CN104478414A - Potassium-doped inorganic nanocomposite material for 3D (three-dimensional) printing and preparation method thereof - Google Patents
Potassium-doped inorganic nanocomposite material for 3D (three-dimensional) printing and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a potassium-doped inorganic nanocomposite material for 3D (three-dimensional) printing. The potassium-doped inorganic nanocomposite material contains the ingredients in percentage by weight: 73-80% of ceramic precursor powder, 5-10% of nanopowder reinforcing material, 2-5% of potassium powder, 2-5% of surfactant, 2-5% of organic solvent, 1-4% of inorganic binder and 5-10% of low-temperature curing agent, wherein the particle size of the nanopowder reinforcing material is 20-200nm. The surfactant is adopted to carry out disaggregation on nanopowder, so that the nanopowder has excellent dispersity; by adding the nanopowder into the ceramic precursor powder, the density and strength of ceramics can be improved, and the toughness of products is further improved; inorganic mixed powder, the inorganic binder and the low-temperature curing agent cooperate with one another, so that rapid binding can be achieved at low temperature; as a shaping raw material of 3D-printing rapid shaping machines, the inorganic nanocomposite material can be rapidly shaped effectively on 3D printers and can be applied to a variety of 3D printers of different models.
Description
Technical field
The present invention relates to 3D print manufacturing technology field, be specifically related to a kind of for 3D print mix potassium inorganic nano composite material and preparation method thereof.
Technical background
Rapid Prototyping technique is born in the later stage eighties 20th century, is the high-new manufacturing technology of one based on bing area method, is considered to the great achievement manufacturing field in recent years.It integrates mechanical engineering, CAD, reverse Engineering Technology, Layered Manufacturing Technology, Numeric Control Technology, Materials science, laser technology, automatically can change the prototype or direct finished parts with certain function, directly, quickly and accurately by design philosophy into, thus be the realization rate that the aspects such as the verification of part prototype, newly design philosophy provide a kind of high efficiency, low cost.That is, Rapid Prototyping technique is exactly the data utilizing three-dimensional CAD, by rapidform machine, material stacking is from level to level become physical prototypes.
It is a kind of rapid shaping technique that 3D prints, it combines the advantage of the multinomial technology such as computer graphical processing, digital information and control, laser technology, mechanical & electrical technology and material technology, the physical form of product can be converted into 3-dimensional digital stereoscopic model by modeling software or spatial digitizer, by delamination software by discrete at Z axis for this model, form a series of thin layer with specific thicknesses, then various method is utilized successively to be piled up by this series of thin layers, eventually pass suitable post-treating method, obtain required product.This forming method does not need mould, eliminates die design, manufacture and the process such as matched moulds, the demoulding, significantly shorten research and development and manufacturing cycle, reduces the cost of product.
3D prints can be divided into two large classes: the first kind is the forming method based on laser technology, as stereolithography (Stereolithography Apparatus, SLA), quires layer (Laminated Object Manufacturing, LOM), selective laser sintering (Selective Laser Sintered, SLS), selective laser melting (Selective Laser Melted, SLM) etc.; Equations of The Second Kind is the forming method of non-laser technology, as fuse deposition (Fused Deposition Modeling, FDM), mask photocuring (Mask Stereo lithography, MS) particulate manufacture (Ballistic Particle Manufacturing, is impacted, BPM), entity grinding solidification (Solid Ground, SGC) etc.The different material therefor of technology is then completely different, such as: (FDM) technological operation of fuse deposition is simple, and material used is environmental protection macromolecule material mainly, such as: PLA, PCL, PA, ABS, PC, PVC etc.At present, the 3D printing shaping material that market is sold substantially monopolize by offshore company, price is high, serious restriction 3D printing technique popularizing in China.
Summary of the invention
Object of the present invention is intended to the defect overcoming prior art, provide a kind of for 3D print mix potassium inorganic nano composite material and preparation method thereof, this strength of materials is high, processability is excellent, cost is low and versatility is good.
Technical scheme of the present invention is as follows:
A kind of for 3D print mix potassium inorganic nano composite material, by weight percentage, comprising: the low temperature curing agent of the organic solvent of the potassium powder of the ceramic forerunner powder of 73-80%, the nanometer powder strongthener of 5-10%, 2-5%, the tensio-active agent of 2-5%, 2-5%, 1-4% mineral binder bond, 5-10%; The particle diameter of described nanometer powder strongthener is 20-200 nanometer.
Described ceramic forerunner powder is selected from the combination of a kind of in aluminum oxide, aluminium nitride, silicon oxide, silicon nitride, silicon carbide or any two kinds, and the particle diameter of described ceramic forerunner powder is 180-280 order;
Described nanoreinforcement material is selected from the one in nano-zinc oxide powder, nano oxidized ti powder;
Described tensio-active agent is selected from the one in polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, tributyl phosphate, Sodium dodecylbenzene sulfonate, sodium lignosulfonate, sodium lauryl sulphate, sodium polyacrylate;
Described low temperature curing agent is selected from the one in silicon sol, Alumina gel;
Described mineral binder bond is the sodium silicate solution that with the addition of silicon oxide, titanium oxide and aluminum oxide;
Described organic solvent is ethanol, acetone, methyl alcohol, normal hexane, the one in isopropylcarbinol, Virahol.
Further, described potassium powder purity is more than 98%, and particle diameter is 1-5 micron.
Further, the solid volume fraction of described low temperature curing agent is 10 ~ 40%.
Further, in described mineral binder bond, the mass ratio of silicon oxide, titanium oxide, aluminum oxide and water glass is 2: 1: 1: 4.
The above-mentioned preparation method mixing potassium inorganic nano composite material for 3D printing is:
(1) tensio-active agent is dissolved in organic solvent form the surfactant soln that concentration is 1.5-10g/L, nanometer powder strongthener is added in this surfactant soln, ultrasonic agitation 30-60 minute, forms modified nanometer powder strongthener suspension liquid;
(2) by after above-mentioned modified nanometer powder strongthener suspension liquid, organic solvent, potassium powder and ceramic forerunner powder Homogeneous phase mixing, and put into the grinding machine for grinding 5-8 hour that rotating speed is 3500-4000 rev/min, then carry out supercritical drying, obtain mixed powder.
(3) by above-mentioned mixed powder and mineral binder bond Homogeneous phase mixing, then to mix with low temperature curing agent and ball milling 1-2 hour, form inorganic nano composite material, described in mix potassium inorganic nano composite material solid content be 75-85%.
Compared with prior art, tool has the following advantages and beneficial effect in the present invention:
(1) adopt tensio-active agent to separate to nanometer powder enforcement process of reuniting, make nanometer powder possess excellent dispersiveness, be added in ceramic forerunner powder, ceramic dense degree and intensity can be improved, and further improving product toughness.
(2) mineral binder bond in the present invention has bonding fast, and the feature such as bond firm, quick Fabrication can go out the mold product of different shape.
(3) inorganic mixed powder, potassium powder, mineral binder bond and the mutual coordinated of low temperature curing agent, can bond fast at low temperatures, composite effect is good.
(4) this inorganic nano composite material is printed the shaping raw material of rapidform machine as 3D, can effective rapid shaping on 3D printer, and can be applicable to the 3D printer of multiple different model.
(5) raw material of the present invention obtains in extensive range, and preparation method is simple, and cost is low, is conducive to the popularization of the marketization.
Embodiment
Below in conjunction with specific embodiment, illustrate the present invention further, these embodiments should be understood only be not used in for illustration of the present invention and limit the scope of the invention, after having read the present invention, the amendment of those skilled in the art to the various equivalent form of value of the present invention has all fallen within the application's claims and limited.
Embodiment 1:
A kind of for 3D print mix potassium inorganic nano composite material, by weight percentage, comprising: the aluminum oxide of 73%, the nano zine oxide of 6%, 2% potassium powder, 4% polyoxyethylene glycol, 10% silicon sol, 1% with the addition of the sodium silicate solution of silicon oxide, titanium oxide and aluminum oxide, the ethanol of 4%; The particle diameter of nano zine oxide is 40 nanometers; The solid volume fraction of silicon sol is 40%; In sodium silicate solution, the mass ratio of silicon oxide, titanium oxide, aluminum oxide and water glass is 2: 1: 1: 4.
This preparation method mixing potassium inorganic nano composite material is:
(1) polyoxyethylene glycol accounting for gross weight 4% is dissolved in the ethanol accounting for gross weight 2%, and form the surfactant soln that concentration is 8g/L, the nano zine oxide accounting for gross weight 6% is added in this surfactant soln, ultrasonic agitation 30 minutes, forms modified nanometer powder strongthener suspension liquid;
(2) by above-mentioned modified nanometer powder strongthener suspension liquid with account for the potassium powder of gross weight 2%, the ethanol accounting for gross weight 2% and the aluminum oxide Homogeneous phase mixing accounting for gross weight 73% after, and put into the grinding machine for grinding 5 hours that rotating speed is 4000 revs/min, then carry out supercritical drying, obtain mixed powder.
(3) by above-mentioned mixed powder and the sodium silicate solution Homogeneous phase mixing that with the addition of silicon oxide, titanium oxide and aluminum oxide accounting for gross weight 1%, then mix with the silicon sol accounting for gross weight 10%, ball milling 2 hours, form inorganic nano composite material, the solid content of described inorganic nano composite material is 75%.
Embodiment 2:
A kind of for 3D print mix potassium inorganic nano composite material, by weight percentage, comprising: the aluminium nitride of 75%, the nano zine oxide of 8%, the potassium powder of 3%, polyvinyl alcohol, the silicon sol of 5%, the sodium silicate solution that with the addition of silicon oxide, titanium oxide and aluminum oxide, 3% acetone of 1% of 5%; The particle diameter of nano zine oxide is 20 nanometers; The solid volume fraction of silicon sol is 10%; In sodium silicate solution, the mass ratio of silicon oxide, titanium oxide, aluminum oxide and water glass is 2: 1: 1: 4.
This preparation method mixing potassium inorganic nano composite material is:
(1) polyoxyethylene glycol accounting for gross weight 5% is dissolved in the acetone accounting for gross weight 1%, and form the surfactant soln that concentration is 10g/L, the nano zine oxide accounting for gross weight 8% is added in this surfactant soln, ultrasonic agitation 60 minutes, forms modified nanometer powder strongthener suspension liquid;
(2) by above-mentioned modified nanometer powder strongthener suspension liquid with account for the potassium powder of gross weight 2%, the acetone accounting for gross weight 2% and the aluminium nitride Homogeneous phase mixing accounting for gross weight 75% after, and put into the grinding machine for grinding 8 hours that rotating speed is 3500 revs/min, then carry out supercritical drying, obtain mixed powder.
(3) by above-mentioned mixed powder and the sodium silicate solution Homogeneous phase mixing that with the addition of silicon oxide, titanium oxide and aluminum oxide accounting for gross weight 1%, then mix with the silicon sol accounting for gross weight 5%, ball milling 1 hour, form inorganic nano composite material, the solid content of described inorganic nano composite material is 78%.
Embodiment 3:
A kind of for 3D print mix potassium inorganic nano composite material, by weight percentage, comprising: the silicon oxide of 78%, the nano-titanium oxide of 5%, 2% potassium powder, 3% tributyl phosphate, 8% silicon sol, 1% with the addition of the sodium silicate solution of silicon oxide, titanium oxide and aluminum oxide, the methyl alcohol of 3%; The particle diameter of nano-titanium oxide is 60 nanometers; The solid volume fraction of silicon sol is 20%; In sodium silicate solution, the mass ratio of silicon oxide, titanium oxide, aluminum oxide and water glass is 2: 1: 1: 4.
This preparation method mixing potassium inorganic nano composite material is:
(1) tributyl phosphate accounting for gross weight 3% is dissolved in the methyl alcohol accounting for gross weight 1%, and form the surfactant soln that concentration is 6g/L, the nano-titanium oxide accounting for gross weight 5% is added in this surfactant soln, ultrasonic agitation 50 minutes, forms modified nanometer powder strongthener suspension liquid;
(2) by above-mentioned modified nanometer powder strongthener suspension liquid with account for the potassium powder of gross weight 2%, the methyl alcohol accounting for gross weight 2% and the silicon oxide Homogeneous phase mixing accounting for gross weight 78% after, and put into the grinding machine for grinding 7 hours that rotating speed is 3800 revs/min, then carry out supercritical drying, obtain mixed powder.
(3) by above-mentioned mixed powder and the sodium silicate solution Homogeneous phase mixing that with the addition of silicon oxide, titanium oxide and aluminum oxide accounting for gross weight 1%, then mix with the silicon sol accounting for gross weight 8%, ball milling 1.5 hours, form inorganic nano composite material, the solid content of described inorganic nano composite material is 76%.
Embodiment 4:
A kind of for 3D print mix potassium inorganic nano composite material, by weight percentage, comprising: the silicon nitride of 80%, the nano-titanium oxide of 5%, 2% potassium powder, 3% Sodium dodecylbenzene sulfonate, 5% silicon sol, 1% with the addition of the sodium silicate solution of silicon oxide, titanium oxide and aluminum oxide, the isopropylcarbinol of 4%; The particle diameter of nano-titanium oxide is 80 nanometers; The solid volume fraction of silicon sol is 30%; In sodium silicate solution, the mass ratio of silicon oxide, titanium oxide, aluminum oxide and water glass is 2: 1: 1: 4.
This preparation method mixing potassium inorganic nano composite material is:
(1) Sodium dodecylbenzene sulfonate accounting for gross weight 3% is dissolved in the isopropylcarbinol accounting for gross weight 2%, and form the surfactant soln that concentration is 3g/L, the nano-titanium oxide accounting for gross weight 5% is added in this surfactant soln, ultrasonic agitation 40 minutes, forms modified nanometer powder strongthener suspension liquid;
(2) by above-mentioned modified nanometer powder strongthener suspension liquid with account for the potassium powder of gross weight 2%, the isopropylcarbinol accounting for gross weight 2% and the silicon nitride Homogeneous phase mixing accounting for gross weight 80% after, and put into the grinding machine for grinding 6 hours that rotating speed is 4000 revs/min, then carry out supercritical drying, obtain mixed powder.
(3) by above-mentioned mixed powder and the sodium silicate solution Homogeneous phase mixing that with the addition of silicon oxide, titanium oxide and aluminum oxide accounting for gross weight 1%, then mix with the silicon sol accounting for gross weight 5%, ball milling 2 hours, form inorganic nano composite material, the solid content of described inorganic nano composite material is 80%.
Embodiment 5:
A kind of for 3D print mix potassium inorganic nano composite material, by weight percentage, comprising: the silicon carbide of 80%, the nano-titanium oxide of 5%, 5% potassium powder, 2% sodium lauryl sulphate, 5% Alumina gel, 1% with the addition of the sodium silicate solution of silicon oxide, titanium oxide and aluminum oxide, the Virahol of 2%; The particle diameter of nano-titanium oxide is 150 nanometers; The solid volume fraction of silicon sol is 20%; In sodium silicate solution, the mass ratio of silicon oxide, titanium oxide, aluminum oxide and water glass is 2: 1: 1: 4.
This preparation method mixing potassium inorganic nano composite material is:
(1) sodium lauryl sulphate accounting for gross weight 2% is dissolved in the Virahol accounting for gross weight 1%, and form the surfactant soln that concentration is 2g/L, the nano-titanium oxide accounting for gross weight 5% is added in this surfactant soln, ultrasonic agitation 40 minutes, forms modified nanometer powder strongthener suspension liquid;
(2) by above-mentioned modified nanometer powder strongthener suspension liquid with account for the potassium powder of gross weight 5%, the Virahol accounting for gross weight 1% and the silicon carbide Homogeneous phase mixing accounting for gross weight 80% after, and put into the grinding machine for grinding 8 hours that rotating speed is 3500 revs/min, then carry out supercritical drying, obtain mixed powder.
(3) by above-mentioned mixed powder and the sodium silicate solution Homogeneous phase mixing that with the addition of silicon oxide, titanium oxide and aluminum oxide accounting for gross weight 1%, then mix with the Alumina gel accounting for gross weight 5%, ball milling 2 hours, form inorganic nano composite material, the solid content of described inorganic nano composite material is 82%.
Embodiment 6:
A kind of for 3D print mix potassium inorganic nano composite material, by weight percentage, comprising: the aluminum oxide of 38%, the aluminium nitride of 38%, 10% nano zine oxide, 4% potassium powder, 2% polyvinylpyrrolidone, 5% Alumina gel, 1% with the addition of the sodium silicate solution of silicon oxide, titanium oxide and aluminum oxide, the normal hexane of 2%; The particle diameter of nano-titanium oxide is 200 nanometers; The solid volume fraction of silicon sol is 40%; In sodium silicate solution, the mass ratio of silicon oxide, titanium oxide, aluminum oxide and water glass is 2: 1: 1: 4.
This preparation method mixing potassium inorganic nano composite material is:
(1) polyvinylpyrrolidone accounting for gross weight 2% is dissolved in the normal hexane accounting for gross weight 1%, and form the surfactant soln that concentration is 2g/L, the nano zine oxide accounting for gross weight 10% is added in this surfactant soln, ultrasonic agitation 60 minutes, forms modified nanometer powder strongthener suspension liquid;
(2) by above-mentioned modified nanometer powder strongthener suspension liquid with account for gross weight 4% potassium powder, account for gross weight 1% normal hexane and account for gross weight 38% aluminum oxide and 38% aluminium nitride Homogeneous phase mixing after, and put into the grinding machine for grinding 8 hours that rotating speed is 4000 revs/min, then carry out supercritical drying, obtain mixed powder.
(3) by above-mentioned mixed powder and the sodium silicate solution Homogeneous phase mixing that with the addition of silicon oxide, titanium oxide and aluminum oxide accounting for gross weight 1%, then mix with the Alumina gel accounting for gross weight 5%, ball milling 2 hours, form inorganic nano composite material, the solid content of described inorganic nano composite material is 84%.
Embodiment 7:
A kind of for 3D print mix potassium inorganic nano composite material, by weight percentage, comprising: the silicon oxide of 38%, the silicon carbide of 38%, 8% nano-titanium oxide, 4% potassium powder, 3% sodium polyacrylate, 6% Alumina gel, 1% with the addition of the sodium silicate solution of silicon oxide, titanium oxide and aluminum oxide, the normal hexane of 2%; The particle diameter of nano-titanium oxide is 100 nanometers; The solid volume fraction of silicon sol is 10%; In sodium silicate solution, the mass ratio of silicon oxide, titanium oxide, aluminum oxide and water glass is 2: 1: 1: 4.
This preparation method mixing potassium inorganic nano composite material is:
(1) sodium polyacrylate accounting for gross weight 3% is dissolved in the normal hexane accounting for gross weight 1%, and form the surfactant soln that concentration is 1.5g/L, the nano-titanium oxide accounting for gross weight 8% is added in this surfactant soln, ultrasonic agitation 60 minutes, forms modified nanometer powder strongthener suspension liquid;
(2) by above-mentioned modified nanometer powder strongthener suspension liquid with account for gross weight 4% potassium powder, account for gross weight 1% normal hexane and account for gross weight 38% silicon oxide and 38% silicon carbide Homogeneous phase mixing after, and put into the grinding machine for grinding 8 hours that rotating speed is 4000 revs/min, then carry out supercritical drying, obtain mixed powder.
(3) by above-mentioned mixed powder and the sodium silicate solution Homogeneous phase mixing that with the addition of silicon oxide, titanium oxide and aluminum oxide accounting for gross weight 1%, then mix with the Alumina gel accounting for gross weight 6%, ball milling 2 hours, form inorganic nano composite material, the solid content of described inorganic nano composite material is 85%.
Claims (7)
1. one kind for 3D print mix potassium inorganic nano composite material, it is characterized in that, by weight percentage, comprising: the low temperature curing agent of the tensio-active agent of the ceramic forerunner powder of 75-85%, the nanometer powder strongthener of 5-10%, 2-5%, the organic solvent of 2-5%, 1-4% mineral binder bond, 5-10%; Described ceramic forerunner powder is selected from the combination of a kind of in aluminum oxide, aluminium nitride, silicon oxide, silicon nitride, silicon carbide or any two kinds, and described nanoreinforcement material is selected from the one in nano-zinc oxide powder, nano oxidized ti powder; Described tensio-active agent is selected from the one in polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, tributyl phosphate, Sodium dodecylbenzene sulfonate, sodium lignosulfonate, sodium lauryl sulphate, sodium polyacrylate; Described low temperature curing agent is selected from the one in silicon sol, Alumina gel; Described mineral binder bond is the sodium silicate solution that with the addition of silicon oxide, titanium oxide and aluminum oxide; Described organic solvent is ethanol, acetone, methyl alcohol, normal hexane, the one in isopropylcarbinol, Virahol; The particle diameter of described nanometer powder strongthener is 20-200 nanometer.
2. according to claim 1 a kind of for 3D print mix potassium inorganic nano composite material, it is characterized in that: described potassium powder purity is more than 98%, and particle diameter is 1-5 micron.
3. according to claim 1 a kind of for 3D print mix potassium inorganic nano composite material, it is characterized in that: the particle diameter of described ceramic forerunner powder is 180-280 order.
4. according to claim 1 a kind of for 3D print mix potassium inorganic nano composite material, it is characterized in that: the solid volume fraction of described low temperature curing agent is 10 ~ 40%.
5. according to claim 1 a kind of for 3D print mix potassium inorganic nano composite material, it is characterized in that: in described mineral binder bond, the mass ratio of silicon oxide, titanium oxide, aluminum oxide and water glass is 2: 1: 1: 4.
6. prepare as claimed in claim 1 for the method for mixing potassium inorganic nano composite material that 3D prints, it is characterized in that, the method comprises:
(1) tensio-active agent is dissolved in organic solvent form the surfactant soln that concentration is 1.5-10g/L, nanometer powder strongthener is added in this surfactant soln, ultrasonic agitation 30-60 minute, forms modified nanometer powder strongthener suspension liquid;
(2) by after above-mentioned modified nanometer powder strongthener suspension liquid, potassium powder, organic solvent and ceramic forerunner powder Homogeneous phase mixing, and put into the grinding machine for grinding 5-8 hour that rotating speed is 3500-4000 rev/min, then carry out supercritical drying, obtain mixed powder.
(3) by above-mentioned mixed powder and mineral binder bond Homogeneous phase mixing, then mix with low temperature curing agent and ball milling 1-2 hour, form inorganic nano composite material, the solid content of described inorganic nano composite material is 75-85%.
7. a kind of preparation method mixing potassium inorganic nano composite material printed for 3D according to claim 5, is characterized in that:
(1) tensio-active agent is dissolved in organic solvent form the surfactant soln that concentration is 3g/L, nanometer powder strongthener is added in this surfactant soln, ultrasonic agitation 40 minutes, form modified nanometer powder strongthener suspension liquid;
(2) by after above-mentioned modified nanometer powder strongthener suspension liquid, potassium powder, organic solvent and ceramic forerunner powder Homogeneous phase mixing, and put into the grinding machine for grinding 6 hours that rotating speed is 4000 revs/min, then carry out supercritical drying, obtain mixed powder.
(3) by above-mentioned mixed powder and mineral binder bond Homogeneous phase mixing, then mix with low temperature curing agent and ball milling 2 hours, form inorganic nano composite material, the solid content of described inorganic nano composite material is 80%.
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| CN101415655A (en) * | 2006-03-31 | 2009-04-22 | 奥尔斯特·费希尔 | Method and apparatus for producing three-dimensional ceramic mouldings |
| CN103407296A (en) * | 2013-07-29 | 2013-11-27 | 南京鼎科纳米技术研究所有限公司 | Method for achieving high-melting-point material 3D printing through nanometer ink together with laser melting |
| CN103936392A (en) * | 2014-03-13 | 2014-07-23 | 济南大学 | Preparation method of 3D printing inorganic powder molding material |
| CN103980397A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing composition, preparation and application methods and product thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101415655A (en) * | 2006-03-31 | 2009-04-22 | 奥尔斯特·费希尔 | Method and apparatus for producing three-dimensional ceramic mouldings |
| CN103407296A (en) * | 2013-07-29 | 2013-11-27 | 南京鼎科纳米技术研究所有限公司 | Method for achieving high-melting-point material 3D printing through nanometer ink together with laser melting |
| CN103936392A (en) * | 2014-03-13 | 2014-07-23 | 济南大学 | Preparation method of 3D printing inorganic powder molding material |
| CN103980397A (en) * | 2014-04-30 | 2014-08-13 | 中国科学院化学研究所 | 3D printing composition, preparation and application methods and product thereof |
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Application publication date: 20150401 |