WO2002083323A2 - Verfahren und vorrichtung zum auftragen von fluiden - Google Patents
Verfahren und vorrichtung zum auftragen von fluiden Download PDFInfo
- Publication number
- WO2002083323A2 WO2002083323A2 PCT/DE2002/001103 DE0201103W WO02083323A2 WO 2002083323 A2 WO2002083323 A2 WO 2002083323A2 DE 0201103 W DE0201103 W DE 0201103W WO 02083323 A2 WO02083323 A2 WO 02083323A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- blade
- coated
- area
- fluid
- rotary movement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
- B05C11/02—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface
- B05C11/023—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
- B05D1/42—Distributing applied liquids or other fluent materials by members moving relatively to surface by non-rotary members
-
- 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
- B29C64/141—Processes of additive manufacturing using only solid materials
- B29C64/153—Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—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
- B33Y10/00—Processes of additive manufacturing
Definitions
- the present invention relates to a method and a device for applying fluids according to the preamble of independent claims 1 and 5. Furthermore, the invention also relates to the use of such a device.
- untreated particle material such as quartz sand
- a binder is sprayed onto the entire particle material in the finest possible distribution.
- a hardener is then dosed onto selected areas, thereby solidifying desired areas of the patikrl material.
- an individually shaped Bodies from the bound particulate material are provided. This body is first embedded in the surrounding, unbound particle material and can be removed from the particle bed after completion of the construction process.
- a casting mold can be produced with the aid of a sulfurous acid as hardening material, which consists of materials that are usually used in mold production and are therefore known to the person skilled in the art ,
- EP 0 538 244 B1 discloses a method for applying a layer of powder to an area, powder material being supplied to the area, a roller being moved over the area and the roller being rotated over the area counter to its linear direction of movement.
- the powder material is contacted by the roller rotating in the opposite direction, so that after the roller is rolled over the area, a layer of powder material is reached on the area.
- the coating step is carried out in such a way that no significant shear stress is transferred to layers previously applied to the area and the shape is not destroyed, which was also generated in such previously applied layers.
- US Pat. No. 5,902,537 also describes the application of particle material by means of a roller which rotates in the opposite direction to the linear direction of travel.
- this object is achieved with a method for applying fluids of the type mentioned at the outset, the blade carrying out an oscillation in the manner of a rotary movement. It has been shown that in such a method, the fluid applied to the area to be coated, for example particle material, is fluidized by the oscillating rotary movement of the blade. As a result, not only can particulate material with a strong tendency to agglomerate be applied as evenly and smoothly as possible, but it is also possible to influence the compression of the fluid by the vibration.
- the method according to the invention is operated in such a way that the fluid is applied in excess to the area to be coated, the excess fluid is seen in the forward movement direction of the blade due to the constant movement of the blade, which oscillates in the manner of a rotary movement , homogenized in front of the blade in a roller formed from fluid or particle material by the forward movement of the blade.
- This allows any voids between individual particle clumps to be filled and larger clumps of particle material are broken up by the roller movement.
- the particle material is homogenized in the roller. From this particle material in front of the blade, a small part is drawn into a gap under the blade, compacted there and thus applied as a uniform layer.
- the application of the fluid or particle material in the area in front of the oscillating blade, viewed in the direction of forward movement of the blade, can be carried out in any conceivable manner known to the person skilled in the art. So it would be conceivable that a supply via a conveyor belt from a reservoir. In particular, it is possible for the supply to be carried out in a manner described in DE 195 30 295, the disclosure of which is incorporated in its entirety.
- a storage container with particle material traveling with a recoater continuously applies some particle material to the surface to be coated in front of the recoater and the moving blade.
- the storage container can be operated by another stationary container or another supply supply.
- a container open at the bottom is provided in order to bring a possibly defined amount of the possibly moist particle material onto the surface.
- the sand is sealed using a vibrating trough located at a short distance from it and the pouring cone that is formed. When the vibrating trough is actuated, the sand runs continuously out of the container.
- a defined application of the particle material could also take place via a corrugated conveyor belt which seals the storage container which is open at the bottom and, when actuated, throws the sand lying in the recesses of the belt onto the surface to be coated. This could be supported, for example, by a shaking motion.
- a device for applying fluids, and in particular particulate matter, to a region to be coated is also particularly suitable for carrying out the method according to the invention, a metering device being provided, by means of which on the specified and viewed in the forward direction of movement of the blade Fluid area is applied and the blade is experienced over the applied fluid.
- the blade is attached in such a way that it can oscillate in the manner of a rotary movement.
- the blade should be attached in such a way that the rotary movement of the blade takes place about an axis of rotation, which, viewed in the direction in the direction of construction of the fluid or particle material, lies above the area to be coated.
- the blade is attached in such a way that the vibration is in the range of an angle of rotation of 0.1 to 5 °.
- the blade extends over an entire width or length of the area to be coated, it is possible to carry out the coating as quickly as possible. In addition, with a coating that takes place simultaneously over the entire area, a more uniform coating is also possible. If, according to a preferred embodiment of the invention, the blade extends essentially orthogonally to the area to be coated, it is possible to arrange the axis of rotation as far as possible from the area to be coated and thus to enable a very precisely adjustable angle.
- the blade is at an angle to the orthogonal axis of the area to be coated, even better layer properties can be achieved when using certain fluids.
- the device can be designed in such a way that the blade is driven by at least one fast-running electric motor which causes the blade to oscillate via an eccentric.
- the blade should be shaped so that an intermediate reservoir of excess fluid can be formed in front of it, viewed in the direction of forward movement, which preferably forms a roller when the device is in operation. If the blade also has a shape such that a sufficiently large inlet for particulate material is provided when the blade is moved, material can thus be reliably and continuously drawn into this inlet.
- the oscillating blade is composed of two parts, a shaped blade body and built up a holder, then the blade body can be unscrewed and also replaced if, for example, the blade body is damaged.
- the device according to the invention has proven to be particularly suitable, in particular, for use in applying particle material provided with a binder.
- the device can be used particularly preferably in a method for building cast models.
- Figure 1 shows a device for coating particulate material on an area to be coated
- FIG. 3 shows a geometry of a further oscillating blade that is improved compared to the oscillating blade of FIG. 2;
- FIG. 5 shows the formation of a roller on the front side of the oscillating blade
- FIG. 6 shows a microscopically enlarged representation of the layer produced
- FIG. 7 shows a microscopically enlarged representation of the layer that has been partially pressed in
- FIG. 8 the mode of operation of an oscillating blade according to the invention.
- the use of such a particle material has the advantage that the step of coating the particle material with binder, which is usually necessary in the rapid prototyping process, is omitted, and the assembly can thus be carried out more quickly and more cost-effectively.
- the use of the method and the device according to the invention has proven to be advantageous.
- particle materials with a small average grain size of less than 20 ⁇ m and, for example, wax powder also have a strong tendency to agglomerate.
- a construction platform 10 on which the casting mold is to be built, is lowered by a layer thickness of the particle material 11.
- particle material 11 for example quartz sand, which according to a preferred embodiment is provided with 2% binder (e.g. Albertus 0401 from Wilsontenes, Resifix from Bachtenes), is applied to the building platform 10 in a desired layer thickness.
- binder e.g. Albertus 0401 from Wilsontenes, Resifix from Bachtenes
- a blade 1 which is made of plastic and carries out a rotary movement 12 about an axis of rotation 12A, is located above the construction platform 10.
- the rotary movement 12 of this blade 1 is driven in such a way that a fast-running electric motor causes the blade to oscillate via an eccentric.
- the motor used has, for example, a nominal speed at 12 V of 3000 rpm, the stroke of the eccentric is 0.54 mm, which corresponds to an amplitude at the blade tip of 0.85 mm according to the example described.
- a speed of 4050 rpm was measured at 15 V. This value corresponds to 67.5 Hz.
- the travel path of the oscillating blade or blade 1 over the area to be coated, here the so-called construction platform 10, is defined via guides 13 mounted on the side.
- the drive is preferably carried out by means of at least one motor, for example in such a way that a toothed belt deflected over two rollers and running along the guide rail is attached to the oscillating blade holder.
- One of the pulleys is driven by a motor.
- a stationary container 14 is used for this purpose, which is emptied via a vibrating channel 15.
- the container 14 is thus open at the bottom in the direction of the building platform 10 and the particulate material 11 in the container 14 is sealed via the vibrating channel 15 which is located at a short distance from the opening and the pouring cone which forms.
- the vibrating channel 15 is actuated, the quartz sand 11 now runs continuously out of the container 14.
- a relatively high excess dosage of the particle material 11 is advantageous in order to also have sufficient particle material 11 available at the end of the building platform 10 to have.
- the amount should preferably be at least 20% larger than necessary, but values in the range of 100% are also advantageous.
- the excess amount of particulate material 11 is pushed by the oscillating blade 1 into a linear shaft 16, which is located at the rear end of the building platform 10.
- this particulate material 11 is conveyed back into the storage container 14.
- an intermediate container 18 is provided on the coater 17, which carries the layer volume and the excess volume of the particle material 11.
- the intermediate container 18 is filled from the storage container 14 via the vibrating trough 15, then moves at high speed over the lower construction platform 10 to the other side, deposits the contents of the intermediate container 18 in front of the oscillating blade 1 and begins after the construction platform 10 in the correct height has been reached with the coating in the direction of the storage container 14. There, the excess particulate material 11 is conveyed back into the storage container 14 by means of a lifting device. This process is shown by arrow 19.
- FIG. 2 now shows a first form of the oscillating blade 1 in accordance with a first embodiment in one for coating
- the geometry of the oscillating blade 1 shown in FIG. 2 can be roughened during a backward movement first generated, substantially smooth surface through the edge 3 be possible.
- FIG. 3 shows an improved geometry of the oscillating blade 1 and FIG. 4a) and b) compared to the improved geometry shown in FIG. 2 in a vertical position (FIG. 4a) and in a tilted position (FIG. 4b) ).
- the blade 1 from FIG. 4 differs from that shown in FIG. 2 in that a pull-in bevel is provided on the edge 3, through which particle material 11 is again drawn under the blade 1 even during a backward movement. In this way, a smooth surface of the material to be coated can also be achieved in the return of the blade 1.
- the travel speed of the blade 1 was chosen to be in the range of up to 70 mm / s, preferably up to 60 mm / s. If the travel speed is too high, the surface of the material to be coated can deteriorate again.
- the travel speed is 60 Hz and 50 mm / s.
- roller formation 4 of the oscillating blade 1 is shown on the front, seen in the forward movement direction of the blade 1, which is represented by the arrow 21.
- FIG. 6 shows the layer produced from particle material 11 provided with a binder under a microscope.
- the layer In contrast to dry sand, in which the grains of sand By pulling together due to the liquid and thereby forming a kind of wall on the outside of the wetted area, the layer remains completely flat.
- FIG. 7 it can be seen that the layer produced could not necessarily be improved by being pressed in.
- the round impression 7 at the bottom right of the picture was created by a spatula tip. It turns out, however, that the behavior of an applied hardener drop 6 does not differ significantly when it is applied to this more compacted surface. A reduced tendency to “bleed” on the edge of the drop 6 is not to be observed.
- the mode of operation of the oscillating blade 1 is shown schematically in FIG.
- a vibrating blade 1 which has edges which are essentially perpendicular to one another, the edges facing the region 2 to be coated being rounded, that is to say provided with a radius 20A, 20B.
- the radius 20A which is provided on the front of the blade 1 as seen in the forward movement direction 21, is 3 mm in accordance with the preferred embodiment shown.
- a roller 4 is formed from excess particulate material 11, which extends over the entire width of the blade 1. Due to the constant rolling movement, the material in the roller 4 is homogenized. This means that the device according to the invention works excellently with overdosing on particulate material 11. The excess leads to the formation of a roller 4. If such a roller 4 is not completely formed in a method according to the invention, this can lead to the formation of imperfections in the particle layer on the area 2 to be coated. From this particle material 11 in the roller 4, a small part is drawn into the gap 8 formed by the radius 20A under the blade 1, compacted there and applied as a uniform layer to the area 2 to be coated.
- the geometry of the oscillating blade 1 should be chosen such that a sufficiently large inlet is created for the particle material 11, so that material is drawn reliably and continuously into this gap and, on the other hand, no impermissibly high compression of the fluid to be coated is obtained.
- A denotes the homogenization area
- B the compression area
- C the smoothing area
- D the compression area in the return stroke.
- the edge of the oscillating blade 1 facing away from the forward movement direction 21 is likewise well rounded with a small radius 2OB.
- the transitions between the individual edges of the oscillating blade 1 are to be rounded well in order to achieve better results. This can be achieved, for example, by slightly breaking the edges or, as already described, by designing the edges as radii. It is also possible to easily and quickly create other conditions in the compression zone B by changing the angle of inclination of the blade 1. This would also make it possible to operate the blade 1 without compression. This is interesting, for example, when coating with dry sand.
- the zero position should be the position perpendicular to the coating area 2.
- the packing density of the layer obtained according to the invention is relatively low and thus the porosity is relatively high. However, it is still significantly lower than when coating dry sand with a gap coater.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Apparatus (AREA)
- Ultra Sonic Daignosis Equipment (AREA)
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Abstract
Description
Claims
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10291577T DE10291577D2 (de) | 2001-04-10 | 2002-03-26 | Verfahren und Vorrichtung zum Auftragen von Fluiden |
| AU2002311072A AU2002311072A1 (en) | 2001-04-10 | 2002-03-26 | Method and device for applying fluids |
| ES02735016.4T ES2242029T5 (es) | 2001-04-10 | 2002-03-26 | Procedimiento y dispositivo para la aplicación de fluidos |
| AT02735016T ATE289531T1 (de) | 2001-04-10 | 2002-03-26 | Verfahren und vorrichtung zum auftragen von fluiden |
| JP2002581116A JP4102671B2 (ja) | 2001-04-10 | 2002-03-26 | 流動体を塗布するための方法および装置 |
| DE50202319T DE50202319D1 (de) | 2001-04-10 | 2002-03-26 | Verfahren und vorrichtung zum auftragen von fluiden |
| EP02735016.4A EP1377389B2 (de) | 2001-04-10 | 2002-03-26 | Verfahren und vorrichtung zum auftragen von fluiden |
| US10/474,301 US7879393B2 (en) | 2001-04-10 | 2002-03-26 | Method and device for applying fluids |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10117875.1 | 2001-04-10 | ||
| DE10117875A DE10117875C1 (de) | 2001-04-10 | 2001-04-10 | Verfahren, Vorrichtung zum Auftragen von Fluiden sowie Verwendung einer solchen Vorrichtung |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2002083323A2 true WO2002083323A2 (de) | 2002-10-24 |
| WO2002083323A3 WO2002083323A3 (de) | 2002-11-28 |
Family
ID=7681085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/DE2002/001103 Ceased WO2002083323A2 (de) | 2001-04-10 | 2002-03-26 | Verfahren und vorrichtung zum auftragen von fluiden |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US7879393B2 (de) |
| EP (1) | EP1377389B2 (de) |
| JP (1) | JP4102671B2 (de) |
| AT (1) | ATE289531T1 (de) |
| AU (1) | AU2002311072A1 (de) |
| DE (3) | DE10117875C1 (de) |
| ES (1) | ES2242029T5 (de) |
| WO (1) | WO2002083323A2 (de) |
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| WO2007134687A1 (de) * | 2006-05-18 | 2007-11-29 | Eos Gmbh Electro Optical Systems | Vorrichtung und verfahren zum herstellen eines dreidimensionalen objektes |
| WO2007134688A1 (de) * | 2006-05-18 | 2007-11-29 | Eos Gmbh Electro Optical Systems | Vorrichtung und verfahren zum schichtweisen herstellen eines dreidimensionalen objekts aus einem pulverförmigen aufbaumaterial |
| US7748971B2 (en) | 2002-04-11 | 2010-07-06 | Voxeljet Technology Gmbh | Method and device for applying fluids |
| US7871551B2 (en) | 2005-05-11 | 2011-01-18 | Arcam Ab | Systems, apparatus, and methods to feed and distribute powder used to produce three-dimensional objects |
| EP1769902A3 (de) * | 2005-09-30 | 2013-01-09 | 3D Systems, Inc. | Herstellungssystem und Verfahren zum schnellen Herstellen von Prototypen |
| EP1769903A3 (de) * | 2005-09-30 | 2013-05-01 | 3D Systems, Inc. | Herstellungssystem und Verfahren zum schnellen Herstellen von Prototypen |
| ITBG20120051A1 (it) * | 2012-10-31 | 2014-05-01 | Technymon Srl | Dispositivo per il deposito di uno strato uniforme di polvere su nastro metallico |
| US8727672B2 (en) | 2007-10-21 | 2014-05-20 | Voxeljet Ag | Method and device for conveying particulate material during the layer-wise production of patterns |
| US8956140B2 (en) | 2010-07-13 | 2015-02-17 | Voxeljet Ag | Apparatus for producing three-dimensional models by means of a layer build up technique |
| US9174392B2 (en) | 2009-06-22 | 2015-11-03 | Voxeljet Ag | Method and device for switching a particulate material flow in the construction of models in layers |
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| US7748971B2 (en) | 2002-04-11 | 2010-07-06 | Voxeljet Technology Gmbh | Method and device for applying fluids |
| US9463488B2 (en) | 2004-02-19 | 2016-10-11 | Voxeljet Ag | Method for applying particle material including a metering system and leveling element |
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| EP1769902A3 (de) * | 2005-09-30 | 2013-01-09 | 3D Systems, Inc. | Herstellungssystem und Verfahren zum schnellen Herstellen von Prototypen |
| EP1769903A3 (de) * | 2005-09-30 | 2013-05-01 | 3D Systems, Inc. | Herstellungssystem und Verfahren zum schnellen Herstellen von Prototypen |
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| RU2370367C1 (ru) * | 2006-05-18 | 2009-10-20 | Эос Гмбх Электро Оптикал Системс | Устройство и способ послойного получения трехмерного объекта из порошкообразного материала |
| WO2007134687A1 (de) * | 2006-05-18 | 2007-11-29 | Eos Gmbh Electro Optical Systems | Vorrichtung und verfahren zum herstellen eines dreidimensionalen objektes |
| US7931462B2 (en) | 2006-05-18 | 2011-04-26 | Eos Gmbh Electro Optical Systems | Device and method for the manufacturing of a three-dimensional object |
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| EP2727653A1 (de) * | 2012-10-31 | 2014-05-07 | Technymon Tecnology Europe SpA | Vorrichtung zum Ablagern einer gleichmäßigen Schicht Pulver auf einer metallischen Schicht |
| ITBG20120051A1 (it) * | 2012-10-31 | 2014-05-01 | Technymon Srl | Dispositivo per il deposito di uno strato uniforme di polvere su nastro metallico |
| WO2017108019A1 (de) * | 2015-12-21 | 2017-06-29 | Voxeljet Ag | Verfahren und vorrichutng zum herstellen von 3d-formteilen mit schichtaufbautechnik und steuerbarer pulverwalze |
| US12208572B2 (en) | 2015-12-21 | 2025-01-28 | Voxeljet Ag | Method and device for producing 3D shaped parts using layering technology, and controllable powder roller |
| WO2019034192A1 (de) | 2017-08-17 | 2019-02-21 | Laempe Mössner Sinto Gmbh | Anordnung und verfahren zur erzeugung einer 3d-struktur |
| DE102017007785A1 (de) | 2017-08-17 | 2019-02-21 | Laempe Mössner Sinto Gmbh | Anordnung und Verfahren zur Erzeugung einer 3D-Struktur |
| US11446868B2 (en) | 2017-08-17 | 2022-09-20 | Laempe Moessner Sinto Gmbh | Assembly and method for creating a 3D structure |
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| US12397509B2 (en) | 2020-06-13 | 2025-08-26 | Laempe Moessner Sinto Gmbh | Method for producing a 3D structure |
Also Published As
| Publication number | Publication date |
|---|---|
| US7879393B2 (en) | 2011-02-01 |
| DE10117875C1 (de) | 2003-01-30 |
| EP1377389B1 (de) | 2005-02-23 |
| DE10291577D2 (de) | 2004-04-15 |
| ES2242029T3 (es) | 2005-11-01 |
| US20040170765A1 (en) | 2004-09-02 |
| ES2242029T5 (es) | 2015-06-26 |
| WO2002083323A3 (de) | 2002-11-28 |
| ATE289531T1 (de) | 2005-03-15 |
| EP1377389B2 (de) | 2015-04-01 |
| EP1377389A2 (de) | 2004-01-07 |
| AU2002311072A1 (en) | 2002-10-28 |
| DE50202319D1 (de) | 2005-03-31 |
| JP4102671B2 (ja) | 2008-06-18 |
| JP2004523356A (ja) | 2004-08-05 |
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