WO2004037902A1 - Procedes de fabrication d'articles tridimensionnels et articles fabriques au moyen de ces procedes - Google Patents

Procedes de fabrication d'articles tridimensionnels et articles fabriques au moyen de ces procedes Download PDF

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Publication number
WO2004037902A1
WO2004037902A1 PCT/GB2003/004564 GB0304564W WO2004037902A1 WO 2004037902 A1 WO2004037902 A1 WO 2004037902A1 GB 0304564 W GB0304564 W GB 0304564W WO 2004037902 A1 WO2004037902 A1 WO 2004037902A1
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WIPO (PCT)
Prior art keywords
powder
precursor
liquid
curable
internal zone
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PCT/GB2003/004564
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English (en)
Inventor
Jacek Paul Obuchowicz
Ranjana Chhaganbhai Patel
Richard John Peace
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Huntsman Advanced Materials (Switzerland) Gmbh
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Application filed by Huntsman Advanced Materials (Switzerland) Gmbh filed Critical Huntsman Advanced Materials (Switzerland) Gmbh
Priority to AU2003274360A priority Critical patent/AU2003274360A1/en
Publication of WO2004037902A1 publication Critical patent/WO2004037902A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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 of manufacturing 3D articles and articles made by such a method.
  • the formed articles may be composites of rapidly manufactured, internally structured porous parts, which may take the form of shells or skeletons, having an outside skin covering the external surfaces, and includes secondary cured materials.
  • US-5,824,260 and US-6,364,986 disclose a method of making an object by first forming a shell using stereolithography; the shell contains internal voids from which uncured stereolithography liquid resin is removed. The voids are then filled with strengthening materials, e.g. a mixed epoxy resin and hardener, to form a high strength part. The removal of the uncured stereolithography resin from the shell and re-filling it with other strengthening materials is time consuming.
  • strengthening materials e.g. a mixed epoxy resin and hardener
  • WO02/064354 discloses a method of making a composite article by buildmg it up in successive layers, each layer being produced by forming a layer of powder and depositing a liquid, e.g. using an inkjet printer, on areas of the powder layer that are to form part of the article. The powder is removed in those areas where no liquid is deposited and the areas of the powder layer to which liquid has been applied are cured. The powder and liquid may together form a curable resin.
  • a method for producing a 3D article comprising: (a) forming a precursor in sequential cross-sectional layers in accordance with a model of the precursor, each layer being formed by:
  • the curable material mentioned in step (c) may comprise the unconsolidated powder referred to in step (b), in which case the powder is reactive.
  • the unconsolidated powder may be inert and simply form a filler for curable material introduced into the internal zone.
  • substantially all of the powder in the internal zones that remains unconsolidated after the precursor is formed is retained within the internal zone, which avoids the time-consuming step of removing it.
  • the consolidation of -the precursor preferably occurs by the powder and the liquid forming a curable composition that at least partly cures shortly after the liquid is applied.
  • the consolidated portion i.e. the precursor, will include the outside surface layer and may also include internal features to provide support within the internal zone.
  • each formed layer has a ratio of consolidated to not consolidated powder material ranging from 1:10 to 1:1.
  • 1:10 ratio there maybe no or little internal structure, resulting in retention of original untreated build material inside the internal zone, with only the edge surface being consolidated.
  • 1:1 ratio there will be a significant proportion of the internal zone consolidated.
  • This consolidation could be highly structured, and could take a geometric pattern e.g. honeycombed or ladder like, or could be more random such as sponge textured, criss-crossed or wholly random and variable.
  • the precursor could be formed as an outside skin of the article.
  • the precursor may include some internal structure, e.g. internal walls.
  • the internal structure could be smooth and even throughout the internal body, or maybe variable. In some areas, such as around curves and corners, a finely dimensioned structure may be formed for additional definition and strength, while in straight areas, larger dimensioned geometric designs can be tolerated.
  • the internal structure may have dimensions measured in mm to microns. If, within the final article, the cured material within the zone(s) is stronger than the outside shell originally formed as the precursor during step (a), it may be desirable to make the precursor shell walls relatively thin.
  • the powder layer may readily be formed, e.g. using a doctor blade. Any method that accurately deposits the liquid onto the powder in step (a)ii) can be used but deposition using an ink jet printing head as described in WO02/064354 is preferred. Suitable equipment for forming powder layers and applying liquids thereto by ink jet printing equipment is available commercially, e.g. from Z-Corporation of 20 North Ave. Burlington, MA 01803, U.S.A. The precursor may be formed in several ways.
  • the powder can comprise a reactive component that reacts with the liquid to form a composite that solidifies or cures up in the shape of the precursor.
  • a reactive component that reacts with the liquid to form a composite that solidifies or cures up in the shape of the precursor.
  • the powder recrystalises on application of a liquid to form a solid precursor structure, e.g. calcium sulphate, which recrystalises on application of an aqueous solution.
  • the powder may be inert, e.g. aluminium oxide, and the liquid is intrinsically reactive and solidifies or cures when jetted.
  • the liquid may be a binder that binds the powder; in the case of a binder, it is usually necessary later on to infiltrate the bound powder with a curable material in order to provide the precursor with substantial strength. This is important since the prcursor will generally form the outside of the final 3D article.
  • the powder material may itself be intrinsically curable without any additional additives, e.g. it may be a mixture of materials that will react together when heated, in which case the consolidated material forming the precursor can be cured directly by heating.
  • a suitable intrinsically curable powder material is for example described in O00/157110 Al, which discloses a composition comprising (A) an epoxide containing at least two epoxy groups per molecule, (B) a polyol containing at least two hydroxy groups per molecule or a primary or secondary amine containing at least two amino-hydrogen atoms per molecule, and (C) a solid compound containing at least two isocyanate groups; such a powder exhibits high storage stability.
  • the liquid may be curable or a binder.
  • the precursor can be infiltrated with a suitable curable material that can be cured up in the final composite solid body to increase the strength of the precursor; in this case, the infiltrating material could be such as to react with the liquid and/or the powder of the consolidated precursor to form a curable mixture or the infiltrating liquid could in itself be a curable composition It has also been found that the fabrication techniques of the present invention help to reduce the time of build, while ultimately producing final articles of increased strength.
  • WO02/064354 discloses 3D articles built using powders and ink jetted fluids to bind the powder according to programmed data, and reference should be made to that specification for further details of forming the powder layer and apply the liquid in a desired pattern in step (a) and also details of suitable reactive powder/liquid combinations.
  • the powder within the internal zone may be intrinsically curable, e.g. it will be cured on heating or when subject to radiation, e.g. US6437045, 6433084, 6169158, 6165558.
  • the precursor may be infiltrated with a curable material through the surface, so the material could also infiltrate into the internal zone and the powder within it.
  • the infiltrating liquid is preferably either intrinsically curable or is curable with the powder in the internal zone.
  • the resultant cured composite has surprisingly greater strength than a similar parts where no internal zones are formed.
  • the powder material used and retained within the internal zone may be a finely divided expansible reactive material which, on curing, e.g. by heating or on exposure to microwaves, expands to fill the internal zone.
  • the expansion of the powder will be beneficial within the internal zone since it will fill the whole internal zone.
  • the same powder is used to form the precursor walls as is used in the internal zone, and so a powder that expands on curing can only be used when either expansion of the precursor can be tolerated or when expansion of the precursor is somehow avoided when curing the powder in the internal zone. Avoidance of the expansion of the powder in the precursor can be achieved by solidifying the precursor to such an extent before curing step (d) that any expanding/foaming agent in the powder will not operate to expand the precursor.
  • Such a result can also be achieved, for example, by using a reactive powder that contains a foaming agent that only operates at elevated temperature; in this case, the powder forming the precursor could be cured at room temperature on application of the liquid in step (a) to form a rigid structure so that, when the composite is heated to cure the powder within the internal zones, the foaming agent will foam the powder in the internal zone but will not expand the rigid precursor.
  • Foamable compositions that melt and then foam up giving a foam having a high compression strength are described in WOOO/24559.
  • material When material is ' infiltrated through the precursor, it may be introduced through the precursor into the unconsolidated region by vacuum and/or under pressure.
  • the curing may be achieved by heat or microwave radiation, or any other suitable curing mechanism.
  • Suitable liquid curable resins that may be infiltrated range from addition polymerisation types to photocuring types. This flexibility of using a secondary resin for infiltration enables a variety of properties to be attained. These include high heat deflection temperatures, high water resistance, high tensile strengths and modulii, better flame resistance (necessary in aero, auto and rail applications), and impact toughness.
  • the infiltrating liquid and/or the powder and/or the liquid applied in step a) may be mixtures which contain latent toughening agents, e.g. butadienes or siloxanes which phase separate out on curing, or toughening elastomeric particles (nano or micro sized particles), particularly surface reactive particles for example as disclosed in
  • Pigments and fillers including inorganic and organic materials such as metal powder, e.g. aluminium particles or whiskers, silica and polymeric core shell particles may also be present as matrix strengthening ingredients; solid particles will generally be incorporated into the powder.
  • metal powder e.g. aluminium particles or whiskers, silica and polymeric core shell particles
  • silica and polymeric core shell particles may also be present as matrix strengthening ingredients; solid particles will generally be incorporated into the powder.
  • nano scale particles are particles having a size of not greater than 50nm along their longest dimensions; nano scale particles give the 3D article increased strength and water resistance. They may be:
  • nano-scale metal particles e.g. copper, aluminium, nickel, zinc, silver etc, which are available commercially from e.g. Argonide Corporation.
  • nano-scale platelet minerals e.g. nanoclays (also known as “planomers”), which are commercially available under the trade name Claytone ® or Cloisette,
  • nano-scale particle e.g. made of silica or barium sulphate, which are also commercially available; nano-silica particles are available under the trade name Highlink OG ® from Clariant International Ltd of Muttenz , Switzerland;
  • nanocarbon materials e.g. buckminsterfullerenes
  • nano-tubes e.g. carbon nano tubes, which are commercially available from Nanoledge S A, or Nanocarbon Inc,
  • nano-scale salt and ceramic particles e.g. nano titanium dioxide from Chengyin Technology (China) Ltd, nano barium sulfate (from Solvay), or nano-glass;
  • nano-polymers e.g. nano elastomeric particles available from from Hanse Chemie, or as described in EP0938026A1;
  • nano-organic metals e.g. nano-polyanilines, which are conducting polymeric particles from Ormecron GmbH;
  • fibres e.g. alumina fibres, such as nano alumina fibres from Argonide Corporation.
  • the nano-scale particles may be porous on an Angstrom scale.
  • a single form of nano-particles may be used or a mixture of compatible nano particles could be used either of the same or of a different chemical type.
  • the fillers especially the nano-scale fillers, maybe suitably surface treated, e.g. with organosilanes and surfactants, to make them compatible with the material that they are dispersed in and may be ionised, e.g. by plasma treatment, so that they do not clump together and are more readily dispersed..
  • compositions which can cure at low temperatures, e.g. less than 100°C, preferably less than 40°C.
  • the curing of the powder in the zone in step d) and the curing of the consolidated powder are such that they do not result in substantial volume shrinkage of the precursor, preferably a shrinkage of less than 1%. Good wetting is important with respect to the internal surfaces of the article.
  • the powder and the liquid applied in step (a) may be chosen freely so long as they forms a stable precursor that can be subject to the curing step (d).
  • Preferred powder/liquid curing resin compositions for forming the consolidated precursor of the curable composition within the internal zones include epoxy/hardener systems, isocyanate/polyol systems, anhydride/epoxy systems maleimide/epoxy systems and acrylic/epoxy/amine mixes.
  • Some preferred powders are epoxy based powders, e.g. as disclosed in US6437045, 6433084, 6169158, 6165558.
  • the powder may be a foamable reactive powder which on heating will foam up to fill the cavity of the fornied article and adhesively bond any internal supports, so that a fully strengthened part is obtained.
  • the powders which foam, adhere and deliver good compressive strengths.
  • the liquid applied in step (a) is aqueous based and the powder includes a crosslinkable agent that crosslinks when the aqueous liquid is applied.
  • a powder/liquid system that may be used in the present invention is as follows, by way of example:
  • crosslinkable agent in the powder is a monomer, oligomer, polymer, or polymer mixture that has functional groups capable of forming covalent bonds (crosslinks), either with itself or with the functional groups of other crosslinkable agents.
  • the crosslinkable agent is selected from the group consisting of amino resins, phenol resins, and mixed amino/phenol resins.
  • Amino resins, phenol resins, and mixed amino/phenol resins are derived from the reaction of formaldehyde and an amine, a phenol, or a mixture of an amine and a phenol, respectively.
  • crosslinkable agents are selected from the group consisting of melamine-formaldehyde resins, urea-formaldehyde resins, melamine-urea-formaldehyde resins, melamine- phenol-formaldehyde resins, benzoguanamine-formaldehyde resins, glycoluril- formaldehyde resins, and acetoguanamine-formaldehyde resins.
  • the crosslinkable agent may be a glyoxal resin or a methylol carbamate.
  • the powder may comprise from about 1% to about 60% by weight of crosslinkable agents in powder form.
  • the size of the particles should be less than the thickness of the layers to be printed.
  • the shape of the particles may be regular or irregular.
  • the crosslinkable agent dissolves and may begin to polymerize and crosslink with itself and other water soluble functional resins, thereby contributing structure and strength to the printed article.
  • the crosslinking occurs within the layer being formed, as well as with previously formed layers.
  • the crosslinkable agent should be soluble in water at room temperature.
  • the agent will a) be crosslinkable under ambient conditions; b) have the ability to catalyze in moderately acidic solutions; and c) have a relatively rapid cure rate.
  • Thin films of the crosslinkable agent may be coated onto a filler material such as glass spheres, flakes or fibers, and used in this form in the powder systems described herein.
  • a filler material such as glass spheres, flakes or fibers
  • lower volumes of binder fluid are required to solubilize the crosslinkable agent.
  • the time required for the solubilized agent to fully penetrate the agent on the other surface treated particles is reduced, and consequently, green strength development and final strength development are enhanced.
  • This embodiment also helps to reduce the spread of fluid into non-image areas.
  • Acid catalysts may be used to accelerate crosslinking of the crosslinkable agent, and these include, e.g., lewis acids (such as ammonium chloride, tin (II) chloride, magnesium chloride, cobalt, sulfate, or iron III chloride), which may be incorporated into the powder (but tend to reduce storage stability). Acid catalysts may also include, e.g., blocked acid catalysts such as Nacure (King Industries, Norwalk, Connecticut), which release acid upon heating and can be incorporated into the powder, binder, or redox systems herein described.
  • lewis acids such as ammonium chloride, tin (II) chloride, magnesium chloride, cobalt, sulfate, or iron III chloride
  • Acid catalysts may also include, e.g., blocked acid catalysts such as Nacure (King Industries, Norwalk, Connecticut), which release acid upon heating and can be incorporated into the powder, binder, or redox systems herein described.
  • the powder may also contain a "strengthening component" that melts and flows upon heating, then resolidifies on cooling, or preferably thermal cures.
  • the powder to which the strengthening component is added can be any powder suitable for 3D printing, such as a standard starch/cellulose or plaster powder, and the crosslinkable agent- containing powder systems described above.
  • the strengthening component is substantially inert when contacted with an aqueous binder at ambient temperature. In other words, when the 3D article is initially printed, the strengthening component does not contribute substantially to the article's strength.
  • the strengthening component melts and flows within the article, filling gaps and pores and engulfing other components of the powder, and then it resolidifies or cures, which adds substantially to the strength of the 3D article.
  • the strengthening component reacts to produce a thermoset polymer when it is heated.
  • the strengthening component may comprise a blend of an epoxy resin and a carboxyl group-containing polyester (such as those used in powder coating applications, e.g. U.S. 6,117,952), which reacts when heated to produce a thermoset polymer.
  • the powder may contain other ingredients such as adhesives, fillers, cohesive aids, thickeners, and polyols, which improve the material system's performance in 3D articles, and provide desired mechanical properties in the printed article.
  • Adhesives suitable for the material systems of this invention should be water soluble at room temperature, so that the adhesive is activated when contacted by the aqueous binder fluid.
  • examples include polyvinyl alcohol and poly(ethyloxazoline).
  • the adhesive should be milled; preferably to less than 100 microns, and more preferably in the range of 20-40 microns.
  • the adhesive powder should be fine enough to enhance dissolution in the aqueous binder, without being so fine as to cause "caking", an undesirable phenomenon wherein unactivated powder adheres to the printed article, resulting in poor resolution.
  • the powder may contain 0%.to about 90% by weight of one or more adhesives.
  • Fillers may be included in the powder and should be insoluble, or only slightly soluble, in the aqueous liquid, should be readily wettable, should be capable of adhesively bonding with the adhesive components of the powder system; may be coated (e.g., with aminosilanes) or uncoated; and should not render the powder system unspreadable.
  • suitable fillers include glass spheres, flakes or fibers; inorganic mineral fillers (such as wollastonite or mica); clay fillers (such as Kaolin); starches (such as maltodextrin); plaster; polymeric fibers (such as cellulose fiber); ceramic fiber; graphite fiber; limestone; gypsum; aluminum oxide; aluminum silicate; potassium aluminum silicate; calcium silicate; calcium hydroxide; calcium aluminate; sodium silicate; metals; metal oxides (such as zinc oxide, titanium dioxide and magnetite); carbides (such as silicon carbide); borides (such as titanium diboride); and inert polymers such as polymethylmethacrylate, polysterene, polyamide and polyvinyl chloride.
  • inorganic mineral fillers such as wollastonite or mica
  • clay fillers such as Kaolin
  • starches such as maltodextrin
  • plaster polymeric fibers (such as cellulose fiber); ceramic fiber; graphite fiber; limestone; gypsum; aluminum oxide;
  • the filler component may include a variety of particle sizes, ranging from about 5 microns up to about 200 microns.
  • the mean size of the particulate material cannot be larger than the layer thickness.
  • Large particle sizes may improve the quality of the printed article by forming large pores in the powder through which the binder fluid can easily migrate. Smaller particle sizes may serve to reinforce article strength.
  • a distribution of particle sizes may be particularly desireable, as it may increase the packing density of the particulate material, which in turn may increase both article strength and dimensional control.
  • the powder systems of this invention may contain from about 0% to about 60% by weight of a main filler (such as glass spheres), and from about 0% to about 30% by weight of one or more other fillers (such as inorganic mineral fillers and/or clay fillers).
  • a main filler such as glass spheres
  • one or more other fillers such as inorganic mineral fillers and/or clay fillers.
  • Solid glass spheres are preferred as the main fillers, because they are readily wetted by liquid components of the composition (e.g. surfactants and wetting agents).
  • Cohesive aids provide light adhesion between the powder grains, thereby reducing dust formation and promoting even spreading of the powder.
  • Examples include polyethylene glycol, sorbitan trioleate, citronellol, ethylene glycol octanoiate, ethylene glycol decanoiate, ethoxylated derivatives of 2,4,7,9-tetramthyl-5-decyn-4,7-diol, sorbitan mono-oleate, sorbitan mono-laurate, polyoxyethylene sorbitan mono-oleate, soybean oil, mineral oil, propylene glycol, fluroalkyl polyoxyethylene polymers, glycerol triacetate, oleyl alcohol, and oleic acid.
  • the powder systems of this invention may contain 0% to about 10% by weight of one or more cohesive aids.
  • Thickeners work to increase the viscosity of the fluid binder, thus minimizing the diffusion of the binder into the surrounding powder. It is believed that thixotropic agents such as CARBOPOL® EZ-2 (polyacrylic acid from Noveon, Inc., Cleveland,
  • the material systems of this invention may contain about 0% to about 15% by weight of one or more thickeners.
  • Surfactants increase the solubility in the aqueous liquid of lipophilic powder components.
  • Surfactants may be present in the binder system and/or in the powder system.
  • the powder system may contain up to about 6% of one or more surfactants.
  • surfactants include perfluoroalkyl polyethers.
  • the powder system may comprise a polyol to increase the extent of crosslinking of the crosslinkable agent.
  • polyols include tetramethylol methane, glycerol, sorbitol, erythritol, polyvinyl alcohol and trimethylolpropane.
  • the powder systems of this invention may contain from 0% to about 90% by weight of one or more polyols.
  • the Aqueous Liquid Applied to the Powder is preferably a binder system is selected to provide the degree of solubility required for the various powder components described above. Powder systems of this invention are compatible with standard aqueous binders, such as ZB-7 (Z Corporation).
  • the binder system of this invention comprises mainly water, but may comprise other additives known to those of skill in the art, such as surfactants, humectants, water absorbing moieties, and dyes.
  • Liquids that may be used for infiltration in accordance with the present invention include epoxy/hardener systems preferably comprise low viscosity ( ⁇ 2500cps, highly preferred being ⁇ 500cps) diglycidyl epoxies, such as bisphenol A or F di glycidyl epoxides, or perhydrogenated bisphenol A diglycidyl epoxide.
  • Diluent epoxies include bisglycidyl butane-diol types.
  • cresol and phenol novalac epoxies can be used, as can the newer types of epoxies derived from siloxane or butadiene sub-units.
  • Polyepoxides and pre-polymers containing epoxide functionality may be used to provide further reactivity.
  • Isocyanates/polyols systems will produce polyurethanes and as with the epoxides, polyisocyanate compounds maybe advantageously utilised.
  • the anhydrides/epoxy systems yield polyesters, and the maleimide/epoxy systems yield polyamides.
  • the acrylic/epoxy/amine hybrid mixes can used to obtain controlled reactions: pure epoxy/amine systems can exotherm out of control resulting in warpage and shrinkage problems. Addition (e.g.
  • the invention also extends to a composite part made by the methods described, having tensile strength greater than 10 MPa, preferably greater than 20MPa and more preferably greater than 30MPa.
  • the method of the present invention can be applied to make rapid prototypes or manufactured products especially those required to be durable during use.
  • the strong, tough composite articles made in accordance with the invention can find uses in aerospace, automobile and rail applications, in leisure goods, in electrical casings and in other areas.
  • dental implants e.g. tooth crowns
  • other prosthetic devices for example substantially two-dimensional prosthetics, e.g. a bone plate, such as an insert in a long bone or a cranial plate, or a substantially three- dimensional prosthetic.
  • substantially two-dimensional prosthetics e.g. a bone plate, such as an insert in a long bone or a cranial plate
  • three-dimensional prosthetic devices may be mentioned inter alia joints, e.g. femural head replacement; complex fracture repairs; and bone restructuring in reconstructive surgery, e.g. jaw-bone, hip-joints, shoulders, elbows, knuckles and more complicated arrangements, e.g. a knee which is believed to combine a hinge action with a gliding and rolling action.
  • a dental crown may be rapidly formed in a dental surgery or laboratory by taking a scan of the tooth to obtain the shape of the tooth surface onto which the crown is to fit. The tooth shape is analysed from the scan in terms of thin cross sections.
  • a crown having a surface to match with the tooth can then be made by depositing successive layers of a wear resistant powder material such as aluminium oxide and depositing a binder or curable resin on the powder layer in a shape corresponding to the successive cross sections of the tooth and the desired crown surfaces using an inkjet print head to form a precursor of the desired shape of the crown.
  • the amount of liquid binder or resin deposited is sufficient to bind the aluminium oxide particles while at the same time leaving voids between the particles.
  • the precursor is then placed in a bath of a tough curable epoxy resin within a vacuum chamber; the epoxy resin is drawn by the vacuum into the precursor and infiltrates it. The resin is then cured to form an extremely tough crown in a shorter time than is generally possible presently.
  • the invention also extends to the products made by those methods.
  • Test bars with external dimensions 100mm x 10mm x 4mm, having internal structures as shown in Figure 1 were built using commercially available calcium sulphate di- hydrate based powder ZP102 and aqueous binder ZP50 (Z-Corporation). ZP102 powder recrystalises when contacted by an aqueous solution to form a porous consolidated precursor.
  • FIG. 1 illustrates four structures in schematic cross-section.
  • Bisphenol A/F Epoxy resin Resin LY113 (100 parts by weight) available from Nantico was mixed with amine hardener HY97 ( 32 parts by weight) also available fromNantico Ltd. The two components were mixed thoroughly for five minutes by hand prior to use.
  • test bars were treated with Composition 1 according to the described examples and cured as described.
  • Flexural strengths of the final composite test bars and comparison test bars were determined according to ISO 178 using a crosshead speed of 2mm / min.
  • Test bars having internal structures as shown in Figure 1 were prepared on a Z406 3D Printer as described above.
  • Comparative examples are test bars which are completely solid having no internal structure.
  • Example 0 is base test bar which is 100% consolidated and not treated with Composition 1.
  • Example 1 is same as Example 0, but treated with Composition 1.
  • the Examples 2-5, test bars were totally immersed in Composition 1 in a shallow dish. The dish was placed in a vacuum oven and the system evacuated for five minutes to eliminate residual air in the article. The test bars were then removed from the vacuum oven, the excess resin removed and the test bars were cured at room temperature for four hours on some release paper.
  • the composite test bars produced were post-cured in an oven at 200°C for 2 hours to give the final fully cured composite test bars.
  • Example 5 the parts having internal structure consisting of unconsolidated powder and cured Composition 1 (Examples 2 — 5) were found to have a greater strength than the solid bar (Example 1). Particularly, Example 5, where there was no consolidation of the internal powder, gave the highest strength, indicating that penetration of Composition 1 into such a structure with unconsolidated internal machine can be achieved very effectively.

Abstract

Procédé servant à fabriquer un article tridimensionnel et consistant à : produire un précurseur en couches présentant une section transversale séquentielle selon un modèle de précurseur par définition d'une couche en matériau pulvérulent, consolider une partie de la poudre dans une configuration correspondant à la couche de section transversale respective du modèle et répéter ces étapes afin de créer des couches successives. Une zone interne délimitée par le matériau consolidé est définie à l'intérieur du précurseur pendant sa formation. Un matériau durcissant est créé à l'intérieur de la zone interne, qui contient la poudre non consolider et ce matériau durcissant est durci afin de produire l'article tridimensionnel sous la forme d'un corps solide composite fini.
PCT/GB2003/004564 2002-10-23 2003-10-22 Procedes de fabrication d'articles tridimensionnels et articles fabriques au moyen de ces procedes WO2004037902A1 (fr)

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AU2003274360A AU2003274360A1 (en) 2002-10-23 2003-10-22 Method of manufacturing 3d articles and articles made by such methods

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GBGB0224716.1A GB0224716D0 (en) 2002-10-23 2002-10-23 Method of manufacturing 3D articles and articles made by such methods
GB0224716.1 2002-10-23

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WO2004037902A1 true WO2004037902A1 (fr) 2004-05-06

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Cited By (11)

* Cited by examiner, † Cited by third party
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US7674300B2 (en) 2006-12-28 2010-03-09 Kimberly-Clark Worldwide, Inc. Process for dyeing a textile web
US7740666B2 (en) 2006-12-28 2010-06-22 Kimberly-Clark Worldwide, Inc. Process for dyeing a textile web
US8182552B2 (en) 2006-12-28 2012-05-22 Kimberly-Clark Worldwide, Inc. Process for dyeing a textile web
US8323429B2 (en) 2009-07-31 2012-12-04 United States Gypsum Company Method for preparing three-dimensional plaster objects
US8632613B2 (en) 2007-12-27 2014-01-21 Kimberly-Clark Worldwide, Inc. Process for applying one or more treatment agents to a textile web
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US20150306821A1 (en) * 2014-04-23 2015-10-29 Seiko Epson Corporation Method of manufacturing three-dimensional structure and three-dimensional structure
WO2020227357A1 (fr) 2019-05-07 2020-11-12 A.M. Toolbox, Llc Pièce de fabrication additive à rigidité renforcée et son procédé de fabrication
US11148358B2 (en) 2017-01-03 2021-10-19 General Electric Company Methods and systems for vacuum powder placement in additive manufacturing systems
US11577458B2 (en) 2018-06-29 2023-02-14 3M Innovative Properties Company Additive layer manufacturing method and articles
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7674300B2 (en) 2006-12-28 2010-03-09 Kimberly-Clark Worldwide, Inc. Process for dyeing a textile web
US7740666B2 (en) 2006-12-28 2010-06-22 Kimberly-Clark Worldwide, Inc. Process for dyeing a textile web
US8182552B2 (en) 2006-12-28 2012-05-22 Kimberly-Clark Worldwide, Inc. Process for dyeing a textile web
US8632613B2 (en) 2007-12-27 2014-01-21 Kimberly-Clark Worldwide, Inc. Process for applying one or more treatment agents to a textile web
US8323429B2 (en) 2009-07-31 2012-12-04 United States Gypsum Company Method for preparing three-dimensional plaster objects
US20150169802A1 (en) * 2013-11-19 2015-06-18 Homeland Technologies Research, Llc Polymer formation and simulation thereof
US20150306821A1 (en) * 2014-04-23 2015-10-29 Seiko Epson Corporation Method of manufacturing three-dimensional structure and three-dimensional structure
JP2015208859A (ja) * 2014-04-23 2015-11-24 セイコーエプソン株式会社 三次元造形物の製造方法および三次元造形物
US11732150B2 (en) 2016-04-15 2023-08-22 Hewlett-Packard Development Company, L.P. Composite particulate build materials
US11148358B2 (en) 2017-01-03 2021-10-19 General Electric Company Methods and systems for vacuum powder placement in additive manufacturing systems
US11577458B2 (en) 2018-06-29 2023-02-14 3M Innovative Properties Company Additive layer manufacturing method and articles
WO2020227357A1 (fr) 2019-05-07 2020-11-12 A.M. Toolbox, Llc Pièce de fabrication additive à rigidité renforcée et son procédé de fabrication
EP3937996A4 (fr) * 2019-05-07 2022-04-20 A.M Toolbox, LLC Pièce de fabrication additive à rigidité renforcée et son procédé de fabrication

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