent controlled valves and / or applied vacuum and / or by said vibration treatment. In this way, the bubbles and voids can be removed much faster esp. From the fiber reinforced layers. Furthermore, the foaming process can be controlled and thus influence on the foam generation, pore size, etc. and on the composite of said layers influence. By the mentioned pressure control also bubbles or voids at the boundary layer foam / other materials are avoided.

In the manufacture of esp. Small objects, it may be advantageous if instead of the movement of the multi-component unit, the manufacturing form or the corresponding core or the like. Performs the necessary movements for coating, for example, during the heat treatment or the polymerization or solidification on or is moved or rotated in a multidimensional manner.

Since the mode of manufacture, for example, the curing or polymerization involved in the production requires exact movements and speeds, the continuous and also the discontinuous movement of the production devices or their movement-executing organs or elements in the plane or in space and the supply and treatment of the material components, the materials and / or the layers according to type, quantity, number, time unit and size or performance-dependent coordinated or program-dependent controlled or regulated. This is done by the corresponding manufacturing devices associated control or regulating devices. As a movement-executing organs or aggregates or elements are the transport and / or multi-component aggregates, the deformation devices, the moving or twisted production forms or the hubs or the like., The vibration or irradiation devices and their associated devices in question. In the production of wound objects, for example, the multicomponent aggregate performs relative movements to the rotary movement of the winding core by its movements, for example in the direction of the winding core and / or along the winding core, depending on whether the aforementioned web-shaped structures or reinforcing materials correspond in width to the winding core length or are narrower.

In the first case, the nozzle and / or bobbin for the supply of the material components, etc. on top of each other and in the latter case, these are arranged side by side and lead the material components, etc. successively.

Claims (20)

Invention claim: 1. A process for the preparation of homogeneous fiber-reinforced articles made with unsaturated polyester or epoxy resin and blended solidification initiators low bubble coated or impregnated filament, rope, strand or ribbon-shaped radiopaque, esp. Glass fiber reinforcement materials, preferably with at least one outer or intermediate layer of at least one other solidified η material or semi-finished product, characterized in that initiators, esp. Sensitivisatoren containing resins and thus coated or impregnated reinforcing materials, esp. Also the other serving as Ausßen- or intermediate layer solidifiable material or semi-finished by preferably from below and perpendicular to the fiber direction exerted mechanical vibrations in the ultrasonic range in relative movements esp. Until the occurrence of a homogeneous composite structure between fibers and resin and esp. Also a homogeneous bond between the other who or the semifinished product are added, that the coated or impregnated reinforcing materials, esp. The composite structure, esp. Also the other material or semifinished preferably in several stages with electromagnetic waves esp. In the light wave range is irradiated to the formation of semi-finished or finished product and that the intermittently emitted waves in wavelength and dose rate depending on the starting materials, layer thickness and transport speed are adapted to the initiator or sensitizer. 2. The method according to item 1, characterized in that the coated or impregnated reinforcing materials, esp. Also the other material or the semi-finished product before or during the supply to and / or after application to surfaces of or in production forms optionally with these in the vibrations are offset also different frequency and adjusted amplitude. 3. The method according to item 1 and 2, characterized in that the resin is mixed with sensitizers which absorb in the light wave range outside the UV range, that these sensitizers preferably from polyvalent metal oxides or carbonyls or their compounds, for. As iron pentacarbonyl, and / or organic amines, eg. As triethanolamine, or their compounds, and in amounts of from 1 to 10ew .-%, preferably 2Gew .-%, are added to the resin. 4. The method according to item 1 to 3, characterized in that the resin with Thixotropiermittein and / or fillers and also with conventional initiators (hardener and / or accelerator) is mixed, that the reinforcing and liner materials are biased and that the solidification of the composite structure is carried out over radiopaque layers or films. 5. The method according to item 1 to 4, characterized in that the composite structure before its solidification, for example, by pressure reduction (application of a vacuum) or pressure increase (feeding gaseous or liquid media or solid body) is transformed. 6. The method of item 1 to 5, characterized in that for the production of purpose-related properties, a mixture of said material components, the materials, esp. The plastics and from solid (very fine to finely crushed and / or in trickling or pourable form) , liquid (suspension) or pasty (as a paste or slurry) other materials is prepared, at least some of which partially or completely react with each other or with the plastics, that this mixture is used as at least one outer and / or intermediate layer and the other Materials esp. Of metals, including polyvalent metals, metal oxides and / or carbonates and / or polyoxides and / or polycarbonates, eg. As the iron and / or at least one other metal and / or building materials, such as sand, gravel, Portland cement, in the form of mortar or mortar, or the like. Exist and this mixture first said mechanical vibrations and then said electromagnetic waves get abandoned. 7. The method according to item 1 to 6, characterized in that as further material metal oxides and / or carbonates and / or polyoxides and / or polycarbonates about the chemical composition a · MO · b Fe ₂ O ₃ where M is iron (Fe) and / or another, especially bivalent, metal, for example of cubic or hexagonal crystal structure, and a and b are a numerical factor equal to or preferably greater than 1. 8. The method according to item 1 to 7, characterized in that instead of the formula component M or MO elements of the I.Group of the Periodic Table, z. For example, sodium or corresponding salts or the II.Gruppe, z. For example, alkaline earth metals, such as calcium or magnesium (which crystallize hexagonal) or the IV. Group, z. Lead or the V. group, e.g. As phosphorus or subgroups, z. As titanium, iron or cobalt, even in mixtures or compounds with each other. 9. The method according to item 1 to 8, characterized in that said solid, liquid or pasty further materials depending on the purpose depending on the order of between 5 and 75%, based on said plastics and / or reinforcing material and the reacting with the plastics in the Magnitude between zero (traces) up to a maximum of 10%, are used. 10. The method according to item 1 to 9, characterized in that the plastics for said physical and / or chemical influence, esp. To influence their viscosity behavior fillers, esp. Thixotropic agent in the form of neutral as chalk (CaCo ₃ ), swelling in the plastic and or with the plastic chemically reacting Thixotropiermittein such as oxides and / or carbonates esp. Of polyvalent metals, eg. As silica gel (silica gel, silica gel, silica xerogel) or zinc oxide, titanium oxide or red iron oxide (Fe ₂ O ₃ ) or the like., Or minerals, optionally in the order of about 7 to 25%, are admixed. 11. The method according to item 1 to 10, characterized in that at least one outer and / or intermediate layer, a porous or porous expectant layer, for. As a foam layer, one of foamable materials, esp. Made of hard foam raw materials or produced layer or a material is used which forms cavities or cavities forming agent, eg. B. salts (NaCl) or gases (CO ₂ ), which optionally reacts under irradiation with the plastic, that possibly the foamable materials reinforcing materials, eg. As glass short or metal fibers or the said chips are added. 12. The method according to item 1 to 11, characterized in that as a foreign and / or intermediate and / or esp. As or instead of a foam layer, a mixture of a) consisting, for example, of 100 parts by weight of an acrylate powder with redox systems or hardener, from about 7 to 25, in particular 14 parts by weight of a filler mixture, from about 20 to 40 parts by weight of aqueous liquids, especially water or, for example, a saline solution, about 60 to 130 parts by weight of a Acrylate monomer mixture, and / or b) a phenol-formaldehyde resin, for example consisting of 80 to 90% phenol, concentrated, preferably 37% formalin and calcium oxide and hardener (in particular from p-toluenesulfonic acid in aqueous or alcoholic solution), the foaming agent possibly known for foaming in the Order of 20 to 150% of the previous amount to be added is used. 13. The method according to item 1 to 12, characterized in that at least one layer produced as outer and / or intermediate layer, preferably a foam layer, esp. From rigid foams, is made of several layers of different cell sizes and / or different hard foam segments, the layers if applicable, have reinforcements, hollow profile bodies and / or spacing or fastening elements made of steel, plastics or fiber-reinforced plastics, if necessary the layer thickness of the foam or supporting core layer has a ratio of 3: 1 to 30: 1 or higher compared to the layer thickness of the fiber-reinforced layer , 14. The method according to item 1 to 13, characterized in that said structures or even with plastic esp. With synthetic resins glued or caked layers or the like. Ind stretched in the respective feeding direction by the transport devices and / or multi-component aggregates and after application the binder or the like are exposed to said vibrations and / or waves. 15. The method according to item 1 to 14, characterized in that for the production of hollow bodies, a corresponding, for example, zigzag or helical mesh cylinder made of said reinforcing materials in the required shape and size, impregnated with the liquid plastics, optionally with other materials or layers and thereby or thereafter treated with said vibrations and / or waves. 16. The method according to item 1 to 15, characterized in that on surfaces to be coated as outer and / or intermediate layer fiber reinforced materials and thereafter and / or thereby lower or higher density materials, e.g. foamable materials or said pourable materials, esp. Of metal or building materials, such as sand or the like., Applied or with high injection speed inbes. sprayed with the aid of multi-component units and thereby or subsequently treated with said vibrations and / or waves and / or fields. 17. The method according to item 1 to 16, characterized in that esp. For generating purpose-related properties on said stationary or moving surface, preferably on the inner surface of a moving, esp. Turned production form said material components, the materials and / or layers , Especially fiber-reinforced materials and materials of higher density, for example, the said pourable or mushy materials, such as metals and / or building materials, and magnetizable or magnetic materials, brought there and said oscillations and / or electromagnetic waves or fields and / or the pressure of Media and / or forming elements are exposed. 18. The method according to item 1 to 17, characterized in that the shape and / or surface shape design by the genannen vibrations and / or by the pressure of preferably stretchable or resiliently shaped support and / or shaping elements on the material components, the materials and / or the layers or the said structures or the like. Produced and the solidification is carried out by said electromagnetic waves. 19. The method according to item 1 to 18, characterized in that the genannen material components, the materials and / or the layers are deformed after treatment with said vibrations and / or after their Irradiation excitation, preferably with the interposition of a cooling or subcooling zone, if necessary and / or for 'further densification, solidification or polymerization and / or for the purpose of sintering treatment of the surfaces mentioned and deformed as a preform at the locations, possibly between dies and dies or in Spritzgieß- or core shooting or other processing machines and here be solidified or polymerized using heat and pressure and / or said electromagnetic We, in particular a radioactive radiation or an activated gas or the like. 20. The method according to item 1 to 19, characterized in that the bubble-free venting, compression and shaping of the material components, the materials and / or the layers in the closed mold by the foamable materials preferably open at normal pressure and pressure-controlled valves and / or applied Vacuum and / or by the vibration treatment, and the solidification by the electromagnetic waves, is performed.