WO2022154775A2 - A 3d printer comprising an apparatus for polymer matrix composites and working method thereof - Google Patents
A 3d printer comprising an apparatus for polymer matrix composites and working method thereof Download PDFInfo
- Publication number
- WO2022154775A2 WO2022154775A2 PCT/TR2022/050021 TR2022050021W WO2022154775A2 WO 2022154775 A2 WO2022154775 A2 WO 2022154775A2 TR 2022050021 W TR2022050021 W TR 2022050021W WO 2022154775 A2 WO2022154775 A2 WO 2022154775A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- dimensional printer
- module
- needle
- layers
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000011160 polymer matrix composite Substances 0.000 title description 7
- 229920013657 polymer matrix composite Polymers 0.000 title description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 229920002430 Fibre-reinforced plastic Polymers 0.000 claims abstract description 8
- 239000011151 fibre-reinforced plastic Substances 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 64
- 239000000835 fiber Substances 0.000 description 28
- 239000000654 additive Substances 0.000 description 21
- 230000000996 additive effect Effects 0.000 description 19
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000013459 approach Methods 0.000 description 2
- 239000000109 continuous material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- QXAITBQSYVNQDR-UHFFFAOYSA-N amitraz Chemical compound C=1C=C(C)C=C(C)C=1N=CN(C)C=NC1=CC=C(C)C=C1C QXAITBQSYVNQDR-UHFFFAOYSA-N 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—Processes of additive manufacturing
- B29C64/188—Processes of additive manufacturing involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control
- B29C64/194—Processes of additive manufacturing involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control during lay-up
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
Abstract
The invention relates to an apparatus that can be mounted on a three-dimensional printer for the production of a short cut fiber-reinforced polymer composite with increased vertical strength between layers (3). The method of working of the three-dimensional printer comprising the said apparatus is also within the scope of the invention. The said method in its most general form comprises the steps of a. extruding at least two layers (3) by means of the extrusion nozzle (2), b. immersing and removing the needle (1a) or needles (1a) at least once and immersing it deeper than the thickness of the layer (3) by moving a module (1) comprising at least one needle (1a) that is longer than the thickness of the extruded final layer (3) and a flattener (1b) in one or more axes towards the layer (3), c. flattening the said layer (3) by means of the flattener (1b) in the module (1) after step b.
Description
A 3D PRINTER COMPRISING AN APPARATUS FOR POLYMER MATRIX COMPOSITES AND WORKING METHOD THEREOF
Field of the Invention
The invention relates to an apparatus placed around the extrusion noz zle , which can be mounted on three-dimensional printers to increase the interlayer adhesion of polymer matrix composites , a three-dimensional printer comprising the apparatus , and the working method of this printer .
Known State of the Art
Strengthening the structures with fiber reinforcement made into the matrix material forms the basis of the composite structure . The ratio , distribution, arrangement of the fibers and the structure of the interface of the fibers with matrix material , af fect the mechanical properties of the composite material . The production of composites with additive manufacturing makes it possible to manufacture parts with especially complex geometries ( sometimes which are not possible to manufacture by conventional methods ) . However, since additive manufacturing is produced in layers , the mechanical properties of the manufactured parts change depending on the direction ( anisotropy) . The tests performed on the carbon fiber reinforced ABS (Acrylonitrile butadiene styrene ) polymer samples produced by the additive manufacturing method showed that the strength in the direction of the fibers is well above ( about two times ) the strength in the direction perpendicular to the fibers . Therefore , the arrangement of the reinforcement fibers in the matrix is very important in terms of strength .
In the production of polymer-based composites using the melt deposition method and additive manufacturing method, the adhesion rate of the layers to each other is one of the factors determining strength of the manufactured components in the vertical direction . The distribution and arrangement of the short cut fiber additives in the laid layer also af fect the strength of the components in other directions .
In the prior art , there are some systems or methods for increasing the adhesion between layers in additive manufacturing ( three-dimensional printers ) . Some of these , especially in large-scale additive manufacturing systems , require the substrate to be heated above its glass transition temperature before laying the new layer, as described in US 2015/ 0314532 . As another example , in the document US 9 , 586 , 371 it is described that agent particles inserted in the polymer matrix forms cavities and the new layer infiltrates into these cavities . As another example , some systems in the art include approaches such as printing the laid layer with a roller mill ( Thermwood LSAM) or a vibrating table ( Cincinnati BAAM) . However, these methods and systems known in the art af fect the arrangement of the short cut fiber reinforcement within the layer and do not achieve the desired distribution between the layers ( in the vertical direction) .
I f fiber orientation (blend) is formed between the layers in the vertical direction, the strength of the parts produced by additive manufacturing will increase signi ficantly and the strength of the composite parts obtained by other methods will be reached . For this purpose , the vertical filling ( Z-pining) method of the spaces left between the layers has been developed . However, this approach imposes longer printing times and geometric constraints on the parts that can be produced .
As another example of the state of the art , the document numbered US2020307147 can be given . The said document is a patent document
relates to an apparatus developed for use in the field of composite-based additive manufacturing ( three-dimensional printer ) for entangling adj acent fibrous layers and thus adhering the layers and increasing the strength . The apparatus of the said document comprises in its most general form; a bed plate on which sheets shaped for a desired 3D obj ect and including a registration aperture , at least one of the printed sheets having fibers therein, registration pins aligned with the bed plate and extending through the registration aperture to maintain printed sheets in alignment , a guide plate having an array of apertures extending vertically and configured to move back-and- f orth/down-up relative to the bed plate , an array of needles having a barb on a peripheral surface thereof configured to intertwine fibers , and a needle board adj acent the guide plate opposite the bed plate and holding the needles . The document mentioned relates to increasing the interlayer bonding of laminated sheets ( fabric, woven fiber layer, etc . ) . It is aimed to direct the fibers present the previous sheet to the upper layer of the material deposited on the laminated sheet with a three-dimensional printer . There is an increase of the adhesion of a material extruded with a three-dimensional printer on a ready-made sheet , fabric, etc . However, the system of the said document does not provide the orientation of the fibers between the extruded layers in the direct melt extruding method and the three-dimensional additive manufacturing technique .
As another example of the state of the art , the document numbered US2017210074 Al can be given . The document mentioned is a patent document that deals with a three-dimensional printer system that enables the production of a fiber-containing obj ect . The aim of the invention is to produce fiber-reinforced plastics at less cost and to mold more complex shapes by using a three-dimensional printer system . The three-dimensional printer system of the mentioned document comprises in its most general form, a head that has a noz zle where a first continuous material including a
resin and a second continuous material including fibers are individually fed into , a platform on which a printing material exiting from the outlet of the noz zle is stacked, a cutting device configured to cut the fibers and a controller configured to control an operation device associated with at least one of the head, the platform, and the cutting device . The mentioned document relates to a continuous fiber-reinforced three- dimensional printer system . Continuous fiber and short cut fiber-reinforced composites are di f ferent material groups and are produced with di f ferent techniques . Therefore , the mentioned document does not provide a system and method applicable to composites with short cut fiber solids .
In order to eliminate the disadvantages of the documents mentioned above , an apparatus has been developed that increases the strength of the composites by ensuring the mixing of the short cut fibers between the extruded layers in the production of polymer matrix composites containing short cut fiber additives by additive manufacturing ( 3D printer ) . The apparatus can be mounted on three-dimensional printers .
Detailed Description of the Invention
The invention relates to the production of polymer matrix composites with additive manufacturing ( 3D printer ) with a vertically strengthened short cut fiber additive between layers .
The invention is based on the principle that needles ( la ) longer than the thickness of the layer ( 3 ) are inserted and removed on the layer ( 3 ) laid in the production of composites , and the reinforcement base fibers in the bottom layer ( 3b ) are oriented vertically and mixed between the two layers ( 3 ) . The flat part of the movable table to which the needles ( la ) are attached smooths the roughness that may occur on the surface .
The invention, in its most general form, is an apparatus mountable on a three-dimensional printer comprises, a module (1) movable in one or more axes comprising
- at least one needle (la) arranged for facing towards an extruded layer (3) and longer than the thickness of the layer (3) and
- a flattener (lb) wherein the module (1) being arranged to provide the needle (la) to be immersed and removed from the layer (3) , wherein the apparatus being arranged to be placed around an extrusion nozzle
(2) of the three-dimensional printer.
Thanks to the developed apparatus, adhesion between the layers
(3) of polymer matrix composites increases. The flattener ( lb) provides the removal of the surface roughness caused by the needle ( la) .
In one embodiment of the invention, layer (3) is a short cut fiber reinforced polymer composite. It is preferably carbon fiber reinforced ABS polymer composite.
In one embodiment of the invention, the needles (la) can be placed in different arrangements depending on the width of the layer (3) laid. In one embodiment of the invention, module (1) is a planar table or a roller.
In more detail, the invention includes an apparatus that can be mounted on existing three-dimensional printer systems and has needles (la) (pins) that move in one or more axes by being placed around the extrusion nozzle (2) . Following the laying of the fiber-reinforced polymer layer (3) extruded by means of the nozzle (2) (before the melt solidifies yet) , the needles (la) move down on the layer (3) and dive deeper than the layer (3) thickness. The needles (la) also enters the heated and molten bottom layer (3b) at a certain rate and moves upwards again. It
ensures the mixing of the fibers between the two layers (3) and provides the vertical orientation of some of them by the local flow it creates. Needles (la) can have different tip designs. The needles (la) can be placed in different orders depending on the width of the layer (3) . Needles (la) can also be placed on a planar table or a roller. The surface roughness created by the needles (la) is smoothed with a subsequent f lattener ( lb) .
The developed apparatus works with existing three-dimensional printer systems. Depending on the three-dimensional printer, the axis movements of the apparatus can be of different constructions. The movement systems of the head carrying the table and nozzle (2) on which the workpiece is deposited may vary. The layer (3) laying method may have variations such that it follows planar or non-planar toolpaths. In all these variations, providing the interference of the laid layer (3) with a bottom layer (3b) with needles (la) constitutes the basis of the invention.
The invention uses needles (la) that dive into the laid layer (3) to ensure adhesion (interference, bond) between layers (3) in additive manufacturing (three-dimensional printer) system with melt deposition method. While the needles (la) moving up and down enter and exit the bottom layer (3b) at a certain rate, they ensure that the additive fibers in these layers (3) are mixed with each other and that some of them are oriented vertically to the laying direction of the layer (3) . In this way, adhesion (interference, bond formation) between the layers (3) increases, increasing the strength of the produced part.
A three-dimensional printer comprising the said apparatus is also within the scope of the invention.
The use of the three-dimensional printer comprising the said apparatus for the short cut fiber-reinforced polymer composite is also within the scope of the invention. Preferably, carbon fiber reinforced ABS polymer is used.
The working method of the three-dimensional printer comprising the said apparatus is also within the scope of the invention. The mentioned method comprising the steps of; a. extruding at least two layers (3) by means of the extrusion nozzle (2 ) , b. immersing and removing the needle (la) or needles (la) at least once and immersing it deeper than the thickness of the layer (3) by moving a module (1) comprising at least one needle (la) that is longer than the thickness of the extruded final layer (3) and a flattener (lb) in one or more axes towards the layer (3) , c. flattening the said layer (3) by means of the flattener ( lb) in the module (1) after step b.
In one embodiment of the invention, a polymer composite with short cut fiber is used as a layer (3) . Preferably, carbon fiber reinforced ABS polymer is used.
In one embodiment of the invention, the module (1) moves up and down, with the needles (la) perpendicular to the layer (3) .
With the method introduced in the invention, in the additive manufacturing of polymer matrix fiber-reinforced composites, the strength weakness in the perpendicular direction to the layers (3) (anisotropic structure) is reduced, making it possible to produce more homogeneous (isotropic structure) parts.
One embodiment of the invention relates to the additive manufacturing (three-dimensional printer) method and the composite obtained by this method. In this method, the adhesion of the produced polymer matrix composites between the layers (3) is increased by mixing with the needle (la) .
With the melt deposition method, which is the subject of the invention, it is possible to produce more homogeneous (isotropic) parts in the additive manufacturing of polymer composites .
As shown in Figure 1, the three-dimensional printer subject to the invention has an apparatus comprising a movable module (1) . By means of the nozzle (2) of the printer, the layers (3) are stacked on top of each other in the x-axis direction. With the up and down movement of the module (1) in the z-axis direction, the needles (la) are taken in and out of the extruded layer (3) and immersed deeper than the thickness of the layer (3) . Then, the roughness on layer (3) is smoothed by the f lattener ( lb) in module (1) . Figure 1 also shows the thickness and length of the layer ( 3 ) .
In Figure 2, the interference and vertical orientation of the short cut fibers in a top layer (3a) and bottom layer (3b) produced by the three-dimensional printer, which is the subject of the invention, are shown in detail.
Despite many important advantages, the low strength of the layers (3) in the vertical direction imposes limitations on the production of composite parts by the additive manufacturing method. Elimination of this important disadvantage will expand the application areas of additive manufacturing and composite manufacturing, enabling the production of parts that could not be produced before or the production of smaller sizes due to increasing the strength of existing parts. In this case, production will be realized with less material usage, lower cost, and energy consumption.
Descriptions of Figures
Figure 1: View of the three-dimensional printer of an embodiment of the invention
Figure 2: Detailed view of interference and vertical orientation of short cut fibers in the layer produced with three-dimensional printing of an embodiment of the invention
Explanations of Reference Numbers in Figures
1. Module la . Needle lb. Flattener
2. Nozzle
3. Layer
3a. Top layer
3b. Bottom layer
Claims
1. An apparatus mountable on a three-dimensional printer comprises , a module (1) movable in one or more axes comprising
- at least one needle (la) arranged for facing towards an extruded layer (3) and longer than the thickness of the layer (3) and
- a flattener (lb) wherein the module (1) being arranged to provide the needle
(la) to be immersed and removed from the layer (3) , wherein the apparatus being arranged to be placed around an extrusion nozzle (2) of the three-dimensional printer.
2. The apparatus according to claim 1, wherein the layer (3) is a short cut fiber-reinforced polymer composite.
3. The apparatus according to claim 2, wherein the layer (3) is a carbon fiber reinforced ABS polymer composite.
4. The apparatus according to claim 1, wherein the module (1) is a planar table or a roller.
5. A three-dimensional printer comprising an apparatus according to any one of preceding claims.
6. Use of a three-dimensional printer according to claim 5 in production of short cut fiber reinforced polymer composites .
7. A method of working of a three dimensional printer according to claim 5 comprises the steps of,
d. extruding at least two layers (3) by means of the extrusion nozzle (2) , e. immersing and removing the needle (la) or needles (la) at least once and immersing it deeper than the thickness of the layer (3) by moving a module (1) comprising at least one needle (la) that is longer than the thickness of the extruded final layer (3) and a flattener (lb) in one or more axes towards the layer (3) , f. flattening the said layer (3) by means of the flattener ( lb) in the module (1) after step b.
8. The method according to claim 7, it comprises moving up and down the module (1) with the needles (la) perpendicular to the layer (3) .
9. The method according to claim 7 or 8, wherein the layer (3) is a short cut fiber-reinforced polymer composite.
10. The method according to claim 9, wherein the layer (3) is a carbon fiber reinforced ABS polymer composite.
11. A composite obtained by a method according to claim 9 or
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR2021/00461A TR202100461A2 (en) | 2021-01-13 | 2021-01-13 | A THREE-DIMENSIONAL PRINTER INCLUDING AN APPARATUS FOR POLYMER MATRIX COMPOSITES AND THE METHOD OF OPERATION OF THIS PRINTER |
| TR2021/00461 | 2021-01-13 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2022154775A2 true WO2022154775A2 (en) | 2022-07-21 |
| WO2022154775A3 WO2022154775A3 (en) | 2023-05-25 |
Family
ID=75573099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/TR2022/050021 WO2022154775A2 (en) | 2021-01-13 | 2022-01-13 | A 3d printer comprising an apparatus for polymer matrix composites and working method thereof |
Country Status (2)
| Country | Link |
|---|---|
| TR (1) | TR202100461A2 (en) |
| WO (1) | WO2022154775A2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105556008B (en) * | 2013-06-05 | 2017-12-15 | 马克弗巨德有限公司 | Method for fiber reinforcement addition manufacture |
| CN108790144A (en) * | 2018-06-15 | 2018-11-13 | 天津工业大学 | A kind of interlaminar improvement technology of fibre reinforced composites 3D printing |
| US11220049B2 (en) * | 2019-10-29 | 2022-01-11 | Saudi Arabian Oil Company | System and method for three-dimensional printing of fiber reinforced thermoplastics with multi-axial reinforcement |
-
2021
- 2021-01-13 TR TR2021/00461A patent/TR202100461A2/en unknown
-
2022
- 2022-01-13 WO PCT/TR2022/050021 patent/WO2022154775A2/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2022154775A3 (en) | 2023-05-25 |
| TR202100461A2 (en) | 2021-01-21 |
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