US20050266110A1 - Fusible water-soluble films for fabricating three-dimensional objects - Google Patents

Fusible water-soluble films for fabricating three-dimensional objects Download PDF

Info

Publication number
US20050266110A1
US20050266110A1 US11/201,993 US20199305A US2005266110A1 US 20050266110 A1 US20050266110 A1 US 20050266110A1 US 20199305 A US20199305 A US 20199305A US 2005266110 A1 US2005266110 A1 US 2005266110A1
Authority
US
United States
Prior art keywords
dimensional object
fabricating
media
film
layers
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.)
Abandoned
Application number
US11/201,993
Inventor
Melissa Boyd
Darrel Cummings
Laura Kramer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US11/201,993 priority Critical patent/US20050266110A1/en
Publication of US20050266110A1 publication Critical patent/US20050266110A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive 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
    • B29C64/10Processes of additive manufacturing
    • B29C64/141Processes of additive manufacturing using only solid materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive 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
    • B29C64/10Processes of additive manufacturing
    • B29C64/141Processes of additive manufacturing using only solid materials
    • B29C64/147Processes of additive manufacturing using only solid materials using sheet material, e.g. laminated object manufacturing [LOM] or laminating sheet material precut to local cross sections of the 3D object
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive 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
    • B29C64/10Processes of additive manufacturing
    • B29C64/141Processes of additive manufacturing using only solid materials
    • B29C64/153Processes of additive manufacturing using only solid materials using layers of powder being selectively joined, e.g. by selective laser sintering or melting
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive 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
    • B29C64/40Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y30/00Apparatus for additive manufacturing; Details thereof or accessories therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y70/00Materials specially adapted for additive manufacturing
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/26Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers

Definitions

  • Three-dimensional (3D) object fabrication techniques such as solid freeform fabrication (SFF), allow a 3D object to be built layer-by-layer or point-by-point without using a pre-shaped tool (die or mold).
  • SFF solid freeform fabrication
  • data representing the geometry or shape of an object to be fabricated are used to control a fabrication tool to build the object.
  • Solid Freeform Fabrication is a general term for using one of several technologies to create three-dimensional objects such as prototype parts, models, and working tools.
  • Solid freeform fabrication is, for example, an additive process in which an object, which is described by computer readable data, is automatically built, usually layer-by-layer, from base materials.
  • Binder-jetting systems create objects by ejecting a binder onto a flat bed of powdered build material.
  • Each powder layer may be dispensed or spread as a dry powder or a slurry. Wherever the binder is selectively ejected into the powder layer, the powder is bound into a cross section or layer of the object being formed.
  • Bulk-jetting systems generate objects by ejecting a solidifiable build material and a solidifiable support material on a platform.
  • the support material which is temporary in nature, is dispensed to enable overhangs in the object and can be of the same or different material from the object.
  • fabrication is typically performed layer-by-layer, with each layer representing another cross section of the final desired object. Adjacent layers are adhered to one another in a predetermined pattern to build up the desired object.
  • solid freeform fabrication systems can provide a color or color pattern on each layer of the object.
  • the binder may be colored such that the functions of binding and coloring are integrated.
  • the build material may be colored.
  • Inkjet technology can be employed in which a number of differently colored inks are selectively ejected from the nozzles of a liquid ejection apparatus and blended on the build material to provide a full spectrum of colors.
  • the liquid ejection apparatus consists of multiple printheads, each ejecting a different base-colored binder or build material, such as cyan, magenta, yellow, black, and/or clear.
  • base-colored binder or build material such as cyan, magenta, yellow, black, and/or clear.
  • conventional two-dimensional multi-pass color techniques and half-toning algorithms can be used to hide defects and achieve a broad range of desired color hues.
  • 3D digital fabrication is primarily used by design engineers. These engineers typically use service bureau technology, such as stereolithography, to make rapid prototypes of their designs. Three-dimensional Rapid Prototyping equipment, as it now exists, costs $30,000 to $3,000,000 and can be expensive and complicated to operate. In addition, due to the messes, odors and noise that typically accompany known 3D digital fabrication processes, these machines are not appropriate for use in most office or home environments. Current market solutions to reduce costs have resulted in machines that are extremely slow, or processes that are complex and messy.
  • Laminated Object Manufacturing a particular type of 3D digital fabrication, has additional disadvantages including the difficult removal of the excess build material which surrounds the created 3D object.
  • excess build material is typically removed by slicing it into small cubes so it can be manually broken loose from the object surface. This process does not work well on partially-enclosed areas, and the material does not separate from horizontal parting lines.
  • FIG. 1 is a perspective view of a three-dimensional fabricator configured to implement the principles of the present invention
  • FIG. 2 is a partial cross-sectional view of a three-dimensional fabricator showing a layer of build film being fused to the top layer of a stack of previously fused build film layers during fabrication of a three-dimensional object;
  • FIGS. 3A-3D illustrate how a portion of a single film layer is fused and how non-fused portions of the film layer are thereafter washed away leaving only the fused portion of the film.
  • a material for use in fabricating three-dimensional objects is both soluble and fusible into an insoluble state.
  • the material is formed as a film that is fusible into a non-water soluble state when exposed to conduction or other heating.
  • the film includes a mixture of thermoplastic particles and a water-soluble polymer matrix.
  • the film further includes a surfactant system bound to the thermoplastic particles. The surfactant system provides an inversion property such that the thermoplastic particles are hydrophilic but, upon a fusing of the film into a bulk, become hydrophobic as the surfactant becomes incorporated into the bulk.
  • the film further includes a filling or reinforcing material (e.g., glass or carbon fibers, clays, glass beads, metal particles, dispersants, surfactants, etc.).
  • the film further includes one or more colorant(s).
  • the film is water-wettable which permits layers of such film to be printed with a color image using low-cost inkjet printing methods. As discussed below in greater detail, the ability to provide soluble and fusible colored films facilitates the formation of full-color 3D objects.
  • thermoplastic particles polymers that are produced by emulsion polymerization can be used for the thermoplastic phase resulting in very small particles (typically 50-500 nm) dispersed in water.
  • Surfactants that can be used to stabilize such polymerizations end up on the surface of the particles and are likely to have a strong effect on how the material behaves in water and when mixed with a matrix polymer, as well as how it fuses.
  • the thermoplastic does not have to be a hydrophilic material.
  • the fusible films of the present invention can be made from emulsions of polystyrene, polystyrene-co-butyl acrylate (SBA), polymethyl methacrylate-co-butyl acrylate (MBA), for example, as well as from other emulsion polymer compositions and stabilization systems.
  • the thermoplastic particles can also be formed using polymethyl methacrylate (MMA).
  • MMA polymethyl methacrylate
  • Emulsion polymerization typically involves the polymerization of a hydrophobic monomer stabilized by a surfactant in water. Once the polymer forms, the mixture (colloidal suspension) of polymer particles in water is often referred to as a latex. As a result of the polymerization, the latex particles are coated with the surfactant giving them more hydrophilic properties.
  • the polymer matrix can include, by way of example, polyvinyl alcohol (PVA) or polyvinyl pyrrolidone (PVP).
  • the polymer matrix includes a mixture of polyvinyl alcohol (PVA) (molecular weight of ⁇ 85,000 g/mol) and pentaerythritol, such as the commercially available material sold under the trade name Sulky Solvy from Sulky of America, 3113 Broadpoint Drive, Punta Gorda, Fla. 33983.
  • PVA polyvinyl alcohol
  • PVP polyvinyl pyrrolidone
  • the polymer matrix includes a mixture of polyvinyl alcohol (PVA) (molecular weight of ⁇ 85,000 g/mol) and pentaerythritol, such as the commercially available material sold under the trade name Sulky Solvy from Sulky of America, 3113 Broadpoint Drive, Punta Gorda, Fla. 33983.
  • Other water soluble polymers can also be used.
  • the glass transition temperature (T g ) of the thermoplastic latex is very important.
  • the glass transition temperatures are slightly higher than room temperature to avoid premature fusing at room temperature.
  • the glass transition temperature should not be so high that an excessive amount of heat is needed to fuse the material.
  • a glass transition temperature range of about 30° C.-150° C. is appropriate in most instances. More preferably, the glass transition temperature range is about 50° C.-110° C.
  • Materials with glass transition temperatures around 75° C. include SBA and MBA emulsions.
  • Dow, Latex PB 6688ANA BK based on polystyrene, is a commercially available material with T g ⁇ 108° C.
  • thermoplastic latex with glass transition temperatures lower than 30° C. e.g., close to room temperature
  • films formed from thermoplastic latex with glass transition temperatures higher than 150° C. are also within the scope of the present invention.
  • the film has a composition ranging from approximately 1:1 to 2:1 (thermoplastic:matrix) and a thickness ranging from approximately 10-250 microns ( ⁇ 0.4-10 mils).
  • An exemplary film thickness is around 100 microns ( ⁇ 4 mils).
  • thinner films provide more layers and greater resolution, whereas thicker films provide for a faster fabrication process, but less resolution.
  • film thickness can be varied within or outside the 10-250 microns range to accommodate different fabrication processes, speed and resolution requirements, etc.
  • An exemplary media for use in fabricating three-dimensional objects is made from SBA thermoplastic particles mixed with a PVA water soluble binder.
  • the SBA material is prepared as an emulsion in water, with very small particle sizes in the range of 50-500 nm.
  • the SBA solution is mixed with a solution of PVA, with a typical ratio of 2:1 (SBA:PVA) to assure that the SBA encapsulates the PVA upon fusing.
  • the resulting mixture is cast into a film, for example, using a bench-top tape caster (doctor blade), although other casting techniques can also be used.
  • Encapsulated fragments of binder within the final part still provide mechanical stability and contribute to material toughness.
  • the PVA may also crosslink and become insoluble when heated further improving material toughness.
  • An example of a film formulation according to the present invention is:
  • the above constituents are mixed on rollers for at least 18 hours, and then cast into a film on a polytetraflouethylene (PTFE) coated Kapton support using a bench-top tape caster. After being cast, the films are left to dry at room temperature, typically overnight. Depending upon their fragility, resulting films may or may not require support until they are fused.
  • PTFE polytetraflouethylene
  • a process for making a film for use in fabricating three-dimensional objects including the steps of: preparing a thermoplastic latex by emulsion polymerization; mixing the latex with a water-soluble polymer (WSP) to form a latex-WSP mixture; casting the latex-WSP mixture into a film; and allowing the film to dry; wherein a composition of the latex-WSP mixture is selected such that portions of the film exposed to a predetermined amount of conduction or other heating fuse into a non-water soluble state and any portions of the film not so exposed remain water-soluble.
  • WSP water-soluble polymer
  • the emulsion polymerization is stabilized by a stabilization system (by a surfactant in water).
  • an exemplary SFF tool such as three-dimensional fabricator 100 includes a build bin 102 , a heating device 104 , and a transport mechanism 106 .
  • the build bin 102 (in which the object sits) is repositioned downward along the z-axis so that the next layer of the object can be formed on top of the previously formed layer.
  • the build bin 102 can have dimensions such as 8′′ ⁇ 10′′ ⁇ 10′′ or 6′′ ⁇ 6′′ ⁇ 6′′ to accommodate fabricators and 3D objects of various sizes.
  • the transport mechanism 106 comprises, by way of example, a motorized transport mechanism which is attached to the heating device 104 and moves in the x axis along a slide bar.
  • the three-dimensional fabricator 100 also includes a controller (not shown) which is programmed to, inter alia, control the aforementioned repositioning of the heating device 104 during the 3D object fabrication process.
  • the controller can take the form of a discrete module positioned proximate to the heating device 104 ; alternatively, the operations performed by the controller can be distributed among a plurality of controllers, processors or the like, and/or the controller can be remotely located relative to the heating device 104 .
  • the heating device 104 includes, by way of example, a page-wide thermal print bar, a scanning thermal head, or a laser beam.
  • the heating device 104 can take the form of an array of heating elements, such as those found on a thin film thermal printhead or flat type printhead.
  • the heating device 104 takes the form of a non-laser heating device.
  • the heating device 104 is configured to applying an amount of conduction or other heating sufficient to fuse desired portions of a first layer of build film that is positioned on the build bin 102 and then to fuse desired portions of subsequent layers of build film, each to the top layer of a stack of previously fused build film layers, during fabrication of a three-dimensional object.
  • the heating device 104 can also include one or more sensor mechanisms (not shown) for identifying the type of film or other media. Such sensor mechanisms can additionally, or alternatively, be separately located from the heating device 104 . Regardless, the one or more sensor mechanisms provide information to the controller that allows the controller to control the amount of conduction or other heating applied by implementing stored protocols, algorithms or the like that are associated with the particular information provided by the sensor(s).
  • an apparatus for fabricating a three-dimensional object includes: a mechanism for identifying a type of media (e.g., by size, physical properties, coded information) and for sequentially fusing layers of the media together into a three-dimensional object by applying an amount of conduction or other heating determined in consideration of a characteristic of the type of media (e.g., a glass transition temperature of fusible particles in the media, a ratio of fusible particles to water-soluble materials in the media, a type of fusible particle in the media, a type of water-soluble material in the media); and a build bin configured to support the fused layer(s) during fabrication of the three-dimensional object.
  • a characteristic of the type of media e.g., a glass transition temperature of fusible particles in the media, a ratio of fusible particles to water-soluble materials in the media, a type of fusible particle in the media, a type of water-soluble material in the media
  • a build bin configured to support the fused layer(s) during fabrication
  • the heating device 104 can be configured to provide the functions of both film fusing and coloring and, in such embodiments, also includes a printer 105 (shown in dashed lines). Integration of these functions can be accomplished, for example, by providing the heating device 104 with a printer 105 including inkjet printing mechanisms. Alternatively, a separate device can be used to color the film before it is provided to the three-dimensional fabricator 100 . In either case, each layer of film can be digitally printed with a color image before fusing. Also, as discussed above, the film can be pre-colored (i.e., formed with colorant(s) in the mixture).
  • FIG. 2 is a partial cross-sectional view of a three-dimensional fabricator 100 ′ showing a layer of build film 150 being fused to the top layer of a stack 160 of previously fused build film layers during fabrication of a three-dimensional object.
  • the three-dimensional fabricator 100 ′ includes a media advancing mechanism in the form of one or more roller 170 , and the layer of build film 150 and an adjacent release film 180 are delivered from a roll.
  • the release film 180 is a polytetraflouethylene (PTFE) coated polyester or PTFE coated polyimide.
  • film is delivered from rolls or sheets onto a build area, one layer at a time, and therefore does not create a safety hazard or cleanliness problem as is the case with the powders and liquids of many current machines.
  • each layer is placed in the build area, it is selectively heated in such a way as to reflow the thermoplastic particles only in the selected areas and bond them to each other and to the sheet below.
  • a three-dimensional object is created in the reflowed area.
  • this selective heating can be accomplished through use of a page-wide thermal print bar moved (e.g., at a steady rate) across the surface of the film, for example, or a scanning thermal head, or a laser beam, etc.
  • a release film may be required between the heating device and the film.
  • FIGS. 3A-3D illustrate how a portion of a single film layer is fused and how non-fused portions of the film layer are thereafter washed away leaving only the fused portion of the film.
  • a single film layer 300 includes thermoplastic particles 302 held together by a water soluble polymer (WSP) matrix or binder 304 .
  • WSP water soluble polymer
  • FIG. 3B the film 300 fuses in the areas where heat is applied creating a uniform, fused thermoplastic matrix or region 310 within which WSP particles 312 are trapped.
  • the thermoplastic particles 302 “invert”, changing from hydrophilic to hydrophobic, when fused into the thermoplastic matrix 310 .
  • the fused thermoplastic region 310 is no longer soluble in water, while the WSP matrix areas 314 that have not been heated can be dissolved by water ( FIG. 3C ), leaving only the fused portion of the film, i.e., the region 310 within which WSP particles 312 are trapped ( FIG. 3D ).
  • the fused area builds up a three-dimensional object. After the object has been fully defined, the unfused film is washed away with water.
  • full-color objects can be created by printing on each layer of film, e.g., with the printer 105 ( FIG. 1 ), before the selective heating process.
  • An example method of using a heating device to fabricate a three-dimensional object begins by placing a water-soluble build film (e.g., containing clear thermoplastic particles) on the work area.
  • a thin non-stick release film temporarily covers the surface of the build film.
  • a page-wide thermal print bar is moved across the build area, selectively heating those areas which will become part of the final object.
  • the release film is lifted, a new layer of build film is fed onto the work area, and the process is repeated until the part is complete.
  • the stack of bonded film is removed from the printer, and the unbonded film is washed away with water.
  • the build area can be varied to minimize material waste, by loading a narrower film roll (width) or cutting the film layers to the minimum size required (length) to build the specific part.
  • a method of using a heating device to fabricate a three-dimensional object includes the steps of: sequentially delivering layers of a build film and an adjacent release film onto a build area, the build film being a water-soluble composite of thermoplastic particles in a binder material; for each layer, employing a heating device to heat selected areas of the layer, and then lifting its release film before the next layer is delivered to the build area, to reflow the thermoplastic particles in the selected areas and bond the thermoplastic particles to each other and to the layer below to form a three-dimensional object; and washing away unbonded portions of the build film with water to reveal the three-dimensional object.
  • the build film and release film are delivered from a roll or as sheets.
  • the build film layers are printed with colorant(s) (e.g., colored ink) before being bonded together.
  • the release film is a PTFE coated polyester or polyimide.
  • an apparatus for fabricating a three-dimensional object includes: a printer with a heating device configured to sequentially fuse layers of media together into a three-dimensional object by applying an amount of conduction or other heating determined in consideration of a glass transition temperature of fusible particles in the media.
  • the glass transition temperature is about 30° C.-150° C.
  • the printer includes a build bin configured to support and reposition the fused layer(s) relative to the heating device between the fusing of each layer.
  • the printer is configured to draw the layers of media from a roll and to sequentially position the layers over the build bin.
  • a method of fabricating a three-dimensional object includes the steps of: providing a film that is fusible into a non-water soluble state when exposed to conduction or other heating, the film being a mixture of thermoplastic particles and a water-soluble polymer matrix, the film further including a surfactant system bound to the thermoplastic particles, the surfactant system providing an inversion property such that the thermoplastic particles are hydrophilic but, upon a fusing of the film into a bulk, become hydrophobic as the surfactant become incorporated into the bulk; positioning layers of the film sequentially along a build axis and, for each of the layers before a subsequent layer is positioned, heating areas of the layers that are to be fused together to form a fused three-dimensional object; and dissolving non-fused portions of the layers with water to reveal the fused three-dimensional object.
  • the present invention facilitates the removal of excess unbonded material (including materials from recessed and complex shapes) by dissolving in water, a process that advantageously does not involve dangerous chemicals.
  • the step of heating provides an amount of energy to the layers that is a function of a glass transition temperature of the thermoplastic particles. In another embodiment, the step of heating provides an amount of energy to the layers that is a function of a composition of the mixture of the thermoplastic particles and the water-soluble polymer matrix.

Abstract

A material for use in fabricating three-dimensional objects includes a mixture of thermoplastic particles and a water-soluble polymer matrix formed as a film that is fusible into a non-water soluble state when exposed to heating. The film further includes a surfactant system bound to the thermoplastic particles, the surfactant system providing an inversion property such that the thermoplastic particles are hydrophilic but, upon a fusing of the film, become hydrophobic as the surfactant become incorporated into the bulk.

Description

    BACKGROUND OF THE INVENTION
  • Three-dimensional (3D) object fabrication techniques, such as solid freeform fabrication (SFF), allow a 3D object to be built layer-by-layer or point-by-point without using a pre-shaped tool (die or mold). Typically, data representing the geometry or shape of an object to be fabricated are used to control a fabrication tool to build the object.
  • Solid Freeform Fabrication (SFF) is a general term for using one of several technologies to create three-dimensional objects such as prototype parts, models, and working tools. Solid freeform fabrication is, for example, an additive process in which an object, which is described by computer readable data, is automatically built, usually layer-by-layer, from base materials.
  • Several principal forms of solid freeform fabrication involve a liquid ejection process. There are two main types of solid freeform fabrication that use liquid-ejection: binder-jetting systems and bulk jetting systems.
  • Binder-jetting systems create objects by ejecting a binder onto a flat bed of powdered build material. Each powder layer may be dispensed or spread as a dry powder or a slurry. Wherever the binder is selectively ejected into the powder layer, the powder is bound into a cross section or layer of the object being formed.
  • Bulk-jetting systems generate objects by ejecting a solidifiable build material and a solidifiable support material on a platform. The support material, which is temporary in nature, is dispensed to enable overhangs in the object and can be of the same or different material from the object.
  • In both cases, fabrication is typically performed layer-by-layer, with each layer representing another cross section of the final desired object. Adjacent layers are adhered to one another in a predetermined pattern to build up the desired object.
  • In addition to selectively forming each layer of the desired object, solid freeform fabrication systems can provide a color or color pattern on each layer of the object. In binder-jetting systems, the binder may be colored such that the functions of binding and coloring are integrated. In bulk-jetting systems, the build material may be colored.
  • Inkjet technology can be employed in which a number of differently colored inks are selectively ejected from the nozzles of a liquid ejection apparatus and blended on the build material to provide a full spectrum of colors. Often, the liquid ejection apparatus consists of multiple printheads, each ejecting a different base-colored binder or build material, such as cyan, magenta, yellow, black, and/or clear. On each individual layer, conventional two-dimensional multi-pass color techniques and half-toning algorithms can be used to hide defects and achieve a broad range of desired color hues.
  • However, most 3D printing technologies do not have color capability due to the technical challenges involved. Even in those cases where it is technically possible, producing full-color parts adds considerable expense.
  • Today, 3D digital fabrication (Rapid Prototyping) is primarily used by design engineers. These engineers typically use service bureau technology, such as stereolithography, to make rapid prototypes of their designs. Three-dimensional Rapid Prototyping equipment, as it now exists, costs $30,000 to $3,000,000 and can be expensive and complicated to operate. In addition, due to the messes, odors and noise that typically accompany known 3D digital fabrication processes, these machines are not appropriate for use in most office or home environments. Current market solutions to reduce costs have resulted in machines that are extremely slow, or processes that are complex and messy.
  • Laminated Object Manufacturing, a particular type of 3D digital fabrication, has additional disadvantages including the difficult removal of the excess build material which surrounds the created 3D object. In Laminated. Object Manufacturing, excess build material is typically removed by slicing it into small cubes so it can be manually broken loose from the object surface. This process does not work well on partially-enclosed areas, and the material does not separate from horizontal parting lines.
  • Thus, it would be useful to be able to provide inexpensive 3D object fabrication devices, processes and materials that are suitable for both office and home environments. In particular, it would be helpful to be able to provide input materials to such devices while avoiding the safety hazards or cleanliness issues associated with the powders and liquids that are processed by many current machines. It would also be helpful to be able to provide the ability to remove excess unbonded material and/or materials from recessed and complex shapes without having to use dangerous chemicals.
  • It would also be helpful if such fabrication devices were as accessible and compact in size as a desktop printer. Moreover, it would be useful and cost effective if such devices included inexpensive and readily available components. It would also be desirable if such devices could operate significantly faster than current low-cost systems, e.g., current systems that rely on a single dispense nozzle.
  • It would also be useful to be able to provide a 3D object fabrication device that accommodates a variety of different types of media, such as media of different types and sizes, media formed from different types of materials, etc.
  • Additionally, it would be useful to be able to provide 3D object fabrication devices and processes that employ printing methods, such as inkjet printing, to form full-color 3D objects.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • Detailed description of embodiments of the invention will be made with reference to the accompanying drawings:
  • FIG. 1 is a perspective view of a three-dimensional fabricator configured to implement the principles of the present invention;
  • FIG. 2 is a partial cross-sectional view of a three-dimensional fabricator showing a layer of build film being fused to the top layer of a stack of previously fused build film layers during fabrication of a three-dimensional object; and
  • FIGS. 3A-3D illustrate how a portion of a single film layer is fused and how non-fused portions of the film layer are thereafter washed away leaving only the fused portion of the film.
  • DETAILED DESCRIPTION
  • The following is a detailed description for carrying out the invention. This description is not to be taken in a limiting sense, but is made merely for the purpose of illustrating the general principles of the invention.
  • According to the present invention, a material for use in fabricating three-dimensional objects is both soluble and fusible into an insoluble state. By way of example, the material is formed as a film that is fusible into a non-water soluble state when exposed to conduction or other heating. In one embodiment, the film includes a mixture of thermoplastic particles and a water-soluble polymer matrix. In another embodiment, the film further includes a surfactant system bound to the thermoplastic particles. The surfactant system provides an inversion property such that the thermoplastic particles are hydrophilic but, upon a fusing of the film into a bulk, become hydrophobic as the surfactant becomes incorporated into the bulk. In another embodiment, the film further includes a filling or reinforcing material (e.g., glass or carbon fibers, clays, glass beads, metal particles, dispersants, surfactants, etc.). In another embodiment, the film further includes one or more colorant(s). By way of example, the film is water-wettable which permits layers of such film to be printed with a color image using low-cost inkjet printing methods. As discussed below in greater detail, the ability to provide soluble and fusible colored films facilitates the formation of full-color 3D objects.
  • With respect to the thermoplastic particles, polymers that are produced by emulsion polymerization can be used for the thermoplastic phase resulting in very small particles (typically 50-500 nm) dispersed in water. Surfactants that can be used to stabilize such polymerizations end up on the surface of the particles and are likely to have a strong effect on how the material behaves in water and when mixed with a matrix polymer, as well as how it fuses. However, it should be appreciated that the thermoplastic does not have to be a hydrophilic material. The fusible films of the present invention can be made from emulsions of polystyrene, polystyrene-co-butyl acrylate (SBA), polymethyl methacrylate-co-butyl acrylate (MBA), for example, as well as from other emulsion polymer compositions and stabilization systems. The thermoplastic particles can also be formed using polymethyl methacrylate (MMA). A discussion of additional materials suitable for forming the thermoplastic particles is included in commonly assigned U.S. Pat. No. 6,417,248 to Gore, which is incorporated herein by reference.
  • Emulsion polymerization typically involves the polymerization of a hydrophobic monomer stabilized by a surfactant in water. Once the polymer forms, the mixture (colloidal suspension) of polymer particles in water is often referred to as a latex. As a result of the polymerization, the latex particles are coated with the surfactant giving them more hydrophilic properties.
  • The polymer matrix can include, by way of example, polyvinyl alcohol (PVA) or polyvinyl pyrrolidone (PVP). In another embodiment, the polymer matrix includes a mixture of polyvinyl alcohol (PVA) (molecular weight of ˜85,000 g/mol) and pentaerythritol, such as the commercially available material sold under the trade name Sulky Solvy from Sulky of America, 3113 Broadpoint Drive, Punta Gorda, Fla. 33983. Other water soluble polymers can also be used.
  • The glass transition temperature (Tg) of the thermoplastic latex is very important. In various embodiments, the glass transition temperatures are slightly higher than room temperature to avoid premature fusing at room temperature. Also, the glass transition temperature should not be so high that an excessive amount of heat is needed to fuse the material. Thus, by way of example, a glass transition temperature range of about 30° C.-150° C. is appropriate in most instances. More preferably, the glass transition temperature range is about 50° C.-110° C. Materials with glass transition temperatures around 75° C. include SBA and MBA emulsions. Dow, Latex PB 6688ANA BK, based on polystyrene, is a commercially available material with Tg ˜108° C. that can also be used to make films according to the present invention. Thermoplastic latex with glass transition temperatures lower than 30° C., e.g., close to room temperature, can also be used, although they may require more careful processing and handling to avoid premature fusing. Likewise, films formed from thermoplastic latex with glass transition temperatures higher than 150° C. are also within the scope of the present invention.
  • In an embodiment of the present invention, the film has a composition ranging from approximately 1:1 to 2:1 (thermoplastic:matrix) and a thickness ranging from approximately 10-250 microns (˜0.4-10 mils). An exemplary film thickness is around 100 microns (˜4 mils). Generally, thinner films provide more layers and greater resolution, whereas thicker films provide for a faster fabrication process, but less resolution. Thus, it should be appreciated that film thickness can be varied within or outside the 10-250 microns range to accommodate different fabrication processes, speed and resolution requirements, etc.
  • An exemplary media for use in fabricating three-dimensional objects is made from SBA thermoplastic particles mixed with a PVA water soluble binder. The SBA material is prepared as an emulsion in water, with very small particle sizes in the range of 50-500 nm. The SBA solution is mixed with a solution of PVA, with a typical ratio of 2:1 (SBA:PVA) to assure that the SBA encapsulates the PVA upon fusing. The resulting mixture is cast into a film, for example, using a bench-top tape caster (doctor blade), although other casting techniques can also be used. Encapsulated fragments of binder within the final part still provide mechanical stability and contribute to material toughness. In the case of PVA containing binder, the PVA may also crosslink and become insoluble when heated further improving material toughness.
  • An example of a film formulation according to the present invention is:
      • 10 g thermoplastic particles (typically delivered ˜50 weight % in water, so 10 g would require 20 g of this solution)
      • 5 g Sulky Solvy (typically start with ˜15 weight % in water, so 5 g would require 33 g of this solution)
      • 1 g colored ink
  • Further by way example, the above constituents are mixed on rollers for at least 18 hours, and then cast into a film on a polytetraflouethylene (PTFE) coated Kapton support using a bench-top tape caster. After being cast, the films are left to dry at room temperature, typically overnight. Depending upon their fragility, resulting films may or may not require support until they are fused.
  • Thus, a process for making a film for use in fabricating three-dimensional objects according to an embodiment of the present invention including the steps of: preparing a thermoplastic latex by emulsion polymerization; mixing the latex with a water-soluble polymer (WSP) to form a latex-WSP mixture; casting the latex-WSP mixture into a film; and allowing the film to dry; wherein a composition of the latex-WSP mixture is selected such that portions of the film exposed to a predetermined amount of conduction or other heating fuse into a non-water soluble state and any portions of the film not so exposed remain water-soluble. In another embodiment, the emulsion polymerization is stabilized by a stabilization system (by a surfactant in water).
  • Referring to FIG. 1, an exemplary SFF tool such as three-dimensional fabricator 100 includes a build bin 102, a heating device 104, and a transport mechanism 106. After each layer of the 3D object is fabricated, the build bin 102 (in which the object sits) is repositioned downward along the z-axis so that the next layer of the object can be formed on top of the previously formed layer. By way of example, the build bin 102 can have dimensions such as 8″×10″×10″ or 6″×6″×6″ to accommodate fabricators and 3D objects of various sizes. The transport mechanism 106 comprises, by way of example, a motorized transport mechanism which is attached to the heating device 104 and moves in the x axis along a slide bar. The three-dimensional fabricator 100 also includes a controller (not shown) which is programmed to, inter alia, control the aforementioned repositioning of the heating device 104 during the 3D object fabrication process. The controller can take the form of a discrete module positioned proximate to the heating device 104; alternatively, the operations performed by the controller can be distributed among a plurality of controllers, processors or the like, and/or the controller can be remotely located relative to the heating device 104.
  • The heating device 104 includes, by way of example, a page-wide thermal print bar, a scanning thermal head, or a laser beam. The heating device 104 can take the form of an array of heating elements, such as those found on a thin film thermal printhead or flat type printhead. In various embodiments, the heating device 104 takes the form of a non-laser heating device. Generally, the heating device 104 is configured to applying an amount of conduction or other heating sufficient to fuse desired portions of a first layer of build film that is positioned on the build bin 102 and then to fuse desired portions of subsequent layers of build film, each to the top layer of a stack of previously fused build film layers, during fabrication of a three-dimensional object.
  • The heating device 104 can also include one or more sensor mechanisms (not shown) for identifying the type of film or other media. Such sensor mechanisms can additionally, or alternatively, be separately located from the heating device 104. Regardless, the one or more sensor mechanisms provide information to the controller that allows the controller to control the amount of conduction or other heating applied by implementing stored protocols, algorithms or the like that are associated with the particular information provided by the sensor(s). For example, an apparatus for fabricating a three-dimensional object according to present invention includes: a mechanism for identifying a type of media (e.g., by size, physical properties, coded information) and for sequentially fusing layers of the media together into a three-dimensional object by applying an amount of conduction or other heating determined in consideration of a characteristic of the type of media (e.g., a glass transition temperature of fusible particles in the media, a ratio of fusible particles to water-soluble materials in the media, a type of fusible particle in the media, a type of water-soluble material in the media); and a build bin configured to support the fused layer(s) during fabrication of the three-dimensional object. Thus, the present invention allows digital fabrication from a variety of different types of media, such as media of different thicknesses, media formed from different types of thermoplastic materials, media formed from different compositions of materials, etc.
  • In other embodiments, the heating device 104 can be configured to provide the functions of both film fusing and coloring and, in such embodiments, also includes a printer 105 (shown in dashed lines). Integration of these functions can be accomplished, for example, by providing the heating device 104 with a printer 105 including inkjet printing mechanisms. Alternatively, a separate device can be used to color the film before it is provided to the three-dimensional fabricator 100. In either case, each layer of film can be digitally printed with a color image before fusing. Also, as discussed above, the film can be pre-colored (i.e., formed with colorant(s) in the mixture).
  • FIG. 2 is a partial cross-sectional view of a three-dimensional fabricator 100′ showing a layer of build film 150 being fused to the top layer of a stack 160 of previously fused build film layers during fabrication of a three-dimensional object. In this example, the three-dimensional fabricator 100′ includes a media advancing mechanism in the form of one or more roller 170, and the layer of build film 150 and an adjacent release film 180 are delivered from a roll. By way of example, the release film 180 is a polytetraflouethylene (PTFE) coated polyester or PTFE coated polyimide.
  • According to various embodiments of the present invention, film is delivered from rolls or sheets onto a build area, one layer at a time, and therefore does not create a safety hazard or cleanliness problem as is the case with the powders and liquids of many current machines. After each layer is placed in the build area, it is selectively heated in such a way as to reflow the thermoplastic particles only in the selected areas and bond them to each other and to the sheet below. By varying the selected heated areas in each layer as the build progresses, a three-dimensional object is created in the reflowed area. As discussed above, this selective heating can be accomplished through use of a page-wide thermal print bar moved (e.g., at a steady rate) across the surface of the film, for example, or a scanning thermal head, or a laser beam, etc. Depending upon the nature of the film and the particulars of the object fabrication process, a release film may be required between the heating device and the film. After the build is completed, the stack of bonded films can be removed from the build area and washed with water to dissolve away the unbonded areas of film.
  • FIGS. 3A-3D illustrate how a portion of a single film layer is fused and how non-fused portions of the film layer are thereafter washed away leaving only the fused portion of the film. Referring to FIG. 3A, a single film layer 300 includes thermoplastic particles 302 held together by a water soluble polymer (WSP) matrix or binder 304. As shown in FIG. 3B, the film 300 fuses in the areas where heat is applied creating a uniform, fused thermoplastic matrix or region 310 within which WSP particles 312 are trapped. In various embodiments, the thermoplastic particles 302 “invert”, changing from hydrophilic to hydrophobic, when fused into the thermoplastic matrix 310. The fused thermoplastic region 310 is no longer soluble in water, while the WSP matrix areas 314 that have not been heated can be dissolved by water (FIG. 3C), leaving only the fused portion of the film, i.e., the region 310 within which WSP particles 312 are trapped (FIG. 3D).
  • By patterning successive layers of film with cross-sectional slices of a solid part, the fused area builds up a three-dimensional object. After the object has been fully defined, the unfused film is washed away with water. As discussed above, full-color objects can be created by printing on each layer of film, e.g., with the printer 105 (FIG. 1), before the selective heating process.
  • An example method of using a heating device to fabricate a three-dimensional object begins by placing a water-soluble build film (e.g., containing clear thermoplastic particles) on the work area. A thin non-stick release film temporarily covers the surface of the build film. A page-wide thermal print bar is moved across the build area, selectively heating those areas which will become part of the final object. The release film is lifted, a new layer of build film is fed onto the work area, and the process is repeated until the part is complete. The stack of bonded film is removed from the printer, and the unbonded film is washed away with water. The build area can be varied to minimize material waste, by loading a narrower film roll (width) or cutting the film layers to the minimum size required (length) to build the specific part.
  • In another embodiment, a method of using a heating device to fabricate a three-dimensional object includes the steps of: sequentially delivering layers of a build film and an adjacent release film onto a build area, the build film being a water-soluble composite of thermoplastic particles in a binder material; for each layer, employing a heating device to heat selected areas of the layer, and then lifting its release film before the next layer is delivered to the build area, to reflow the thermoplastic particles in the selected areas and bond the thermoplastic particles to each other and to the layer below to form a three-dimensional object; and washing away unbonded portions of the build film with water to reveal the three-dimensional object. In another embodiment, the build film and release film are delivered from a roll or as sheets. In another embodiment, the build film layers are printed with colorant(s) (e.g., colored ink) before being bonded together. In another embodiment, the release film is a PTFE coated polyester or polyimide.
  • In another embodiment, an apparatus for fabricating a three-dimensional object includes: a printer with a heating device configured to sequentially fuse layers of media together into a three-dimensional object by applying an amount of conduction or other heating determined in consideration of a glass transition temperature of fusible particles in the media. In another embodiment, the glass transition temperature is about 30° C.-150° C. In another embodiment, the printer includes a build bin configured to support and reposition the fused layer(s) relative to the heating device between the fusing of each layer. In another embodiment, the printer is configured to draw the layers of media from a roll and to sequentially position the layers over the build bin.
  • In another embodiment, a method of fabricating a three-dimensional object includes the steps of: providing a film that is fusible into a non-water soluble state when exposed to conduction or other heating, the film being a mixture of thermoplastic particles and a water-soluble polymer matrix, the film further including a surfactant system bound to the thermoplastic particles, the surfactant system providing an inversion property such that the thermoplastic particles are hydrophilic but, upon a fusing of the film into a bulk, become hydrophobic as the surfactant become incorporated into the bulk; positioning layers of the film sequentially along a build axis and, for each of the layers before a subsequent layer is positioned, heating areas of the layers that are to be fused together to form a fused three-dimensional object; and dissolving non-fused portions of the layers with water to reveal the fused three-dimensional object. Thus, the present invention facilitates the removal of excess unbonded material (including materials from recessed and complex shapes) by dissolving in water, a process that advantageously does not involve dangerous chemicals. In another embodiment, the step of heating provides an amount of energy to the layers that is a function of a glass transition temperature of the thermoplastic particles. In another embodiment, the step of heating provides an amount of energy to the layers that is a function of a composition of the mixture of the thermoplastic particles and the water-soluble polymer matrix.
  • Although the present invention has been described in terms of the preferred embodiment above, numerous modifications and/or additions to the above-described preferred embodiment would be readily apparent to one skilled in the art. It is intended that the scope of the present invention extends to all such modifications and/or additions.

Claims (18)

1-63. (canceled)
64. An apparatus for fabricating a three-dimensional object, the apparatus including:
a printer with a heating device configured to sequentially fuse layers of media together into a three-dimensional object by applying an amount of heating determined in consideration of a glass transition temperature of the media.
65. The apparatus for fabricating a three-dimensional object of claim 64, wherein the printer is configured to print the layers of media with colorant(s) before the layers of media are fused together.
66. The apparatus for fabricating a three-dimensional object of claim 64, wherein the glass transition temperature is about 30° C.-150° C.
67. The apparatus for fabricating a three-dimensional object of claim 64, wherein the printer includes a build bin configured to support and reposition the fused layer(s) relative to the heating device between the fusing of each layer.
68. The apparatus for fabricating a three-dimensional object of claim 67, wherein the printer is configured to draw the layers of media from a roll and to sequentially position the layers over the build bin.
69. The apparatus for fabricating a three-dimensional object of claim 64, wherein the heating device includes a thermal print bar.
70. The apparatus for fabricating a three-dimensional object of claim 69, wherein the thermal print bar is at least as wide as the layers of media.
71. The apparatus for fabricating a three-dimensional object of claim 64, wherein the heating device includes thin film heating elements.
72. The apparatus for fabricating a three-dimensional object of claim 64, wherein the heating device includes a scanning thermal head.
73. The apparatus for fabricating a three-dimensional object of claim 64, wherein the heating device includes a laser.
74. The apparatus for fabricating a three-dimensional object of claim 64, wherein the heating device is a non-laser heating device.
75. An apparatus for fabricating a three-dimensional object, the apparatus including:
means for identifying a type of media and for sequentially fusing layers of the media together into a three-dimensional object by applying an amount of heating determined in consideration of a characteristic of the type of media; and
a build bin configured to support the fused layer(s) during fabrication of the three-dimensional object.
76. The apparatus for fabricating a three-dimensional object of claim 75, further including:
a printer configured to print the layers of media with colorant(s) before the s layers of media are fused together.
77. The apparatus for fabricating a three-dimensional object of claim 75, wherein the characteristic is a glass transition temperature of fusible particles in the media.
78. The apparatus for fabricating a three-dimensional object of claim 75, wherein the characteristic is a ratio of fusible particles to water-soluble materials in the media.
79. The apparatus for fabricating a three-dimensional object of claim 75, wherein the characteristic is a type of fusible particle in the media.
80. The apparatus for fabricating a three-dimensional object of claim 75, wherein the characteristic is a type of water-soluble material in the media.
US11/201,993 2003-05-07 2005-08-10 Fusible water-soluble films for fabricating three-dimensional objects Abandoned US20050266110A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US11/201,993 US20050266110A1 (en) 2003-05-07 2005-08-10 Fusible water-soluble films for fabricating three-dimensional objects

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/434,313 US6966960B2 (en) 2003-05-07 2003-05-07 Fusible water-soluble films for fabricating three-dimensional objects
US11/201,993 US20050266110A1 (en) 2003-05-07 2005-08-10 Fusible water-soluble films for fabricating three-dimensional objects

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US10/434,313 Division US6966960B2 (en) 2003-05-07 2003-05-07 Fusible water-soluble films for fabricating three-dimensional objects

Publications (1)

Publication Number Publication Date
US20050266110A1 true US20050266110A1 (en) 2005-12-01

Family

ID=33416664

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/434,313 Active 2024-03-24 US6966960B2 (en) 2003-05-07 2003-05-07 Fusible water-soluble films for fabricating three-dimensional objects
US11/201,993 Abandoned US20050266110A1 (en) 2003-05-07 2005-08-10 Fusible water-soluble films for fabricating three-dimensional objects

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US10/434,313 Active 2024-03-24 US6966960B2 (en) 2003-05-07 2003-05-07 Fusible water-soluble films for fabricating three-dimensional objects

Country Status (5)

Country Link
US (2) US6966960B2 (en)
CN (1) CN1784460A (en)
DE (1) DE112004000682T5 (en)
TW (1) TW200504127A (en)
WO (1) WO2004101661A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105711084A (en) * 2014-08-06 2016-06-29 深圳市微航磁电技术有限公司 3D colored laser printer by taking film as raw material

Families Citing this family (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6007318A (en) 1996-12-20 1999-12-28 Z Corporation Method and apparatus for prototyping a three-dimensional object
EP1658342B1 (en) * 2003-08-25 2010-05-12 Dip Tech. Ltd. Ink for ceramic surfaces
US7365129B2 (en) * 2003-10-14 2008-04-29 Hewlett-Packard Development Company, L.P. Polymer systems with reactive and fusible properties for solid freeform fabrication
WO2005097476A2 (en) * 2004-04-02 2005-10-20 Z Corporation Methods and apparatus for 3d printing
US7387359B2 (en) * 2004-09-21 2008-06-17 Z Corporation Apparatus and methods for servicing 3D printers
US7824001B2 (en) * 2004-09-21 2010-11-02 Z Corporation Apparatus and methods for servicing 3D printers
US20070026102A1 (en) * 2005-07-28 2007-02-01 Devos John A Systems and methods of solid freeform fabrication with improved powder supply bins
JP5243413B2 (en) 2006-05-26 2013-07-24 スリーディー システムズ インコーポレーテッド Apparatus and method for processing materials with a three-dimensional printer
WO2008118263A1 (en) * 2007-03-22 2008-10-02 Stratasys, Inc. Extrusion-based layered deposition systems using selective radiation exposure
DE102009030113A1 (en) 2009-06-22 2010-12-23 Voxeljet Technology Gmbh Method and device for supplying fluids during the layering of models
GB0917936D0 (en) * 2009-10-13 2009-11-25 3D Printer Aps Three-dimensional printer
JP2011143569A (en) * 2010-01-13 2011-07-28 Seiko Epson Corp Forming method and formed object
JP2011143570A (en) * 2010-01-13 2011-07-28 Seiko Epson Corp Forming method and formed object
JP2011143572A (en) * 2010-01-13 2011-07-28 Seiko Epson Corp Forming method and formed object
JP2011143571A (en) * 2010-01-13 2011-07-28 Seiko Epson Corp Forming method and formed object
JP5672854B2 (en) * 2010-08-25 2015-02-18 ソニー株式会社 Manufacturing method of structure
GB201216636D0 (en) * 2012-09-18 2012-10-31 Blueprinter Aps Powder feed mechanism for a three-dimensional printer
EP2920255B1 (en) * 2012-11-19 2019-03-13 Hewlett-Packard Development Company, L.P. Compositions for three-dimensional (3d) printing
US9604437B2 (en) 2012-12-13 2017-03-28 Canon Kabushiki Kaisha Method for manufacturing structural body and manufacturing apparatus therefor
CA2927334C (en) * 2013-10-14 2023-08-29 Zim Laboratories Limited Water soluble pharmaceutical film with enhanced stability
US20170015063A1 (en) * 2014-03-07 2017-01-19 Canon Kabushiki Kaisha Method of producing three-dimensional shaped article
US20150314532A1 (en) * 2014-05-01 2015-11-05 BlueBox 3D, LLC Increased inter-layer bonding in 3d printing
KR102168792B1 (en) * 2014-05-08 2020-10-23 스트라타시스 엘티디. Method and apparatus for 3d printing by selective sintering
EP3212383A4 (en) * 2014-10-29 2017-11-08 Hewlett-Packard Development Company, L.P. Three-dimensional (3d) printing method
DE102015222207A1 (en) * 2014-11-11 2016-05-12 DMG Mori USA TOOL MACHINES SYSTEM AND METHOD FOR ADDITIVE MANUFACTURING
US10576685B2 (en) 2015-04-30 2020-03-03 Hewlett-Packard Development Company, L.P. Three-dimensional (3D) printing
CN104786507B (en) * 2015-05-12 2017-02-22 北京金达雷科技有限公司 Weight tray of photocuring 3D printer and printing object separation method
EP3153307B1 (en) * 2015-10-05 2020-12-02 Airbus Defence and Space GmbH Generating a fibre compound by layers
US10000020B2 (en) 2015-10-12 2018-06-19 Xerox Corporation Method and device for producing areas in a printed object having different coefficients of friction
CN105538726A (en) * 2016-02-18 2016-05-04 苏州苏大维格光电科技股份有限公司 Three-dimensional molding device and method based on film substrate
US10730109B2 (en) 2016-04-11 2020-08-04 Stratasys Ltd. Method and apparatus for additive manufacturing with powder material
CN108496055B (en) * 2016-04-15 2020-10-27 惠普发展公司,有限责任合伙企业 Three-dimensionally printed load cell component
JP6934946B2 (en) * 2016-10-18 2021-09-15 株式会社クラレ Use of polyhydroxy compounds as plasticizers for polyvinyl alcohol in 3D printing
WO2018156938A1 (en) 2017-02-24 2018-08-30 Hewlett-Packard Development Company, L.P. Three-dimensional printing
CN110198796B (en) 2017-02-24 2022-02-08 惠普发展公司,有限责任合伙企业 Three-dimensional (3D) printing
CN110494236B (en) 2017-03-20 2022-07-26 斯特拉塔西斯公司 Method and system for additive manufacturing of materials using powders
WO2018194583A1 (en) 2017-04-19 2018-10-25 Hewlett-Packard Development Company, L.P. Additive manufacturing process using fusing and non-fusing printing fluids
US11351724B2 (en) 2017-10-03 2022-06-07 General Electric Company Selective sintering additive manufacturing method
US11420384B2 (en) 2017-10-03 2022-08-23 General Electric Company Selective curing additive manufacturing method
US11254052B2 (en) 2017-11-02 2022-02-22 General Electric Company Vatless additive manufacturing apparatus and method
US11590691B2 (en) 2017-11-02 2023-02-28 General Electric Company Plate-based additive manufacturing apparatus and method
US11027485B2 (en) * 2017-11-30 2021-06-08 The Boeing Company Sheet-based additive manufacturing methods
RU2664962C1 (en) * 2017-12-19 2018-08-23 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Method for producing three-dimensional products of a complex shape of high viscosity polymers and a device for its implementation (options)
US10821669B2 (en) 2018-01-26 2020-11-03 General Electric Company Method for producing a component layer-by-layer
US10821668B2 (en) 2018-01-26 2020-11-03 General Electric Company Method for producing a component layer-by- layer
US10926325B2 (en) * 2018-09-28 2021-02-23 The Boeing Company Methods and apparatus for additively manufacturing a structure with in-situ reinforcement
US10926460B2 (en) * 2018-09-28 2021-02-23 The Boeing Company Methods and apparatus for additively manufacturing a structure with in-situ reinforcement
US10926461B2 (en) * 2018-09-28 2021-02-23 The Boeing Company Methods and apparatus for additively manufacturing a structure with in-situ reinforcement
WO2020086099A1 (en) * 2018-10-26 2020-04-30 Hewlett-Packard Development Company, L.P. Three-dimensional printing
US11794412B2 (en) 2019-02-20 2023-10-24 General Electric Company Method and apparatus for layer thickness control in additive manufacturing
US11498283B2 (en) 2019-02-20 2022-11-15 General Electric Company Method and apparatus for build thickness control in additive manufacturing
CN113795370A (en) * 2019-03-12 2021-12-14 特里奥实验室公司 Method and apparatus for digital manufacturing of objects using actuated micro-pixelation and dynamic density control
US11179891B2 (en) 2019-03-15 2021-11-23 General Electric Company Method and apparatus for additive manufacturing with shared components
CN114619667A (en) * 2020-12-11 2022-06-14 中国科学院福建物质结构研究所 Synchronous pushing and linear stripping device for printing ultrahigh-viscosity resin and resin preparation method
US11731367B2 (en) 2021-06-23 2023-08-22 General Electric Company Drive system for additive manufacturing
US11826950B2 (en) 2021-07-09 2023-11-28 General Electric Company Resin management system for additive manufacturing
US11813799B2 (en) 2021-09-01 2023-11-14 General Electric Company Control systems and methods for additive manufacturing
CN114210373B (en) * 2021-12-28 2023-11-14 烟台大学 Cathode WSP catalytic conductive composite film and preparation process and application thereof

Citations (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4247508A (en) * 1979-12-03 1981-01-27 Hico Western Products Co. Molding process
US4575330A (en) * 1984-08-08 1986-03-11 Uvp, Inc. Apparatus for production of three-dimensional objects by stereolithography
US4705584A (en) * 1980-07-10 1987-11-10 Jacob Schlaepfer & Co., Ag Application of polymeric materials to substrates
US4863538A (en) * 1986-10-17 1989-09-05 Board Of Regents, The University Of Texas System Method and apparatus for producing parts by selective sintering
US5126529A (en) * 1990-12-03 1992-06-30 Weiss Lee E Method and apparatus for fabrication of three-dimensional articles by thermal spray deposition
US5136515A (en) * 1989-11-07 1992-08-04 Richard Helinski Method and means for constructing three-dimensional articles by particle deposition
US5192559A (en) * 1990-09-27 1993-03-09 3D Systems, Inc. Apparatus for building three-dimensional objects with sheets
US5204055A (en) * 1989-12-08 1993-04-20 Massachusetts Institute Of Technology Three-dimensional printing techniques
US5260009A (en) * 1991-01-31 1993-11-09 Texas Instruments Incorporated System, method, and process for making three-dimensional objects
US5263130A (en) * 1986-06-03 1993-11-16 Cubital Ltd. Three dimensional modelling apparatus
US5287435A (en) * 1987-06-02 1994-02-15 Cubital Ltd. Three dimensional modeling
US5286573A (en) * 1990-12-03 1994-02-15 Fritz Prinz Method and support structures for creation of objects by layer deposition
US5348693A (en) * 1991-11-12 1994-09-20 Advanced Cardiovascular Systems, Inc. Formation of three dimensional objects and assemblies
US5354414A (en) * 1988-10-05 1994-10-11 Michael Feygin Apparatus and method for forming an integral object from laminations
US5386500A (en) * 1987-06-02 1995-01-31 Cubital Ltd. Three dimensional modeling apparatus
US5387380A (en) * 1989-12-08 1995-02-07 Massachusetts Institute Of Technology Three-dimensional printing techniques
US5503785A (en) * 1994-06-02 1996-04-02 Stratasys, Inc. Process of support removal for fused deposition modeling
US5555481A (en) * 1993-11-15 1996-09-10 Rensselaer Polytechnic Institute Method of producing solid parts using two distinct classes of materials
US5578155A (en) * 1992-10-28 1996-11-26 Sanyo Machine Works, Ltd. Method and apparatus for manufacturing a solid object through sheet laminating
US5593531A (en) * 1994-11-09 1997-01-14 Texas Instruments Incorporated System, method and process for fabrication of 3-dimensional objects by a static electrostatic imaging and lamination device
US5695707A (en) * 1988-04-18 1997-12-09 3D Systems, Inc. Thermal stereolithography
US5730817A (en) * 1996-04-22 1998-03-24 Helisys, Inc. Laminated object manufacturing system
US5876550A (en) * 1988-10-05 1999-03-02 Helisys, Inc. Laminated object manufacturing apparatus and method
US6056843A (en) * 1993-12-29 2000-05-02 Kira Corporation Sheet lamination modeling method and sheet lamination modeling apparatus
US6103176A (en) * 1997-08-29 2000-08-15 3D Systems, Inc. Stereolithographic method and apparatus for production of three dimensional objects using recoating parameters for groups of layers
US6153142A (en) * 1999-02-08 2000-11-28 3D Systems, Inc. Stereolithographic method and apparatus for production of three dimensional objects with enhanced thermal control of the build environment
US6165406A (en) * 1999-05-27 2000-12-26 Nanotek Instruments, Inc. 3-D color model making apparatus and process
US6214279B1 (en) * 1999-10-02 2001-04-10 Nanotek Instruments, Inc. Apparatus and process for freeform fabrication of composite reinforcement preforms
US6224969B1 (en) * 1997-09-01 2001-05-01 Stichting Voor De Technische Wetenschappen Optical phantom suitable for stimulating the optical properties of biological material and a method of producing said phantom
US6322728B1 (en) * 1998-07-10 2001-11-27 Jeneric/Pentron, Inc. Mass production of dental restorations by solid free-form fabrication methods
US20020016387A1 (en) * 2000-05-30 2002-02-07 Jialin Shen Material system for use in three dimensional printing
US20020025411A1 (en) * 2000-08-23 2002-02-28 Korea Chemical Co., Ltd. Dissolution type thermal transfer film for three dimentional patterns and method for manufacturing the same
US6376148B1 (en) * 2001-01-17 2002-04-23 Nanotek Instruments, Inc. Layer manufacturing using electrostatic imaging and lamination
US20020062909A1 (en) * 2000-11-29 2002-05-30 Jang Bor Z. Layer-additive method and apparatus for freeform fabrication of 3-D objects
US20020065197A1 (en) * 2000-01-28 2002-05-30 Rong-Chang Liang Heat sensitive recording material
US6401002B1 (en) * 1999-04-29 2002-06-04 Nanotek Instruments, Inc. Layer manufacturing apparatus and process
US6417248B1 (en) * 1999-04-21 2002-07-09 Hewlett-Packard Company Preparation of improved inks for inkjet printers
US20020093115A1 (en) * 2001-01-12 2002-07-18 Jang B. Z. Layer manufacturing method and apparatus using a programmable planar light source
US20020113331A1 (en) * 2000-12-20 2002-08-22 Tan Zhang Freeform fabrication method using extrusion of non-cross-linking reactive prepolymers
US20020145213A1 (en) * 2001-04-10 2002-10-10 Junhai Liu Layer manufacturing of a multi-material or multi-color 3-D object using electrostatic imaging and lamination
US20020149137A1 (en) * 2001-04-12 2002-10-17 Bor Zeng Jang Layer manufacturing method and apparatus using full-area curing
US20040207123A1 (en) * 2001-02-15 2004-10-21 Ranjana Patel 3-D model maker

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09234799A (en) * 1996-03-01 1997-09-09 Tamura Seisakusho Co Ltd Method and apparatus for forming three-dimensional image, and heat-transferring body for forming three-dimensional image
CA2272629A1 (en) 1996-11-21 1998-05-28 Thaumaturge Pty. Limited Improved object manufacture
EP1027378B1 (en) 1997-10-31 2004-01-02 Hewlett-Packard Company, A Delaware Corporation Durable, film-forming, water-dispersive polymers
KR100631935B1 (en) * 2000-06-30 2006-10-04 주식회사 하이닉스반도체 Self refresh circuit of semiconductor device
US6585367B2 (en) 2001-01-29 2003-07-01 Hewlett-Packard Company Inkjet printed images with wettable, fusible toner
US6991329B2 (en) 2001-01-29 2006-01-31 Hewlett-Packard Development Company, L.P. Inkjet printed images with wettable, fusible toner

Patent Citations (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4247508A (en) * 1979-12-03 1981-01-27 Hico Western Products Co. Molding process
US4247508B1 (en) * 1979-12-03 1996-10-01 Dtm Corp Molding process
US4705584A (en) * 1980-07-10 1987-11-10 Jacob Schlaepfer & Co., Ag Application of polymeric materials to substrates
US4575330B1 (en) * 1984-08-08 1989-12-19
US4575330A (en) * 1984-08-08 1986-03-11 Uvp, Inc. Apparatus for production of three-dimensional objects by stereolithography
US5263130A (en) * 1986-06-03 1993-11-16 Cubital Ltd. Three dimensional modelling apparatus
US4863538A (en) * 1986-10-17 1989-09-05 Board Of Regents, The University Of Texas System Method and apparatus for producing parts by selective sintering
US5287435A (en) * 1987-06-02 1994-02-15 Cubital Ltd. Three dimensional modeling
US5386500A (en) * 1987-06-02 1995-01-31 Cubital Ltd. Three dimensional modeling apparatus
US5695707A (en) * 1988-04-18 1997-12-09 3D Systems, Inc. Thermal stereolithography
US5354414A (en) * 1988-10-05 1994-10-11 Michael Feygin Apparatus and method for forming an integral object from laminations
US5876550A (en) * 1988-10-05 1999-03-02 Helisys, Inc. Laminated object manufacturing apparatus and method
US5136515A (en) * 1989-11-07 1992-08-04 Richard Helinski Method and means for constructing three-dimensional articles by particle deposition
US5387380A (en) * 1989-12-08 1995-02-07 Massachusetts Institute Of Technology Three-dimensional printing techniques
US5204055A (en) * 1989-12-08 1993-04-20 Massachusetts Institute Of Technology Three-dimensional printing techniques
US5340656A (en) * 1989-12-08 1994-08-23 Massachusetts Institute Of Technology Three-dimensional printing techniques
US5192559A (en) * 1990-09-27 1993-03-09 3D Systems, Inc. Apparatus for building three-dimensional objects with sheets
US5637169A (en) * 1990-09-27 1997-06-10 3D Systems, Inc. Method of building three dimensional objects with sheets
US5286573A (en) * 1990-12-03 1994-02-15 Fritz Prinz Method and support structures for creation of objects by layer deposition
US5301415A (en) * 1990-12-03 1994-04-12 Prinz Fritz B Method for fabrication of three-dimensional articles
US5126529A (en) * 1990-12-03 1992-06-30 Weiss Lee E Method and apparatus for fabrication of three-dimensional articles by thermal spray deposition
US5260009A (en) * 1991-01-31 1993-11-09 Texas Instruments Incorporated System, method, and process for making three-dimensional objects
US5348693A (en) * 1991-11-12 1994-09-20 Advanced Cardiovascular Systems, Inc. Formation of three dimensional objects and assemblies
US5578155A (en) * 1992-10-28 1996-11-26 Sanyo Machine Works, Ltd. Method and apparatus for manufacturing a solid object through sheet laminating
US5555481A (en) * 1993-11-15 1996-09-10 Rensselaer Polytechnic Institute Method of producing solid parts using two distinct classes of materials
US6056843A (en) * 1993-12-29 2000-05-02 Kira Corporation Sheet lamination modeling method and sheet lamination modeling apparatus
US5503785A (en) * 1994-06-02 1996-04-02 Stratasys, Inc. Process of support removal for fused deposition modeling
US5593531A (en) * 1994-11-09 1997-01-14 Texas Instruments Incorporated System, method and process for fabrication of 3-dimensional objects by a static electrostatic imaging and lamination device
US5730817A (en) * 1996-04-22 1998-03-24 Helisys, Inc. Laminated object manufacturing system
US6103176A (en) * 1997-08-29 2000-08-15 3D Systems, Inc. Stereolithographic method and apparatus for production of three dimensional objects using recoating parameters for groups of layers
US6224969B1 (en) * 1997-09-01 2001-05-01 Stichting Voor De Technische Wetenschappen Optical phantom suitable for stimulating the optical properties of biological material and a method of producing said phantom
US6322728B1 (en) * 1998-07-10 2001-11-27 Jeneric/Pentron, Inc. Mass production of dental restorations by solid free-form fabrication methods
US20020033548A1 (en) * 1998-07-10 2002-03-21 Dmitri Brodkin Dental restorations formed by solid free-form fabrication methods
US6153142A (en) * 1999-02-08 2000-11-28 3D Systems, Inc. Stereolithographic method and apparatus for production of three dimensional objects with enhanced thermal control of the build environment
US6417248B1 (en) * 1999-04-21 2002-07-09 Hewlett-Packard Company Preparation of improved inks for inkjet printers
US6401002B1 (en) * 1999-04-29 2002-06-04 Nanotek Instruments, Inc. Layer manufacturing apparatus and process
US6165406A (en) * 1999-05-27 2000-12-26 Nanotek Instruments, Inc. 3-D color model making apparatus and process
US6214279B1 (en) * 1999-10-02 2001-04-10 Nanotek Instruments, Inc. Apparatus and process for freeform fabrication of composite reinforcement preforms
US20020065197A1 (en) * 2000-01-28 2002-05-30 Rong-Chang Liang Heat sensitive recording material
US20020016387A1 (en) * 2000-05-30 2002-02-07 Jialin Shen Material system for use in three dimensional printing
US20020025411A1 (en) * 2000-08-23 2002-02-28 Korea Chemical Co., Ltd. Dissolution type thermal transfer film for three dimentional patterns and method for manufacturing the same
US20020062909A1 (en) * 2000-11-29 2002-05-30 Jang Bor Z. Layer-additive method and apparatus for freeform fabrication of 3-D objects
US20020113331A1 (en) * 2000-12-20 2002-08-22 Tan Zhang Freeform fabrication method using extrusion of non-cross-linking reactive prepolymers
US20020093115A1 (en) * 2001-01-12 2002-07-18 Jang B. Z. Layer manufacturing method and apparatus using a programmable planar light source
US6376148B1 (en) * 2001-01-17 2002-04-23 Nanotek Instruments, Inc. Layer manufacturing using electrostatic imaging and lamination
US20040207123A1 (en) * 2001-02-15 2004-10-21 Ranjana Patel 3-D model maker
US20020145213A1 (en) * 2001-04-10 2002-10-10 Junhai Liu Layer manufacturing of a multi-material or multi-color 3-D object using electrostatic imaging and lamination
US20020149137A1 (en) * 2001-04-12 2002-10-17 Bor Zeng Jang Layer manufacturing method and apparatus using full-area curing

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105711084A (en) * 2014-08-06 2016-06-29 深圳市微航磁电技术有限公司 3D colored laser printer by taking film as raw material
CN105711084B (en) * 2014-08-06 2019-05-10 深圳市微航磁电技术有限公司 A kind of film material is the 3D color laser printer of raw material

Also Published As

Publication number Publication date
US20040224173A1 (en) 2004-11-11
TW200504127A (en) 2005-02-01
CN1784460A (en) 2006-06-07
US6966960B2 (en) 2005-11-22
DE112004000682T5 (en) 2006-04-20
WO2004101661A1 (en) 2004-11-25

Similar Documents

Publication Publication Date Title
US6966960B2 (en) Fusible water-soluble films for fabricating three-dimensional objects
US6133355A (en) Selective deposition modeling materials and method
US6936212B1 (en) Selective deposition modeling build style providing enhanced dimensional accuracy
EP1434683B1 (en) Selective deposition modeling with curable phase change materials
EP1432566B1 (en) Quantized feed system for solid freeform fabrication
US7329379B2 (en) Method for solid freeform fabrication of a three-dimensional object
EP3589477B1 (en) 3-d printing using spray forming
EP1759791A1 (en) Apparatus and method for building a three-dimensional article
Windle et al. Ink jet printing of PZT aqueous ceramic suspensions
WO2016013198A1 (en) Method and apparatus for manufacturing three-dimensional object
CN113478822B (en) Three-dimensional object printing method and device, storage medium and computer device
US10773460B2 (en) Method and apparatus for manufacturing three-dimensional body
US11685119B2 (en) Enhanced fused filament multi-color three-dimensional (3D) printing
JP6630853B2 (en) Formation of microstructure in 3D printing
WO2017109144A1 (en) Colour 3d printing apparatus and a corresponding colour 3d printing method
Frazelle Out-of-this-world additive manufacturing
JP2002001828A (en) Adhesive liquid, coloring material and method for coloring
EP3880434B1 (en) Three-dimensional article with sacrificed support defined with build material
Frazelle Out-of-this-World Additive Manufacturing: From thingamabobs to rockets, 3D printing takes many forms.
CN113811437A (en) Reducing agglomeration of build material
JP2020059227A (en) Manufacturing method and apparatus for three-dimensional modeling object
WO2019231431A1 (en) Fusing three dimensional (3d) parts
Koushik et al. Ceramic three-dimensional printing
Mitrić TECHNOLOGIES AND SOFTWARE IN 3D PRINTING WITH EXAMPLE OF USAGE IN APICULTURE

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION