WO2018228450A1 - Procédé d'impression 3d - Google Patents

Procédé d'impression 3d Download PDF

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Publication number
WO2018228450A1
WO2018228450A1 PCT/CN2018/091153 CN2018091153W WO2018228450A1 WO 2018228450 A1 WO2018228450 A1 WO 2018228450A1 CN 2018091153 W CN2018091153 W CN 2018091153W WO 2018228450 A1 WO2018228450 A1 WO 2018228450A1
Authority
WO
WIPO (PCT)
Prior art keywords
degreasing
binder
printing
printing method
green body
Prior art date
Application number
PCT/CN2018/091153
Other languages
English (en)
Chinese (zh)
Inventor
吴敏
刘业
李斌
但奇善
顾晓川
蒋荣归
Original Assignee
深圳升华三维科技有限公司
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 深圳升华三维科技有限公司 filed Critical 深圳升华三维科技有限公司
Publication of WO2018228450A1 publication Critical patent/WO2018228450A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/227—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by organic binder assisted extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the present application relates to the field of 3D printing technologies, and in particular, to a 3D printing method.
  • 3D printing production technology belongs to static molding additive manufacturing technology. It uses software to decompose the three-dimensional component solid image of computer design into several layers of planar slices, and then prints and outputs through 3D printer to produce different-shaped parts of different materials.
  • Commonly used low-temperature hot-melt deposition molding method 3D printing additive molding can only use 3D printed wire materials such as PLA or ABS as thermoplastic materials to produce various model products; 3D for metal materials or inorganic non-metal materials
  • metal powder or inorganic non-metal powder is generally used as a raw material, and laser high-temperature melt deposition method or selective laser high-temperature sintering method is used to realize 3D printing.
  • the main object of the present application is to propose a 3D printing method aimed at improving the strength of a 3D printed article during sintering and avoiding defects such as collapse, deformation or cracking of the article.
  • a 3D printing method proposed by the present application includes the following steps:
  • Step S1 preparing a 3D printing raw material by melt-kneading the raw material and the binder, the binder is a multi-component binder, and the multi-component binder comprises a main binder and a filler;
  • Step S2 heating and melting the 3D printing material to be transported to a 3D print head, and printing the blank by the 3D print head;
  • Step S3 performing the first degreasing of the green body, removing the filler and retaining the main binder;
  • Step S4 performing the high-temperature sintering shrink-molding 3D printed product through the first degreased green body, in the high-temperature sintering process, the first degreased green body is degreased and removed after the second degreasing process.
  • the primary binder
  • step S3 the first degreasing is performed in a degreasing furnace, and the filler is removed by at least one of catalytic degreasing, thermal degreasing, and solvent degreasing.
  • the catalytic degreasing is carried out in a catalytic degreasing furnace using concentrated nitric acid as a medium, the degreasing temperature is 80-130 ° C, and the degreasing time is 5-8. h.
  • the second degreasing is thermal degreasing, and the sintering is performed in the sintering furnace together with the high temperature sintering, the sintering temperature is 1280-1320 ° C, and the sintering time is 18-24 h.
  • the primary binder comprises at least one of polypropylene and polyethylene; and/or,
  • the filler includes at least one of paraffin wax, polyoxymethylene, and polyvinyl alcohol.
  • the multi-component binder further comprises a coupling agent, the coupling agent comprising at least one of stearic acid and glycerin.
  • the main binder accounts for 4.5-45% of the total mass fraction
  • the filler accounts for 50-95% of the total mass fraction
  • the couplant accounts for the total mass fraction. 0.5-5%.
  • step S1 the adhesive accounts for 30-45% of the total number of integrals of the raw material and the adhesive.
  • the raw material comprises a metallic material and an inorganic non-metallic material.
  • the metal material comprises stainless steel, titanium and titanium alloys, copper and copper alloys, aluminum and aluminum alloys, high specific gravity tungsten alloys, and hard alloys.
  • the raw material and the binder are kneaded, and then the 3D printer is fed by low temperature extrusion, after the blank is printed by the print head, the first degreasing is performed, the filler is removed, and the main bond is retained.
  • the agent is then degreased a second time during the sintering process to remove the main binder, which not only reduces the processing temperature of the 3D printing, but also retains the main binder during the first degreasing process, so that the product is subsequently sintered. It is not easy to collapse, deform or crack during the process, which improves the performance of the product.
  • FIG. 1 is a schematic flow chart of an embodiment of a 3D printing method provided by the present application.
  • the directional indication is only used to explain in a certain posture (as shown in the drawing)
  • first”, “second”, etc. in the embodiments of the present application, the description of "first”, “second”, etc. is used for descriptive purposes only, and is not to be construed as an Its relative importance or implicit indication of the number of technical features indicated.
  • features defining “first” or “second” may include at least one of the features, either explicitly or implicitly.
  • the technical solutions between the various embodiments may be combined with each other, but must be based on the realization of those skilled in the art, and when the combination of the technical solutions is contradictory or impossible to implement, it should be considered that the combination of the technical solutions does not exist. Nor is it within the scope of protection required by this application.
  • the prior art proposes a hot melt extrusion molding technology, which melts the feed by low temperature, makes it fluid, and prints the green body through a 3D printer, and then in a degreasing furnace and sintering.
  • Mass production in the furnace but the commonly used method is to completely degrease the printed green body in the degreasing furnace and then sintering, which causes the collapse, deformation or cracking of the product during the sintering process.
  • the application proposes a 3D printing method, so that the 3D printed product is less prone to collapse, deformation or cracking during the sintering process.
  • the 3D printing method includes: Step S1: preparing a 3D printing raw material by melt-kneading a raw material and a binder, wherein the adhesive is a multi-component adhesive.
  • a multi-component adhesive comprising a main binder and a filler; in step S2, the 3D printing material is heated and melted and then transported to a 3D print head, and the raw blank is printed by the 3D print head; step S3 And the green body is degreased for the first time, the filler is removed and the main binder is retained; and in step S4, the green body after the first degreasing is subjected to high temperature sintering shrinkage molding 3D printing products. In the high-temperature sintering process, the first degreased green body is degreased a second time to remove the main binder.
  • the raw material and the binder are kneaded, and then fed to the 3D printer through low temperature extrusion, after the blank is printed by the print head, the first degreasing is performed, the filler is removed and the main binder is retained, and then sintered.
  • the main binder is removed, which not only reduces the processing temperature of the 3D printing, but also retains the main binder during the first degreasing process, so that the product is less likely to collapse during the subsequent sintering process. Deformation or cracking improves the performance of the product.
  • the raw material includes a metal material and an inorganic non-metal material
  • the metal material includes stainless steel, titanium and titanium alloy, copper and copper alloy, aluminum and aluminum alloy, high specific gravity tungsten alloy, cemented carbide, etc., and the inorganic non-metal material
  • a stainless steel 17-4 material is taken as an example, and a stainless steel 17-4 powder having an average particle diameter of 10 ⁇ m is used as a raw material.
  • the multi-component binder includes a main binder and a filler, wherein the filler is a polymer binder which is melt-decomposed or solvo-decomposed or catalytically removed at a lower temperature, such as paraffin, polyoxymethylene, Polyvinyl alcohol or the like; the main binder is a polymer binder which is melt-decomposed and removed at a relatively high temperature, and is mostly a polyolefin-based polymer material such as polyethylene, polypropylene, etc.;
  • the binder further includes a coupling agent such as stearic acid, glycerin, etc.; and in the multi-component binder, the primary binder accounts for 4.5-45% of the total mass fraction, and the filler accounts for the total 50-95% of the mass fraction, the couplant accounts for 0.5-5% of the total mass fraction.
  • the multi-component binder is composed of paraffin wax, polypropylene (PP), polyvinyl alcohol (PEG) 4000, and stearic acid (SA), wherein paraffin, PP, PEG
  • the mass scores for 4000 and SA are 30%, 30%, 35%, and 5%, respectively.
  • a 3D printing raw material is prepared by using the above stainless steel powder and a multi-component binder, and 3D printing of the metal component is performed, and the specific steps are as follows:
  • Step S1 3D printing raw material preparation, the above stainless steel powder and multi-component binder are put into an internal mixer for melt-kneading, specifically, in the embodiment of the present application, stainless steel powder and multi-component adhesive
  • the volume percentage is 53% and 47% respectively.
  • the volumetric capacity of the internal mixer is 10L
  • the mixing temperature is set at 220 °C
  • the mixing time is 12 hours.
  • the mixing temperature is higher than the temperature.
  • the melting point of the multi-component binder is such that the mixture of the stainless steel powder and the binder can be melted to have a certain fluidity, and the kneading time only needs to thoroughly mix the stainless steel powder with the binder, and kneading A high temperature requires a shorter mixing time, and a lower mixing temperature requires a longer mixing time. Further, the melt-kneading method is not limited to the kneading, and the stainless steel powder and the thermoplastic molding binder mixture may be melt-kneaded by an open roll mill or a single-screw extruder.
  • the mixture obtained by kneading is granulated to obtain cylindrical pellets of uniform size, that is, the 3D printing raw material is prepared, and of course, 3D printing of various shapes such as filament, rod, and tube can be prepared according to actual needs.
  • raw material The multi-component binder is mixed with stainless steel powder to prepare a mixture, so that the metal material can also be fed at a low temperature, thereby avoiding the need to use high temperature to completely melt the metal powder and then performing 3D printing, which reduces the processing temperature and reduces the processing temperature. Cost of production.
  • Step S2 3D printing and molding the green body, firstly designing a three-dimensional metal component model to be printed in the computer by using 3D printing software, setting printing parameters, and then heating and melting the prepared 3D printing material to the 3D printing head.
  • the 3D printer used in the 3D printing is provided with a feeding layer and a working layer, the feeding layer includes a heating zone and a feeding zone, and the 3D printing material is heated in the heating zone.
  • the fluidized molten state is then transported to the 3D print head through a single screw extrusion provided in the feed zone, and the 3D printhead is extruded to cool the stacked component blank.
  • the temperature of the heating zone was set to 180 ° C
  • the temperature of the 3D print head was set at 200 ° C
  • the temperature of the working layer was set at 100 ° C.
  • the 3D printing material is melted and then transported to the 3D print head for printing the green body, so that the 3D printing material can be smoothly squeezed out from the 3D printing head, and the raw material is prevented from being too late due to the short time in the 3D printing head. Melting, resulting in poor printing.
  • Step S3 the green body is degreased for the first time, the green body is degreased for the first time, and the filler in the multi-component binder is removed, and the first degreasing may be solvent degreasing, thermal degreasing and One method of catalytic degreasing is carried out.
  • the green body is degreased for the first time by a method of catalytic degreasing.
  • the green body is placed in a catalytic degreasing furnace with concentrated nitric acid as a medium, the temperature is set at 130 ° C, and the degreasing time is set to 7 h, removing the filler in the green body and retaining the main binder, where the main binder is retained, so that the green body of the preliminary binder removal has a certain strength, so that deformation is less likely to occur during subsequent processing. Cracks and the like occur.
  • Step S4 high-temperature sintering molding, the green body after the first degreasing is subjected to high-temperature sintering shrink-molding 3D printed product, and in the high-temperature sintering process, the green body of the preliminary binder removal is subjected to the second Degreasing, removing the primary binder in the multicomponent binder, and the second degreasing is thermal degreasing.
  • the high-temperature sintering can be performed by a vacuum sintering furnace, an atmosphere sintering furnace or a pressure sintering furnace. In the embodiment of the present application, a vacuum sintering furnace is used for vacuum high-temperature sintering.
  • the sintering temperature curve is first set, and the liquid phase sintering temperature is set. Set to 1300 ° C, vacuum sintering time set to 22 h, then the green body which is initially removed from the binder is placed in a vacuum sintering furnace to complete high-temperature sintering, and in the vacuum high-temperature sintering process, the green body after the first degreasing is further subjected to the second degreasing, and the green body is removed.
  • the main binder, and shrinking and forming the metal component product while the main binder is removed shrinks the green body and completes densification, and obtains a metal component product having a certain mechanical property.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Powder Metallurgy (AREA)

Abstract

La présente invention concerne un procédé d'impression 3D. Le procédé d'impression 3D comprend les étapes suivantes : étape S1, préparation d'une matière première et d'un liant pour obtenir un matériau d'impression 3D au moyen d'un mélange à l'état fondu, le liant étant un liant multicomposant qui comprend un liant principal et une charge; étape S2, chauffage et fusion du matériau d'impression 3D, puis distribution de celui-ci vers une tête d'impression 3D, et impression d'un corps vert par la tête d'impression 3D; étape S3, dégraissage du corps vert une première fois pour éliminer la charge et retenir le liant principal; et étape S4, conduite d'un frittage à haute température et d'un moulage de retrait sur le corps vert ayant subi le premier dégraissage pour obtenir un produit d'impression 3D, où, dans le processus de frittage à haute température, le corps vert ayant subi le premier dégraissage est dégraissé une deuxième fois pour éliminer le liant principal.
PCT/CN2018/091153 2017-06-14 2018-06-13 Procédé d'impression 3d WO2018228450A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710451736.4A CN107470626A (zh) 2017-06-14 2017-06-14 一种3d打印方法
CN201710451736.4 2017-06-14

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WO2018228450A1 true WO2018228450A1 (fr) 2018-12-20

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WO (1) WO2018228450A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107470626A (zh) * 2017-06-14 2017-12-15 吴敏 一种3d打印方法
CN108160920B (zh) * 2018-01-23 2020-02-14 北京机科国创轻量化科学研究院有限公司 一种新型砂型（芯）3d打印成形方法
CN108503355B (zh) * 2018-04-18 2020-08-04 昆山卡德姆新材料科技有限公司 一种3d打印用料、其制备方法和用途
CN110282985A (zh) * 2019-06-24 2019-09-27 西北工业大学 一种光固化3d打印氧化铝陶瓷素坯的助溶剂辅助脱脂方法
CN110681858A (zh) * 2019-10-28 2020-01-14 重庆理工大学 一种用于3d打印的镁合金原料的制备方法及其打印方法
CN110976846A (zh) * 2019-12-06 2020-04-10 重庆工港致慧增材制造技术研究院有限公司 用于3d打印的镁基复合材料、制备方法及其3d打印方法
CN111331132A (zh) * 2020-03-17 2020-06-26 苏州复浩三维科技有限公司 3d打印方法
CN111747741A (zh) * 2020-07-10 2020-10-09 重庆工港致慧增材制造技术研究院有限公司 一种3d打印材料及其制备方法、3d打印方法
CN113910600B (zh) * 2021-10-12 2023-10-24 江苏精研科技股份有限公司 一种制备高精度3d打印产品的方法

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