CN112060572A - Three-dimensional object forming method and forming device - Google Patents
Three-dimensional object forming method and forming device Download PDFInfo
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- CN112060572A CN112060572A CN201910500876.5A CN201910500876A CN112060572A CN 112060572 A CN112060572 A CN 112060572A CN 201910500876 A CN201910500876 A CN 201910500876A CN 112060572 A CN112060572 A CN 112060572A
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- heat
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- dimensional object
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- powder
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Images
Classifications
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- 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
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- 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
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
-
- 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
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE 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
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention provides a three-dimensional object forming method and a three-dimensional object forming device, and relates to a 3D printing technology. The three-dimensional object forming method comprises the following steps: forming a powder particle layer, wherein the powder particles for forming the powder particle layer comprise core particles and a coating layer coated on at least a part of surfaces of the core particles; according to layer printing data, spraying heat promoting materials on the powder particle layer, enabling the heat promoting materials to be in contact with the coating materials to release heat, and enabling the core particles to be melted and formed under the action of the heat to form a sliced layer; and repeating the steps from the powder particle layer formation to the slice layer formation, and superposing the obtained multiple slice layers layer by layer to form the three-dimensional object. According to the three-dimensional object forming method provided by the invention, the core particles coated by the coating material are melted and formed by utilizing the heat released by the contact of the coating material and the heat-promoting material, so that the energy consumption in the three-dimensional object printing process can be reduced.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to a three-dimensional object forming method and a three-dimensional object forming device.
Background
The 3D printing technology is called a rapid prototyping technology, an additive manufacturing technology, and the like, and its basic principle is to slice a 3D model based on slice software, convert slice data of the 3D model into layer printing data by a data processor, and control a printing device to print layer by layer according to the layer printing data and form a 3D object by superposition.
The mainstream forming process of the 3D printing technology at the present stage is as follows: the powder paving component paves a powder particle layer on the supporting platform, the controller controls the ink-jet printing head to selectively spray the adhesive on the powder particle layer according to layer printing data, so that the adhesive bonds the powder particles together to form a slicing layer or a forming layer, and then the powder paving step and the ink-jet printing step are repeated to form a three-dimensional object layer by layer and are superposed to form the three-dimensional object. However, the mechanical strength of the 3D object printed by this molding method is low.
In order to improve the mechanical strength of the 3D object, at present, the 3D object is mostly placed in a heating furnace for heating treatment, so as to further melt the powder particles therein, and enhance the bonding force between the powder particles, thereby improving the mechanical strength of the 3D object. However, the above-mentioned heating method often requires a large amount of heat energy, which results in high energy consumption and manufacturing cost of the 3D printed product.
Disclosure of Invention
Aiming at the defects, the invention provides a three-dimensional object forming method which can reduce energy consumption and manufacturing cost in the manufacturing process of a 3D printed product.
The invention also provides a three-dimensional object forming device which is used for implementing the three-dimensional object forming method.
To achieve the above object, an aspect of the present invention provides a three-dimensional object forming method, including the steps of:
forming a powder particle layer, wherein powder particles for forming the powder particle layer comprise core particles and a coating layer coated on at least a part of surfaces of the core particles;
according to the layer printing data, spraying heat-promoting materials on the powder particle layer, enabling the heat-promoting materials to be in contact with a coating material for forming a coating layer to release heat, and enabling the core particles to be melted and formed under the action of the heat to form a sliced layer;
and repeating the steps from the powder particle layer formation to the slice layer formation, and superposing the obtained multiple slice layers layer by layer to form the three-dimensional object.
Specifically, in the three-dimensional object molding process, slicing software can be adopted to slice the 3D model, and slice data is converted into layer printing data through a data processor; supplying powder particles onto the molding platform through the powder supply part to form a powder particle layer having a desired thickness on the molding platform; according to layer printing data, a liquid injection head is adopted to inject heat-promoting materials on a powder particle layer, the heat-promoting materials penetrate into the powder particle layer and are fully contacted with a coating material to release heat, so that a core material is melted and formed under the action of the heat, and a slicing layer is formed on a forming platform. And then repeating the operations from the powder particle layer formation to the slice layer formation, so that the formed multiple slice layers are overlapped layer by layer, and finally the three-dimensional object is formed.
Therefore, the invention provides a three-dimensional object forming method, wherein the core particles are melted and formed by heat released by contact between the cladding material and the heat-promoting material. Compared with the mode of heating the 3D object to melt the powder particles in the 3D object at the present stage, the three-dimensional object forming method provided by the invention has the advantages that the energy consumption in the 3D object printing process is obviously reduced, and the manufacturing cost of the 3D object is reduced.
Another aspect of the present invention is to provide a three-dimensional object forming apparatus for carrying out the above three-dimensional object forming method, the three-dimensional object forming apparatus including at least a powder supply part, a forming table, and a liquid ejection head, wherein: the powder supply part is used for forming a powder particle layer on the forming platform; the liquid ejection head is used to eject heat-promoting material on the powder particle layer according to the layer print data.
Specifically, a powder supply part may be used to supply powder particles onto a molding platform to form a layer of powder particles having a desired thickness; a liquid ejection head is used to eject heat-promoting material on the powder particle layer in accordance with the layer print data. The heat-promoting material permeates into the powder particle layer and contacts with the coating material to release heat, and the core particles are melted and molded under the action of the heat to form the slice layer. And then, the forming platform is lowered by the height of one or more slicing layers, or the powder supply component and/or the liquid injection head are raised by the height of one or more slicing layers, the forming process of the next slicing layer is continued, and finally, the slicing layers are overlapped layer by layer to form the target three-dimensional object.
The invention provides a three-dimensional object forming method, wherein powder particles for forming a solid structure of a three-dimensional object comprise a coating material which is contacted with a heat-promoting material to release heat and inner core particles coated by the coating material. The heat-promoting material is sprayed onto the surface of the powder particle layer, and in the process of the falling point position and the penetration into the powder particle layer, the heat-promoting material is contacted with the coating material to release heat, and the core particle can be melted and formed under the heat. Therefore, the three-dimensional object forming method provided by the invention fully utilizes heat on the premise of ensuring the forming precision of the three-dimensional object, avoids large loss of heat in the transfer process, and saves energy consumption required by melting powder particles through heating, thereby reducing the manufacturing cost of the three-dimensional object.
The three-dimensional object forming device provided by the invention is used for implementing the three-dimensional object forming method, and can reduce the energy consumption and the manufacturing cost in the three-dimensional object manufacturing process.
Drawings
Fig. 1 is a schematic diagram of a three-dimensional object forming method according to an embodiment of the invention;
FIG. 2 is a schematic diagram of the structure of the powder particles of the present invention;
FIG. 3 is another schematic structural view of the powder particles of the present invention;
fig. 4 is a schematic structural diagram of a three-dimensional object forming apparatus according to an embodiment of the present invention.
Description of reference numerals:
11-a powder supply member; 12-a forming table;
13-a liquid ejection head; 14-a layer of powder particles;
15-an exothermic material; 16-slicing;
17-control means.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
The embodiment provides a three-dimensional object forming method, as shown in fig. 1, including the following steps:
s1, forming a powder particle layer, wherein the powder particles for forming the powder particle layer comprise core particles and coating layers coated on at least partial surfaces of the core particles;
s2, according to the layer printing data, spraying heat promoting materials on the powder particle layer, enabling the heat promoting materials to be in contact with a coating material for forming a coating layer to release heat, and enabling the core particles to be melted and formed under the action of the heat to form a slicing layer;
and S3, repeating the steps from the powder particle layer forming to the slice layer forming, and overlapping the obtained multiple slice layers layer by layer to form the three-dimensional object.
Specifically, the execution body of the three-dimensional object molding method may be a molding device that finally manufactures the target three-dimensional object by performing the steps S1, S2, and S3 by controlling the supply of the powder particle layer, the ejection of the heat-promoting material, and the layer-by-layer superimposition of the plurality of sliced layers.
Specifically, in step S1, the powder particle layer may be formed on the forming platform by using a powder supplying component. In this embodiment, the thickness of the powder particle layer can be set reasonably according to the precision requirement of the target three-dimensional object, and it should be ensured that the heat-promoting material can penetrate into the bottom of the current layer of the powder particle layer, so that the heat-promoting material and the coating material can be in full contact. In the specific implementation process, the thickness of the powder particle layer is generally controlled to be 5-500 μm.
Referring further to fig. 1, before implementing step S2, step S1' may also be executed first: preheating the powder particle layer. Specifically, the current layer of the powder particle layer is heated.
By preheating the powder particle layer, on one hand, partial heat can be provided, and the heat released by the contact of the heat promoting material and the coating material is added, so that enough heat is ensured to fully melt and mold the core particles in the printing area, and the molding speed is improved; on the other hand, the preheating process can also enable the subsequent heat-promoting materials to be in contact with the coating materials at a proper temperature, so that heat can be released smoothly.
It will be appreciated that the temperature of preheating should be below the melting point of the powder particles and will also depend on such factors as the amount of heat released by the exothermic material upon contact with the coating material.
Specifically, in step S2, according to the layer printing data, the liquid jet head is used to jet the heat release promoting material onto the powder particle layer, the heat release promoting material accurately drops on the powder particle layer and enters the gaps between the powder particles, and contacts with the coating material coated outside the core particles to release heat, and the released heat is directly absorbed by the core particles to be fused and molded, thereby achieving the full utilization of energy and reducing the energy loss.
Specifically, in performing step S2, the powder particle layer is divided into a plurality of regions, and the volumes of the heat-promoting materials sprayed on the different regions may be the same or different. In a specific implementation process, heat-promoting materials can be uniformly sprayed on the whole printing area of the powder particle layer according to layer printing data, so that the formed sliced layer and even the whole three-dimensional object have very consistent mechanical properties; or different quantities of heat-promoting materials can be sprayed on different areas of the powder particle layer, so that the heat released by the heat-promoting materials contacting with the coating material is different in different area ranges, the melting degree of the core particles is different, different areas of the final slicing layer and even different areas of the three-dimensional object have different mechanical properties, and the requirements of the actual three-dimensional object are better met. Compared with the prior art that the mechanical performance of the three-dimensional object is adjusted by ejecting a plurality of ejection materials and/or adopting a plurality of ejection heads, the method of the embodiment reduces the number of the ejection heads and the types of the ejection materials, and reduces the manufacturing cost of the three-dimensional object forming device and the printing cost of the three-dimensional object.
And repeating the steps S1, S1', S2 and S3 to form a plurality of slice layers correspondingly, and superposing the slice layers layer by layer to finally obtain the target three-dimensional object.
The powder particle layer formed by the invention preferably only contains one type of powder particles, the powder particles comprise core particles and a coating layer coated on at least part of the surface of the core particles, wherein the coating material forming the coating layer comprises a component capable of participating in heat release, and the core particles are melted and formed by absorbing heat. Since only a single kind of powder particles is used, there is no phenomenon in which the distribution of powder particles in the formed powder particle layer is not uniform due to non-uniform mixing of a plurality of kinds of powder particles in forming the powder particle layer, whereby one of the factors affecting the molding accuracy of the target object can also be reduced from the source.
The particle size of the powder particles is not too small, otherwise the heat-promoting material is difficult to permeate to the bottom of the current layer of the powder particle layer in a short time, and the heat release of the heat-promoting material is not facilitated by the contact with the coating material of the powder particles; the particle size of the powder particles should not be too large, otherwise the gaps between the powder particles are too large, which may affect the forming accuracy of the three-dimensional object. Therefore, in this embodiment, the diameter of the powder particles can be controlled to be generally 1 to 300 μm.
The schematic structure of the powder particles can be seen in particular in fig. 2 and 3. As shown in fig. 2, the coating material forms a continuous coating layer on the surface of the core particle; of course, the coating material may form a continuous coating layer on a part of the surface of the core particle. Wherein the thickness of the clad layer may be uniform or non-uniform. The thickness of the coating layer in this embodiment is not particularly limited as long as it can ensure that the heat emitted during the contact between the coating material and the heat-generating material is sufficient to melt-mold the core particles. It is understood that if the thickness of the coating layer is small, the content of the component participating in the exothermic reaction is too small, and the released heat hardly melts the core particles, whereas if the thickness of the coating layer is large, that is, the interval between the core particles is large, the shrinkage deformation of the three-dimensional object increases after melt molding, and the accuracy is lowered. Therefore, the thickness of the coating layer is generally controlled to be 50 to 1500 nm.
Alternatively, as shown in FIG. 3, the coating comprises a plurality of discrete beads surrounding the surface of the core particle. That is, the coating material is coated or bonded on the surface of the core particle in the form of beads, and the beads are spaced apart from each other. Such as a plurality of beads, uniformly or non-uniformly spaced on the outer surface of the core particle. In the present embodiment, the particle size of the beads for forming the coating layer is not particularly limited as long as the heat released during the contact between the plurality of beads coated on the surface of the core particle and the heat-release promoting material is enough to melt-mold the core particle, and the diameter of the beads is generally 50 to 1500 nm.
The specific manner of coating or bonding the coating material on the surface of the core particle to obtain the powder particle is not particularly limited in this embodiment, and a suitable method may be selected according to actual needs. For example, emulsion polymerization, polymer precipitation, coating, electropolymerization, etc., wherein the coating may include spray drying, dip drying, stirring, mixing and adding, etc., and may be performed using publicly known commercially available coaters, granulators, etc.
In this embodiment, the heat release promoting material and the coating material may release heat by contacting, but the embodiment is not limited to this, as long as the heat release promoting material and the coating material can release heat by contacting, and the released heat can melt and mold the core particle. For example, the contact exotherm may be achieved by initiating an exotherm, catalytic exotherm, redox exotherm, dissolution exotherm, or the like.
Specifically, for initiating the heat release, the heat-promoting material contains an initiator, and the coating material reacts under the initiation of the initiator to release heat. The initiator may be at least one of benzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, azobisisoheptonitrile, etc.; the coating material contains a compound having a vinyl group, and may be at least one of polyester acrylate, urethane acrylate, epoxy acrylate, hyperbranched acrylate, unsaturated polyester, tris (2-hydroxyethyl) isocyanurate triacrylate, and the like.
Specifically, for catalytic heat release, at least one of the heat-promoting material and the coating material contains a catalyst, and the other of the heat-promoting material and the coating material reacts under the catalysis of the catalyst to release heat, i.e., the heat-promoting material or the coating material contains a component capable of undergoing an exothermic reaction under the catalysis of the catalyst. For example, the heat release promoting material contains hydrogen peroxide, and the coating material contains manganese dioxide. Hydrogen peroxide in the heat-promoting material is reacted and decomposed under the catalysis of manganese dioxide to generate water and oxygen, and a large amount of heat is released. For another example, the heat-generating material contains a metal catalyst, the coating material contains a compound having a hydroxyl group, and the compound having a hydroxyl group reacts with the metal catalyst in the presence of oxygen to generate heat. The metal catalyst satisfying the above conditions may be, for example, at least one of copper, silver, palladium, and the like; the compound having a hydroxyl group may be, for example, at least one of polyvinyl alcohol, polyether polyol, polyester polyol, hydroxyacrylic resin, and the like. The compound with hydroxyl is oxidized to generate carbon dioxide and water under the catalysis of a metal catalyst, and a large amount of heat is released.
Specifically, for the oxidation-reduction heat release, one of the heat release promoting material and the coating material contains an oxidizing agent, the other contains a reducing agent, and the oxidizing agent and the reducing agent undergo an oxidation-reduction reaction to release heat. Wherein, the oxidant can be at least one selected from potassium permanganate, potassium perchlorate, ammonium nitrate, ammonium perchlorate, ferric trichloride, potassium dichromate and the like; the reducing agent is at least one selected from sucrose, sorbitol, mannitol, glucose, fructose, etc.
Specifically, for the exothermic dissolution, the exothermic material is water or a solution containing water, and the coating material contains at least one hydroxide which can be dissolved in water or a solution containing water to release heat. The hydroxide may be at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide, etc., and the heat-generating material may be water, aqueous hydrochloric acid, etc. The hydroxide is dissolved in water, or the hydroxide is dissolved in a solution containing water to generate acid-base neutralization reaction, so that heat is released.
The heat-promoting material in this embodiment may further comprise a colorant, which may be at least one of the colorants commonly used in three-dimensional objects today, such as dyes and pigments, preferably pigments, especially self-dispersed nano-scale pigment pastes, according to the color requirements of the target three-dimensional object. The surface of the self-dispersion nano pigment color paste is chemically modified, so that the pigment can be prevented from flocculating and coagulating, and the stability of the first material is ensured.
In specific implementation, the self-dispersing nano-scale pigment color paste can be self-dispersing nano-scale inorganic pigment color paste or self-dispersing nano-scale organic pigment color paste. Wherein, the self-dispersing nano-scale inorganic pigment color paste can be white pigment color paste, such as titanium dioxide, zinc oxide, lithopone, lead white and the like; and can also be black pigment color paste, such as carbon black, graphite, iron oxide black, aniline black, carbon black and the like. The self-dispersed nanoscale organic pigment color paste can be a color pigment color paste, such as aurora red (PR21), lithol scarlet (PR 49: 1), pigment red G (PR37), pigment red 171(PR171), lightfast yellow G (PY1), hansa yellow R (PY10), permanent yellow GR (PY13), pigment yellow 129(PY129), pigment yellow 150(PY150), pigment yellow 185(PY185), phthalocyanine blue (PB15), indanthrone (PB60) and the like.
The heat-generating material in this embodiment may further include a dielectric material for dissolving or dispersing other components in the heat-generating material other than the dielectric material, or for adjusting the ejection performance of the heat-generating material. Specifically, the dielectric material may be suitably selected depending on the actual condition of the heat-generating material, and may be at least one of water, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, triethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, ethyl acetate, butyl acetate, n-butyl ether, petroleum ether, cyclohexane, methyl ethyl ketone, and the like.
The heat release promoting material in this embodiment may further include a dispersant for uniformly dispersing a pigment, solid particles, and the like, which are insoluble in the medium material, into the medium material, and the specific kind thereof is not limited. May be selected from at least one of ANTI-TERRA-U100, BYK-9076, BYK-9077, BYKJET-9131, BYKJET-9142, BYKJET-9151, BYKJET-9171, DISPERBYK-106, DISPERBYK-118 and the like of BYK, TEGO DISPERs 670, Tego DISPERs 610S, Tego DISPERs 650, Tego DISPERs 651, Tego DISPERs 700, Tego DISPERs 715W, Tego DISPERs 735W and the like of TEGO.
The exothermic material of this embodiment may further comprise a surfactant to adjust the surface tension of the exothermic material. The specific type of the surfactant is not limited in this embodiment, and a suitable surfactant can be selected according to the specific composition of the heat-generating material, such as at least one selected from BYK-307, BYK-333, BYK-337, BYK-348, BYK-371, BYK-377, BYK1798, BYK-DYNFET 800N, etc. of BYK, and/or at least one selected from Tego wet 270, TEGO wet 500, Tego Glide 450, etc. of TEGO.
The heat release promoting material in this embodiment may further include a filler, and when the droplets of the heat release promoting material are ejected, the filler having a fine particle size in the droplets is filled in the gaps between the powder particles, thereby reducing shrinkage deformation of the three-dimensional object after melt molding. Specifically, the filler used may be an inorganic filler, and includes at least one of calcium carbonate, barium sulfate, calcium sulfate, kaolin, quartz powder, talc powder, mica powder, montmorillonite, aluminum powder, copper powder, zinc powder, iron powder, graphite, diamond, alumina, zirconia, magnesia, ceramic, carbon, silicate, borate, phosphate, silica, titanium dioxide, and the like.
In the present embodiment, the core particles are melt-molded to obtain a sliced layer or a three-dimensional object, and may specifically be thermoplastic particles and/or thermosetting particles. Wherein the thermoplastic particles may be selected from at least one of polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyacrylonitrile-butadiene-styrene, polyamide, polyimide, polycarbonate, polyurethane, polytetrafluoroethylene, polyethylene terephthalate, polycarbonate, polyetheretherketone, polysulfone, polyethersulfone and polyphenylsulfone particles, for example; the thermosetting plastic particles may be selected from at least one of epoxy resin, unsaturated polyester resin, acrylate resin, phenol resin, cyanate resin, modified polyimide resin, bismaleimide particles, and the like, for example.
Referring further to fig. 1, when the core particles include thermosetting plastic particles, the method for forming a three-dimensional object may further include a step of heating the three-dimensional object, i.e., step S4, so that the formed three-dimensional object is secondarily cured. The heating temperature can be set reasonably according to the material of the core particles, for example, 70-350 ℃. Specifically, the three-dimensional object may be heated by a temperature-raising heating method, such as a temperature-programming method, in which the heating is divided into a plurality of stages, and each stage includes a temperature-raising section and a temperature-holding section that are sequentially performed. The heating mode is adopted, which is helpful for the slow and sufficient reaction of the active groups on the thermosetting plastic particles, which can initiate thermal polymerization, thereby improving the performance of the three-dimensional object.
Referring to fig. 1, the method for forming a three-dimensional object may further include step S3': removing the powder particles which are not melted and formed.
In the actual three-dimensional object manufacturing process, the shape and area of the ejection area (or called printing area) of the heat-promoting material on the powder particle layer are determined according to the layer printing data, and the total area of the powder particle layer should be at least not smaller than the area of the printing area, that is, the heat-promoting material is ejected on a partial area of the powder particle layer, so that the powder particle layer of the partial area is inevitably not involved in the three-dimensional object molding. The part of the powder particles which do not participate in the forming is preferably removed to ensure the quality of the target three-dimensional object.
In particular, the powder particles that are not covered and infiltrated by the exothermic material can be automatically separated by mechanical automation or manually separated, without limitation, such that the resulting green three-dimensional object contains no or substantially no powder particles that are not melt-formed.
Example two
The present embodiment provides a three-dimensional object forming apparatus for implementing the three-dimensional object forming method in the first embodiment, as shown in fig. 4, the three-dimensional object forming apparatus includes at least a powder supplying part 11, a forming platform 12, and a liquid ejection head 13, wherein:
the powder supply part 11 is used for forming a powder particle layer 14 on the forming platform 12;
the liquid ejection head 13 is used to eject the heat-promoting material 15 on the powder particle layer 14 in accordance with the layer print data.
Specifically, the process of printing the three-dimensional object by using the three-dimensional object forming device comprises the following steps: forming a powder particle layer 14 by supplying powder particles, which include core particles and a coating material, on a molding table 12 using a powder supply member 11; then, according to the layer print data, the liquid ejection head 13 selectively ejects the heat-promoting material 15 on the powder particle layer 14, the heat-promoting material 15 covering and penetrating into the powder particle layer 14, and releasing heat by contacting with the covering material; the released heat causes the core particles to melt form, forming a sliced layer 16 on the forming table 12.
After each sliced layer 16 or sliced layers 16 is formed, the forming table 12 is moved down one or more layers thick, and then the next layer or layers of powder supply and heat-promoting material 15 is sprayed, so that the sliced layers 16 are stacked in the z-direction (i.e., in the height direction) as shown in fig. 4, and finally a three-dimensional object is obtained.
The structure of the powder supply member 11 is not particularly limited in the present embodiment, as long as the powder particles can be supplied to the forming table 12 to form the powder particle layer 14 having a desired thickness on the forming table 12. The number of the powder supplying parts 11 may be one, and may be two or more. When the powder supply parts 11 are two or more, they may be provided on different sides of the molding stage 12.
In this embodiment, the forming platform 12 is used to provide support for printing the three-dimensional object, and may be a support platform used in a common 3D printing process. It will be appreciated that the forming table 12 is preferably capable of up and down movement for ease of printing.
In the present embodiment, the type and specification of the liquid ejecting head 13 are not particularly limited, and the liquid ejecting head 13 may be a single-orifice or multi-orifice liquid ejecting head, or may be a piezoelectric head or a thermal bubble head. The number of liquid ejection heads 13 may be determined according to the color requirements of the three-dimensional object to be printed, and the like.
Further, the three-dimensional molding apparatus may further include a preheating part (not shown in fig. 4) for preheating the powder particle layer 14 before the heat-promoting material 15 is sprayed. Specifically, this preheating part can set up in the top of powder grained layer 14, through preheating powder grained layer 14 in advance, can reduce the requirement to the heat that exothermic reaction released, makes the powder granule in the printing area can quick melt the setting, improves the shaping precision.
Referring further to fig. 4, the three-dimensional forming apparatus may further include a control unit 17 for controlling the operation of at least one of the powder supply unit 11, the forming table 12 and the liquid ejecting head 13. Preferably, the control unit 17 controls the powder supply unit 11, the forming table 12, the liquid ejecting head 13, and the preheating unit to operate according to the above steps, thereby completing the automatic printing of the three-dimensional object.
To further illustrate the technical solution of the present invention, the solution of the foregoing embodiment is further described below with reference to specific application examples.
Application example 1
In this application embodiment, according to the three-dimensional object forming method in the first embodiment and by using the three-dimensional object forming device in the second embodiment, the three-dimensional object is processed and manufactured, which specifically includes the following steps:
first, the control part 17 controls the powder supply part 11 to supply powder particles on the molding stage 12 to form the powder particle layer 14 having a thickness of about 50 μm. The core particle of the powder particle is polyacrylonitrile-butadiene-styrene (ABS), the coating material is glucose, and the thickness of the coating layer is 100 nm.
The powder particles are prepared by coating glucose on the surface of polyacrylonitrile-butadiene-styrene particles by adopting a spray drying method. The main process is as follows: dissolving glucose in water to obtain a coating solution; suspending ABS powder in an atomizing cavity; and adding glucose coating liquid into the atomization cavity to atomize the coating liquid in the atomization cavity, wherein the atomized coating liquid is coated on the surface of the ABS particles to form a coating layer.
Next, the control part 17 controls the liquid ejection head 13 to eject the heat generation promoting material 15 on the powder particle layer 14 in accordance with the layer print data, the heat generation promoting material 15 covering at least a part of the powder particle layer 14 and penetrating into the powder particle layer 14.
The heat-promoting material 15 contains an oxidant potassium permanganate and contacts with the coating material glucose to generate an oxidation-reduction reaction to release heat, so that the core particles are melted and molded to form a slice layer 16;
finally, the control part 17 controls the forming platform 12 to descend by a height of one layer thickness, the forming process of the next sliced layer 16 is continued, and the formed sliced layers 16 are overlapped layer by layer to finally form the target three-dimensional object.
Application example 2
The difference between the application example and the application example 1 is that: in the embodiment of the present application, the core particles of the powder particles are cyanate ester resin, the coating material is hyperbranched acrylate, the thickness of the coating layer is 1300nm, and the thickness of the powder particle layer 14 is 400 μm.
In the application embodiment, the hyperbranched acrylate particles are distributed on the surfaces of the cyanate ester resin particles by adopting a spray drying method. The main process is as follows: dispersing hyperbranched acrylate particles in water to obtain a dispersion liquid; suspending cyanate resin powder in an atomization cavity; adding hyperbranched acrylic ester dispersion liquid into the atomization cavity to atomize the dispersion liquid in the atomization cavity, and coating the atomized dispersion liquid on the surfaces of the cyanate ester resin particles to form a hyperbranched acrylic ester particle distribution layer.
Next, the control part 17 controls the liquid ejection head 13 to eject the heat generation promoting material 15 on the powder particle layer 14 according to the layer print data, the heat generation promoting material 15 covering at least a part of the powder particle layer 14 and penetrating into the powder particle layer 14; the exothermic material 15 includes Azobisisobutyronitrile (AIBN) initiator and filler silica.
The heat-promoting material 15 is contacted with the coating material, and the hyperbranched acrylic ester reacts under the initiation of the azodiisobutyronitrile initiator to release heat, so that the core particles are melted and molded to form a slice layer 16;
secondly, the control part 17 controls the forming platform 12 to descend by a height of one layer thickness, the forming process of the next sliced layer 16 is continued, and the formed sliced layers 16 are overlapped layer by layer to finally form a three-dimensional object;
and finally, placing the formed three-dimensional object in a heating furnace, raising the temperature to 200 ℃, heating the three-dimensional object, activating active groups in the cyanate ester resin particles, and further carrying out curing reaction to obtain the target three-dimensional object with obviously improved mechanical properties.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (20)
1. A method of forming a three-dimensional object, comprising the steps of:
forming a layer of powder particles, wherein the powder particles used to form the layer of powder particles comprise core particles and a coating layer coated on at least a portion of the surface of the core particles;
spraying heat-promoting materials on the powder particle layer according to layer printing data, enabling the heat-promoting materials to be in contact with a coating material for forming the coating layer to release heat, and enabling the core particles to be melted and formed under the action of the heat to form a sliced layer;
and repeating the steps from the powder particle layer formation to the slice layer formation, and superposing the obtained multiple slice layers layer by layer to form the three-dimensional object.
2. The method according to claim 1, wherein the heat-generating material contains an initiator, and the coating material reacts to generate heat by the initiation of the initiator;
or at least one of the heat-generating material and the coating material contains a catalyst, and the other of the heat-generating material and the coating material reacts under the catalysis of the catalyst to generate heat;
or, one of the heat-generating material and the coating material contains an oxidizing agent, and the other contains a reducing agent, and the oxidizing agent and the reducing agent undergo a redox reaction to generate heat;
alternatively, the coating material contains a component that can be dissolved in the heat-generating material to generate heat.
3. The method of claim 2, wherein the heat-generating material contains an initiator; the coating material contains a compound with a vinyl group.
4. The method of claim 3, wherein the initiator is selected from at least one of benzoyl peroxide, dicumyl peroxide, cyclohexanone peroxide, potassium persulfate, ammonium persulfate, azobisisobutyronitrile, and azobisisoheptonitrile;
the coating material contains at least one of polyester acrylate, polyurethane acrylate, epoxy acrylate, hyperbranched acrylate, unsaturated polyester and tris (2-hydroxyethyl) isocyanurate triacrylate.
5. The method of claim 2, wherein the heat-generating material comprises hydrogen peroxide, and the cladding material comprises manganese dioxide; alternatively, the first and second electrodes may be,
the heat-promoting material contains a metal catalyst, the coating material contains a compound with hydroxyl, and the compound with hydroxyl reacts under the action of the metal catalyst in the presence of oxygen to release heat.
6. The three-dimensional object forming method according to claim 5, wherein the metal catalyst is selected from at least one of copper, silver, and palladium; the compound with hydroxyl is selected from at least one of polyvinyl alcohol, polyether polyol, polyester polyol and hydroxyl acrylic resin.
7. The three-dimensional object forming method according to claim 2, wherein the oxidizing agent is selected from at least one of potassium permanganate, potassium perchlorate, ammonium nitrate, ammonium perchlorate, ferric trichloride, and potassium dichromate; the reducing agent is at least one selected from sucrose, sorbitol, mannitol, glucose and fructose.
8. The method of forming a three-dimensional object according to claim 2, wherein the heat-promoting material is water or a solution containing water; the coating material contains at least one hydroxide; the hydroxide is capable of releasing heat by dissolving in water or the solution containing water.
9. The method of claim 8, wherein the hydroxide is selected from at least one of lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, and aluminum hydroxide.
10. The method of forming a three-dimensional object according to any one of claims 1 to 9, wherein the exothermic material further contains at least one of a filler, a colorant, a surfactant, a dispersant, and a dielectric material; wherein the dielectric material is used to dissolve or disperse other components of the exothermic material.
11. The method of claim 1, wherein the coating layer is a continuous film layer covering part or all of the surface of the core particle, wherein the coating layer has a thickness of 50 to 1500nm, and the powder particle has a diameter of 1 to 300 μm; alternatively, the first and second electrodes may be,
the coating layer comprises a plurality of discrete beads surrounding the surface of the inner core particle, wherein the diameter of the beads is 50-1500 nm, and the diameter of the powder particle is 1-300 μm.
12. The method of forming a three-dimensional object according to any one of claims 1 to 9, wherein the core particles comprise thermoplastic particles and/or thermosetting particles.
13. The method of claim 12, wherein the thermoplastic particles are selected from at least one of polyethylene, polyvinyl chloride, polypropylene, polystyrene, polyacrylonitrile-butadiene-styrene, polyamide, polyimide, polycarbonate, polyurethane, polytetrafluoroethylene, polyethylene terephthalate, polycarbonate, polyetheretherketone, polysulfone, polyethersulfone, and polyphenylsulfone particles;
the thermosetting plastic particles are selected from at least one of epoxy resin, unsaturated polyester resin, acrylate resin, phenolic resin, cyanate resin, modified polyimide resin and bismaleimide particles.
14. The method of claim 12, wherein the core particles comprise thermoset plastic particles, the method further comprising the step of heating the three-dimensional object; the heating temperature is 70-350 ℃.
15. The three-dimensional object forming method according to any one of claims 1 to 9, further comprising, before spraying heat-promoting material on the powder particle layer: preheating the layer of powder particles.
16. The method of claim 15, wherein the temperature of the preheating is below the melting point of the powder particles.
17. The method of forming a three-dimensional object according to any one of claims 1 to 9, wherein the layer of powder particles is divided into a plurality of zones, and the volumes of the heat-promoting material sprayed on the different zones are the same or different.
18. A three-dimensional object forming apparatus for carrying out the three-dimensional object forming method according to any one of claims 1 to 17, characterized by comprising at least a powder supply part, a forming stage, and a liquid ejection head, wherein:
the powder supply part is used for forming the powder particle layer on the forming platform;
the liquid ejection head is configured to eject the heat-promoting material on the powder particle layer according to layer print data.
19. The three-dimensional object forming apparatus according to claim 18, further comprising a preheating part for preheating the powder particle layer.
20. The three-dimensional object forming apparatus according to claim 18 or 19, further comprising a control means for controlling operation of at least one of the powder supply means, the forming table and the liquid ejection head.
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| PCT/CN2020/081532 WO2020248653A1 (en) | 2019-06-11 | 2020-03-27 | Three-dimensional object prototyping method, and prototyping device |
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Application publication date: 20201211 |