WO1998051477A1 - Method and device for producing a shaped body - Google Patents
Method and device for producing a shaped body Download PDFInfo
- Publication number
- WO1998051477A1 WO1998051477A1 PCT/NL1998/000261 NL9800261W WO9851477A1 WO 1998051477 A1 WO1998051477 A1 WO 1998051477A1 NL 9800261 W NL9800261 W NL 9800261W WO 9851477 A1 WO9851477 A1 WO 9851477A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- pulverulent material
- powder
- shaped body
- liquid
- bound
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000011230 binding agent Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000945 filler Substances 0.000 claims description 9
- 239000004375 Dextrin Substances 0.000 claims description 5
- 229920001353 Dextrin Polymers 0.000 claims description 5
- 235000019425 dextrin Nutrition 0.000 claims description 5
- 239000012815 thermoplastic material Substances 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 239000001828 Gelatine Substances 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000011505 plaster Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- 229920002861 MOWIOL ® 3-83 Polymers 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 235000021552 granulated sugar Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002966 varnish Substances 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
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
- B29B13/023—Half-products, e.g. films, plates
-
- 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
- B29C64/165—Processes of additive manufacturing using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
Definitions
- the present invention relates to a method for producing a shaped body, which method comprises the following steps:
- a method of this kind is known from EP-A-0 , 431 , 924.
- a binder is applied as the liquid to the layer of powder applied on the surface, so that a layer of pattemwise bound-together powder is produced.
- this takes place using one or more inkjet cartridges.
- a drawback of this method is that the risk of the inkjet cartridges becoming blocked by the binder is high, certainly if a conventional inkjet printer is used.
- the use of a liquid binder has the disadvantage that it is generally slightly sticky and is therefore more difficult to handle.
- the object of the present invention is to provide a solution to these problems and to this end is characterized in that the liquid comprises water and the pulverulent material comprises at least one component which forms a binder after contact with water in step (2) .
- the advantage of this method is that a liquid is used which is not in itself sticky, so that this liquid is easy to handle and that the risk of blockage when inkjet cartridges are used is minimal .
- a drop-on-demand inkjet cartridge of this nature is known and generally comprises two rows of openings which deliver drops of the liquid to be sprayed out when an electrical signal is received.
- EP-A-0 , 431 , 924 It is also known from EP-A-0 , 431 , 924 to heat the bound-together layers of powder, optionally during the application of the liquid binder, in order to promote hardening of the bound-together powder and to stimulate any chemical curing reactions which take place at elevated temperature .
- step (1) and/or (2) it is preferred to dry the bound-together layers of powder, by heating them, after each execution of step (1) and/or (2) or after every two or more executions of step (1) and/or (2) .
- drying is carried out after every two to six executions of step (1) or (2) .
- This heating can take place in numerous ways, for example by means of hot air, infrared irradiation and exposure to microwaves.
- the drying is carried out immediately after step (1) and before step (2) by placing a heated plate on or just above the layer of pulverulent material which was applied last.
- the advantage of carrying out drying after step (1) is that the layer of powder which was applied last is still dry, with the result that there will be less tendency for powder to adhere to the plate when the plate is placed on the layer of powder which was applied last.
- the temperature to which heating is carried out is dependent on the type of powder which is employed. However, the temperature preferably lies below the melting temperature of that component of the powder composition which has the lowest melting point. The temperature will generally lie between 50 and 120°C. If desired, the heated plate can also be used to apply pressure to the applied layer of powder.
- the water containing liquid which is applied to each layer of pulverulent material is preferably applied in the form of one or more fine jets of droplets.
- the liquid is applied in the form of a plurality of fine jets of droplets, the liquids in the different jets being of different colours. This can be achieved very effectively by making use of an inkjet printer, which are known per se .
- the liquid used preferably also comprises 1-50% by weight, preferably 5-25% by weight, of one or more flow promoters.
- Flow promoters of this nature are surface-active agents and are intended to reduce the surface tension, so that the liquid can be sprayed out of the very small openings in the inkjet cartridges in drops.
- suitable flow promoters are glycols, such as diethylene glycol and monoethylene glycol, and lower alkanols, such as ethanol, 1-propanol and 2-propanol. It is also possible to use combinations of two or more flow promoters of this nature. A very suitable combination is, for example, a mixture of diethylene glycol and 2-propanol.
- the liquid may contain one or more colorants.
- the pulverulent material comprises a component which, as a result of coming into contact with the liquid sprayed on, forms a binder (the "adhesive component") .
- the powder may comprise a filler. If fillers are applied the shaped body obtained by the method according to the invention can for instance be sintered, fired or annealed, to remove the binder component and to obtain a shaped body from the material of the filler. Examples of fillers are metal powder, glass beads, glass fibres, ceramic materials, plastics, silica, sand etc. Thus it is for example possible to produce a shaped body completely consisting of glass, steel, iron etc .
- the pulverulent material comprises apart from the component, which as a result of coming into contact with the water sprayed, forms a binder, a secondary binder.
- a secondary binder comprises in particular a thermosetting material or thermoplastic material.
- Thermosetting materials are materials which cure under the influence of heat, such as polyester powder coatings.
- An example of this is the polyester powder coating type LT produced by Lakfabriek Korthals B.V.
- Thermoplastic materials are materials which soften or melt by heating and which solidify again upon cooling.
- the above thermosetting and thermoplastic materials are called secondary binders in the present context.
- the presence of secondary binders provides the possibility to manufacture quickly and simple a shaped body by means of the method according to the invention, which can be additionally reinforced after completion by a heat treatment .
- Suitable adhesive components are in particular powders which form a binder after coming into contact with the water containing liquid.
- Examples are dextrin powder, (carboxy) methylcellulose, wallpaper adhesive powder, gelatin, inulin, gum arabic, polyvinyl alcohol, cement, plaster, a water soluble salt and finely ground granulated sugar.
- a powder in which the adhesive component is polyvinyl alcohol, (carboxy) methylcellulose, gelatin and/or dextrin is preferred.
- suitable polyvinyl alcohol powders are completely or partially hydrolysed polyvinyl alcohols, such as those which are sold under the trade name Mowiol .
- Suitable grades are, for example, Mowiol 3-83, Mowiol 18-88 and Mowiol 10-98.
- a polyvinyl alcohol powder can be prepared by grinding a polyvinyl alcohol granulate at a temperature below the glass transition temperature of polyvinyl alcohol, for example under liquid nitrogen.
- An example of a commercially available dextrin is 37 -LAC-19, sold by the Avebee company.
- the particle size of the powder particles generally varies from 25 to 250 ⁇ m, and preferably lies between 50 and 175 ⁇ m. If the powder particles are larger than 250 ⁇ m, the dimensional accuracy of the shaped body to be formed is excessively determined by the particle size of the powder, which is generally undesirable.
- An example of a powder composition which can be used is a composition which contains approximately 3 parts by volume of glass beads (approx. 50-100 ⁇ m) , 3 parts by volume of polyester powder coating and 1 part by volume of dextrin.
- the powder composition may also comprise polyvinyl alcohol, optionally with the addition of a secondary binder and/or a filler.
- the surplus powder which has not been bound together is removed.
- the shaped body obtained is then preferably placed in an oven in order to remove the liquid still present and to allow any powder components present, like a secondary binder to perform the respective function.
- the strength of the shaped body is optimized in this way. If desired, before or after heating in an oven, if this takes place, the shaped body may be covered on the outside with a (colourless) lacquer or varnish. As well as having an advantageous effect on the strength of the shaped body, this may also be beneficial to the colourfastness of the shaped body, particularly if it is produced in different colours.
- step (3) It is preferred however to subject the combination of non-binded powder and the manufactured shaped body after step (3) to a drying treatment.
- a drying treatment can for example be effected in an oven.
- the shaped bodies which can be produced in the method according to the invention are employed in a variety of fields.
- the shaped bodies can be used to make scale models of, for example, furniture, means of transportation (cars, trains, aircrafts and the like) , molecules, toys, prostheses and other implements and decorative objects.
- the method is also very suitable for producing models of buildings and landscapes, as well as moulds for producing, for example, plaster objects.
- the powder composition contains, in addition to the adhesive component, a filler, it may be advantageous to bind the adhesive component to the filler in advance.
- filler and adhesive component and any other components can be mixed in advance, in the presence of water or some other suitable liquid, after which the composition is dried and, if necessary, comminuted.
- inkjet printers can be used which are known and commercially available.
- An example of an extremely suitable inkjet printer is the HP-deskjet 850 printer of Hewlett Packard.
- the ink spraying part of this printer is mounted such that this can print on top of the layer of powder.
- the printer comprises spraying openings for black ink and for three different base colours.
- Extremely suitable inkjet cartridges are the commercially available drop-on-demand inkjet cartridges of the type HP 51645 (also of Hewlett Packard) . Such an inkjet cartridge comprises about 300 spray openings.
- EXAMPLE A 3D model of a Porsche was downloaded from Internet (www.3dcafe.com). With the programm 3D-Studio this model was coloured and exported to a Polyray file. From this Polyray file with a special programm 112 -sections were calculated. All locations on the sections having a smaller distance than 1 mm from the closest outer side of the model obtained the colour of said closest outside. These sections were sent to a printer according to EP-A-0 , 431 , 924 , the printing part being derived from a HP-deskjet. Thus, within 20 min a model of the car was printed, which car contained a completely coloured outside.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Thermal Sciences (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Moulding By Coating Moulds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Machines For Manufacturing Corrugated Board In Mechanical Paper-Making Processes (AREA)
- Air Bags (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Fish Paste Products (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Pens And Brushes (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CA002290435A CA2290435A1 (en) | 1997-05-14 | 1998-05-12 | Method and device for producing a shaped body |
AU75538/98A AU7553898A (en) | 1997-05-14 | 1998-05-12 | Method and device for producing a shaped body |
EP98923199A EP1009621B1 (en) | 1997-05-14 | 1998-05-12 | Method for producing a shaped body |
DE69807236T DE69807236T2 (en) | 1997-05-14 | 1998-05-12 | METHOD FOR PRODUCING A MOLDED BODY |
DK98923199T DK1009621T3 (en) | 1997-05-14 | 1998-05-12 | Process for making a mold body |
AT98923199T ATE222174T1 (en) | 1997-05-14 | 1998-05-12 | METHOD FOR PRODUCING A MOLDED BODY |
US09/423,756 US6403002B1 (en) | 1997-05-14 | 1998-05-12 | Method and device for producing a shaped body |
JP54907998A JP4553989B2 (en) | 1997-05-14 | 1998-05-12 | Method and apparatus for producing molded body |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL1006059 | 1997-05-14 | ||
NL1006059A NL1006059C2 (en) | 1997-05-14 | 1997-05-14 | Method and device for manufacturing a shaped body. |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998051477A1 true WO1998051477A1 (en) | 1998-11-19 |
Family
ID=19764971
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL1998/000261 WO1998051477A1 (en) | 1997-05-14 | 1998-05-12 | Method and device for producing a shaped body |
Country Status (12)
Country | Link |
---|---|
US (1) | US6403002B1 (en) |
EP (1) | EP1009621B1 (en) |
JP (1) | JP4553989B2 (en) |
AT (1) | ATE222174T1 (en) |
AU (1) | AU7553898A (en) |
CA (1) | CA2290435A1 (en) |
DE (1) | DE69807236T2 (en) |
DK (1) | DK1009621T3 (en) |
ES (1) | ES2179495T3 (en) |
NL (1) | NL1006059C2 (en) |
PT (1) | PT1009621E (en) |
WO (1) | WO1998051477A1 (en) |
Cited By (5)
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EP1163999A2 (en) * | 2000-05-30 | 2001-12-19 | DaimlerChrysler AG | Material system for use in a 3D printing process |
US6375874B1 (en) | 1996-12-20 | 2002-04-23 | Z Corporation | Method and apparatus for prototyping a three-dimensional object |
EP1491516A2 (en) * | 2003-06-24 | 2004-12-29 | Hewlett-Packard Development Company, L.P. | Calcium aluminate cement compositions for solid freeform fabrication |
EP1415792A3 (en) * | 1999-11-05 | 2006-06-07 | Z Corporation | Methods and compositions for three-dimensional printing |
EP2305454A1 (en) * | 2008-05-26 | 2011-04-06 | Sony Corporation | Shaping apparatus and shaping method |
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CA2388046A1 (en) | 1999-11-05 | 2001-05-17 | Z Corporation | Material systems and methods of three-dimensional printing |
KR100838878B1 (en) * | 2000-04-14 | 2008-06-16 | 제트 코포레이션 | Compositions for three-dimensional printing of solid objects |
US20010050031A1 (en) * | 2000-04-14 | 2001-12-13 | Z Corporation | Compositions for three-dimensional printing of solid objects |
WO2002026419A1 (en) | 2000-09-25 | 2002-04-04 | Generis Gmbh | Method for producing a part using a deposition technique |
DE10047615A1 (en) * | 2000-09-26 | 2002-04-25 | Generis Gmbh | Swap bodies |
DE10047614C2 (en) * | 2000-09-26 | 2003-03-27 | Generis Gmbh | Device for building up models in layers |
DE10049043A1 (en) * | 2000-10-04 | 2002-05-02 | Generis Gmbh | Process for unpacking molded articles embedded in unbound particulate material |
DE10117875C1 (en) * | 2001-04-10 | 2003-01-30 | Generis Gmbh | Method, device for applying fluids and use of such a device |
DE10222167A1 (en) | 2002-05-20 | 2003-12-04 | Generis Gmbh | Device for supplying fluids |
DE10224981B4 (en) * | 2002-06-05 | 2004-08-19 | Generis Gmbh | Process for building models in layers |
US7087109B2 (en) * | 2002-09-25 | 2006-08-08 | Z Corporation | Three dimensional printing material system and method |
US6742456B1 (en) * | 2002-11-14 | 2004-06-01 | Hewlett-Packard Development Company, L.P. | Rapid prototyping material systems |
EP1594679B1 (en) * | 2003-02-18 | 2010-04-14 | Daimler AG | Powder particles for producing three-dimensional bodies by a layer constituting method |
EP1459871B1 (en) * | 2003-03-15 | 2011-04-06 | Evonik Degussa GmbH | Method and apparatus for manufacturing three dimensional objects using microwave radiation and shaped body produced according to this method |
US7807077B2 (en) * | 2003-06-16 | 2010-10-05 | Voxeljet Technology Gmbh | Methods and systems for the manufacture of layered three-dimensional forms |
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US20050046067A1 (en) * | 2003-08-27 | 2005-03-03 | Christopher Oriakhi | Inorganic phosphate cement compositions for solid freeform fabrication |
US20050059757A1 (en) * | 2003-08-29 | 2005-03-17 | Z Corporation | Absorbent fillers for three-dimensional printing |
US7422713B2 (en) * | 2003-10-14 | 2008-09-09 | Hewlett-Packard Development Company, L.P. | Hybrid organic-inorganic composition for solid freeform fabrication |
US7455805B2 (en) * | 2003-10-28 | 2008-11-25 | Hewlett-Packard Development Company, L.P. | Resin-modified inorganic phosphate cement for solid freeform fabrication |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0081218A2 (en) * | 1981-12-07 | 1983-06-15 | Firma Carl Freudenberg | Process for the production of a fleece web |
GB2233928A (en) * | 1989-05-23 | 1991-01-23 | Brother Ind Ltd | Forming an article from computer controlled jet of photosetting resin droplets. |
EP0431924A2 (en) * | 1989-12-08 | 1991-06-12 | Massachusetts Institute Of Technology | Three-dimensional printing techniques |
WO1993025336A1 (en) * | 1992-06-05 | 1993-12-23 | Massachusetts Institute Of Technology | Three-dimensional printing techniques ___________________________ |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5902441A (en) * | 1996-09-04 | 1999-05-11 | Z Corporation | Method of three dimensional printing |
DE19723892C1 (en) * | 1997-06-06 | 1998-09-03 | Rainer Hoechsmann | Method for producing components by build-up technology |
-
1997
- 1997-05-14 NL NL1006059A patent/NL1006059C2/en not_active IP Right Cessation
-
1998
- 1998-05-12 PT PT98923199T patent/PT1009621E/en unknown
- 1998-05-12 ES ES98923199T patent/ES2179495T3/en not_active Expired - Lifetime
- 1998-05-12 DK DK98923199T patent/DK1009621T3/en active
- 1998-05-12 EP EP98923199A patent/EP1009621B1/en not_active Expired - Lifetime
- 1998-05-12 CA CA002290435A patent/CA2290435A1/en not_active Abandoned
- 1998-05-12 AT AT98923199T patent/ATE222174T1/en not_active IP Right Cessation
- 1998-05-12 DE DE69807236T patent/DE69807236T2/en not_active Expired - Lifetime
- 1998-05-12 WO PCT/NL1998/000261 patent/WO1998051477A1/en active IP Right Grant
- 1998-05-12 US US09/423,756 patent/US6403002B1/en not_active Expired - Lifetime
- 1998-05-12 JP JP54907998A patent/JP4553989B2/en not_active Expired - Lifetime
- 1998-05-12 AU AU75538/98A patent/AU7553898A/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0081218A2 (en) * | 1981-12-07 | 1983-06-15 | Firma Carl Freudenberg | Process for the production of a fleece web |
GB2233928A (en) * | 1989-05-23 | 1991-01-23 | Brother Ind Ltd | Forming an article from computer controlled jet of photosetting resin droplets. |
EP0431924A2 (en) * | 1989-12-08 | 1991-06-12 | Massachusetts Institute Of Technology | Three-dimensional printing techniques |
WO1993025336A1 (en) * | 1992-06-05 | 1993-12-23 | Massachusetts Institute Of Technology | Three-dimensional printing techniques ___________________________ |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6375874B1 (en) | 1996-12-20 | 2002-04-23 | Z Corporation | Method and apparatus for prototyping a three-dimensional object |
EP1415792A3 (en) * | 1999-11-05 | 2006-06-07 | Z Corporation | Methods and compositions for three-dimensional printing |
EP1163999A2 (en) * | 2000-05-30 | 2001-12-19 | DaimlerChrysler AG | Material system for use in a 3D printing process |
EP1163999A3 (en) * | 2000-05-30 | 2003-07-23 | DaimlerChrysler AG | Material system for use in a 3D printing process |
EP1491516A2 (en) * | 2003-06-24 | 2004-12-29 | Hewlett-Packard Development Company, L.P. | Calcium aluminate cement compositions for solid freeform fabrication |
US7258736B2 (en) | 2003-06-24 | 2007-08-21 | Hewlett-Packard Development Company, L.P. | Calcium aluminate cement compositions for solid freeform fabrication |
EP1491516A3 (en) * | 2003-06-24 | 2008-02-20 | Hewlett-Packard Development Company, L.P. | Calcium aluminate cement compositions for solid freeform fabrication |
EP2305454A1 (en) * | 2008-05-26 | 2011-04-06 | Sony Corporation | Shaping apparatus and shaping method |
EP2305454A4 (en) * | 2008-05-26 | 2013-01-09 | Sony Corp | Shaping apparatus and shaping method |
US9636870B2 (en) | 2008-05-26 | 2017-05-02 | Sony Corporation | Modeling apparatus and modeling method |
Also Published As
Publication number | Publication date |
---|---|
AU7553898A (en) | 1998-12-08 |
DE69807236D1 (en) | 2002-09-19 |
DK1009621T3 (en) | 2002-11-11 |
JP2001524897A (en) | 2001-12-04 |
US6403002B1 (en) | 2002-06-11 |
EP1009621A1 (en) | 2000-06-21 |
JP4553989B2 (en) | 2010-09-29 |
ATE222174T1 (en) | 2002-08-15 |
PT1009621E (en) | 2002-12-31 |
ES2179495T3 (en) | 2003-01-16 |
CA2290435A1 (en) | 1998-11-19 |
NL1006059C2 (en) | 1998-11-17 |
DE69807236T2 (en) | 2003-04-10 |
EP1009621B1 (en) | 2002-08-14 |
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