COMPOSITE MATERIAL, METHOD FOR MANUFACTURING A PRODUCT MADE OF A COMPOSITE MATERIAL, AND MACHINE FOR MANUFACTURING A PRODUCT MADE OF A COMPOSITE MATERIAL

Abstract

A composite material, comprising a first component and a second component, the first component forming a three-dimensional mesh-type structure and the second component forming a matrix at least regionally filling the interstices between the first component, wherein the second component at least partially comprises an expanded material.

Claims

1. A composite material, comprising a first component and a second component, the first component forming a three-dimensional mesh-type structure and the second component forming a matrix at least regionally filling the interstices between the first component, wherein the second component at least partially comprises an expanded material, preferably an expanded foam.

2. The composite material of claim 1 wherein the first component and/or the second component comprises fibers.

3. The composite material of claim 2 wherein the fibers comprise one or more biopolymers preferably selected from the group comprising: polylactide, cellulose, flax, wool, cotton, hemp, bamboo, silk.

4. The composite material of claim 1 wherein the second component comprises one or more biopolymers preferably selected from the group comprising: polylactide, polyhydroxyalcanoate, protein, polysaccharide (starch, alginates, lignin, or the like).

5. The composite material of at least one the preceding claim 1 wherein a density of the second component is lower than a density of the first component.

6. The composite material of claim 1 wherein it comprises at least a first area and a second area, the material density in the first area being different than in the second area.

7. A method for manufacturing a product made of a composite material comprising the following steps: a. providing a blend of at least a fibrous material and an expandable material; b. placing the blend into a mold cavity; c. applying energy, preferably heat to the blend within the mold cavity; d. keeping the mold cavity open at a certain and limited extent or increasing the volume of the mold cavity to a certain and limited extent, such that the heated expandable material can expand, the certain and limited extent being selected such that the expandable material does not fully expand; e. keeping the mold cavity essentially in the state where the volume is increased to the first extent until the material inside the mold cavity has stabilized.

8. The method of claim 7 wherein the fibrous material comprises one or more biopolymers preferably selected from the group comprising: polylactide, cellulose, flax, wool, cotton, hemp, bamboo, silk, and/or wherein the expandable material comprises one or more biopolymers preferably selected from the group comprising: polylactide, polyhydroxyalcanoate, protein, polysaccharide (starch, alginates, lignin, or the like).

9. The method of claim 7 wherein the blend comprises additionally at least one of the following components: lignin, recycled paper, water.

10. The method of claim 7 wherein in step c heating is performed by means of high frequency electromagnetic radiation.

11. The method of claim 7 wherein after step b the volume of the mold cavity is reduced.

12. The method of claim 7 wherein the expandable material is provided in the form of a powder or in the form of pellets.

13. A machine for manufacturing a product made of a composite material comprising: a mold cavity for receiving a blend of at least a fibrous material and an expandable material; a device for applying energy, preferably heat, to the blend within the mold cavity; means for keeping the mold cavity open at a certain and limited extent or for increasing the volume of the mold cavity to a certain and limited extent such that the expandable material can expand, the first extent being selectable such that the expandable material does not fully expand; means for keeping the mold cavity essentially in the state where the volume is increased to the first extent until the material inside the mold cavity has stabilized.

14. The machine of claim 13 wherein the mold cavity is at least partially delimited by an elastic wall.

15. The machine of claim 13 wherein the heating device comprises an emitter for emitting high frequency electromagnetic radiation.

Description

[0024] Embodiments of the invention are now described in further detail with reference to the attached drawing. In the drawing is shown by

[0025] FIG. 1 an enlarged sectional view of a composite material according to the invention having a first component forming a mesh-type solid structure and a second component comprising an expanded foam;

[0026] FIG. 2 a schematic representation of a machine for manufacturing a product made of the composite material of FIG. 1 at a first moment of time during manufacturing;

[0027] FIG. 3-5 views similar to FIG. 2 at further moments of time;

[0028] FIG. 6 a sectional view of the final product manufactured according to FIGS. 2-5;

[0029] FIG. 7 a diagram of the glass temperature over the moisture content of a blend for manufacturing the composite material of FIG. 1;

[0030] FIG. 8 a schematic representation of a final product having regions with different densities;

[0031] FIGS. 9-12 an alternative embodiment of a machine for manufacturing a product made of the composite material of FIG. 1 at different moments of time during the manufacturing process;

[0032] FIGS. 13-18 a further alternative embodiment of a machine for manufacturing a product made of the composite material of FIG. 1 at different moments of time during the manufacturing process; and

[0033] FIGS. 19-22 further alternative embodiments of a machine for manufacturing a product made of a composite material, and alternative embodiments of the composite material.

[0034] In the following detailed description functionally equivalent elements and regions are designated with the same reference numerals. Furthermore, for the sake of clarity not in all figures all possible reference numerals are shown.

[0035] A composite material 10 comprises a first component 12 and a second component 14. The first component 12 forms a mesh-type and essentially solid structure 16. It is to be understood that the first component 12 forms a three-dimensional mesh-type structure, that is a structure which is mesh-type not only in the plane of FIG. 1 but also in a direction perpendicular to the plane of FIG. 1. It is to be understood that the term mesh also encompasses any type of porous structure having open and/or closed cells. The second component 14 forms a three-dimensional matrix which fills the interstices or cells, respectively, between the first component 12. The second component 14 is in the form of an expanded foam 18. The foam 18 is an essentially solid material comprising a multitude of small gas bubbles separated by thin solid (i.e. non-liquid) walls 22. The foam 18 acts as a binder between the structure 16.

[0036] The first component 12 comprises fibers 24 which in the present exemplary embodiment are made of cellulose. In other non-shown embodiments the fibers may comprise one or more other biopolymers. Those biopolymers may be selected from the group comprising: polylactide, flax, wool, cotton, hemp, bamboo, silk. In other non-shown embodiments the first component may comprise yarns. It is to be understood that the first component may comprise a combination of fibers and yarns, and may comprise a combination of the above mentioned biopolymers.

[0037] In the present exemplary embodiment the second component 14 is also made from a biopolymer, namely thermoplastic starch. However, in other non-shown embodiments the second component may comprise one or more other polysaccharides than starch, such as alginates, lignin, or the like. In other non-shown embodiments the second component may comprise polylactide, polyhydroxyalcanoate, and/or protein.

[0038] As can be seen from FIG. 1, the solid structure 16 of the first component 12 in the present exemplary embodiment comprises irregularly shaped lengthy cells 26 with a more or less, that is essentially parallel orientation. This is indicated by way of example by two longitudinal axes 28 of adjacent cells 26. While the solid structure 16 has a relatively high density and therefore provides a relatively high stability to the composite material 10, the foam 18 has a relatively low density and therefore reduces the overall weight of the composite material 10.

[0039] In FIG. 2, a machine for manufacturing a product made of the composite material 10 is generally designated with reference numeral 30. The machine 30 comprises a mixing device 32 for mixing a number of raw materials and for providing a blend 34. It is to be understood that the mixing device 32 is not necessarily part of the machine 30. This means that the machine 30 may receive the blend 34 also from a storage hopper or any other storage device. The mixing device 30 receives a number of different raw materials, such as thermoplastic starch particles or pellets 36 as an expandable material, cellulose fibers 38 as a fibrous material, and lignin 40, recycled paper 42, water 44, and other suitable additives 46.

[0040] The thermoplastic starch may be provided in the form of pellets at a size in the range of 2-5 mm. The thermoplastic starch pellets may be grinded to obtain a powder with particles at a size from 200 to 1000 m. Cellulose may be provided as wood fibers or other plant fibers, such as from flax or hemp, however being free from lignin.

[0041] Other materials added to the mixing device 32 are preferably other natural polymers. Natural polymers are biobased polymers which are not chemically modified, such as other polysaccharides than cellulose and starch as lignin, pullulans, alginates, chitin, chitosan, natural rubbers, rosinic acid, dextrin or proteins such as gluten, zein, casein, collagen, gelatin, phospholipids, caseins and their derivatives such as for example esters or ethers. Preferably lignin is used for its hydrophobic properties and microcrystalline cellulose for its rheological properties and its mechanical performances.

[0042] Some chemically biobased modified polymers, for example from home compostable, can be added as polyhydroxyalcanoate (PHA) polymers. Also, industrially compostable polymers can be added as PBAT, PBT or PLA. Fossil based polymers which are non-compostable can be used as additives but in small contents and only as processing aid: Vinyl polymers as polyvinyl alcohol, polyolefin as low density polyethylene or polyethylene glycol or ethylene-vinyl alcohol. Glycerin, polyglycerol, sorbitol, mannitol, erythritol, low molecular weight polyvinyl alcohol, as well as oxyethylate or oxypropylate derivates can also be used. Inorganic additives can be added as nucleating agent and charges: talc (magnesium silicate), calcium carbonate, and/or nanoparticles such as montmorillonites and hydrotalcites.

[0043] The blend 34 comprises water 44 for providing a desired viscosity and for providing an agent which can be heated by radiation, as will be explained further below. The blend 34 also comprises the fibers 38, fillers, and additives 40, 42, and 46 in order to obtain the desired properties of the composite material 10 and a final product made of the composite material 10. The moisture content in the blend preferably is in the range of 20 to 90% and more preferably around 60%. Preferably, some thermoplastic starch particles or pellets 36 are in the mixture and preferably the pellets have an hydrophobic skin layer, for example a lignin coating. The objective of this type of thermoplastic starch pellets 36 (in the form of micropellets or powder) is to control expansion during later expansion, as will be described herein below.

[0044] A typical example for producing the blend 34 in the mixing device 32 is given hereinafter: 90 kg of water 44 and 10 kg of corn starch 36 are introduced in a tank and kneaded at 85 C. for 15 min at 100 rpm. After 15 min an homogeneous gelatinized starch (thermoplastic starch) is obtained. 12 kg of cellulose fibers 38 are added to the mixture. The cellulose fibers 38 have an average length of 2.5 mm. After another 5 min of kneading, an homogeneous matrix is obtained. Thereafter, another 8 kg of thermoplastic starch 36 with 13% water content is introduced to the mixture. The thermoplastic starch 36 is in the form of pellets having an average diameter of 2.5 mm. The mixture is kneaded for another 5 minutes in order to obtain the blend 34.

[0045] The blend 34 is placed into an open mold cavity 48 of a first mold half 50. Preferably, the blend 34 is placed in the open mold cavity 48 by means of a nozzle 52 of a 5-axis robotic device (non-shown). This is particularly preferred in the case that the blend 34 has a rather high viscosity. In another not shown embodiment the blend is injected into the mold cavity as is known from standard injection molding.

[0046] As can be seen from FIG. 3, in the present exemplary embodiment the mold cavity 48 is closed by means of a second mold half 54. The second mold half 54 is used to reduce the volume of the mold cavity 48 and thus to compress the blend 34 received in the mold cavity 48. This ensures that the blend 34 entirely fills out the mold cavity 48 and that all air and excess water are evacuated from the blend 34 and the mold cavity 48, respectively. In order to evacuate air and water, grooves (not shown) may be provided in the surface of the first and/or second mold half 50, 54, respectively, outside of the mold cavity 48.

[0047] Both mold halfs 50 and 54 are made of a dielectric material, such as plastic. Preferred materials for the mold are PTFE, PEEK, PEKK, PEI because of their transparency to electromagnetic radiation and their temperature resistance. Other materials having lower temperature resistance also can be used, but in this case they preferably should not come into direct contact with the heated material inside the mold cavity 48. Such materials are for example PS, PP, PE.

[0048] These materials are known to be non-polar materials leading to very low sensitivity to electricity, heating and electromagnetic fields. An important advantage of many plastic materials, especially of thermoplastic materials, such as PTFE, PEEK, PEKK, PEI, PS, PP, and PE is that they can be 3D printed which reduces time and cost for manufacturing the mold halfs 50 and 54 compared to traditional metal machined mold halfs.

[0049] As can be seen from FIG. 4, the compressed blend 34 received within the mold cavity 48 is heated by means of high frequency electromagnetic radiation 56. To this end, the machine 30 comprises a suitable heating device (not shown) which in the present exemplary embodiment may comprise two plate means, namely a passive plate means and an active plate means.

[0050] For heating, an electric current is applied to the active plate means creating an electromagnetic field and a type of capacitor effect. An oscillation is applied to the electric current creating an oscillation of the water content in the blend 34 which, by consequence, causes heating of the blend 34. The frequency applied preferably is in the range from 6 to 40 MHz with a wavelength longer than the maximum dimension of the mold cavity 48 to avoid any hot/cold spots.

[0051] During heating, the expandable material provided by the starch particles 36 is in a glassy state in some areas within the mold cavity 48 (particles) and in a rubbery state in other areas within the mold cavity 48 (matrix). This difference is related to the water content which may vary from one area to another area and to the fact that the glass transition temperature (Tg) of thermoplastic starch depends on the water content (see FIG. 7).

[0052] Preferably, the mold cavity 48 is sealedly closed prior to the above mentioned heating step. By consequence, during heating not only the water temperature but also the pressure inside the mold cavity 48 raises. This allows the water and thus the blend 34 to reach a temperature which may be higher than 100 C., which in turn allows the starch particles 36 to change into a rubbery state even in regions having only a rather low water content. With the temperature of the water 44 in the blend 34 being above the boiling temperature and the thermoplastic starch particles 36 being in a rubbery state, cells 20 start to appear in the material (cell nuclei). Steam migrates into these cells. Nucleating agent as talc helps to increase cell apparition.

[0053] After heating has occurred, the thermoplastic starch particles 36 have reached the rubbery state and the cell nuclei have appeared. Now, the volume of the mold cavity 48 is increased to a certain and limited extent 58, as can be seen from FIG. 5. The extent 58 is selected such that the expandable starch particles 36 do not fully expand by a further and unlimited but only by a limited increment of the sizes of the cells 20 and that a final product 60 (FIG. 6) has a desired shape and dimension. After the defined volume increment, the volume of the mold cavity 48 is kept essentially constant until the material 10 inside the mold cavity 48 has stabilized.

[0054] Preferably, the above described volume increment of the mold cavity 48 is realized within a relatively short period of time, that is suddenly. When the volume of the mold cavity 48 suddenly increases, the pressure inside the mold cavity 48 drops. This makes hot steam to expand the cells 20 and to leave the intermediate material and the mold cavity 48. Since the hot steam leaves the mold cavity 48, the temperature of the material inside the mold cavity 48 decreases. When the temperature of the material decreases below the glass Temperature Tg of the starch 36, the material stabilizes and preserves the dimension and shape, even if the mold cavity 48 is further opened in order to remove the final product 60 (FIG. 6). In the composite material 10 of the product 60 the volume is taken mostly by expanded starch, and a network of fiber and expanded starch is located around these areas.

[0055] In a non-shown embodiment, the machine 30 may comprise a first and/or second mold half forming a mold cavity for manufacturing a product having regions with different thicknesses. When the mold cavity is slightly open to during the expansion step, the material inside the mold cavity will expand differently from region to region. This leads to a final product having regions of a defined density varying from one region to another region. This is schematically shown in FIG. 8 for a product 60 having four different density areas 62a-d.

[0056] The final product 60 made of the composite material 10 in the present exemplary embodiment may have a density of 45 g/l. It comprises areas (cells 26) of pure expanded foam 18 having a size from 3-25 mm. These cells 26 filled with foam 18 have a relatively low density from 10-30 g/l. The cells 26 are enclosed by the above mentioned solid structure 16 of cellulose fibers 24. The thickness of the elements of the solid fiber structure 16 may be in the range from 0.1-3.0 mm. This disparity of wall thicknesses is mainly caused by the heterogeneity of the blend 34.

[0057] Now, reference is made to FIG. 9-12 showing another embodiment of a machine 30. The machine 30 of FIGS. 9-12 comprises a hopper 64 for introducing the raw materials composing the blend 34. In the present exemplary embodiment, the fibrous material 38 is provided as pellets of cellulose fibers with a length lower than 1 mm. The expandable material 36 is provided as gelatinized starch from peas. The relation is 60% cellulose fibers 38 and 40% starch 36. Furthermore, PVA (not shown) and water 44 are also introduced into the hopper 64.

[0058] The machine 10 further comprises a screw 66 within a barrel 68 having an injection nozzle 70. The hopper 64 is connected to the inside of the barrel 68. Radially outwardly of the barrel 68 a heating device 72 is provided. The screw 66 doses the desired blend amount and conveys the blend 34 directly into a mold cavity 48.

[0059] During the dosing process provided by the screw 66 the cellulose fiber pellets 38 are melt. The rotational speed of the screw 66 is selected in order to avoid too much shearing effects and to keep the melted material just below 100 C. The melted blend 34 is conveyed by means of the injection nozzle 70 into the mold cavity 48 (FIG. 10). As was explained with respect to the first embodiment of a machine 10, the blend 34 received within the mold cavity 48 is heated by means of high frequency electromagnetic radiation 56 (FIG. 11). Thereafter, the volume of the mold cavity 48 is suddenly increased (FIG. 12) by a certain and limited extent 58.

[0060] The final product 60 obtained by this method has a density of 90 g/l with areas 26 with pure foam 18 having a size ranging from 0.1 to 3 mm. These areas have low densities ranging from 10 to 30 g/l. These cell-type areas 26 with foam 18 are enclosed in a cellulose fiber network structure 16.

[0061] A still further embodiment of a machine 30 for manufacturing a final product 60 made of a composite material 10 and its functional principles are now explained with reference to FIGS. 13-18. The mold cavity 48 is formed between the first mold half 50 and the second mold half 54. Towards the second mold half 54, the mold cavity 48 is delimited by a bladder type elastic wall 72, for example formed from a silicone material.

[0062] The edges of the elastic wall 72 are air tightly fixed to the second mold half 54. A space 74 between the second mold half 54 and the elastic wall 72 is fluidly connected to a pressurized gas supply which allows to apply a gas pressure to the space 74, as desired. At least the wall of the first mold half 50 delimiting the mold cavity 48 is made of PTFE.

[0063] The machine 30 of FIGS. 13-18 may be used as follows: 90 kg of water and 10 kg of native pea starch are introduced into a receptacle (not shown) and kneaded at 85 C. for 50 minutes at 100 rpm. When kneading has ended after 15 minutes, an homogeneous gelatinized starch (thermoplastic starch) is obtained. Thereafter, 12 kg of cellulose fibers are added to the starch. The fibers have an average length of approximately 1.5 mm. The mixture of fibers and starch is further kneaded for 5 minutes, and after these 5 minutes an homogeneous matrix is obtained. Thereafter, 8 kg of thermoplastic cornstarch powder with 13% water content are introduced to the matrix. The cornstarch powder has a particle size distribution of D(1,0) 1200 m and D(0,5) 800 m. Again, the mixture is kneaded for further 5 minutes. The result is a blend 34 which is ready to be used in the machine 30.

[0064] In a first step (FIG. 13), the first mold half 50 and the second mold half 54 are approached to each other such that the mold cavity 48 becomes closed. In a second step (FIG. 14), gas pressure is applied to the space 74 such that the flexible wall 72 expands and comes to lie against the wall of the first mold half 50 delimiting the mold cavity 48. The gas pressure inside the space 74 may be approximately 3 bar.

[0065] In a third step (FIG. 15), the blend 34 is injected through the nozzle 52 into the mold cavity 48 with a pressure between approximately 3.5 and 5 bar. After a predefined volume or mass of blend 34 has been injected into the mold cavity 48, injection is stopped, and the pressure inside the space 74 is further increased to approximately 9 bar. Furthermore, the heating device (not shown) starts emitting high frequency electromagnetic radiation 56 (FIG. 16) for approximately 30 seconds. This raises the temperature of the blend 34 within the mold cavity 48 to approximately 190 C.

[0066] As can be seen from FIG. 17, thereafter the pressure in the space 74 is suddenly reduced to environmental pressure. This allows the volume of the mold cavity 48 to suddenly increase until the elastic wall 72 comes to lie against the 30 second mold half 54. In this case, expansion of the material inside the mold cavity 48 occurs not only in one direction but rather in multiple directions as is indicated by arrows 76 in FIG. 17. These directions are the moving directions of the elastic wall 72 during the sudden pressure decrease in space 74. After the material inside the mold cavity 48 has stabilized after its expansion, the mold cavity 48 can be opened and the final product 60 can be removed (FIG. 18).

[0067] The final product 60 obtained by the method and machine 30 of FIGS. 13-18 has a density of 60 g/l. In the final product 60 exist areas (cells 26) of pure foam 18 having an extension of 0.5 to 8 mm and a density in the range from 10 to 30 g/l. These three-dimensional cells 26 of pure foam 18 are at least partially enclosed in a solid structure 16 of fibers 24 having wall thicknesses in the range from 0.1 to 3 mm.

[0068] A further alternative embodiment of a composite material 10 will be explained with reference to FIGS. 19-21: expanded starch beads 78 are wrapped in coated paper 80, the paper being coated with a starch glue 82. The three components 78, 80, and 82 form already expanded pellets 84. A multitude of such wrapped and already expanded pellets 84 is then filled in the mold cavity 48 by means of so-called bead fill guns 86, which are a sort of injector for introducing the pellets 84 into the mold cavity 48. By means of hot steam, the paper 80 and the glue 82 are transformed into a three-dimensional mesh-type and essentially solid structure 16 (first component 12), the glue 82 binding the paper 80 together, whereas the already expanded starch beads 78 form the expanded material 18 (second component 14) of the composite material 10.

[0069] A further alternative embodiment of a composite material 10 will be explained with reference to FIG. 22: Recycled expanded polystyrene beads 36 are mixed with hemp fibers 38 impregnated by a fire retardant ammonium polyphosphate. The mixture is placed for 24 hours in a high humidity environment having 78% relative humidity. Ammonium polyphosphate is a salt. It helps to catch environmental humidity. When the mixture has a humidity of approximately 18% wt., it is introduced in a mold, as shown above with respect to the other embodiments. High frequency is applied in order to heat the fibers up to 100 C. By doing so, the water comprised in the mixture vaporizes and welds the expanded polystyrene beads 36 together.

LIST OF REFERENCE NUMERALS

[0070] 10 composite material [0071] 12 first component [0072] 14 second component [0073] 16 3D mesh type structure [0074] 18 foam [0075] 20 gas bubbles [0076] 22 walls [0077] 24 fibers [0078] 26 cell [0079] 28 longitudinal axis [0080] 30 machine [0081] 32 mixing device [0082] 34 blend [0083] 36 starch particles [0084] 38 cellulose fibers [0085] 40 lignin [0086] 42 recycled paper [0087] 44 water [0088] 46 suitable additives [0089] 48 mold cavity [0090] 50 first mold half [0091] 52 nozzle [0092] 54 second mold half [0093] 56 electromagnetic radiation [0094] 58 certain and limited extent [0095] 60 final product [0096] 62 density areas [0097] 64 hopper [0098] 66 screw [0099] 68 barrel [0100] 70 injection nozzle [0101] 72 elastic wall [0102] 74 space [0103] 76 arrows in FIG. 17 [0104] 78 expanded starch beads [0105] 80 coated paper [0106] 82 starch glue [0107] 84 pellets [0108] 86 bead fill guns