Composite material sheet and the process for manufacturing the same.

Abstract

The invention relates to a composite material sheet or panel obtained by extruding a mixture composed of at least one thermoplastic material, particularly of the polyolefin family, and of mineral fibers having predetermined dimensional characteristics (diameter and length). The extrusion process is performed with such parameters to generate in the sheet a three-dimensional structure embedded in the thermoplastic material.

Description

RENOLIT GOR SPA.Composite material sheet and process for manufacturing the same .The invention relates to a composite material sheet and process for manufacturing the same.The term "composite" means a material obtained by combining two or more components, called also as phases, combined according to various proportions and shapes , such that the final product has a non-homogeneous structure and has chemical-physical properties different from those of the individual constituents. One of the phases, called as matrix, has a continuous form and it mainly acts for maintaining the cohesion of the reinforcement phase or phases, for guaranteeing a certain shape of the piece, as well as for protecting and uniformly transmitting the load to the other reinforcement phase. This latter on the contrary is composed of a discontinuous constituent, generally made of fibers or particles whose task is to guarantee mechanical strength and stiffness, most of the external load being borne by it.In particulate composites the reinforcement is composed of "particles", which (unlike fibers) can be considered equiaxial, namely the diameter to length ratio of each particle is equal about to one (while the fibers are more developed in length direction) .The composite materials with the dispersed phase made of fibers exhibit a strong anisotropy. Such anisotropy is not found (or at least it is very lower) in particulate composites, provided that said particles are equiaxial .The basic idea of the composites is to optimize the performances of the so called traditional materials, as regards the chemical-physical , mechanical and lightweight properties .By combining a material having a given property (for example a polymer) with another one having different properties (for example carbon fibers) , it is possible to obtain a material, composed of such two materials, that enhances the best properties thereof. The composite materials are particularly interesting since they offer particular combinations of different properties that cannot be contemporaneously present in conventional materials such as metal alloys, ceramics and polymers.In the automotive industry, it is known to use panels made of composite material for manufacturing internal parts of motor vehicles such as headliners, load spaces, rear shelves etc.Said panels have to exhibit a considerable mechanical strength in combination with a good flexibility level and a weight as low as possible.The panels made of thermoplastic material filled with vegetable fillers are a good compromise due to their mouldability, for example by thermoforming, their good mechanical strength, their good fracture behavior, in combination with low manufacturing costs. Moreovervegetable fillers allow very light panels to be produced with obvious advantages as regards handling and fuel consumption for the vehicles bearing them.The document EP2247653 describes a composite material sheet having a polypropylene matrix and a filler composed of vegetable fibers, in particular cellulose.An alternative to vegetable fibers is the use of mineral or inorganic fibers, particularly glass fibers. Such type of fibers is more resistant, more rigid, have a high melting point and are completely flame-resistant. On the contrary, except for metal fibers, they are very brittle .In particular glass fibers have a high bending and impact strength and a low thermal and electrical conductivity together with a relatively low density, which make them particularly useful for being used in the automotive industry.On the other side, if they are not well embedded in the matrix of the composite, which guarantees the mouldability thereof, they can be spread in the environment and be dangerous for the health, unlike vegetable fibers.The aim of the present invention is to provide a composite material sheet or plate with a polymer matrix and a filler of inorganic fibers, particularly glass fibers, wherein the matrix is able to perfectly embed the filler, firmly incorporating it therein, thus avoiding the presence of surface fibers that can detach therefrom and be dispersed in the environment, particularly in a vehicle compartment.The invention achieves the aim by providing a composite material sheet having the characteristic of being obtained by extrusion of a mixture composed of a thermoplastic material, particularly of polyolefin family, such as for example polyethylene, polypropylene, mixtures of polyolefins or the like and of groups of non- vegetable fibers, typically glass fibers, having a predetermined length and wherein the extrusion is performed with such parameters to generate a three- dimensional fiber structure called as fiber "mat", where the fibers are entangled on themselves.In particular, such mat is composed of the combination of fibers mainly arranged in the extrusion direction, but, at the same time, exhibiting a kind of isotropy in the other two directions of the plane, due to the mechanical action exerted by the extruder opening and aligning the individual fiber bundles.The invention is based on a unexpected technical effect. As it is known, it is possible to produce composite sheets by impregnating a preformed layer of glass fibers with a polymer matrix, for example polypropylene. The fibers that compose the layer, oriented or not according to a main direction, woven or non-woven, can be dampened by the matrix by coating and compression with a calender or by using softening techniques with cycles at different temperatures. The inventors have found that it is possible to obtain three- dimensional fiber structures completely covered by a polymer matrix by an extrusion process while keeping the dimensions of the fibers under control .In particular, the invention relates to the use of fibers, with a diameter ranging from 5 to 50 micron and a length ranging from 1 to 20 mm.In particular, the invention relates to the use of fibers with the characteristics described at the previous point grouped together in bundles of fibers, that are disgregated into individual units and oriented by forming a three-dimensional structure by the mechanical action exerted firstly by the mixer, then by the screw or screws of the extruder and then by the output die of the extruder .The maximum effect occurs when the groups of fibers have the shape of cylinders having a thickness ranging from 0.5 to 2 mm, preferably about 1 mm, and a length ranging from 2 to 20 mm, preferably in the order of 2-3 mm. Such effect is well clear if a calcination of the composite material is performed by using a muffle furnace. The inorganic component composing the so called mat in the composite material, remains unchanged while organic matter, by being calcinated, is removed from the system. Therefore, it is possible to analyse the amount and the arrangement of the inorganic filler that was embedded in the polymer matrix.The mechanical action exerted by the extrusion on an heterogeneous mixture composed of granules or powder of a thermoplastic polymer and agglomerates of glass fibers is able to break the fiber groups and to disperse the filaments in the polymer matrix.Specifically, the process for producing a composite material sheet according to the invention provides to mixthe thermoplastic material in the form of granules or powder with groups of fibers having a predetermined length and to form the sheet by extruding the mixture through an extrusion die. Mixing and extrusion are performed with such parameters to generate a three- dimensional fiber structure called as mat, embedded in the thermoplastic material. It is the mixing step that causes the fiber bundles to be disgregated without considerably changing the dimensional characteristics thereof. In the extrusion step the individual fibers are arranged to form the mat, in turn completely impregnated by the thermoplastic material .It has to be noted how the sheets according to the invention are completely recyclable. To this end, according to one embodiment, the process provides the step of preliminarily grinding the recycle composite sheets to obtain the thermoplastic material and the fibers to be mixed. In this case a further step is provided such to add in the mixture an amount of the material obtained by grinding the side trims and waste pieces in general (provided that they are consistent with each other as regards the formulation) .If one considers that the thermoplastic material and the fibers are typically present in the sheet substantially under the same proportion, that is 50 and 50 by weight, by feeding the mixer with recycle material and with polymer material in the same amount, the final extrusion will be able to maintain the same proportion of the components if the same amount of fibers is added in a step following the mixing step.The mixing and extrusion steps advantageously are performed in an extruder, particularly a twin-screw extruder, with an output flat die. The fibers entangle with each other due to the mechanical action exerted by the mixing screws and the extrusion die thus generating a fiber entanglement contemporaneously to the mixing / extrusion step.The plates or sheets according to the invention are particularly useful for being used in the automotive industry. For example, they can be used for forming rear shelves, load spaces, headliners for motor vehicles, bodywork parts, truck cabs, spoilers, control boards, tool-holding panels, housings for lights and the like.However also other applications are possible, particularly in those fields requiring small encumbrances and contemporaneously high levels of mechanical strength especially in low cost products and lightweight products.Examples of the present invention are described hereinafter by means of the following figures in which:Figure 1 illustrates a graphic representation of the percentage of the disptrbutionm of the orientation of the fibers in relation to the extrusion direftion which corresponds to an angle of 90° and for different settings of the temeprtaure and of the length of the extrusion die of platform in a direction of extrusion.Figure 2 illustrate a similar graph as in figure 1 but the measurement is limited to a layer of about 0,5mm depth along each of the two opposite surfaced of the sheet .Figure 3, is a graph putting in relation the ratioof the flexural modulus along the direction of extrusion and perpendicular to the direction of extrusion of the sheets according to the examples of the figures 1 and 2 with the peak values of the graphs of figures 1 and 2.In the following some examples will be described with the help of the annexed drawings.An extruded sheet comprising a blend of poliolefine resins and of glass fibres according to the present invention has been extruded. The sheet thickness is of 2,2mm.The length of the die in the direction of extrusion has been varied in four steps between 40 and 100mm.The temperature of the material being extruded is between 200 and 220° degress C.Figure 1 shows the curves of distribution of the fibres relatively to their orientation in respect to the direction of extrusion and expressed in percent.The measurement of the data has been carried out by evaluating the fibres oriented along a certain angle with respect to the direction of extrusion which coincides with a 90° angle in figure 1.Maximum angle of orientation of the fibres is 0° and 180° which corresponds to an orientation of the fibres perpendicular to the direction of extrusion and in the two directions strting from the direction of extrusion.Measurement has been carried out by means of an RX tomograph which has been angulalrly displaced each time of 0.5° relatively to a centre of rotation falling on an axis oriented in the direction of extrusion.At each angle of acquisition, the correspondingpercentage of fibres oriented along the said angle has been determined.The curves have been rescaled in order that their integral from 0° to 180° corresponds to the 100% of the fibers comprised in the sheet.The different curves relate to different length of the extrusion die starting from 30cm up to 100cm.The four curves are identified by symbols and by a name 2141PDC, 2141PSS, 2141PSC, 2141PDD.As it appears form the curves by varying the length of the die, the distribution of the fibres becomes more and more non isotropic. The curve defined as 2141PDC is the flattest one. This means that the fibres are isotropically oriented in relation to the direction of extrusion.This has an effect on the ratio of flexural modulus values in longitudinal and in transverse direction as referred to the direction of extrusion and where this direction is paralle to the longitudinal direction.The ratio of the distributions at the maximum of the curve to the minimum of the curve relating to the example 2141PDC is about 1,2.By varying the length of the die a higher number of fibres are aligned in the direction paralle to the direction of extrusion. The cirve relating to the example 2141PDD shows the hogher dynamic in range and indicates a ratio of the distributions at the maximum of the curve to the minimum of the curve of about 5.7:1.This means that in this case a higher percentage of the fibers are oriented in a direction parallel to thedirection of extrusion than the ones oriented transversally to it. In this case the ratio between longitudinal and transversal flexural modulus as defined above is different and the higher so that the sheet has a higher resistance against flexural stresses in the longitudinal direction.Figure 2 shows what happens to the distribution of the orientation of the fibres in respect to the direction fo extrusion in a thin superficial layer of about 0,5mm depth from a surface of the sheet.Again the measurements are taken in relation to the direction of extrusion corresponding to the 90° angle in the graph and using the same RX tomograph as for figure 1.Four sheets obtained with four die length has been scanned as explained above. The foru sheets and the relative cuirves are identified as already donme above.In reading the curves it appears that varying the die length has the effect not only of flattening the curve, meaning having a higher degree of isotropy or unisotropy of the fibres orientation distribution, but it varies also the angular width of the possible orientation of the fibres centerd along the direction of extrusion (90°). Curve 2141PDC is more flattened and most fibres will be distributed in a isotropic way along directions comprised between about -50° and +50° relatively to the direction of extrusion (90°) . Curve 2141PDD shows a more unisotropic distribution of the fibres on the different orientations but the angular width of the possible orientations is reducing to abou -30° to +30° relativelyto the direction of extrusion. Examples 2141 Psc and Pss show an intermediate behavior between 21 1PDC and 2141PDD.Although the eabove examples are limited to a variation in the length of the dye, experiemnts has shown also a similar influence on the distribution of the fibres on different angular irentations in respect to the direction of extrusion determined by varying the temperature of the mixture being extrused.Fgiure 3 shows the ratio of the longitudinal flexural modulus to the transverse flexural modulus on sheets according to the present invention showing different distributions of the fibres along different orientations with respect of the direction fo extrusion.As already indicated above the term longitudinal direction means here paralle to the direction fo extrusion, while the term transverse direction means a direction perpendicular to the direction of extrusion.Two further examples have been added to the one indicated by 2141 and discussed in relation to the four cases of figure 1 and 2.As it appers from the above description, the invention allows to optimize the mechanical properties of the sheet in relation to two different directions (longitudinal and transverse) paralle and perpendicular to the direction fo extrusion of the sheet. This is achieved without the need of modifying the composition of the sheet material or the thickness of the sheet but only setting different distribution of the fibers onto different orientations in relation to the direction foextrusion by varying only some parameters of the extrusion process and particulalrly length of the extrusion die and / or temperature of the mass of material to be extruded.

Claims

Revised 11 Sep 2018. Claim 1. The process for the production of composite material sheets consists of the following steps: supply of thermoplastic material, especially of the polyolefin family, in the form of granules or powder; supply of non-plant fibers, especially glass fibers, in the form of bundles or bunches of fibers of predetermined length, width and thickness; mixing of such thermoplastic material and such non-plant fibers and separating the fiber bundles during mixing; feeding such mixture into an extruder that forms the sheet by extruding the mixture through the extrusion die of the extruder; the resulting sheet consists of a three-dimensional fiber structure, the fibers are intertwined with each other, and the structure is embedded in the thermoplastic material; the percentage distribution of fiber orientation to extrusion direction is established between a ratio of 1:1 and a ratio of 6:1 between the percentage of fibers oriented in the extrusion direction and the ratio of fibers oriented perpendicular to the extrusion direction. +++++++++++++++++++++++++++++ Page 1 of 1 page. Claim 1.The process for manufacturing composite sheets involves the following steps:

1. Supply of thermoplastic material, particularly polyolefins, in granular or powder form; 2. Supply of non-plant fibers, particularly glass fibers, in bundles or clusters of fibers with predetermined length, width, and thickness; 3. Mixing of the thermoplastic material and non-plant fibers, and separation of fiber bundles during mixing; 4. Feeding the mixture to an extruder, which then extrudes the mixture through the extrusion die. The resulting sheet comprises a three-dimensional fiber structure, with fibers intertwined and embedded in the thermoplastic material. The percentage distribution of fiber orientation to extrusion direction is set between a ratio of 1:1 and 6:1, between the percentage of fibers oriented in the extrusion direction and the ratio of fibers oriented perpendicular to the extrusion direction.

1. The process under claim 1, in which the establishment of the percentage of fiber orientation in relation to the extrusion direction is obtained by varying, in turn, the temperature of the mixture of such thermoplastic material and such non-plant fibers and the length of the printing plate between 30 and 150, or as desired, between 40 and 100 centimeters.

3. The process under claim 1 or 2, in which the percentage distribution of fiber orientation between the directions perpendicular to the extrusion direction and the directions parallel to the extrusion direction varies continuously according to a polynomial function of degree two or higher.

4. The process under one or more of the preceding claims, in which fiber bundles are assembled from groups of individual interconnected fibers, each fiber having a length between 2 and 20 millimeters, or as desired, between 2-3 millimeters, and bundles in the shape of rods or cylinders with a thickness ranging from 0.5 to 2 millimeters, or as desired, approximately 1 millimeter.

5. The process under claim 4, in which a step is arranged to create fiber bundles from each bundle. 6.

7. A process under one or more preceding claims where the steps of crushing composite sheets and adding recycled material to thermoplastic and fiber materials in quantities to maintain the same initial formulation; 8. A process under one or more preceding claims where the mixing and extrusion steps are performed in an extruder, specifically a twin-screw extruder, with a flat output die on face 2 of 2 faces where the fibers are entangled due to mechanical action performed by the mixing screw and die, thus creating a three-dimensional fiber structure along with the mixing / extrusion steps; 9. A process under claim 7 where the separation of fiber bundles is achieved by mechanical action performed by the mixing screw, and the entanglement and distribution direction are created by mechanical action performed by the open end of the extrusion die and the alignment of individual fibers of the bundle; 10.Extruded composite sheets or panels classified as containing thermoplastic materials, particularly of the polyolefin family, embedded with non-plant fibers of predetermined length and forming a three-dimensional fiber structure where the fibers are intertwined with each other, the non-plant fibers of a three-dimensional distribution showing the percentage distribution of fiber orientation relative to the extrusion direction between a ratio of 1:1 and a ratio of 6:1 between the percentage of fibers oriented in the extrusion direction and the ratio of fibers oriented perpendicular to the extrusion direction.

10. Extruded composite sheets under claim 9 with a thickness in which the percentage distribution of fiber orientation relative to the extrusion direction varies with the sheet thickness.11.Extruded composite sheets under claim 10, in which approximately half of the number of fibers within the sheet layer forming the two opposite surfaces of the sheet, are oriented between approximately +60(symbol) and -60(symbol) directions, specifically +45(symbol) to -45(symbol) respectively with respect to the extrusion direction, the ratio of the percentage distribution of fiber orientation in relation to the extrusion direction, between fiber orientation in the +60(symbol) or -60(symbol) direction, is desired to be between +40(symbol) and -40(symbol) respectively with respect to the extrusion direction, and the orientation for fibers parallel to the extrusion direction is between a ratio of 1:1 and a ratio of 6:112.Extruded composite sheet pursuant to one or more prior claims2 where such a three-dimensional fiber structure is composed of a combination of fibers predominantly arranged in the extrusion direction, and for a portion, at the same time, exhibiting isotropy in two other directions of the plane, due to mechanical action performed by the open end of the extrusion and the orientation of each fiber bundle13. Extruded composite sheet pursuant to one or more prior claims9 to12 where the thermoplastic material is a member of the group composed of polyethylene, polypropylene or a polyolefin mixture 14. Extruded composite sheet pursuant to one or more prior claims9 to13 where the non-plant fibers are combined with glass fibers 15. Extruded composite sheet pursuant to one or more prior claims where the thermoplastic material and fibers appear predominantly in equal proportions 16.Composite panels, specifically those for forming rear shelving units, are classified as consisting of one or more sheets according to one or more preceding claims9 to 15;