CN104448744A - Raw material for rapid molding and corresponding three-dimensional rapid molding method - Google Patents
Raw material for rapid molding and corresponding three-dimensional rapid molding method Download PDFInfo
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- CN104448744A CN104448744A CN201410722130.6A CN201410722130A CN104448744A CN 104448744 A CN104448744 A CN 104448744A CN 201410722130 A CN201410722130 A CN 201410722130A CN 104448744 A CN104448744 A CN 104448744A
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Abstract
The invention provides a preparation method of a raw material for rapid molding based on a colloid and a rapid molding method developed by use of the raw material. The raw material for rapid molding is characterized by mainly comprising 20%-75% of superfine powder material, 0.05-20% of dispersant, 0.05%-10% of flocculant, 0.05%-5% of thickener, 0.01%-5% of flow promoting agent and 0%-10% of molding promoter, wherein the superfine powder can be prepared from a plurality of materials such as a polymer, ceramics and a metal. As the raw material for rapid molding has the characteristics of aquosity, room-temperature processibility and the like, the corresponding rapid molding method has the advantages of environmental friendliness, biocompatibility, flexibility and variability, and the like. The rapid molding method is suitable for ordinary families or occasions requiring environmental friendliness, suitable for manufacturing products with biological activity and also especially suitable for rapid molding three-dimensional objects needing to be controlled in internal and external structures.
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 three classes, photoetching, lamination, and extruding technology, forming the process of object primarily of material is rely on optionally to solidify (photoetching), is directly stacked into the two-dimensional surface (lamination) previously created, or by one dimension drip or silk is piled up (extruding) and is distinguished.
Stereo lithography (SLA) technology described in U.S. Patent number 4575330, 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 deck, and liquid covers solid surface subsequently.Be layering by the process constantly repeated above and just can form a 3D solid.The normally photo curable polymer monomer of its liquid medium used; Illumination is visible ray or uv-radiation normally.Photocurable materials can only be used in this item technology.
Selective laser sintering (SLS) described by U.S. Patent number 4863538 is another kind of stereo lithography.It makes object by the laser scanning one deck heat fused powder computerizedd control.The characteristic dimension of SLS depends on available raw material powder particle size, is usually greater than 50 microns.
Describe 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 be pushed one deck to manufacture top, room.Then splash head is with a kind of X-Y scheme atomizing of liquids tackiness agent to powder surface, is gluedd joint by the powder of spraying area, forms object layer.Be similar to SLS, the characteristic dimension of 3DP also depends on powder size.In addition, 3DP needs dependence with an organic solvent to dissolve bonding polymer powder usually.
Shaping (FDM) technology that melt extrudes described by U.S. Patent number 5121329 is by plastic wire heating and melting being extruded formation drop from a nozzle, being then piled into one deck object according to certain figure.The plastics extruded are met cold-curing and are then bonded together with lower one deck.The problem of this technology is material may degrade at melting process, impacts material property or surrounding environment.
Multiple jets shaping (MJM) technology is described in WO 97-11835 and WO 97-11837 patent.Changing technology is utilize the equipment being similar to ink jet-print head, and drop sprays from multiple spray orifice by selectivity, is in layer piled into three-dimensional body.Normally there is for shaping material a kind of special polymkeric substance of low-down fusing point.Other technology based on nozzle also comprise the liquid polymers utilizing and can solidify 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 be used to different biologies and the range of application of medical science, comprise the customized production from surgery planning model, Using prosthesis, and medical science applied other field.Then for biomedical application, the three-dimensional body formed usually is needed to have good biocompatibility and certain biological function.Such as make the geometry that tissue engineering bracket guides the Growth of Cells of implantation to become correct, 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 the process of biological activity object in generation and there is intrinsic difficulty and limitation: (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 biodegradable bioavailable polymer can be adopted, as poly-(lactic acid) (PCL), PLGA (PLGA) carries out rapid shaping, but adds and must dissolve in organic solvent man-hour, and this just may leave the integral part of residual toxic substance.Also have rapid shaping technique can process under the condition of water-based and room temp, but material can be limited to again and only has the low-down polymkeric substance of water-soluble polymers and hydrogel or fusing point, the usual intensity of these materials is very poor, and molecular structure not malleable.If require that the material of rapid shaping photocuring reaction can occur, or chemical crosslink reaction etc., that selection will be less.Therefore, the needs of Material selec-tion and processing conditions gentleness widely being solved, solving this problem with regard to needing the new material prescription technology of exploitation and special complete processing.
Summary of the invention
The method of the compound method that 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 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.
The feature of this rapid shaping raw material is 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 forming formed material with water, give 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, in 1 nanometer to 100 micron, is preferably 10 nanometers to 1 micron.Described ultrafine powder particle can be organic polymer powder, also can be inorganic ceramic powder or metal-powder.Described organic polymer refers to all non-soluble polymers that can be processed into ultrafine powder, comprise degradable poly(lactic acid) (PLA), 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 non-water soluble metal materials 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 has hydrophilic radical and hydrophobic group usually simultaneously, and Main Function is the surface being adsorbed on ultrafine powder, forms static charge or sterically hindered, 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
-,-SO
4 2-,-SiO
3 2-,-PO
4 3-,-CO
3 2-,-SO
3 2-,-S
2o
3 2-,-S
2-,-Cl
-,-Br
-,-I
-,-NO
3 -,-NO
2 -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-dimethylpropionamide, poly N-isopropyl acrylamide, polymethacrylic acid copolymer.
Described thickening material Main Function is 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.
Described flocculation agent Main Function is that hydrogen bond etc. are cross-linked by forming ionic linkage, and space steric effect or the part of reduction dispersion agent to a certain degree neutralize its surface charge, make colloid generation reversible coagulation.One class flocculation agent is ionic, comprise and (comprise hydrochloric acid with the free H+ solion that contains of above-mentioned dispersion agent opposite charges, nitric acid, sulfuric acid, acetic acid), (comprise ammoniacal liquor containing free OH-solion, sodium hydroxide, potassium hydroxide), containing negatively charged ion or cationic water-soluble polymers (identical with above-mentioned ionic dispersant, but electric charge is contrary).The high valence ion of boracic, calcium, magnesium, iron, chromium, zirconium, manganese high valence ion and its corresponding oxide boric acid, chromic acid, mangaic acid.Another kind of flocculation agent is non-ionic type, comprises formaldehyde, glutaraldehyde.
Described flow promotor Main Function is the mobility by improving material, levelling property, the effects such as froth breaking, promotes the flowing of formed material and eliminates the tangerine peel processing idiosome, the defects such as shrinkage cavity.Described flow promotor comprises polysiloxane, polyoxyethanyl siloxanes, 1 ~ 14 carbon alkyl polyoxyethyl propyl siloxanes, fluorocarbon compound modified polyacrylic ester.
Described shaping assistant Main Function is the temperature being reduced aftertreatment by the minimum film-forming temperature of reduction colloid, is conducive to the combination of material and temperature sensitive medicine or 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, uses dispersal mechanism standby one-tenth colloid.
2. thickening material and flocculation agent be dissolved in water or directly join in colloid, using dispersion machine or three-roll grinder to prepare the flocculated colloid of final paste body shape, 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.Cohesion degree too small (Fig. 1, A) or excessive (Fig. 1, B) are unfavorable for extruding with shaping of raw material, only have appropriate cohesion degree (Fig. 1, B) just can obtain reliable finished product.It should be 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 of condensing 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 in rapid shaping raw material easily to be processed, and need not worry be subject to the factor such as high temperature, organic solvent and go bad.Therefore by small-molecule drug or macromolecular polypeptides and proteolytic in water, or can 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 performing the preferred unit of rapid shaping 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 be fixed on Z axis motion platform 30.Four axis controllers control mass transport module 31 and 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 by certain speed for controlling raw material from nozzle.
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 to be encased in the distributor of aforesaid device (3) and to drive mass transport module to be extruded according to certain figure from nozzle by raw material by rapid prototyping system, stacking formation idiosome from level to level.(4) idiosome is put into baking oven heating carry out drying and sintering 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 can not organic solvent be produced, the hazardous and noxious substances such as high temperature degradation product, and processing and post-processing temperature low, problem such as scald murder by poisoning etc. can not be there is.
This quick molding method is also applicable to the manufacture with 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, even can be solidified into continuous solid body in room temperature, obtain final physical strength.Additionally by aftertreatment, also can control the sintering degree of idiosome, make finished product have the character of porous, ensure the controlled release of follow-up integrated medicine.
This quick molding method is also particularly suitable for the rapid shaping needing to control inside and outside structure three-dimensional object.Because rapid shaping raw material of the present invention has good visco-elasticity, so have the ability of crossing over certain distance, so may be used for the entity (Fig. 4 making vesicular structure, A) different distributors is utilized to load the raw material of heterogeneity, 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, also can tilt certain angle, formed and do not have the acclive entity (Fig. 4, D) of the tool of step effect.
Accompanying drawing explanation
Fig. 1 is that cohesion degree is to shaping effect diagram;
Fig. 2 is the preferred unit figure for rapid shaping of the present invention;
Fig. 3 is typical rapid shaping production process charts;
Fig. 4 is the entity type figure utilizing the present invention to process;
In figure, 10-equipment bay; 30-Z axis motion platform; 31-mass transport module; 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), joining 50g contains in sodium alginate (anionic water-soluble polymer) solution of 1% weight ratio, disperse energetically to obtain colloid in 10 minutes with ultrasonic grinder, form the rapid shaping raw material of 50% solid content.After being idiosome with this raw material rapid shaping, putting into baking oven drying and sintering 10 minutes at a temperature of 60 degrees c, obtain finished product.
Embodiment 2
Get 50g polyethylene acrylic acid ultrafine powder (median size 1 micron), joining 50g contains in sodium alginate (anionic water-soluble polymer) solution of 2% weight ratio, disperse energetically to form colloid in 10 minutes with ultrasonic grinder, 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, putting into baking oven drying and sintering 10 minutes at the temperature of 30 degrees Celsius, obtain finished product.
Embodiment 3
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 of controlled release bovine serum albumin.
Embodiment 4
Get 50g polyoxygenated titanium ultrafine powder (median size 0.02 micron), join 50g cold containing 2% weight ratio polyoxyethylene poly-oxygen propylene aether multipolymer (non-ionic water-soluble polymer) solution in, colloid is formed with ultrasonic dispersing machine dispersion 10min, then be warmed up to room temperature and form 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, putting 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 49.5g cold containing 1% weight ratio polyacrylic acid (anionic water-soluble polymer) solution in, colloid is formed with ultrasonic dispersing machine dispersion 10min, 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.Be 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, putting 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 preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., be all included within protection scope of the present invention.
Claims (10)
1. based on a rapid shaping raw material for colloid, it is characterized 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%.
2. rapid shaping raw material as claimed in claim 1, is characterized in that: the average particle size of described ultrafine powder is 0.1 nanometer to 10 micron, is preferably 10 nanometers to 1 micron; 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.
3. rapid shaping raw material as claimed in claim 1, is characterized in that described dispersion agent comprises containing-N
+,-S
+, or-P
+the water-soluble polymers of cation group, containing-COO
-,-SO
4 2-,-SiO
3 2-,-PO
4 3-,-CO
3 2-,-SO
3 2-,-S
2o
3 2-,-S
2-,-Cl
-,-Br
-,-I
-,-NO
3 -, or-NO
2 -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-dimethylpropionamide, poly N-isopropyl acrylamide, polymethacrylic acid copolymer.
4. rapid shaping raw material as claimed in claim 1, is characterized in that described flocculation agent comprises containing free H
+solion, containing free OH
-solion, or containing negatively charged ion or cationic water-soluble polymers, boron, calcium, magnesium, iron, chromium, zirconium, manganese high valence ion and its corresponding oxide boric acid, chromic acid, mangaic acid high valence ion solution, and formaldehyde, glutaraldehyde.
5. 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, polyoxyethanyl siloxanes, 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.
6. rapid shaping raw material as claimed in claim 1, its preparation method is as follows: 1) by dispersion agent, flow promotor, and shaping assistant is dissolved in water, then joins in solution by ultrafine powder, uses dispersal mechanism standby one-tenth colloid; 2) thickening material and flocculation agent be dissolved in water or directly join in colloid, using dispersion machine or three-roll grinder to prepare the described rapid shaping raw material of final paste body shape.
7. rapid shaping preparation method for raw material as claimed in claim 6, it is characterized in that: can by small-molecule drug or macromolecular polypeptides and proteolytic in water, or be wrapped in ultra-fine polymer powder, be distributed in lotion, preparation has can the material of medicine controlled releasing.
8. 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 be encased in the distributor of aforesaid device, (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 carry out drying and sintering and obtain final 3D solid finished product.
9. quick molding method as claimed in claim 8, is characterized in that: the condition of the course of processing is room temperature and water-based.
10. quick molding method as claimed in claim 8, is characterized in that: the sintering degree that can control aftertreatment, controls the porosity of finished product, can be rotated by A axle, forms the entity not having step effect.
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| CN104997643A (en) * | 2015-07-19 | 2015-10-28 | 谢宝军 | Raw material for all-ceramic dental restoration system and rapid prototyping method of raw material |
| CN107365158A (en) * | 2017-08-28 | 2017-11-21 | 武汉理工大学 | A kind of structural ceramics lotion for extruded type 3D printing and preparation method thereof |
| CN108245432A (en) * | 2018-02-09 | 2018-07-06 | 嘉兴雅宝医疗科技有限公司 | A kind of increasing material manufacturing method of full porcelain mouth mending material |
| CN108602727A (en) * | 2015-12-04 | 2018-09-28 | 高雄医学大学 | The method that lamination manufactures 3D printing article |
| CN108727028A (en) * | 2018-05-11 | 2018-11-02 | 航天特种材料及工艺技术研究所 | A method of rigid thermal insulation tile green body is made by increasing material manufacturing legal system |
| 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 |
| CN111867812A (en) * | 2018-04-27 | 2020-10-30 | 大金工业株式会社 | Powder for molding |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104997643A (en) * | 2015-07-19 | 2015-10-28 | 谢宝军 | Raw material for all-ceramic dental restoration system and rapid prototyping method of raw material |
| 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 |
| CN108602727A (en) * | 2015-12-04 | 2018-09-28 | 高雄医学大学 | The method that lamination manufactures 3D printing article |
| CN108602727B (en) * | 2015-12-04 | 2021-02-26 | 高雄医学大学 | Method for manufacturing 3D printed article in lamination mode |
| CN107365158A (en) * | 2017-08-28 | 2017-11-21 | 武汉理工大学 | A kind of structural ceramics lotion for extruded type 3D printing and preparation method thereof |
| 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 |
| CN108245432A (en) * | 2018-02-09 | 2018-07-06 | 嘉兴雅宝医疗科技有限公司 | A kind of increasing material manufacturing method of full porcelain mouth mending material |
| CN108245432B (en) * | 2018-02-09 | 2021-05-14 | 嘉兴学院 | Additive manufacturing method of all-ceramic dental prosthesis |
| CN111867812A (en) * | 2018-04-27 | 2020-10-30 | 大金工业株式会社 | Powder for molding |
| CN108727028A (en) * | 2018-05-11 | 2018-11-02 | 航天特种材料及工艺技术研究所 | A method of rigid thermal insulation tile green body is made by increasing material manufacturing legal system |
| 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 |
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