CN104448744B - A kind of raw material for rapid shaping and corresponding three-dimensional fast shaping method - Google Patents
A kind of raw material for rapid shaping and corresponding three-dimensional fast shaping method Download PDFInfo
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Abstract
The method of the compound method that the technical scheme of the present invention comprises a kind of rapid shaping raw material based on colloid and a kind of rapid shaping of utilizing this raw material to develop. Described rapid shaping raw material, it is characterised in that it mainly comprises: ultra-fine powder materials 20% ~ 75%, dispersion agent 0.05% ~ 20%, flocculation agent 0.05% ~ 10%, thickening material 0.05% ~ 5%, flow promotor 0.01% ~ 5%, shaping assistant 0% ~ 10%. Ultrafine powder can by multiple material preparations such as polymkeric substance, pottery and metals. Because this kind of rapid shaping raw material has water-based, can the characteristic such as room temperature processing, therefore impart corresponding quick molding method environmental friendliness, physiologically acceptable, the advantage such as flexible and changeable. This quick molding method can be suitable at average family or require that eco-friendly occasion uses, and is applicable to have the manufacture of bio-active products, is also particularly suitable for needing the rapid shaping of the inner and outside structure three-dimensional object of control.
Description
Technical field
The invention belongs to material field, specifically a kind of raw material for rapid shaping and corresponding three-dimensional fast shaping method.
Background technology
The exploitation of rapid shaping or three-dimensional printing technology indicates new product design and manufactures the beginning in revolution epoch. Different from traditional production method, rapid shaping can directly make a project organization from three-dimensional computer aided design (CAD) model, and without the need to any mould. The material processing characteristics that adds of rapid shaping technique is make to have complicated three-dimensional internal space structure, Functionally Graded Materials, and other specialty products that traditional batch machining production method can not be used to make provide possibility.
Current rapid prototyping system can be divided into three classes, photoetching, layer pressure, and extruding technology, the process forming object primarily of material relies on optionally to solidify (photoetching), is directly stacked into the two-dimensional surface (layer pressure) of previously establishment, or by a dimension drip or silk is piled up (extruding) and is distinguished.
Stereolithography technology (SLA) technology described in U.S. Patent number 4575330, it is by once forming one layer of polymeric with certain Geometry focus to liquid medium surface with the illumination of specific wavelength and intensity, then support platform declines the thickness of one layer, and liquid covers solid surface subsequently. It is layering just can form a 3D solid by constantly repeating process above. The normally photo curable polymer monomer of its liquid medium used; Illumination is visible ray or uv-radiation normally. This kind of item technology can only use photocurable materials.
At the selective laser sintering (SLS) described by U.S. Patent number 4863538, it is another kind of stereolithography technology.It makes object by the laser scanning one layer of heat fused powder computerizedd control. The characteristic dimension of SLS depends on available raw material powder particle size, is usually greater than 50 microns.
Describing a kind of three-dimensional printing technology based on powder (3DP) at U.S. Patent number 5204055, this technology utilizes a roller polymer powder once to push a floor to manufacture top, room. Then splash head is with a kind of two dimension figure atomizing of liquids tackiness agent to powder surface, is gluedd joint by the powder of spraying area, forms object layer. Being similar to SLS, the characteristic dimension of 3DP also depends on powder size. In addition, 3DP needs to rely on use organic solvent usually to dissolve bonding polymer powder.
It is by plastic wire heating and melting is extruded formation drop from a nozzle in melting extrusion moulding (FDM) technology described by U.S. Patent number 5121329, then it is piled into one layer of object according to certain figure. The plastics extruded are met cold-curing and are then bonded together with next layer. The problem of this kind of technology is material may degrade at melting process, material property or surrounding environment is impacted.
WO97-11835 and WO97-11837 patent describes multiple jets shaping (MJM) technology. Changing technology is the equipment utilizing and being similar to ink jet-print head, and drop is sprayed by selectivity from multiple spray orifice, is in layer piled into three-dimensional body. Normally there is a kind of special polymkeric substance of very low fusing point for shaping material. Other technology based on nozzle also comprise the liquid polymers utilizing and can solidifying under ultraviolet light, by nozzle print pattern from level to level, and form the method for three-dimensional body with photocuring.
Due to the manufacturing capacity of its handiness and customization, rapid shaping or three-dimensional printing technology are not only applied to precision casting widely, Modelling, product original shape, the fields such as fine arts model, and it is used to different biologies and the range of application of medical science, comprise the customized production from surgery planning model, Using prosthesis, and the other field of medical science. Then for the application of biomedicine, it usually needs the three-dimensional body of formation has good biocompatibility and certain biological function. Such as making tissue engineering bracket guides the cell of implantation to grow into correct geometry, just need the material used by quick molding method must have good biocompatibility with, the ability of controllable biodegradable, even can carry out the release of the cells grown factor according to set Time and place. Unfortunately, rapid shaping techniques all at present all has in generation and there is intrinsic difficulty and limitation in the process of biological activity object: (1) material is limited to light-cured resin, (2) poisonous formed material, (3) poisonous organic solvent is contacted, (4) very high processing temperature (5) requires that formed material has the ability of chemically crosslinked, and (6) physical strength is weak and structural stability is poor. Although such as can adopt can the bioavailable polymer of biological degradation, such as poly-(lactic acid) (PCL), PLGA (PLGA) carries out rapid shaping, but adds and must dissolve in organic solvent man-hour, this it is possible to can stay residual toxic substance integral part. Also having rapid shaping technique can process when water-based and room temp, but material can be limited to again the polymkeric substance only having water-soluble polymers and hydrogel or fusing point very low, the usual intensity of these materials is very poor, and molecular structure not malleable. If photocuring reaction can be there is in the material requiring rapid shaping, or chemical crosslink reaction etc., that selection will be less. Therefore, the needs of Material selec-tion and processing conditions gentleness widely to be solved, it is necessary to develop new material prescription technology and special complete processing addresses this problem.
Summary of the invention
The method of the compound method that the technical scheme of the present invention comprises a kind of rapid shaping raw material based on colloid and a kind of rapid shaping of utilizing this raw material to develop.Because this kind of rapid shaping raw material has water-based, can the characteristic such as room temperature processing, therefore impart corresponding quick molding method environmental friendliness, physiologically acceptable, the advantage such as flexible and changeable.
This rapid shaping raw material is characterised in that basic containing composition below:
Ultra-fine powder materials 20% ~ 75%,
Dispersion agent 0.05% ~ 20%
Flocculation agent 0.05% ~ 10%
Thickening material 0.05% ~ 5%
Flow promotor 0.01% ~ 5%
Shaping assistant 0% ~ 10%
Other are water;
Described ultrafine powder particle mixes the main body of composition formed material with water, gives material water-based, the workability of low temperature and the good mechanical properties of formed material. The average particle size of described ultrafine powder particle is at 1 nanometer to 100 microns, it is preferable to 10 nanometers to 1 micron. Described ultrafine powder particle can be organic polymer powder, it is also possible to be inorganic ceramic powder or metal-powder. Described organic polymer refers to all non-soluble polymers that can be processed into ultrafine powder, comprise the poly(lactic acid) (PLA) of degradable, poly lactic-co-glycolic acid (PLGA), poly-epsilon-caprolactone (PCL), PPDO (PPDO), PTMC (PTMC), chitosan and nondegradable Alathon and multipolymer, alfon and multipolymer, polyvinylidene dichloride, polyacrylic acid homopolymer and multipolymer, epoxy resin homopolymer and multipolymer, polyester, styrene homopolymers and multipolymer. Inorganic ceramic material refers to all water-insoluble stupaliths that can be processed into ultrafine powder, comprises aluminum oxide, magnesium oxide, zirconium white, boron oxide, titanium oxide, sodium oxide, silicon carbide, norbide, silicon nitride, boron nitride, calcium phosphate. Metal material refers to all water-insoluble metallic substance that can be processed into ultrafine powder, comprises iron, tungsten, molybdenum, copper, cobalt, nickel, titanium, tantalum, aluminium, tin, lead. Described ultrafine powder with comprising spraying dry, can pulverize grinding, collosol and gel (Sol-gel), the method preparations such as chemical gas phase reaction (CVD).
Described dispersion agent usually has hydrophilic radical simultaneously and hates water group, mainly act as the surface being adsorbed on ultrafine powder, forms static charge or space steric hindrance, promotes that ultrafine powder and water form stable colloid. The processing aid of one type is ionic, comprises containing-N+��-S+��-P+The water-soluble polymers of cation group, and containing-COO-��-SO4 2-��-SiO3 2-��-PO4 3-��-CO3 2-��-SO3 2-��-S2O3 2-��-S2-��-Cl-��-Br-��-I-��-NO3 -��-NO2 -The water-soluble polymers of anionic group. The processing aid of one type is non-ionic type, comprise 8 ~ 14 carbon polyoxyethylenated alcohol, 8 ~ 14 carbon alcohol polyethenoxy ethers, polyoxyethylene polyoxypropylene ether multipolymer, polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyvinylamine, polyacrylamide copolymer, poly-N, N-dimethyl propylene acid amides, poly N-isopropyl acrylamide, polymethyl acid copolymer.
Described thickening material mainly act as the viscosity increasing colloid, is beneficial to the forming process in later stage. Comprise 1 ~ 3 carbon alkylcellulose, hydroxyl 1 ~ 3 carbon alkoxy cellulose, Xylo-Mucine, sodium alginate, chitin, agar.
It is that hydrogen bond etc. are cross-linked by forming ionic linkage that described flocculation agent mainly acts on, and space steric effect or the part of reduction dispersion agent to a certain degree neutralize its surface charge, make colloid that reversible cohesion occur. One class flocculation agent is ionic, comprise the free H+ solion that contains with above-mentioned dispersion agent opposite charges and (comprise hydrochloric acid, nitric acid, sulfuric acid, acetic acid), (comprise ammoniacal liquor containing free OH-ion solution, sodium hydroxide, potassium hydroxide), containing negatively charged ion or cationic water-soluble polymers (identical with above-mentioned ionic dispersant, but opposite charge). Containing the high valence ion of boron, calcium, magnesium, iron, chromium, zirconium, manganese high valence ion and its corresponding oxide boric acid, chromic acid, mangaic acid. Another class flocculation agent is non-ionic type, comprises formaldehyde, glutaraldehyde.
It is mobility by improving material that described flow promotor mainly acts on, levelling property, and the bubble that disappears waits effect, promotes the flowing of formed material and eliminates the tangerine peel of processing idiosome, the defects such as shrinkage cavity.Described flow promotor comprises polysiloxane, poly-oxygen ethylsiloxane, 1 ~ 14 carbon alkyl polyoxyethyl propyl siloxanes, fluorocarbon compound modified polyacrylic ester.
It is the temperature being reduced aftertreatment by the minimum film-forming temperature of reduction colloid that described shaping assistant mainly acts on, and is conducive to the medicine of material and temperature sensitive or the combination of biomolecules. Described shaping assistant comprises glyceryl diacetate (GDA) glycerine triacetate (GTA), triethyl citrate (TEC), acetyltriethyl citrate (ATEC) and Uniflex DBS (DBS) and polyoxyethylene glycol (PEG).
The preparation of this rapid shaping raw material is made up of the following steps, main point of dispersion and two stages of cohesion.
1. by dispersion agent, flow promotor, and shaping assistant is dissolved in water, then joins in solution by ultrafine powder, it may also be useful to dispersal mechanism standby become colloid.
2. thickening material and flocculation agent are dissolved in water or directly join in colloid, it may also be useful to dispersion machine or three-roll grinder prepare the flocculated colloid of final paste body shape, be i.e. described rapid shaping raw material.
Agglomeration phase is to giving the good visco-elasticity of material and later stage anti-adaptability to changes has keying action. What cohesion degree excessively little (Fig. 1, A) or excessive (Fig. 1, B) were unfavorable for raw material extrudes with shaping, and only appropriate cohesion degree (Fig. 1, B) just can obtain reliable finished product. It is noted that except dispersion agent and flocculation agent needs successively add, other thickening material, flow promotor, shaping assistant can in dispersion and the different steps condensed once adds or gradation adds. Under special circumstances, dispersion agent (such as polyoxyethylene polyoxypropylene ether multipolymer) self can condense under temperature variation, and without the need to additionally adding flocculation agent.
Because the physiologically acceptable processing environment of water-based, low temperature, medicine and bioactive molecules can be integrated into easily in rapid shaping raw material and process, and need not worry to be subject to the factor such as high temperature, organic solvent and go bad. Therefore small-molecule drug or macromole peptide and protein can being dissolved in water, or be wrapped in ultra-fine polymer powder, be distributed in lotion, preparation has can the material of medicine controlled releasing.
According in embodiments of the invention, for perform rapid shaping first-selected equipment as shown in Figure 2. The motion controller (X, Y, Z and A axle) that this type printer comprises four axles and the mass transport module 31 being fixed on Z axle motion platform 30. Four axis controller control mass transport modules 31 move in X, Y, Z axis, and rotate at A axle. Mass transport module 31 includes the distributor 32,33,34 that three store different components rapid shaping raw material, extrudes from nozzle by certain speed for controlling raw material.
The quick molding method of the present invention is mainly following 4 steps: (1) utilizes computer aided design (CAD) (CAD) to create the model that comprises material and spatial information, then the corresponding machining locus of Software Create is utilized, (2) prepare rapid shaping raw material as stated above and be encased in the distributor of aforesaid device (3) by rapid prototyping system drive mass transport module raw material is extruded from nozzle according to certain figure, stacking formation idiosome from level to level. (4) idiosome is put into baking oven heating be dried and sinter and obtain final 3D solid finished product. Fig. 3 is typical manufacturing process flow diagram.
This quick molding method is suitable at average family or requires that eco-friendly occasion uses.Because the Rapid Prototyping Process described in this patent relies on rheological characteristics completely, can carry out when room temperature and water-based, so organic solvent can not be produced, the hazardous and noxious substances such as high temperature degradation product, and process and post-processing temperature low, the scald problem such as murder by poisoning can not be there is.
This quick molding method also is applicable to have the manufacture of bio-active products. Because the characteristic of colloid, the shaping and aftertreatment sintering temperature of ultrafine powder, usually well below the fusing point of material, for some polymer materials, it is even possible that be solidified into continuous solid in room temperature, obtains final physical strength. Additionally by aftertreatment, it is also possible to the sintering degree of control idiosome, makes finished product have the character of porous, ensure that the control of follow-up integrated medicine is released.
This quick molding method also is particularly suitable for needing the rapid shaping of the inner and outside structure three-dimensional object of control. Because the rapid shaping raw material of the present invention has good visco-elasticity, so having the ability crossing over certain distance, so may be used for making entity (Fig. 4 of vesicular structure, A) different distributors is utilized to load not congruent raw material, different raw materials can be extruded according to different tracks, form special pattern (Fig. 4, B). Also can process on mixing limit, limit, form gradient material (Fig. 4, C). Utilize the function that nozzle can rotate around A axle, it is also possible to tilt certain angle, form the entity (Fig. 4, D) with the gradient not having step effect.
Accompanying drawing explanation
Fig. 1 is that cohesion degree is to shaping effect diagram;
Fig. 2 is the first-selected equipment drawing for rapid shaping of the present invention;
Fig. 3 is typical rapid shaping production process charts;
Fig. 4 is the entity type map utilizing the present invention to process;
In figure, 10 equipment base plates; 30 Z axle motion platforms; 31 mass transport modules; 32 cloth performer A; 33 cloth performer B; 34 cloth performer C.
Embodiment
Embodiment 1
Get 50g poly(lactic acid) ultrafine powder (median size 1 micron), join in sodium alginate (anionic water-soluble polymer) solution that 50g contains 1% weight ratio, disperse energetically to obtain colloid in 10 minutes with ultrasonic grinding machine, form the rapid shaping raw material of 50% solid content. After being idiosome with this raw material rapid shaping, put into baking oven drying and sintering 10 minutes at a temperature of 60 degrees c, obtain finished product.
Embodiment 2
Get 50g polyethylene-vinylformic acid ultrafine powder (median size 1 micron), join in sodium alginate (anionic water-soluble polymer) solution that 50g contains 2% weight ratio, disperse energetically to form colloid in 10 minutes with ultrasonic grinding machine, then adding a small amount of 10% salt acid for adjusting pH is 5 make colloidal gel, by three-roll grinder homogenizing 3 times, finally obtain the rapid shaping raw material of 50% solid content. After being idiosome with this raw material rapid shaping, put into baking oven drying and sintering 10 minutes at the temperature of 30 degrees Celsius, obtain finished product.
Embodiment 3
Being mixed after example 2 rapid shaping raw material forms colloid by 0.1g bovine serum albumin (BSA), then carry out shaping according to the method for example 2 and make finished product, this finished product has the ability that bovine serum albumin is released in control.
Embodiment 4
Get 50g polyoxygenated titanium ultrafine powder (median size 0.02 micron), join in cold polyoxyethylene poly-oxygen propylene aether multipolymer (non-ionic water-soluble polymer) solution containing 2% weight ratio of 50g, 10min is disperseed to form colloid with ultrasonic dispersing machine, then it is warmed up to room temperature and forms lotion, by three-roll grinder homogenizing 3 times, finally obtain the rapid shaping raw material of 50% solid content.After being idiosome with this raw material rapid shaping, put into baking oven drying and sintering 1 hour at the temperature of 1200 degrees Celsius, obtain finished product.
Embodiment 5
Get 50g titanium metal ultrafine powder (median size 0.2 micron), join in cold polyacrylic acid (anionic water-soluble polymer) solution containing 1% weight ratio of 49.5g, 10min is disperseed to form colloid with ultrasonic dispersing machine, then add 0.5g polymine (cationic water-soluble polymer) and form lotion to room temperature, by three-roll grinder homogenizing 3 times, finally obtain the rapid shaping raw material of 50% solid content. It is respectively charged in different syringes with the raw material in this raw material and example 4, after being idiosome according to the common rapid shaping of certain pattern, puts into baking oven drying and sintering 1 hour at the temperature of 1200 degrees Celsius, obtain finished product. This finished product is for having pottery and metal composite gradient material.
The foregoing is only the better embodiment of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. done within the spirit and principles in the present invention, are all included within protection scope of the present invention.
Claims (8)
1. the rapid shaping raw material based on colloid, it is characterised in that it mainly comprises: ultra-fine powder materials 20% ~ 75%, dispersion agent 0.05% ~ 20%, flocculation agent 0.05% ~ 10%, thickening material 0.05% ~ 5%, flow promotor 0.01% ~ 5%, shaping assistant 0% ~ 10%, other are water, described rapid shaping raw material, and its preparation method is as follows: 1) by dispersion agent, flow promotor, it is dissolved in water with shaping assistant, then ultrafine powder is joined in solution, it may also be useful to dispersal mechanism standby one-tenth colloid; 2) thickening material and flocculation agent are dissolved in water or directly join in colloid, dispersion machine or three-roll grinder is used to prepare the described rapid shaping raw material of final paste body shape, the average particle size of described ultrafine powder is 0.1 nanometer to 10 microns, and ultrafine powder refers to be processed into the powder that the water-insoluble organic polymer of ultrafine powder, inorganic ceramic or metallic substance are formed.
2. rapid shaping raw material as claimed in claim 1, it is characterised in that described dispersion agent comprises containing-N+��-S+, or-P+The water-soluble polymers of cation group, containing-COO-��-SO4 2-��-SiO3 2-��-PO4 3-��-CO3 2-��-SO3 2-��-S2O3 2-��-S2-��-Cl-��-Br-��-I-��-NO3 -, or-NO2 -The water-soluble polymers of anionic group, 8 ~ 14 carbon polyoxyethylenated alcohol, 8 ~ 14 carbon alcohol polyethenoxy ethers, polyoxyethylene polyoxypropylene ether multipolymer, polyvinyl alcohol, Polyvinylpyrolidone (PVP), polyvinylamine, polyacrylamide copolymer, poly-N, N-dimethyl propylene acid amides, poly N-isopropyl acrylamide, polymethyl acid copolymer.
3. rapid shaping raw material as claimed in claim 1, it is characterised in that described flocculation agent comprises containing free H+Solion, containing free OH-Solion, or containing negatively charged ion or cationic water-soluble polymers, or formaldehyde, glutaraldehyde.
4. rapid shaping raw material as claimed in claim 1, it is characterized in that described thickening material comprises 1 ~ 3 carbon alkylcellulose, hydroxyl 1 ~ 3 carbon alkoxy cellulose, Xylo-Mucine, sodium alginate, chitin, agar, described flow promotor comprises polysiloxane, poly-oxygen ethylsiloxane, 1 ~ 14 carbon alkyl polyoxyethyl propyl siloxanes, fluorocarbon compound modified polyacrylic ester, described shaping assistant comprises glyceryl diacetate GDA, glycerine triacetate GTA, triethyl citrate TEC, acetyltriethyl citrate ATEC, Uniflex DBS DBS or polyoxyethylene glycol PEG.
5. rapid shaping raw material as claimed in claim 1, it is characterised in that: small-molecule drug or macromole peptide and protein being dissolved in water, or be wrapped in ultra-fine polymer powder, be distributed in lotion, preparation has can the material of medicine controlled releasing.
6. utilize rapid shaping raw material as claimed in claim 1 to carry out the method for rapid shaping, comprise the following steps: (1) utilizes computer aided design (CAD) (CAD) to create the model that comprises material and spatial information, then the corresponding machining locus of Software Create is utilized, (2) prepare rapid shaping raw material as stated above and it is encased in the distributor of equipment, (3) mass transport module is driven to be extruded from nozzle according to certain figure by raw material by rapid prototyping system, stacking formation idiosome from level to level, (4) idiosome is put into baking oven heating be dried and sinter and obtain final 3D solid finished product.
7. quick molding method as claimed in claim 6, it is characterised in that: the condition of the course of processing is room temperature and water-based.
8. quick molding method as claimed in claim 6, it is characterised in that: by controlling the sintering degree of aftertreatment, the porosity of control finished product.
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| CN104997643B (en) * | 2015-07-19 | 2019-03-08 | 谢宝军 | A kind of quick molding method for the production of full porcelain mouth mending material |
| CN108602727B (en) * | 2015-12-04 | 2021-02-26 | 高雄医学大学 | Method for manufacturing 3D printed article in lamination mode |
| CN107365158B (en) * | 2017-08-28 | 2020-08-25 | 武汉理工大学 | Structural ceramic paste for extrusion type 3D printing and preparation method thereof |
| CN108245432B (en) * | 2018-02-09 | 2021-05-14 | 嘉兴学院 | Additive manufacturing method of all-ceramic dental prosthesis |
| TWI722423B (en) * | 2018-04-27 | 2021-03-21 | 日商大金工業股份有限公司 | Powder for shaping |
| CN108727028B (en) * | 2018-05-11 | 2020-08-07 | 航天特种材料及工艺技术研究所 | Method for manufacturing rigid heat-insulating tile blank by additive manufacturing method |
| CN110698571A (en) * | 2019-10-10 | 2020-01-17 | 华南农业大学 | Method for chemically treating crab shell powder, reinforced polylactic acid 3D printing material and preparation method thereof |
| CN113563055A (en) * | 2021-08-13 | 2021-10-29 | 深圳协同创新高科技发展有限公司 | High-precision ceramic 3D printing paste and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093646A (en) * | 2010-10-29 | 2011-06-15 | 华南理工大学 | Material for rapid three dimensional printing forming and preparation method thereof |
| CN103936428A (en) * | 2014-03-13 | 2014-07-23 | 济南大学 | Preparation method of rapid molding powder material used for three dimensional printing |
| CN104057084A (en) * | 2013-03-20 | 2014-09-24 | 江苏天一超细金属粉末有限公司 | Water-soluble ink for printing metal and ceramic products |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102093646A (en) * | 2010-10-29 | 2011-06-15 | 华南理工大学 | Material for rapid three dimensional printing forming and preparation method thereof |
| CN104057084A (en) * | 2013-03-20 | 2014-09-24 | 江苏天一超细金属粉末有限公司 | Water-soluble ink for printing metal and ceramic products |
| CN103936428A (en) * | 2014-03-13 | 2014-07-23 | 济南大学 | Preparation method of rapid molding powder material used for three dimensional printing |
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