DE202017003888U1 - oilcontainer - Google Patents

Abstract

Oil tank, preferably oil pan, containing at least one single-layer fiber-matrix semi-finished product wherein 1 to 100 semi-finished fiber layers of continuous fibers, wherein the semi-finished fiber layers each have a basis weight in the range of 5 g / m2 to 3000 g / m2, and the entirety of all semi-finished fiber layers with at least one Thermoplastic is impregnated with a MVR according to ISO 1133 in the range of 1 cm3 / 10 min to 100 cm3 / 10 min, wherein the thermoplastic from the group of polyolefins, vinyl polymers, polyacrylates, polyamides, polyurethanes, polyureas, polyimides, polyesters, polyethers, polystyrenes , Polyhydantoins, polyphenylene oxides, polyarylene sulfides, polysulfones, polycarbonates, polyphthalamides, polymethylmethacrylates, styrene-acrylonitriles, thermoplastic olefin-based elastomers, thermoplastic polyurethanes and polyoxymethylenes, and this fiber-matrix semi-finished product has a volume fraction of fiber materials in the range from 5 to 90 as defined by DIN 1310 Vol .-% and a Vo lumenanteil in air or gas of less than 15 vol .-%, having.

Description

The present invention relates to oil containers containing at least one single-layer, continuous fiber-reinforced fiber-matrix semifinished product obtained by impregnating semifinished fiber products with at least one thermoplastic and their use in vehicles or in buildings.

State of the art

In today's vehicle industry there are efforts to structure - as well as trim parts made of fiber-reinforced plastic form. Fiber reinforced plastics (FRP) are generally used in vehicle construction where high strength and stiffness are required. Basically, FRPs include reinforcing fibers embedded in a matrix of plastic. The fibers give the component its mechanical properties. The highest mechanical properties are achieved when the fibers are oriented in a stretched position in the direction of the force flow. In order to further reduce the component weight with sufficiently high mechanical properties, particularly thin-walled components are produced which are reinforced only at predetermined locations. In the production of such FRP-based components, however, it must be ensured with great effort that the reinforcing elements do not leave their preselected position or slip unintentionally.

Oil reservoirs, in particular oil pans, are well known, for example from the DE 10 2008 027 662 A1 , In generic oil pans, the contact surface is sealingly applied to a housing of an internal combustion engine, in particular to a crankcase, or a housing of a transmission and connected to this housing. Usually oil pans for internal combustion engines are made of metal. For reasons of weight reduction are also known oil pans made of plastic. Such an embodiment is in DE 10 2008 038 958 A1 disclosed. By incorporating fibers therein, the strength of a plastic material is increased. However, there is the problem with oil pans that the oil is warm when the internal combustion engine is running and, accordingly, the oil pan is exposed to increased service temperatures and constant temperature fluctuations. The temperature fluctuations occur in the region of the ambient temperature at standstill of the internal combustion engine and in the range of their operating temperature. This leads to a certain softening of the plastic material, even if the plastic material is reinforced by means of fibers. The softening of the plastic material in turn leads in particular in the area of the contact surface to changes, due to which a tightness between the contact surface and the counterpart surface formed by the motor or transmission-side housing can no longer be ensured with the required accuracy.

Therefore, according to WO 2007/128395 A1 Oil pans in the form of a hybrid component based on a base made of metal, which can be additionally encapsulated with plastic, preferably a thermoplastic. In WO 2012/126910 A1 so-called organo sheets are used for the production of, among other oil sumps. DE 10 2012 205 078 A1 discloses the use of fiber-reinforced plastic mats, preferably embedded in polyamide, as part of an oil sump body, to which in addition a frame is formed by encapsulating a plastic. Finally revealed CN 201573367 U Oil tanks with a layered structure based on glass fiber reinforced plastics.

The production of organic sheets, also referred to in the context of the present invention as composites or fiber-matrix semi-finished products, is known to the person skilled in the art. Common to all is the embedding of fiber materials / fiber semi-finished products in a plastic matrix. Usual embedding methods are the (injection) pour according to DE 10 2008 052 000 A1 , the foaming, the (flow) pressing, the pressing of resin-impregnated fabric sheets (prepregs) according to EP 0291629 A2 , the pultrusion according to EP 2028231 A1 , calendering according to DE 10 2009 053 502 A1 or laminating according to EP 1923420 A1 , In particular, the latter describes the typically layered construction of organic sheets, wherein a first group of reinforcing fibers is coupled to the plastic matrix via a first fiber-matrix adhesion and a second group of reinforcing fibers is bonded to the plastic matrix via a second fiber-matrix adhesion is coupled. The second fiber matrix adhesion is less than the first fiber matrix adhesion formed. Due to the different design of the fiber-matrix adhesion improved fracture behavior should be achieved in total failure. However, a disadvantage of fiber-matrix semi-finished products of the prior art is the not always satisfactory adhesion of the layers to one another within such a composite, and in particular the adhesion of the outer layers to the lower layers. This adhesion can be additionally impaired by the action of media, in particular in the form of synthetic or fossil fuels and lubricants, as well as by frequent temperature fluctuations. The consequence is an at least partial onset of delamination of the outer layers of a composite. In contrast, modern oil pans have to on the one hand be resistant to media against fossil fuels and lubricants, on the other hand, but also withstand the constant change between outside temperatures and operating temperatures of internal combustion engines and also have a low temperature stability, if it is oil pans used in motor vehicles in extremely cold climates. For the purposes of the present invention, low temperatures are temperatures ≤ -30 ° C. Finally, oil pans, which are usually mounted on the underside of internal combustion engines and therefore exposed to external forces, for example in the form of rockfall, have a sufficient (long-term) impact resistance.

Object of the present invention was to provide oil containers based on organo sheets, which meet both the high demands on lightweight construction in vehicles, resist the frequent temperature fluctuations and the action of synthetic and fossil oils, fuels and their combustion residues and at the same time by a high impact resistance and characterized as far as possible by low-temperature stability by less prone to delamination compared to organo sheets of the prior art.

invention

• – 1 bis 100 Faserhalbzeuglagen aus Endlosfasern, bevorzugt 2 bis 40 Faserhalbzeuglagen aus Endlosfasern, besonders bevorzugt 2 bis 10 Faserhalbzeuglagen aus Endlosfasern,
• – wobei die Faserhalbzeuglagen jeweils ein Flächengewicht im Bereich von 5 g/m² bis 3000 g/m², bevorzugt im Bereich von 100 g/m² bis 900 g/m², besonders bevorzugt im Bereich von 150 g/m² bis 750 g/m² aufweisen,
• – und die Gesamtheit aller Faserhalbzeuglagen mit wenigstens einem Thermoplast mit einem MVR nach ISO 1133 im Bereich von 1 cm³/10 min bis 100 cm³/10 min imprägniert ist,
• – wobei der Thermoplast aus der Gruppe der Polyolefine, Vinylpolymerisate, Polyacrylate, Polyamide, Polyurethane, Polyharnstoffe, Polyimide, Polyester, Polyether, Polystyrole, Polyhydantoine, Polyphenylenoxide (PPO), Polyarylensulfide, Polysulfone, Polycarbonate (PC), Polyphthalamide (PPA), Polymethylmethacrylate (PMMA), Styrolacrylnitrile (SAN), TPO (Thermoplastische Elastomere auf Olefinbasis), TPU (Thermoplastische Polyurethane) und Polyoxymethylene (POM) ausgewählt wird,
• – und das Faser-Matrix-Halbzeug einen nach DIN 1310 definierten Volumenanteil an Fasermaterialien im Bereich von 5 bis 90 Vol.-%, vorzugsweise im Bereich von 30 bis 60 Vol.-%, besonders bevorzugt im Bereich 45 bis 55 Vol.-%, und einen Volumenanteil an Luft oder Gas von weniger als 15 Vol.-%, vorzugsweise weniger als 10 Vol.-%, besonders bevorzugt weniger als 5 Vol.-%, aufweist.

The object and the object of the present invention are oil containers, preferably oil pans, comprising at least one monolayer, fiber-matrix semifinished product in which

• 1 to 100 semi-finished fiber layers of continuous fibers, preferably 2 to 40 semi-finished fiber layers of continuous fibers, more preferably 2 to 10 semi-finished fiber layers of continuous fibers,
• - Wherein the semifinished fiber layers each have a basis weight in the range of 5 g / m ² to 3000 g / m ² , preferably in the range of 100 g / m ² to 900 g / m ² , particularly preferably in the range of 150 g / m ² to 750 have g / m ² ,
• - And the entirety of all semi-finished fiber layers with at least one thermoplastic with an MVR after ISO 1133 is in the range from 1 cm ^3/10 min to 100 cm ^3/10 min impregnated,
• - The thermoplastic from the group of polyolefins, vinyl polymers, polyacrylates, polyamides, polyurethanes, polyureas, polyimides, polyesters, polyethers, polystyrenes, polyhydantoins, polyphenylene oxides (PPO), polyarylene sulfides, polysulfones, polycarbonates (PC), polyphthalamides (PPA), polymethyl methacrylates (PMMA), styrene acrylonitrile (SAN), TPO (thermoplastic elastomers based on olefins), TPU (thermoplastic polyurethanes) and polyoxymethylene (POM) are selected,
• - And the fiber-matrix semi-finished one after DIN 1310 defined volume fraction of fiber materials in the range of 5 to 90 vol .-%, preferably in the range of 30 to 60 vol .-%, particularly preferably in the range 45 to 55 vol .-%, and a volume fraction of air or gas of less than 15 % By volume, preferably less than 10% by volume, more preferably less than 5% by volume.

According to the invention, single-layer fiber-matrix semifinished products to be used in oil containers, preferably oil sumps, preferably have a material thickness in the range from 0.05 mm to 6 mm, particularly preferably in the range from 0.1 mm to 2 mm, very particularly preferably in the range from 0.3 mm to 1.0 mm, on.

The present invention also relates to a method for producing an oil container, preferably oil sump, by subjecting a single-layer fiber-matrix semifinished product to a shaping process, then curing it and removing it from the negative mold of an oil container, preferably an oil sump.

For clarification, it should be noted that the scope of the invention includes all listed, more general or preferred definitions and parameters in any combination.

Monolayer in the sense of the present invention means that it is within the fiber-matrix semifinished product to be used according to the invention, which is usually initially in sheet form, ie. H. in the region between the upper surface and the lower surface, there are no regions or sections which have a volume fraction of air or gas or a volume fraction of fiber materials outside the above-mentioned or claimed areas. A distinction between matrix resin composition and surface resin composition as in the prior art is no longer possible due to the high degree of impregnation of the entirety of all semi-finished fiber layers with thermoplastic and the concomitant or subsequent consolidation. Thermoplastic in the context of the present invention also means any mixtures of the aforementioned thermoplastics and mixtures of the aforementioned thermoplastics with at least one filler and / or reinforcing agent or additive, also referred to as compounds. All standards described in the present application are valid as of the filing date, unless otherwise stated.

The technical superiority of single-layer fiber-matrix semi-finished products is occupied in the context of the present invention by means of the rib deduction test by Kopfzugprobe as they Expert from W. Siebenpfeiffer, lightweight technologies in the automotive industry, Springer-Wieweg, 2014, pages 118-120 , is known and as described in the examples section.

definitions

The melt volume flow rate (MVR) is used to characterize the flow behavior of a thermoplastic under certain pressure and temperature conditions. It is a measure of the viscosity of a plastic melt. From it can be concluded that the degree of polymerization, ie the average number of monomer units in a molecule. The MVR after ISO 1133 is determined by means of a capillary rheometer, wherein the material, preferably in the form of granules or powder, is melted in a heatable cylinder and pressed under a pressure resulting from the contact load through a defined nozzle, preferably capillary. The exiting volume or mass of the polymer melt, the so-called extrudate, is determined as a function of time. A significant advantage of the melt volume flow rate lies in the simple measurement of the piston travel with known piston diameter for determining the leaked melt volume. The unit for the MVR is cm ^3/10 min.

Compounding or compound is a term from the field of plastics technology, which can be equated with plastic processing and describes the refining process of plastics by admixing additives, in particular fillers, additives, etc., for the targeted optimization of the property profiles. The compounding is preferably carried out in extruders and includes the process operations conveying, melting, dispersing, mixing, degassing and pressure build-up. The dispersion is preferably carried out by means of a melt mixing process in at least one mixing tool. Mixing tools are preferably single or twin screw extruders or Banbury mixers. The individual components of a thermoplastic composition are mixed in at least one mixing tool, preferably at temperatures in the range around the melting point of the at least one thermoplastic in the thermoplastic composition and discharged as a strand. Usually, the strand is cooled to Granulierfähigkeit and then granulated. The thermoplastic or the thermoplastic composition is usually present as granules, flakes or in the form of other macroscopic parts.

The terms "over," "at," or "about" as used in the present specification are intended to mean that the amount or value thereafter may be the concrete value or an approximately equal value. The term is intended to convey that similar values lead to equivalent results or effects according to the invention and are encompassed by the invention.

A "fiber" in the context of the present invention is a macroscopically homogeneous body with a high ratio of length to its cross-sectional area. The fiber cross-section may be any shape, but is usually round or oval.

• – geschnittene Fasern, auch als Kurzfasern bezeichnet, mit einer Länge im Bereich von 0,1 bis 1 mm,
• – Langfasern mit einer Länge im Bereich von 1 bis 50 mm und
• – Endlosfasern mit einer Länge L > 50 mm.

According to " http://de.wikipedia.org/wiki/Faser-Kunststoff-Verbund " a distinction is made

• Cut fibers, also referred to as short fibers, having a length in the range of 0.1 to 1 mm,
• Long fibers with a length in the range of 1 to 50 mm and
• - continuous fibers with a length L> 50 mm.

Fiber lengths can be determined, for example, by microfocus X-ray computed tomography (μ-CT); J. Kastner et. al., Quantitative measurement of fiber lengths and distribution in fiber-reinforced plastic parts by means of μ-X-ray computed tomography, DGZfP Annual Meeting 2007 - Lecture 47, pages 1-8 , Fiber-matrix semifinished products to be used according to the invention contain continuous fibers. In one embodiment, they may contain long fibers in addition to the continuous fibers.

The term "semi-finished fiber layers" as used in the present application means a material which is preferably selected from the group consisting of fabrics, scrims including multi-axial scrims, embroidery, braids, nonwovens, felts, and mats, or which is in the form of unidirectional fiber strands. Furthermore, semifinished fiber layers according to the invention also mean a mixture or combinations of two or more of the materials mentioned in this section.

To make semi-finished fiber layers, the fibers to be used are bonded together so that at least one fiber or fiber strand contacts at least one other fiber or fiber strand to form a continuous material. Or else, for the production of the Fibrous web layers used fibers contact each other in such a way that a continuous mat, fabric, textile or similar structure is formed.

The term "basis weight" refers to the mass of a material as a function of the area and in the context of the present invention refers to the dry fiber layer. The weight per unit area will decrease DIN EN ISO 12127 certainly.

"Impregnated" in the sense of the present invention means that the at least one thermoplastic or optionally the thermoplastic composition penetrates into the depressions and cavities of the entirety of all semi-finished fiber layers and wets the fiber material. "Consolidated" in the sense of the present invention means that an air content of less than 15% by volume is present in the composite structure. Impregnation (wetting of the fiber material by the polymer composition) and consolidation (minimizing the fraction of trapped gases) may be carried out and / or performed simultaneously and / or sequentially.

In the context of the present invention, the following signs have the respective meaning: ≥ means greater than or equal to, ≤ means less than or equal to,> means greater than, <means less than.

For the sake of clarity, it should be noted that the monolayer nature of the total semifinished fiber layer, its basis weight, the thermoplastic to be used, the volume fraction of fibers and the volume fraction of air or gas with respect to the entire fiber matrix semifinished product, d. H. in the area of the upper surface and the lower surface, is defined. A fiber-matrix semifinished product to be used according to the invention is preferably characterized by the fact that these features are uniformly present in the same by the impregnation process and by the consolidation. The term "uniform" describes, therefore, in particular the fact that within the fiber-matrix semifinished product according to the invention, preferably in the area between upper surface and lower surface, there are no regions or sections containing a volume fraction of air or gas or a volume fraction of fiber materials outside of have the above-mentioned or claimed areas.

Preferred embodiments of the invention

However, the present invention also relates to a method for producing an oil container by subjecting at least one single-layer fiber matrix semifinished product as described above a shaping process, then cured and removes the negative mold of an oil container.

Preferably, for the production of an oil container, preferably an oil pan, the fiber-matrix semifinished product is provided as a plate-shaped continuous product. Such plate-shaped fiber-matrix semi-finished products can be easily cut to the desired final contour, so that little material is lost during cutting.

Fiber-matrix semi-finished products are the subject of extensive research and are used, for example, in Composites Technologies, The Processing of FV Thermoplastics, ETH Zurich IMES-ST, Chapter 9, Version 3.0, October 2004 , described. While the fibers in fiber-matrix semifinished products significantly determine the mechanical properties of such a composite, such as strength and rigidity, the polymer matrix transfers the forces between the fibers, supports the fibers against buckling and protects them from external attack. The fibers may, on the one hand, be oriented in one direction only (unidirectionally, eg, as a tape), perpendicular to each other in two directions (orthotropic or balanced), or quasi-isotropically placed at any desired angle to each other become. Endless fibers have the advantage that they can be very stretched with a high degree of orientation and thus incorporated in larger quantities in the polymer matrix. In addition, they allow the flow of force between force application points within fiber-matrix semi-finished products alone via the fibers, which increases the mechanical performance of a component based on such continuous fiber-reinforced fiber-matrix semi-finished products.

Fiber-matrix semifinished products to be used according to the invention are produced by impregnating the semi-finished fiber products to be used according to the invention from endless fibers. The invention therefore also relates to a method for producing an oil container, preferably an oil pan, by subjecting at least one single-layer fiber-matrix semifinished product to a shaping process, then hardening it and removing it from the mold.

• a) Bereitstellen wenigstens eines Thermoplasten oder Bereitstellen einer Thermoplastzusammensetzung,
• b) Bereitstellen von Faserhalbzeuglagen aus Endlosfasern,
• c) Auftragen des wenigstens einen Thermoplasten bzw. der Thermoplastzusammensetzung auf die Gesamtheit aller Faserhalbzeuglagen,
• d) Imprägnieren der Gesamtheit aller Faserhalbzeuglagen mit wenigstens einem Thermoplasten bzw. mit der Thermoplastzusammensetzung,
• e) Entlüftung der mit wenigstens einem Thermoplast bzw. Thermoplastzusammensetzung imprägnierten Gesamtheit aller Faserhalbzeuglagen und Entfernen des Thermoplastharzüberschusses (Konsolidieren),
• f) Formgebung zum Ölbehälter,
• g) Härtung des Ölbehälters aus wenigstens mit einem Thermoplast bzw. Thermoplastzusammensetzung imprägnierten und konsolidierten Gesamtheit aller Faserhalbzeuglagen (Solidifikation) und Entnahme aus der Form.

Preferably, the manufacturing process of the fiber-matrix semifinished product is combined with the shaping process. In this case, before the forming step, the process steps of impregnation and consolidating and optionally solidifying the entirety of all semi-finished fiber layers with at least one thermoplastic or preceded by a thermoplastic composition. The overall process preferably contains the process steps

• a) providing at least one thermoplastic or providing a thermoplastic composition,
• b) providing semi-finished fiber layers of continuous fibers,
• c) applying the at least one thermoplastic or the thermoplastic composition to the entirety of all semi-finished fiber layers,
• d) impregnating the entirety of all semi-finished fiber layers with at least one thermoplastic or with the thermoplastic composition,
• e) deaeration of the impregnated with at least one thermoplastic or thermoplastic composition of all fiber semi-finished product layers and removing the thermoplastic resin excess (consolidate),
• f) shaping to the oil container,
• g) hardening of the oil container from at least one thermoplastic or thermoplastic composition impregnated and consolidated totality of all semi-finished fiber layers (solidification) and removal from the mold.

In one embodiment, process step h) may also be followed by process step h) tempering.

In one embodiment, the process step i) of a subsequent treatment of the oil container may follow process step g) or process step h).

Preferably, a lamination process is used during the impregnation. In one embodiment, in addition to the continuous fibers, long fibers and / or short fibers may also be contained in the single-layer fiber-matrix semifinished product to be used according to the invention.

The process according to the invention is particularly suitable for semi-continuous or continuous pressing processes, preferably in double-belt presses, interval heating presses or in continuous compression molding presses. The inventive method is characterized by rapid impregnation and high productivity and allows fiber-matrix semi-finished products and thus to produce oil containers in high rates and low proportion of pores or air bubbles in a single process.

Process step a)

According to the invention, a thermoplastic from the group polyamide (PA), polycarbonate (PC), thermoplastic polyurethane (TPU), polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), polyphthalamide (PPA), polypropylene (PP), polyethylene terephthalate (PET), Polyethylene (PE), polylactic acids (PLA), acrylonitrile-butadiene-styrene (ABS), styrene-acrylonitrile (SAN), polyetheretherketone (PEEK), polyetherimide (PEI), polyethersulfone (PES), polymethylmethacrylate (PMMA), polyoxymethylene (POM) and polystyrene (PS) selected or used as a base component for the thermoplastic composition.

Preferred vinyl polymers are to be selected from the group consisting of polyvinyl halides, polyvinyl esters and polyvinyl ethers.

Preferred polyolefins are polyethylene [CAS No. 9002-88-4] or polypropylene [CAS No. 9003-07-0].

Preferred polyesters are polyethylene terephthalate PET [CAS No. 25038-59-9] or polybutylene terephthalate PBT [CAS No. 24968-12-5].

Preferred polycarbonates are those based on 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) sulfone (bisphenol S), dihydroxydiphenylsulfide, tetramethylbisphenol A, 1,1-bis (4-hydroxyphenyl ) -3,3,5-trimethylcyclohexane (BPTMC) or 1,1,1-tris (4-hydroxyphenyl) -ethane (THPE). Particular preference is given to using a PC based on bisphenol A.

PPA are partially aromatic polyamides or semi-crystalline aromatic polyamides in which the amide groups are alternately bonded to aliphatic groups and to benzenedicarboxylic acid groups. The amide groups are preferably bonded to terephthalic acid groups. Particularly preferred PAAs according to the invention are PA 6T, PA 10T or PA 12T.

Particularly suitable are polyamides having a relative solution viscosity in m-cresol in the range from 2.0 to 4.0, preferably in the range from 2.2 to 3.5, very particularly in the range from 2.4 to 3.1. The measurement of the relative solution viscosity η _rel is based on EN ISO 307 , The ratio of the flow time t of the polyamide dissolved in m-cresol to the flow time t (0) of the solvent m-cresol at 25 ° C. gives the relative solution viscosity according to the formula η _rel = t / t (0).

Particularly preferred polyamides are to be selected from the group PA 66, PA 6 and PA 12. The used in the context of the present application marking the polyamides corresponds EN ISO 1874-1: 2010 , partially replaced by ISO 16396-1: 2015, wherein the first digit (s) indicate the C atomic number of the starting diamine and the last digit (s) indicate the C atomic number of the dicarboxylic acid. If only one number is given, as in the case of PA 6, this means that it has been assumed that α, ω-aminocarboxylic acid or the lactam derived therefrom, in the case of PA 6, ie ε-caprolactam.

Particular preference is given to at least one thermoplastic from the group PA 66 [CAS No. 32131-17-2], PA 6 [CAS No. 25038-54-4], PA 12, PPA, polypropylene (PP), polyphenylene sulfide (PPS), TPU and PC selected for the plastic matrix of the fiber-matrix semifinished product.

Very particular preference is given to selecting at least one thermoplastic from the group TPU, PA 6 and PC, in particular preferably PA 6.

The thermoplastics to be used in the single-layer fiber matrix semifinished product for oil containers can also be used in various combinations with one another, preferably a combination of PC / ABS (ABS [CAS No. 9003-56-9]) is used.

In particular, at least one thermoplastic in flame-retardant form is used for the plastic matrix or as the matrix polymer of the fiber-matrix semifinished product. Flame retardants which are preferred according to the invention for polyamide-based fiber-matrix semi-finished products are disclosed in US Pat EP 1762592 A1 . EP 2060596 A1 . EP 2028231 A1 . JP 2010 222486 A or EP 2410021 A1 whose contents are fully covered by the present application. Flame retardants preferred according to the invention for polycarbonate-based fiber-matrix semi-finished products are disclosed in US Pat EP 3020752 A1 described. Flame retardants preferred according to the invention for TPU-based fiber-matrix semi-finished products are disclosed in US Pat WO 2013/087733 A2 described. It is preferred to use from 0.001 to 20 parts by weight of flame retardant additive per 100 parts by weight of thermoplastic, in particular polyamide.

Apart from flame retardant additives, the thermoplastic may alternatively or additionally contain further additives, preferably at least one heat stabilizer. Preferred thermal stabilizers are metal-based stabilizers, preferably based on copper or iron, or organic heat stabilizers, in particular polyhydric alcohols. Preferred copper stabilizers are copper (I) halides, in particular copper bromide or copper iodide, which are preferably used in combination with at least one alkali metal halide, preferably potassium bromide or potassium iodide. Preferred iron-based thermal stabilizers are iron powder, iron oxides or iron salts of organic acids, in particular iron citrate or iron oxalate. Preferably used polyhydric alcohol is Dipentyerthrit. In one embodiment, it is also possible to use mixtures of said thermoablizers in the thermoplastic or in the thermoplastic composition. Preferably, the said heat stabilizers are used in polyamide. Particular preference is given to using 100 parts by weight of thermoplastic, in particular polyamide, 0.001 to 20 parts by weight of thermal stabilizer.

Other additives in the thermoplastics to be used according to the invention for producing a thermoplastic composition for the monolayer fiber-matrix semifinished product to be used according to the invention are, however, also the above-described short glass fibers and other fillers or reinforcing materials, preferably selected from the group of carbon fibers, glass spheres, amorphous silica, calcium silicate, Calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium silicate, wollastonite, montmorillonite, boehmite, bentonite, vermiculite, hectorite, laponite, carbon black and feldspar. Furthermore, sterically hindered phenols, antioxidants, dyes, antioxidants, mold release agents, nucleating agents, plasticizers or impact modifiers can be used as an additive. Preferred impact modifiers are rubber-elastic polymers.

Preferably, the short glass fibers and optionally other fillers and reinforcing substances or additives are dispersed or compounded in the thermoplastic before the application to the entirety of all semifinished fiber layers for the purpose of producing a monolayer fiber material to be used according to the invention. Matrix semifinished product takes place. The dispersion is preferably carried out by melt blending. Mixing tools to be used for such a melt mixing process are preferably single or twin screw extruders or Banbury mixers. The additives are mixed either all at once in a single step, or stepwise and then in the melt. During the stepwise addition of the additives to the at least one thermoplastic, a portion of the additives is first added to the thermoplastic and mixed in the melt. Subsequently, further additives are added and then mixed until a homogeneous composition is obtained.

Process step b)

The entirety of all semi-finished fiber layers in the single-layer fiber-matrix semifinished product to be used according to the invention is preferably based on glass fibers and / or carbon fibers, particularly preferably glass fibers. For glass fibers preferably silicate or non-silicate glasses are used. In addition to the glass fibers, in the entirety of all semifinished fiber layers additionally other fibers may be contained, more preferably from the group of carbon, boron, aramid, silicon carbide, metal alloys, metal oxides, metal nitrides, metal carbides, metals and silicates and organic materials, in particular natural or synthetic polymers, preferably polyesters, polyamides or natural fibers, in particular cotton or cellulose and combinations thereof.

According to the invention, continuous fibers are preferably used in combination with at least 10 mm long long fibers. The continuous fibers are preferably present in the semi-finished fiber layers as rovings, strands, yarns, threads or ropes, particularly preferably as rovings.

Endless fibers, also referred to as endless reinforcing fibers, are understood to mean those which, as described above, generally have a length of more than 50 mm, but in particular those whose length corresponds approximately to the longitudinal extent of the respective oil container to be produced.

The continuous fibers preferably have filament diameters in the range from 0.5 μm to 25 μm. The determination of filament diameters and cross-sectional areas of filament yarns made of glass, aramid or carbon takes place in accordance with the present invention DIN 65571-1: 1992-11 , The mean filament diameter is measured after removal of any sizing. The determination of filament diameter and cross-sectional area of filament yarns is carried out according to DIN 65571 by means of optical methods either with light microscope and micrometer eyepiece (distance measurement cylinder diameter) or with light microscope and digital camera with subsequent planimetry (cross section measurement) or by laser interferometry or by projection. Alternatively, the mean filament diameter of glass fibers according to ISO 1888 be determined.

In one embodiment, the long glass fibers optionally in addition to the continuous fibers in the fiber matrix semifinished product are of flat shape with non-circular cross-sectional area, wherein the ratio of perpendicular cross-sectional axes is greater than or equal to 2, in particular greater than or equal to 3, and the smaller Cross-sectional axis has a length of ≥ 3 microns. In particular, a long-glass fiber which is as rectangular as possible in cross-section is preferred in which the ratio of the cross-sectional axes is greater than 3, in particular greater than or equal to 3.5.

The long glass fibers which are preferably also to be used as rovings have a diameter in the range from 3 to 20 μm, particularly preferably in the range from 3 to 10 μm.

Particularly preferred flat long glass fibers are used with a ratio of the cross-sectional axes in the range of 3.5 to 5.0.

E-glass fibers are particularly preferably used both for the continuous fibers and for the long glass fibers. In one embodiment, 5-glass fibers are additionally used in addition to the E-glass fibers, since these have a 30% higher tensile strength compared to the E-glass fibers. However, it is also possible to use all other glass fibers, such as A, C, D, M or R glass fibers or any mixtures thereof or mixtures with E and / or S glass fibers. E-glass has the following properties: density 2.6 g / cm ³ at 20 ° C, tensile strength 3400 MPa, tensile modulus of elasticity 73 GPa, elongation at break 3.5-4%.

The inventively used fiber semi-finished layers of continuous fibers give the oil tank the desired mechanical properties. You can in their structure, but also in their number, on expected loads in the oil tank are adjusted so that it has an optimal strength and / or rigidity for real load cases.

The semifinished fiber layers in the monolayer fiber-matrix semifinished product to be used according to the invention do not form any layers separate from the polymer matrix as in the prior art, but are penetrated by it so that fibers and polymer form an integral component.

In particular, it is advantageous if the semi-finished fiber layers are used in the form of woven or non-woven structures. Preferably, semi-finished fiber sheets are used based on woven fabrics, including multiaxial fabrics, stitches, braids, nonwovens, felts, mats, a mixture of two or more of these materials, and combinations thereof.

Nonwovens may be selected with random fiber orientation or with aligned fiber structures. Random fiber orientations are preferably found in mats, in needled mats or as felt. Aligned fibrous structures are preferably found in unidirectional fiber strands, bidirectional fiber strands, multidirectional fiber strands, multiaxial textiles. Preferably, semi-finished fiber layers to be used according to the invention are unidirectional scrims or fabrics, in particular woven fabrics.

Particular preference is given to combining glass fibers with carbon fibers, also referred to as carbon fibers or graphite fibers. By replacing a portion of the glass fibers with carbon fibers, a hybrid-fiber-reinforced fiber-matrix semifinished product whose stiffness is increased in comparison to a pure glass-fiber-based fiber-matrix semifinished product is produced.

The content of carbon fibers in a single-layer fiber-matrix semifinished product to be used according to the invention for oil containers is preferably in the range from 0.1% by volume to 30% by volume, particularly preferably in the range from 10% by volume to 30% by volume. %, based on the total fiber content, the total fiber content in the fiber-matrix semifinished product to be used according to the invention being in the range from 5 to 90% by volume, preferably in the range from 30 to 60% by volume, particularly preferably in the range from 45 to 55% by vol .-% lies.

The fiber material or fiber braid in the semi-finished fiber layers can be oriented only in one direction or oriented in two directions at any angle to each other, preferably at right angles to each other.

steht,
q für eine ganze Zahl von 2 bis 10, bevorzugt 3 bis 4 steht,
r für eine ganze Zahl von 1 bis 5, bevorzugt 1 bis 2 steht und
k für eine ganze Zahl von 1 bis 3, bevorzugt 1 steht.In order to obtain a better compatibility of the continuous fibers with the at least one thermoplastic or with the thermoplastic composition, these are preferably pretreated with a silane compound on their surface. Particular preference is given to silane compounds of the general formula (I) (X- (CH ₂ ) _q ) _k -Si (O-CrH _{2r + 1} ) _4-k (I) wherein
X for NH ₂ , carboxyl, HO or

stands,
q is an integer from 2 to 10, preferably 3 to 4,
r is an integer from 1 to 5, preferably 1 to 2, and
k is an integer from 1 to 3, preferably 1.

Particular preference is given to silane compounds from the group of aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl or a carboxyl group as substituent X in formula (I), carboxyl groups being particularly particularly preferred.

The equipment of the glass fibers with at least one silane compound of the formula (I) is preferably carried out in amounts of from 0.05 to 2 parts by weight of silane compound per 100 parts by weight of glass fiber.

The semifinished fiber layers preferably contain no comminuted fibers or particles, in particular no short fibers having a length in the range from 0.1 to 1 mm.

Preferably, glass fibers and / or carbon fibers are used, particularly preferably glass fibers.

In one embodiment, the semifinished fiber layers are provided as roll goods for method step b).

Process step c)

For application to the entirety of all semifinished fiber layers, the at least one thermoplastic or the thermoplastic composition is initially charged as granules, powder, flakes, foil or in the form of other macroscopic parts, in the form of a melt or in the form of a dispersion in a solvent. Particular preference is given to powders or films. According to the invention, preference is given to powder application or application in the form of a film, in particular powder application.

The application of the thermoplastic or the thermoplastic composition to the entirety of all semi-finished fiber layers in process step c) by means of conventional means, preferably by scattering, trickling, printing, spraying, spraying, impregnating, wetting in the melt, thermal spraying or flame spraying, or by fluidized bed coating process , In one embodiment, a plurality of thermoplastic layers or layers of one or different thermoplastic compositions can be applied to the entirety of all semi-finished fiber layers. In one embodiment, the thermoplastic or the thermoplastic composition is applied in the form of a film to the entirety of all semi-finished fiber layers made of continuous fibers.

Preferably, the application of the thermoplastic or the thermoplastic composition takes place on the entirety of all semi-finished fiber layers in quantities from which one after DIN 1310 defined volume fraction of fiber materials in the fiber-matrix semifinished product in the range of 5 to 90 vol .-%, preferably in the range of 30 to 60 vol .-%, particularly preferably in the range 45 to 55 vol .-% results.

In one embodiment, the application may be followed by a sintering step in which the thermoplastic or the thermoplastic composition is sintered on the entirety of all semi-finished fiber layers. By sintering, optionally under pressure, the thermoplastic or the thermoplastic composition is heated, but the temperature remains below the melting temperature of the particular thermoplastic to be used. It usually comes to a shrinkage, because the thermoplastic particles of the starting material compact and pore spaces are filled in the totality of fiber semi-finished layers.

Process step d)

Subsequently, the applied totality of all semi-finished fiber layers in process step d) is subjected to the influence of pressure and temperature. This is preferably done by preheating the total of all fiber semi-finished product layers, also referred to as fiber material, which is charged with polymer or the polymer composition, outside the print zone.

In process step d), the thermoplastic or thermoplastic composite of all semi-finished fiber layers is heated to initiate the impregnation and consolidation of the fiber material. As a result of the influence of pressure and heat, the at least one thermoplastic or thermoplastic composition melts and penetrates the entirety of all semi-finished fiber layers which thus impregnate it. Preferably, pressures in the range of 2 to 100 bar, particularly preferably in the range of 10 to 40 bar, are used.

The temperature to be used in method step d) is ≥ the melting temperature of the at least one thermoplastic or thermoplastic composition to be used. In one embodiment, the temperature to be used is at least 10 ° C above the melting temperature of the at least one thermoplastic to be used. In a further embodiment, the temperature to be used is at least 20 ° C. above the melting temperature of the at least one thermoplastic to be used. The heating may be accomplished by a variety of means, preferably contact heating, radiant gas heating, infrared heating, convection or forced convection, induction heating, microwave heating or combinations thereof. Immediately thereafter or at the same time the consolidation takes place.

The impregnation depends in particular on the parameters of temperature and pressure. In one embodiment, method step d) additionally depends on time.

In order to achieve optimum mechanical properties, the most complete possible impregnation of the filaments of the fiber material with the at least one thermoplastic or with the thermoplastic composition is desirable in method step d). Fiberglass fiber material has been found to provide a rapid rate of impregnation of fibrous material from carbon fibers, resulting in an overall faster total cycle of single-layer fiber-matrix semi-finished products containing both glass and carbon fibers.

The principle of impregnation consists in impregnating a dry fiber structure with a matrix of polymer or polymer composition. The flow through the semi-finished fiber product is comparable to the flow of an incompressible fluid through a porous base medium. The flow is described using the Navier-Stokes equation: ρ dV / dt = -∇P + η∇ ² v where ρ is the density, v the velocity vector, ∇P the pressure gradient and η the viscosity of the fluid used. Assuming that the flow rate of the polymer or polymer composition - also referred to as matrix - in the reinforcing structure is classified as low the inertial forces in the above equation (the left side) are neglected. Consequently, the equation simplifies to the form known as the Stokes equation: 0 = -∇P + η∇ ² v

Process step e)

Simultaneously with the impregnation or subsequent impregnation, consolidation takes place, which means the expression of entrapped air and other gases. Consolidation, too, depends in particular on the parameters of temperature and pressure and, if appropriate, on time.

The gases contain ambient gas (eg, air or nitrogen) and / or water (steam) and / or thermal decomposition products of the at least one thermoplastic to be used.

Consolidation also depends on the parameters of temperature and pressure. In one embodiment, method step e) additionally depends on time.

Preferably, said parameters are applied until the fiber matrix semifinished product has a voids content of less than 5%. It is particularly preferred that the void content be less than 5% within a period of less than 10 minutes, achieved at temperatures above 100 ° C, more preferably at temperatures in the range of 100 ° C to 350 ° C. Preferably, pressures above 20 bar are used.

The pressurization may be by a static process or by a continuous process (also known as a dynamic process), with a continuous process being preferred for speed reasons. Preferred impregnation techniques include, without limitation, calendering, flat bed lamination, and double belt press lamination. The impregnation step is preferably carried out as a lamination process. When the impregnation is carried out as lamination, it is preferable to use a refrigerated double belt press (see also US Pat EP 0 485 895 B1 ) or an interval heating press.

Both properties, the degree of impregnation in process step d) and the consolidation in process step e) can be measured or checked by determining mechanical characteristics, in particular by measuring the tensile strength on composite structural specimens. To determine the tensile strength is the tensile test, a quasi-static, destructive test method, in the case of plastics after ISO 527-4 or -5 ,

Since both the process of impregnation and the process of consolidation depends on the parameters of temperature and pressure, the skilled person will adapt these parameters to the particular thermoplastic to be used or to the thermoplastic composition. In addition, it will also adjust the period over which the pressure is applied according to the matrix polymer.

Process step f)

After process step e), the fibers are completely impregnated and consolidated with thermoplastic or with thermoplastic composition within a monolayer fiber-matrix semifinished product to be used according to the invention, ie. H. the fibers are completely wetted with plastic, there is almost no air or glass in the material.

For solidification, the fiber composite structure or the fiber-matrix semifinished product is allowed to cool to a temperature below the melting temperature of the thermoplastic or the thermoplastic composition. The term solidification describes the solidification of the mixture of the entirety of all semifinished fiber layers and molten matrix by cooling or by chemical crosslinking to form a solid.

In one embodiment, after method step e), method steps f) shaping and g) solidification are carried out simultaneously or at least in quick succession.

In one embodiment, when using a double-belt press, a solidification and a shaping of the single-layer fiber-matrix semifinished product preferably takes place to plate goods. In this case, the single-layer fiber-matrix semifinished product, after cooling to a temperature below the melting temperature of the thermoplastic or the thermoplastic composition, preferably to room temperature (23 +/- 2 ° C), taken in the form of plate goods the pressing tool. The transformation to the oil tank is then carried out by reheating or plasticizing the type described above and by subsequent shaping. Preferably, short cycle times are used. It is crucial that the single-layer fiber-matrix semifinished product undergoes no chemical conversion during the forming.

In the production of such thermoplastic FKV plate semi-finished products, a distinction is made depending on the material throughputs to be achieved in film stacking, prepreg and direct processes. For high material throughput, in the case of direct processes, the matrix and textile components are brought together directly in the region of the material inlet of the pressing process. This is usually associated with a high level of system complexity. For small to medium quantities, the film-stacking process is frequently used in addition to the prepreg process. In this case, a structure consisting of alternating film and textile layers undergoes the pressing process. The type of pressing process is based on the required material output and the variety of materials. Here, a distinction is made between static, semi-continuous and continuous processes as material throughput increases. The plant-technical expenditure and the plant costs rise thereby with the increase of the material throughput ( AKV-Industrievereinigung Reinforced Plastics e. V., Handbuch Faserverbund-Kunststoffe, 3rd ed. 2010, Vieweg-Teubner, 236 ).

If, however, a shaping takes place simultaneously in process step e), cooling to a temperature below the melting temperature of the thermoplastic or of the thermoplastic composition, preferably to room temperature (23 +/- 2 ° C.), is effected and the oil container is cooled as a negative mold of an oil container removed molded molding tool.

If, however, the single-layer fiber-matrix semifinished product is used as a finished sheet product, this is subsequently subjected to a shaping step after its production. The manufacturing processes of plastic deformation are in Germany DIN 8580 assigned. Preferred molding processes are the compression molding process (see, for example, U.S. Pat EP 1 980 383 A2 ) and the stamp forming, preferably the stamping method (see: C. Hopmann, R. Schöldgen, M. Hildebrandt, Inline Impregnation Technology with Thermoplastics, Flexible Serial Production of Thermoplastic FRP Components, IKV of RWTH Aachen, Plastverarbeiter October 15, 2014 ).

During press molding, all the required process steps are carried out in the order Forming → Heating → Impregnating / Consolidating → Cooling in a closed mold. The textile semifinished product or is placed in a mold made of metal, cold formed and heated by conduction through contact with the mold at low pressure. After reaching the melting temperature of the matrix polymer, ie the at least one thermoplastic or the thermoplastic composition, a higher pressure for impregnation and consolidation is applied and then cooled.

In the case of stamping, the single-layer fiber-matrix semifinished product to be used, already cut to size from sheet material, is heated outside the molding tool by a heating system until it is plasticized. Then provides a transfer system for the transport of the plasticized fiber-matrix-semifinished product section from the heating system to the pressing tool, which at a constant temperature below the Solidification temperature of the thermoplastic or the thermoplastic composition is maintained. The fiber-matrix semifinished product cutout is then shaped in the mold to the component and passively cooled.

In a preferred embodiment, in process step f), the fiber-matrix semifinished product to be produced-that is to say during its production-is shaped into the desired geometry or configuration of an oil container by a shaping method which is to be used simultaneously. H. Process steps f) and g) are carried out simultaneously. Preferred shaping methods for the simultaneous production thereof with a geometric design of a fiber matrix semifinished product to be produced in method step f) are compression molding, stamping, pressing or any method using heat and / or pressure. Particularly preferred are pressing and punching. Preferably, in the molding process, the pressure is applied by the use of a hydraulic molding press. During pressing or punching, the fiber-matrix semifinished product is preheated to a temperature above the melting temperature of the at least one thermoplastic or thermoplastic composition and brought into the desired shape or geometry with a forming or shaping device or a molding tool, in particular at least one molding press ,

Shaping processes to be used according to the invention are described in Chapter 10, Pressing Methods for Continuous FV Thermoplastics, Urs Thomann, in Composites Technology, Prof. dr. Paolo Ermanni, Script for the ETH Lecture 151-0307-001, Zurich August 2007, Version 4.0 described.

Process step h)

In one embodiment, process step h) may be followed by at least one aftertreatment.

In a preferred embodiment, the aftertreatment is an annealing step. Annealing is a temperature treatment that serves to increase crystallinity to improve strength and chemical resistance, reduce internal stress caused by extrusion or machining, and increase dimensional stability over a wide temperature range. By tempering, in particular in the case of polyamide by a half to one day heat post-treatment, preferably in an annealing liquid at 140 ° C to 170 ° C, residual stresses within the single-layer fiber matrix semifinished product and thus within the oil tank can be largely eliminated. The tempering also leads to the recrystallization of not completely crystallized products, on the one hand density, abrasion resistance, stiffness and hardness increase and on the other hand, a slight Nachschwindung, sometimes even a small distortion of the parts occurs. The type, temperature and duration of tempering depends on the particular thermoplastic or thermoplastic composition used and on the wall thickness of the single-layer fiber-matrix semifinished product used. By means of suitable preliminary tests, the skilled person will determine the decisive parameters for method step h). Suitable tempering liquids are heat-resistant mineral, paraffin and silicone oils. The tempered parts must be cooled slowly. See also:
https://de.wikipedia.org/wiki/Kristallisation_(Polymer)

In a further preferred embodiment, the aftertreatment is the molding of functional elements or the encapsulation of the edges of the Ölbehalters. The molding of further functional elements by casting or injection molding, preferably injection molding, can take place over the entire surface, partially or circumferentially. Injection molding can be injection molding and / or injection molding and / or extrusion coating. Preference is given to using in-mold molding (IMF), an integrative injection molding special process which is used to produce hybrid structural components made of different materials; please refer http://www.industrieanzeiger.de/home/-/article/12503/11824771/ , IMF makes it possible to enclose exposed reinforcing fibers in the edge region of a fiber-matrix semifinished product. As a result, a structural component is produced with particularly smooth edges. However, a functional element to be formed is also formed by the IMF and at the same time connected to the fiber-matrix semi-finished component, in particular without the use of additional adhesives. The principle of the IMF is also subject in DE 41 01 106 A1 . US 6036908 B . US 6475423 B1 or WO 2005/070647 A1 ,

For an injection molding composition to be used according to the invention for use in IMF, preference is given to thermoplastics, preferably polyamides, in particular PA 6, PA 66 or aromatic polyamides such as polyphthalamide, polysulfone PSU, polyphenylene sulfide PPS, polyphthalamides (PPA), poly (arylene ether sulfones), such as PES, PPSU or PEI, polyester, preferably polybutylene terephthalate (PBT) or polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE) or polyimides (PI). Other variants can be found in DE 10 2006 013 684 A1 ,

In a very particularly preferred embodiment of an oil container, both the fiber matrix semifinished component and the injection molding component to be used, preferably in the IMF, are manufactured from the same thermoplastic polymer. The matrix of the single-layer fiber-matrix semifinished product and the injection-molding component based on polyamide are particularly preferably carried out. Durethan ^® BKV 235XCP or Durethan ^® BKV 55 TPX from Lanxess Deutschland GmbH, Cologne are suitable in this case and especially for oil tanks or oil pans.

Preferred functional elements of the injection molding component are fasteners or mounts, filling or outlet openings and other applications that need not be imaged by the fiber-matrix semi-finished component, but due to any geometric complexity through the injection molding component.

The attachment of functional elements can be done later during the molding process in step f) or in the context of process step h). For retrofitting of functional elements, in particular for carrying out the IMF, the oil container obtainable according to method step e) is placed in a mold, preferably an injection mold, with a correspondingly designed mold cavity. Preferably, it is previously plasticized in the region of attachment of the functional element. Subsequently, the injection-molded component is injected. The aim is that it comes between the thermoplastic of the fiber-matrix semi-finished component and the thermoplastic of the injection-molded component to a cohesive connection. The best way to achieve such a cohesive connection by these two plastics have the same polymer base. According to the invention, it is preferred if both components are based on polyamide, in particular polyamide 6. In addition, process parameters such as melt temperature and pressure also play a role.

It is preferred if the injection molding in process step h) at a temperature in the range of 200 ° C to 320 ° C, preferably in the range of 240 ° C to 290 ° C, more preferably in the range of 240 ° C to 270 ° C, he follows.

Furthermore, it is advantageous if injection molding in process step h) takes place at a pressure in the range from 10 bar to 2000 bar, preferably in the range from 200 bar to 1500 bar, more preferably in the range from 500 bar to 1300 bar.

use

Finally, the present invention relates to the use of at least one single-layer, continuous fiber-reinforced fiber-matrix semifinished product as an oil container, preferably in buildings or as an oil sump in vehicles. Preferred vehicles are motor vehicles. Preferred motor vehicles are those based on internal combustion engines, electric motor vehicles or hybrid motor vehicles.

• – 1 bis 100 Faserhalbzeuglagen aus Endlosfasern, bevorzugt 2 bis 40 Faserhalbzeuglagen aus Endlosfasern, besonders bevorzugt 2 bis 10 Faserhalbzeuglagen aus Endlosfasern,
• – wobei die Faserhalbzeuglagen jeweils ein Flächengewicht im Bereich von 5 g/m² bis 3000 g/m², bevorzugt im Bereich von 100 g/m² bis 900 g/m², besonders bevorzugt im Bereich von 150 g/m² bis 750 g/m², aufweisen,
• – und die Gesamtheit aller Faserhalbzeuglagen mit wenigstens einem Thermoplast mit einem MVR nach ISO 1133 im Bereich von 1 cm³/10 min bis 100 cm³/10 min imprägniert ist,
• – und das Faser-Matrix-Halbzeug einen nach DIN 1310 definierten Volumenanteil an Fasermaterialien im Bereich von 5 bis 90 Vol.-%, vorzugsweise im Bereich von 30 bis 60 Vol.-%, besonders bevorzugt im Bereich 45 bis 55 Vol.-%, und
• – einen Volumenanteil an Luft von weniger als 15 Vol.-%, vorzugsweise weniger als 10 Vol.-%, besonders bevorzugt weniger als 5 Vol.-%, aufweist,
• – und der Thermoplast aus der Gruppe der Polyolefine, Vinylpolymerisate, Polyacrylate, Polyamide, Polyurethane, Polyharnstoffe, Polyimide, Polyester, Polyether, Polystyrole, Polyhydantoine, Polyphenylenoxide (PPO), Polyarylensulfide, Polysulfone, Polycarbonate (PC), Polyphthalamide (PPA), Polymethylmethacrylate (PMMA), Styrolacrylnitrile (SAN), TPO (Thermoplastische Elastomere auf Olefinbasis), TPU (Thermoplastische Polyurethane) und Polyoxymethylene (POM) ausgewählt wird, zur Herstellung von Ölbehältern, vorzugsweise Ölmodulen.

The present invention preferably relates to the use of single-layer fiber-matrix semifinished products

• 1 to 100 semi-finished fiber layers of continuous fibers, preferably 2 to 40 semi-finished fiber layers of continuous fibers, more preferably 2 to 10 semi-finished fiber layers of continuous fibers,
• - Wherein the semifinished fiber layers each have a basis weight in the range of 5 g / m ² to 3000 g / m ² , preferably in the range of 100 g / m ² to 900 g / m ² , particularly preferably in the range of 150 g / m ² to 750 g / m ² ,
• - And the entirety of all semi-finished fiber layers with at least one thermoplastic with an MVR after ISO 1133 is in the range from 1 cm ^3/10 min to 100 cm ^3/10 min impregnated,
• - And the fiber-matrix semi-finished one after DIN 1310 defined volume fraction of fiber materials in the range of 5 to 90 vol .-%, preferably in the range of 30 to 60 vol .-%, particularly preferably in the range 45 to 55 vol .-%, and
• A volume fraction of air of less than 15% by volume, preferably less than 10% by volume, particularly preferably less than 5% by volume,
• And the thermoplastic from the group of polyolefins, vinyl polymers, polyacrylates, polyamides, polyurethanes, polyureas, polyimides, polyesters, polyethers, polystyrenes, polyhydantoins, polyphenylene oxides (PPO), polyarylene sulfides, polysulfones, polycarbonates (PC), polyphthalamides (PPA), polymethyl methacrylates (PMMA), styrene acrylonitrile (SAN), TPO (thermoplastic elastomers based on olefins), TPU (thermoplastic polyurethanes) and polyoxymethylene (POM) is selected for the production of oil containers, preferably oil modules.

• – signifikant höhere Energieabsorption gegenüber einer reinen Kunststoff-Lösung, einer reinen Metallvariante, und auch gegenüber einer Kunststoff-Metall-Hybrid-Variante bei jeweils gleichem Gewicht, was im Falle eines Crashs erhebliche Bedeutung hat;
• – die Bauteile müssen im Vergleich mit duroplastischen, langglasfaserverstärkten Werkstoffen nicht nachgearbeitet werden;
• – gegenüber reinen Metallblech-Varianten und Kunststoff-Metall-Hybriden ist kein Invest für Blechumformwerkzeuge nötig;
• – Kunststoff-Bauteile können angeschweißt werden und am Ölbehälter somit weitere Funktionen eng mit diesem bzw. mit seiner Funktion verbunden werden, z. B. Aufnahmen für Sensoren.

An inventive oil container is particularly suitable for use in vehicles, preferably in motor vehicles and in particular as an oil pan for engine oil or gear oil. Inventive oil containers are characterized by the following properties:

• - Significantly higher energy absorption compared to a pure plastic solution, a pure metal variant, and also compared to a plastic-metal hybrid variant in each case the same weight, which in the case of a crash has considerable significance;
• - the components need not be reworked in comparison with duroplastic, long glass fiber reinforced materials;
• - Compared to pure metal sheet variants and plastic-metal hybrids, no investment is needed for sheet metal forming tools;
• - Plastic components can be welded and the oil reservoir thus other functions are closely linked to this or with its function, eg. B. recordings for sensors.

• – niedrigeres Gewicht (gegenüber Kunststoff-Metall-Hybriden, Metallblech, Aluguss)
• – besseres mechanisches Verhalten, höhere Energieaufnahme
• – bessere Beständigkeit im Falle eines Crashs auch bei besonders tiefen Temperaturen ≤ –30°C
• – Medienbeständigkeit
• – keine Delamination.

Compared to prior art oil tanks, an oil reservoir according to the invention offers significant advantages:

• - lower weight (compared to plastic-metal hybrids, sheet metal, cast aluminum)
• - better mechanical behavior, higher energy absorption
• - better resistance in case of a crash even at very low temperatures ≤ -30 ° C
• - Media resistance
• - no delamination.

Examples

To demonstrate that a single-layer fiber-matrix semifinished product to be processed according to the invention into an oil tank or to an oil pan or at least in the abovementioned applications proportionately incorporated single-layer fiber matrix semifinished product is less prone to delamination than a multi-layer composite according to the prior art In technical terms, test specimens were subjected to a mechanical test and from this the bond strength was determined by tensile tests EN ISO 527 for determining the breaking stress, the elongation at break and the modulus of elasticity at a defined temperature. The EN ISO 527-1 (last issue of April 1996, current ISO version February 2012) is a European standard for plastics for the determination of tensile properties, which are determined by a tensile test with a tensile tester. For this purpose, a specially designed test specimen holder was used, which allowed a simple insertion and fixation of the head tensile test specimen used under tensile load.

The test was carried out on a universal testing machine of the type Zwick UTS 50 from Zwick GmbH & Co. KG, Ulm, whereby the force was introduced by a mechanical clamping head. Each test piece, hereinafter referred to as a head pull sample, consisted of a fiber-matrix semi-finished strip (55 × 40 × 2 mm ³ ) on which a rib (40 × 40 × 4 mm ³ ) of polyamide 6 was injected.

APPLICATION MATERIALS

Thermoplastic Matrix 1: Polyamide 6 (PA 6)

Polyamide 6: Injection molding grade, easy flowing, finely crystalline and very rapidly processed (BASF Ultramid ^® B3s) having a density of 1.13 g / cm ³ and a melt flow index MVR of 160 cm ^3/10 min [Measuring conditions: ISO 1133 , 5 kg, 275 ° C] or a relative viscosity number (0.5% in 96% H ₂ SO ₄ , ISO 307, 1157, 1628 ) of 145 cm ³ / g.

Thermoplastic matrix 2: polyamide 6 (PA 6)

Polyamide 6: (film type, unreinforced, (BASF Ultramid ^® B33 L) with a medium bodied density of 1.14 g / cm ³ and a relative viscosity of 0.5% in 96% H ₂ SO _4, ISO 307, 1157, 1628 ) of 187-203 cm ³ / g.

Semi-finished fiber

Balanced Rovingglasgewebe (YPC ROF RE600) consisting of 1200 tex warp and weft threads in 2/2 twill weave with a thread density of 2.5 threads / cm.

Basis weight total 600 g / m ² , of which 50% in warp and 50% in weft direction. Fabric width 1265 mm, roll length 150 running meters Equipment of weft yarns with special size, which was adapted to the polymer system (in the example part PA).

Fiber-matrix semi-finished products (1)

Fiber matrix semifinished product (1) was produced on a static hot plate press. The fiber-matrix semifinished product (1) with an edge length of 420 mm × 420 mm consisted of 4 semi-finished fiber layers and a polymer amount exclusively of the thermoplastic matrix 1, which was uniformly applied to the fiber layers and distributed and in a fiber volume content of 47% or 47%. resulted in a thickness of 2.0 mm. For consolidation and impregnation, a surface pressure of 24 bar and a temperature of 300 ° C. for 240 s was impressed. The subsequent cooling to room temperature was carried out at constant pressure in 300 s. In the resulting plate-shaped fiber-matrix semifinished product (1), the semi-finished fiber layers were thus homogeneously embedded, due to the uniform single-layer matrix system, no material / phase boundaries developed within the matrix; it could not be differentiated between internal investment material and surface material.

Fiber matrix semi-finished products (2)

Fiber matrix semifinished product (2), as an example of a multilayer construction according to the prior art, was also produced on a static hot plate press. The intended for the multi-layer structure semi-finished with an edge length of 420 mm × 420 mm consisted of 4 semi-finished fiber layers and a polymer amount exclusively of the thermoplastic matrix 1, which was evenly applied to the fiber layers and distributed and in a fiber volume content of 49% or a thickness of 1.9 mm resulted. For consolidation and impregnation, a surface pressure of 24 bar and a temperature of 300 ° C. for 240 s was impressed. The subsequent cooling to room temperature was carried out at constant pressure in 300 s.

In order to produce a layered structure, a 50 μm thick film of thermoplastic matrix 2 was applied to this intermediate product in a subsequent process step on both sides. This was again done on a static hot plate press at a temperature of 260 ° C and a surface pressure of 9 bar, which was maintained for 120 seconds. The cooling to room temperature within 60 s was carried out at a surface pressure of 7.5 bar. Due to the different viscosities of the thermoplastic Matrizes 1 and 2, there was a non-uniform structure of the fiber-matrix semifinished product. Inside the plate-shaped fiber-matrix semifinished product (2) produced in this way, the semi-finished fiber layers were homogeneously embedded in the matrix 1, while on the two surfaces (surface) exclusively matrix 2 was present, analogous to the semifinished products according to FIG WO 2012/132 399 A1 and WO 2010/132 335 A1 ,

exam

As a test specimen for the mechanical testing of the bond between fiber-matrix semifinished product (1) or (2) and molded thermoplastic, a so-called head tensile test was used. Each of these head pull specimens consisted of a fiber-matrix semifinished strip (55 × 40 × 2 mm ³ ) on which a rib (40 × 40 × 4 mm ³ ) of polyamide 6 was injected. For head pull test see also W. Siebenpfeiffer, lightweight technologies in automotive engineering, Springer-Vieweg, 2014, pages 118-120 , When Kopfzugversuch then the Kopfzugprobe was clamped in a holder and loaded on one side with a tensile force. The tensile test was shown in a stress-strain diagram (modulus of elasticity).

For the head tensile tests to be carried out in the context of the present invention, a respectively heated, undeformed fiber matrix semifinished product (1) and also a fiber matrix semifinished product (2) with multilayer structure according to the prior art, each having a total of 22 identical ribs, were used back-molded. The respective fiber-matrix semifinished product (1) or fiber-matrix semifinished product (2) was previously provided with an 8 mm bore at the point of the sprue, so that no additional resistance was created for the polyamide melt to be sprayed to form ribs. After processing, individual sections suitable for testing were sawed out at selected positions along the flow path using a band saw type "System Flott" from Kräku GmbH, Großseifen.

For mechanical testing of the bond strength, characteristic values were determined from tensile tests on the head tensile specimens. Here, a specially designed test specimen holder was used, which allowed a simple insertion and fixation of the head tension test under tensile load. The exam was on a Universal testing machine type Zwick UTS 50 of the company Zwick GmbH & Co. KG, Ulm, carried out, whereby the force was introduced by a mechanical clamping head. The parameters used in the mechanical test are shown in Table 1.

Fiber matrix semifinished product (1) and fiber matrix semifinished product (2) were prepared according to DIN 1310 examined in terms of fiber volume content. For statistical reasons, 5 specimens each were examined. The mean fiber volume content described above was determined for both fiber-matrix semi-finished products.

Both fiber-matrix semi-finished products were further investigated experimentally with regard to the pore content, ie the inclusion of air or gas. For this purpose, a cross-section of fiber-matrix semifinished product (1) and fiber-matrix semifinished product (2) was examined by means of a computer tomograph Micro CT nanotom S of the manufacturer General Electric. For statistical reasons, three test specimens were examined, each with 5 repeat measurements. By means of an optical evaluation software a porosity of 4-5% could be determined for both fiber-matrix semi-finished products. For statistical reasons, three test specimens were examined, each with 5 repeat measurements.

Fiber matrix semifinished product (1) was experimentally examined for local fiber volume fraction. For this purpose, a cross-section of fiber-matrix semifinished product (1) and fiber-matrix semifinished product (2) was examined by means of a computer tomograph Micro CT nanotom S of the manufacturer General Electric. The glass fiber content within the samples was evaluated to a depth of 50 μm. For statistical reasons, three test specimens of each fiber-matrix semifinished product were examined, on each of which 5 repetition measurements were carried out. With fiber-matrix semifinished product (2), no glass fibers were found to a depth of 50 μm, since these were all separated from the surface covered by the unfilled surface layer. Thus, the fiber volume fraction in this area was 0%. In fiber-matrix semi-finished product (1) no separating cover layer was determined, but the glass fiber bundles were homogeneously enclosed and to the surface before, so that even in the area between the surface to a depth of 50 microns, the claimed fiber volume fraction was found. Experimental results test parameters value Condition of the specimens Dry (80 ° C, vacuum dryer, approx. 200 h) Test speed [mm / min] 10 Maximum force absorption [kN] 50 Pre-power [N] 5 Table 1: Test parameters in the tensile test

As a criterion for the bond strength, the maximum measured force determined in the tensile test was defined. First measurable force drops were caused by initial cracks in the material, peelings, deformations or similar effects before reaching maximum force and appeared to be unsuitable as a bond strength criterion. The maximum measured force was reached in case of failure of the head tension test; It is therefore referred to below as the breaking force. Basically, it should be noted that the maximum force in addition to the bond adhesion and the geometry can always depend on the test method and the test conditions.

For each fiber-matrix semifinished product, 10 rib examinations were carried out in each case in order to make a statistically reliable statement possible.

In the case of the fiber matrix semifinished product (1) (according to the invention), in all cases a purely cohesive failure of the thermoplastic matrix 1 occurred directly at the uppermost semifinished fiber layer of the semi-finished fiber product.

In the case of the fiber-matrix semifinished product (2) (not according to the invention), by contrast, a mixed fracture of cohesive and adhesive failure in the boundary layer between thermoplastic matrix 1 and thermoplastic matrix 2 was always observed. A cohesive failure of thermoplastic matrix 1 above the uppermost semi-finished fiber layer was not observed.

In the non-inventive fiber-matrix semifinished product (2) thus the near-surface layer (surface) of thermoplastic matrix 2 from the substrate consisting of semifinished fiber and thermoplastic matrix 1, demolished, while the invention, single-layer fiber-matrix semifinished product (1) no Such separation was observed within a surface-parallel layer in the thermoplastic matrix 1. No. Test result of fiber-matrix semi-finished products (1) Test result of fiber-matrix semi-finished products (2) 1 + - 2 + - 3 + - 4 + - 5 + - 6 + - 7 + - 8th + - 9 + - 10 + - Table 2: Statistical summary of 10 rib proof tests

The evaluation of the results was based on the amount of the deduction. A "+" indicates the respective higher pull-off force of the two compared fiber-matrix semi-finished products, while a "-" indicates the lower force, with a "+" symbolizing an at least 15% higher pull-off force.

The test results show that the maximum force in the comparisons of the two fiber-matrix semifinished products in the single-layer fiber-matrix semifinished product (1) according to the invention always turned out to be higher than in the case of the fiber-matrix semifinished product (2) with layered structure. Also, the mean value of the individual test results of the measurement series was significantly higher than that of the fiber-matrix semifinished product (2) in the single-layer fiber-matrix semifinished product (1) according to the invention.

In summary, the rib peel strength of the monolayer fiber-matrix semifinished product (1) according to the invention was markedly higher than in the case of the fiber-matrix semifinished product (2), which is why a monolayer fiber-matrix semifinished product according to the invention, used as an oil container or as an oil pan Has advantages over fiber-matrix semi-finished products according to the prior art.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 102008027662 A1 [0003]
• DE 102008038958 A1 [0003]
• WO 2007/128395 A1 [0004]
• WO 2012/126910 A1 [0004]
• DE 102012205078 A1 [0004]
• CN 201573367 U [0004]
• DE 102008052000 A1 [0005]
• EP 0291629 A2 [0005]
• EP 2028231 A1 [0005, 0045]
• DE 102009053502 A1 [0005]
• EP 1923420 A1 [0005]
• EP 1762592 A1 [0045]
• EP 2060596 A1 [0045]
• JP 2010222486 A [0045]
• EP 2410021 A1 [0045]
• EP 3020752 A1 [0045]
• WO 2013/087733 A2 [0045]
• EP 0485895 B1 [0084]
• EP 1980383 A2 [0093]
• DE 4101106 A1 [0100]
• US 6036908 B [0100]
• US 6475423 B1 [0100]
• WO 2005/070647 A1 [0100]
• DE 102006013684 A1 [0101]
• WO 2012/132399 A1 [0119]
• WO 2010/132335 A1 [0119]

Cited non-patent literature

• ISO 1133 [0007]
• DIN 1310 [0007]
• Expert from W. Siebenpfeiffer, lightweight technologies in automotive engineering, Springer-Wieweg, 2014, pages 118-120 [0012]
• ISO 1133 [0013]
• http://de.wikipedia.org/wiki/Fiber-Kunststoff-Verbund [0017]
• J. Kastner et. al., Quantitative measurement of fiber lengths and distribution in fiber-reinforced plastic parts using μ-X-ray computed tomography, DGZfP Annual Meeting 2007 - Lecture 47, pages 1-8 [0018]
• DIN EN ISO 12127 [0021]
• Composites Technologies, The Processing of FV Thermoplastics, ETH Zurich IMES-ST, Chapter 9, Version 3.0, October 2004 [0027]
• EN ISO 307 [0040]
• EN ISO 1874-1: 2010 [0041]
• ISO 16396-1: 2015, [0041]
• DIN 65571-1: 1992-11 [0052]
• DIN 65571 [0052]
• ISO 1888 [0052]
• DIN 1310 [0072]
• ISO 527-4 or -5 [0085]
• AKV-Industrievereinigung Reinforced Plastics e. V., Handbuch Faserverbund-Kunststoffe, 3rd ed. 2010, Vieweg-Teubner, 236 [0091]
• DIN 8580 [0093]
• C. Hopmann, R. Schöldgen, M. Hildebrandt, Inline Impregnation Technology with Thermoplastics, Flexible Series Production of Thermoplastic FRP Components, IKV of RWTH Aachen, Plastverarbeiter October 15, 2014 [0093]
• Chapter 10, Pressing Methods for Continuous FV Thermoplastics, Urs Thomann, in Composites Technology, Prof. dr. Paolo Ermanni, Script for the ETH Lecture 151-0307-001, Zurich August 2007, Version 4.0 [0097]
• https://en.wikipedia.org/wiki/Crystallization_(Polymer) [0099]
• http://www.industrieanzeiger.de/home/-/article/12503/11824771/ [0100]
• ISO 1133 [0108]
• DIN 1310 [0108]
• EN ISO 527 [0111]
• EN ISO 527-1 (latest edition of April 1996, current ISO version February 2012) [0111]
• ISO 1133 [0113]
• ISO 307, 1157, 1628 [0113]
• ISO 307, 1157, 1628 [0114]
• W. Siebenpfeiffer, Lightweight Technologies in Automotive Engineering, Springer-Vieweg, 2014, pages 118-120 [0120]
• DIN 1310 [0123]

Claims (13)

Oil tank, preferably oil pan, comprising at least one single-layer fiber-matrix semi-finished product wherein 1 to 100 semi-finished fiber layers of continuous fibers, wherein the semi-finished fiber layers each have a basis weight in the range of 5 g / m ² to 3000 g / m ² , and the entirety of all semi-finished fiber layers at least one thermoplastic having a MVR according to ISO 1133 in the range of 1 cm ^3/10 min to 100 cm ^3/10 min is impregnated, wherein the thermoplastic is selected from the group of polyolefins, vinyl polymers, polyacrylates, polyamides, polyurethanes, polyureas, polyimides, polyesters , Polyethers, polystyrenes, polyhydantoins, polyphenylene oxides, polyarylene sulfides, polysulfones, polycarbonates, polyphthalamides, polymethylmethacrylates, styrene-acrylonitriles, thermoplastic olefin-based elastomers, thermoplastic polyurethanes and polyoxymethylenes, and this fiber-matrix semi-finished product has a volume fraction of fiber materials defined in DIN 1310 in the range from 5 to 90 vol.% and egg NEN volume fraction of air or gas of less than 15 vol .-%, having. Oil container according to claim 1, characterized in that the fiber-matrix semi-finished product has a material thickness in the range of 0.05 mm to 6 mm. Oil container according to one of claims 1 or 2, characterized in that vinyl polymers from the group polyvinyl halides, polyvinyl esters and polyvinyl ethers are used. Oil container according to one of claims 1 or 2, characterized in that are used as polyolefins polyethylene or polypropylene. Oil container according to one of claims 1 or 2, characterized in that are used as polyester polyethylene terephthalate or polybutylene terephthalate. Oil container according to one of claims 1 or 2, characterized in that polycarbonates based on 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, dihydroxydiphenyl sulfide, tetramethylbisphenol A, 1,1-bis (4 -hydroxyphenyl) -3,3,5-trimethylcyclohexane or 1,1,1-tris (4-hydroxyphenyl) -ethane. Oil container according to one of claims 1 or 2, characterized in that are used as polyphthalamide PA 6T, PA 10T or PA 12T. Oil container according to one of claims 1 or 2, characterized in that polyamides are selected with a relative solution viscosity in m-cresol in the range of 2.0 to 4.0, wherein the measurement of the relative solution viscosity η _rel according to EN ISO 307 in m- Cresol is carried out at 25 ° C. Oil container according to claim 8, characterized in that a polyamide from the group PA 66, PA 6 and PA 12 is used. Oil container according to one of claims 1 to 9, characterized in that the thermoplastic contains at least one thermal stabilizer. Oil container according to claim 10, characterized in that metal-based thermal stabilizers or organic heat stabilizers are used. Oil container according to claim 11, characterized in that polyhydric alcohols are used. Oil container according to claim 11, characterized in that copper stabilizers, preferably copper (I) halides, are used