CN107216153A - A kind of 3D printing method of ceramic material - Google Patents

A kind of 3D printing method of ceramic material Download PDF

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CN107216153A
CN107216153A CN201710501591.4A CN201710501591A CN107216153A CN 107216153 A CN107216153 A CN 107216153A CN 201710501591 A CN201710501591 A CN 201710501591A CN 107216153 A CN107216153 A CN 107216153A
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script
type
dielectric loss
printing method
sintering
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左飞
孟凡
于俊杰
林华泰
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Guangdong University of Technology
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Guangdong University of Technology
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • B33Y70/00—Materials specially adapted for additive manufacturing
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • C04B2235/3274—Ferrites
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/667—Sintering using wave energy, e.g. microwave sintering
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The invention provides a kind of 3D printing method of ceramic material, comprise the following steps：A) material with high dielectric loss is distributed in low-dielectric loss material powder, type-script is formed；B) by step A) obtained type-script is placed in microwave electromagnetic field, realizes solidification and the sintering of type-script.The above-mentioned 3D printing method that the present invention is provided is based on the characteristics of electromagnetic wave selectively heating and overall heating, in the fully wrapped around type-script of supporting construction, realizes the selectivity heating, solidification and sintering of print area, improves structural homogeneity；Outfield booster action can promote mass transport process simultaneously, realize the fast densified of product；It can obtain the heterogeneous microstructure different from normal sintering product while design outline macrostructure, realize the controllable manufacture of different scale undertissue structure, and then realize material structure-function combining design technology and manufacture.Have material treatment process simple simultaneously and print the characteristics of cost is low, possess industrial applications potentiality.

Description

A kind of 3D printing method of ceramic material
Technical field
The present invention relates to material science and manufacturing engineering technical field, more particularly to a kind of 3D printing side of ceramic material Method, it is possible to achieve the integrated design and manufacture of ceramic material profile macrostructure and heterogeneous microstructure.
Background technology
One of important directions of advanced ceramics material research, are materials with structure-function integration and corresponding Advanced technology of preparing.Carry out advanced ceramics material " composition-technique-structure-performance " co-design and research, reduction is manufactured into Originally, lifting material quality, it will produce huge science and economic value.
Shaping and the key link that sintering is in high-performance ceramic preparation process, the two influences the macroscopical and micro- of material respectively Structure is seen, and then determines properties of product.The appearance of 3D printing technique, has for the rapid shaping and preparation of complicated shape material Significance.At present, the 3D printing of metal material and macromolecule resin relative maturity, and ceramic material 3D printing is at raw material In terms of science and engineering skill, raising product structure uniformity, consistency and dimensional accuracy, still need to make further research.Developing low-cost And the 3D moulding process easily realized, and be combined with advanced sintering technology, integrated design has special macroscopical-microcosmic with manufacture The product of structure and performance, will be the Main Trends of The Development of ceramic material 3D printing.
At present, the common technology of ceramic material 3D printing includes inkjet printing, selective laser sintering and Stereo Lithography Deng.On the whole, above-mentioned 3D printing method is remained in some following problem：
(1) density of macroscopic view shaping, structural homogeneity are relatively low
Consistency is low and structure is uneven comes from Method of printing first in itself, binding agent it is a large amount of using and successively bond work Skill, the problem of hole and interface aspect can be all brought to molding blank；Next to that sintering process, the complexity obtained by 3D printing Moulding is further exacerbated by the inequality of structure the problems such as meeting is because of anisotropic shrinkage and internal and external temperature gradient during normal sintering Even property.
(2) process is complicated, need to improve product quality using aftertreatment technology
Existing 3D printing technique is conceived to the rapid shaping of complicated macroshape material mostly, and in compact density, structure There is certain defect in terms of uniformity and dimensional accuracy, generally need to burn using infiltration, reaction bonded, isostatic pressed, high temperature The aftertreatment technologys such as knot further improve the consistency and mechanical property of shaping base substrate.
(3) cost of macroscopic view shaping is high and efficiency is low
Although organic precursor-Stereo Lithography technology can be obviously improved the performance of product, cost height and effect are still suffered from The problem of rate is low.Organic precursor or photocuring raw material are mostly with high costs, and with more harsh use and condition of storage； In addition, the 3D printing procedure is slower, less efficient, the yield of product is relatively low, therefore cost performance is extremely low, does not possess big rule Mould, the basis commercially produced.
(4) the disposable design to product macroscopic view-microstructure and manufacture are difficult to
Existing 3D printing method, due to the limitation of printing precision, can only realize that the product structure under macro-scale is set mostly Meter and manufacture.The integrated design of structure-function proposes higher requirement to 3D printing technique with manufacture.
The content of the invention
In view of this, the technical problem to be solved in the present invention is a kind of 3D printing method for providing ceramic material, can be with Realize under different scale, the ceramic material macroscopic view-controllable manufacture of microstructure.
The invention provides a kind of 3D printing method of ceramic material, comprise the following steps：
A) material with high dielectric loss is distributed in low-dielectric loss material powder, type-script is formed；
B) by step A) obtained type-script is placed in microwave electromagnetic field, realizes solidification and the sintering of type-script.
It is preferred that, the step A) be specially：
According to the space structure between the macroshape of complex phase ceramic product and each composition phase, there will be high dielectric The material of loss is distributed in low-dielectric loss material powder, forms type-script.
It is preferred that, the sintering is specially：
Type-script is heated to by electromagnetic field to remove, then type-script is taken out from supporting construction, moved to micro- Ripple agglomerating plant, applies electromagnetic field and completes integral sintered.
It is preferred that, the sintering is specially：
Type-script is placed in low-dielectric loss materials for support structure, by applying electromagnetic field, by printing body portion selection Property be rapidly heated and sinter, the disposable 3D shapings for completing material and sintering process.
It is preferred that, the material with high dielectric loss is to be coupled under normal temperature or low temperature with microwave electromagnetic field And the material heated by electromagnetic field, preferably MgO, SiO2, SiC, C, TiN, TiC, ferrite, ZrB2、MoSi2、ZrO2、HfO2、 SnO2, any one or more in PZT and metal dust.
It is preferred that, the low-dielectric loss material for coupled under normal temperature to type-script sintering temperature with microwave electromagnetic field compared with Low material, preferably Y2O3、Al2O3、SiO2、Si3Ni4, BN, spinelle and CaF2In any one or more.
Compared with prior art, the invention provides a kind of 3D printing method of diphase ceramic material, comprise the following steps： A) material with high dielectric loss is distributed in low-dielectric loss material powder, type-script is formed；B) by step A) obtain Type-script be placed in microwave electromagnetic field, realize solidification and the sintering of type-script.The above-mentioned 3D printing method base that the present invention is provided The characteristics of electromagnetic wave selectively heating and overall heating, in the fully wrapped around type-script of supporting construction, print area is realized Selectivity heating, solidification and sintering, improve structural homogeneity；Outfield booster action can promote mass transport process simultaneously, realize product It is fast densified；The heterogeneous microstructure different from normal sintering product can be obtained while design outline macrostructure, The controllable manufacture of different scale undertissue structure is realized, and then realizes structure-function combining design technology and the manufacture of material.Simultaneously With material treatment process is simple and the characteristics of low printing cost, is adapted to heavy industrialization application.
Brief description of the drawings
Fig. 1 is the 3D printing structural scheme of mechanism based on Microwave Sintering Techniques；Figure A is " powdering-ink-jet " configuration；It is " many to scheme B Shower nozzle links " configuration；
Fig. 2 is the microstructure photograph of molded samples, and figure a is obtained by " powdering-ink-jet " configuration printer；It is " many sprays to scheme b Obtained by head linkage " configuration printer；
Fig. 3 is 3D printing method schematic diagram of the present invention；
Fig. 4 is that low-dielectric loss wave transparent phase inhales the citing of ripple phase different spaces structure design with high dielectric loss；
Fig. 5 is the aluminum oxide 3D printing body micro-structure diagram that SLS selective laser sintering techniques are obtained；
Fig. 6 is the micro-structure diagram for the aluminum oxide 3D printing product that comparative example 2 is obtained.
Embodiment
The invention provides a kind of 3D printing method of diphase ceramic material, comprise the following steps：
A) material with high dielectric loss is distributed in low-dielectric loss material powder, type-script is formed；
B) by step A) obtained type-script is placed in microwave electromagnetic field, realizes solidification and the sintering of type-script.
Specifically, the present invention combines the technology character and superiority of " increasing material manufacturing " and " electromagnetism field assisted sintering ", it is proposed that The controllable manufacture method of ceramic material institutional framework under a kind of different scale.This method will have using printing principle shown in accompanying drawing 1 There is the material of high dielectric loss as " inhaling ripple phase ", in the powder for being distributed in low-dielectric loss material, form type-script, it is right afterwards Whole powder bed (or type-script) applies microwave electromagnetic field, and printing body region is selected by " inhaling ripple phase " and the coupling of electromagnetic field Selecting property it is brought rapidly up, realizes solidification and the sintering of type-script.Due to outfield booster action, it is possible to achieve under different scale, pottery The integrated design and manufacture of the special macroscopic view-microstructure of ceramic material and function.
It is preferred that, the step A) be specially：
Using the absorbing material with high dielectric loss as the second phase, according to the macroshape of complex phase ceramic product and each thing Alternate space structure, is distributed in the electromagnetic wave transparent material powder with low-dielectric loss, forms type-script.
The complex phase ceramic product refers to final ceramic material.
Then it is overall to type-script (or powder bed) to apply microwave electromagnetic field, due between different materials inside complex phase type-script Different dielectric is lost, and can produce couplings different from electromagnetic field.Electromagnetic coupled acts through a variety of Polarization Mechanisms, makes Gao Jie Electrically lossy material is brought rapidly up, and finally realizes that the selective local of print area is quickly heated.
After type-script is locally heated, its internal temperature field is uniform, but exists substantially with outside electromagnetic wave transparent material supporting construction Temperature difference, as shown in Figure 3, which show under microwave electromagnetic field environment, 3D printing region supports with surrounding electromagnetic wave transparent material and tied The electromagnetic coupled difference and temperature difference of structure.
The final sintering of material preferably following two modes：
First, print area is heated to by certain temperature by electromagnetic field, making the type-script of print area has certain force Intensity is learned, and then it can be taken out from supporting construction, microwave sintering apparatus is moved to, overall burn is completed by applying electromagnetic field Knot.
Second, in the case of the fully wrapped around print area of supporting construction, microwave electricity is integrally applied to powder bed and type-script Magnetic field, type-script by electromagnetic field be partially selectively rapidly heated and sintered, and the disposable 3D shapings for completing material are with burning Knot process.
The present invention is according to above-mentioned steps A) link is to high dielectric loss phase absorbing material and low-dielectric loss phase electromagnetic wave transparent material Different three-D space structures and relative position design, a variety of different macroscopic views-microstructure matched combineds can be obtained, such as it is attached Shown in Fig. 4.Under the effect of electromagnetic field selective absorbing, temperature field and electromagnetic field can occur not inside type-script, between each phase With distribution and coupling effect, the multi- scenarios method effect of this electromagnetic field, temperature field, stress field etc. can make material form difference In the heterogeneous microstructure of normal sintering product.
Institutional framework under different scale determines its respective performance characteristics.Therefore, above-mentioned outfield booster action is passed through Under 3D printing and sintering method, can while designing material profile macrostructure, obtain be different from normal sintering product Heterogeneous microstructure, realize the controllable manufacture of different scale undertissue structure, and then realize the structure-function integration of material Design and manufacture.
The present invention, to the selective absorbing of electromagnetic field, realizes the concept and method of complex phase ceramic 3D printing using material； And 3D printing technique is aided in outfield, the concept to material macroscopic view-controllable manufacture of microstructure integration and side is realized Method.
It is currently preferred, the material with high dielectric loss be under normal temperature or low temperature with microwave electromagnetic field occur The material for coupling and then being heated by electromagnetic field, the normal temperature is 20~30 DEG C, and the low temperature is less than 200 DEG C.
Above-mentioned material preferred MgO, SiO with high dielectric loss2, SiC, C, TiN, TiC, ferrite, ZrB2、MoSi2、 ZrO2、HfO2、SnO2, any one or a few in PZT and metal dust.
The metal dust be metal well known to those skilled in the art powder, preferably Fe, W, Co, Ni, Cu etc. and Its alloy.
The low-dielectric loss material for coupled under normal temperature to type-script sintering temperature with microwave electromagnetic field it is relatively low without The material that can be acutely heated by electromagnetic field.
Above-mentioned low-dielectric loss material is preferably Y2O3、Al2O3、SiO2、Si3Ni4, BN, spinelle and CaF2In it is any one Plant or a variety of.
Compared with prior art, the present invention has following three points advantage：
(1) it is the characteristics of based on electromagnetic wave selectively heating with overall heating, real in the fully wrapped around type-script of supporting construction Selectivity heating, solidification and the sintering of existing print area, improve structural homogeneity；
(2) type-script is heated using electromagnetic coupling effect, heating is rapid, rapidly and efficiently；
(3) outfield booster action promotes mass transport process, realizes the fast densified of product；
(4) while design outline macrostructure, the heterogeneous microstructure different from normal sintering product is obtained, is realized not With the controllable manufacture of yardstick undertissue structure, and then realize structure-function combining design technology and the manufacture of material.
In order to further illustrate the present invention, the 3D printing method of the ceramic material provided with reference to embodiment the present invention It is described in detail.
Embodiment 1
Using " powdering-ink-jet " configuration printer shown in A figures in Fig. 1, the alumina material with low-dielectric loss is made For matrix, magnesia, silica and ferritic mixed slurry are as high dielectric loss " inhaling ripple ink material ", successively equably Spray attachment forms print area on the matrix material after the execution of feed powdering mechanism.After 3D printing process is fully completed, 2.45GHz multimode electromagnetic fields are applied to whole powder bed (including 3D printing region), by adjusting electromagnetic wave input power, control rises Warm speed is interval in 60-70 DEG C/min, to 1580 DEG C after be incubated 5min, it is rear to stop microwave input, furnace cooling.By 3D printing sample Product take out from alumina substrate powder bed, and simple process can remove the alumina powder particle of surfaces stick.The micro- knot of sample Structure is as shown in Figure 2 a, although the space at interface layer is more obvious, but each layer of submicroscopic structure even compact, without substantially Defect.It is 75-79% to measure sample relative density through Archimedes method (measurement medium is absolute ethyl alcohol).
Embodiment 2
Using " many shower nozzle linkages " configuration printer shown in B figures in Fig. 1, two groups of shower nozzles are each responsible for low-dielectric loss wave transparent Phase alumina and high dielectric loss inhale the feed of ripple phase (magnesia, silica and ferritic mixed slurry), according to design Multi-phase alumina ceramic contour structures and each phase space relative position, successively complete 3D printing.Afterwards, type-script is integrally moved to 2.45GHz multimode cavitys, by adjusting electromagnetic wave input power, control programming rate is interval in 60-70 DEG C/min, to 1580 DEG C After be incubated 5min, it is rear to stop microwave input, furnace cooling.As shown in Figure 2 b, microstructure presents overall equal sample microstructure Even and densification, no significant defect.It is 80- to measure sample relative density through Archimedes method (measurement medium is absolute ethyl alcohol) 85%.
Comparative example 1
Shown in Fig. 5, the aluminum oxide 3D printing body microstructure obtained by SLS selective laser sintering techniques.Can To find, its primary granule is larger, and intergranular space is substantially, and relative density is less than 35% (Shi Yusheng, Liu Kai, He Wenting, Lee Morning brightness, Wei Qingsong selective laser sinterings/isostatic cool pressing composite manufacturing high density Al2O3The research applications of special-shaped ceramics part swash Light, 2013,33 (1):1-6.).Later stage needs to handle by isostatic cool pressing process, and with 10 DEG C/min heating rate, extremely 1600 DEG C of insulations obtain the alumina product that relative density is more than 92% in 2 hours after sintering.
Comparative example 2
Shown in Fig. 6, after being reacted by aluminium powder oxidation, the aluminum oxide 3D obtained by 1600 DEG C of insulations, 2 hours sintering is beaten Print the microstructure of product.It can be found that its sintering period is longer, initial size is more thick, and void among particles are also more Substantially, relative density only has 55% or so (Yao DX, Gomes C, Zeng YP, Jiang DL, G ü nster, Heinrich JG.Near zero shrinkage porous Al2O3prepared via 3D-printing and reaction bonding.Mater Lett,2015,147:116-118)。
The complex phase ceramic 3D printing method provided from above-described embodiment and comparative example, the present invention, based on electromagnetic wave choosing The characteristics of selecting property is heated and entirety is heated, in the fully wrapped around type-script of supporting construction, you can realize the selectivity of print area Heating, solidification with sintering, and institute product uniform microstructure height；Secondly, heated and printed using electromagnetic coupling effect Body, heating is rapid, and the sintering period greatly shortens, energy-saving consumption-reducing；Again, outfield booster action promotes mass transport process, realizes product It is fast densified, higher consistency can be obtained in lower sintering temperature in the case of without specially treated；Separately Outside, 3D printing method of the present invention, while design outline macrostructure, obtains microcosmic group different from normal sintering product Structure is knitted, the controllable manufacture of different scale undertissue structure is realized, and then realizes the structure-function combining design technology and system of material Make.
The explanation of above example is only intended to the method and its core concept for helping to understand the present invention.It should be pointed out that pair , under the premise without departing from the principles of the invention, can also be to present invention progress for those skilled in the art Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.

Claims (8)

1. a kind of 3D printing method of ceramic material, it is characterised in that comprise the following steps：
A) material with high dielectric loss is distributed in low-dielectric loss material powder, type-script is formed；
B) by step A) obtained type-script is placed in microwave electromagnetic field, realizes solidification and the sintering of type-script.
2. 3D printing method according to claim 1, it is characterised in that the step A) be specially：
According to the space structure between the macroshape of complex phase ceramic product and each composition phase, there will be high dielectric loss Material be distributed in low-dielectric loss material powder, formed complex phase type-script.
3. 3D printing method according to claim 1, it is characterised in that the sintering is specially：
Type-script is heated to by electromagnetic field can integrally to remove, then type-script is taken out from supporting construction, moved to micro- Ripple agglomerating plant, applies electromagnetic field and completes integral sintered.
4. 3D printing method according to claim 1, it is characterised in that the sintering is specially：
Type-script is placed in low-dielectric loss materials for support structure, by applying electromagnetic field, by type-script partially selectively It is rapidly heated and sinters, the disposable 3D shapings for completing material and sintering process.
5. 3D printing method according to claim 1, it is characterised in that the material with high dielectric loss is normal The material for coupling and then being heated by electromagnetic field with microwave electromagnetic field under temperature or low temperature.
6. 3D printing method according to claim 5, it is characterised in that the material with high dielectric loss be MgO, SiO2, SiC, C, TiN, TiC, ferrite, ZrB2、MoSi2、ZrO2、HfO2、SnO2, in PZT and metal dust any one or It is several.
7. 3D printing method according to claim 1, it is characterised in that the low-dielectric loss material is extremely to be beaten in normal temperature Relatively low material is coupled with microwave electromagnetic field under print body sintering temperature.
8. 3D printing method according to claim 7, it is characterised in that the low-dielectric loss material is Y2O3、Al2O3、 SiO2、Si3Ni4, BN, spinelle and CaF2In any one or more.
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CN108555283A (en) * 2018-06-08 2018-09-21 贵州大学 A kind of Fe-Mn-Si memorial alloys/PZT composite powders and its application
CN108655407A (en) * 2018-06-13 2018-10-16 沈阳精合数控科技开发有限公司 A kind of ultra-fine grain carrier fluid injection microwave sintering manufacturing process
CN109514862A (en) * 2018-01-02 2019-03-26 陈勃生 A kind of apparatus and method for polymer three-dimensional product increasing material manufacturing
CN109764992A (en) * 2018-12-27 2019-05-17 西安交通大学 A kind of residual stress lossless detection method for 3D printing zirconia ceramics structure
CN112058192A (en) * 2020-09-04 2020-12-11 湖南大学 Continuous flow micro-reactor, manufacturing method and application
CN112373014A (en) * 2020-10-09 2021-02-19 青岛大学 Method for preparing magnetoelectric composite material based on magnetic field assisted 3D printing technology
CN113546614A (en) * 2020-04-16 2021-10-26 中国石油天然气股份有限公司 Catalyst alumina carrier material with gradient micro-morphology structure and preparation method thereof

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CN109514862A (en) * 2018-01-02 2019-03-26 陈勃生 A kind of apparatus and method for polymer three-dimensional product increasing material manufacturing
CN109514862B (en) * 2018-01-02 2020-03-10 陈勃生 Method for additive manufacturing of polymer three-dimensional product
CN108555283A (en) * 2018-06-08 2018-09-21 贵州大学 A kind of Fe-Mn-Si memorial alloys/PZT composite powders and its application
CN108655407A (en) * 2018-06-13 2018-10-16 沈阳精合数控科技开发有限公司 A kind of ultra-fine grain carrier fluid injection microwave sintering manufacturing process
CN109764992A (en) * 2018-12-27 2019-05-17 西安交通大学 A kind of residual stress lossless detection method for 3D printing zirconia ceramics structure
CN113546614A (en) * 2020-04-16 2021-10-26 中国石油天然气股份有限公司 Catalyst alumina carrier material with gradient micro-morphology structure and preparation method thereof
CN113546614B (en) * 2020-04-16 2023-10-27 中国石油天然气股份有限公司 Catalyst alumina carrier material with gradient microstructure and preparation method thereof
CN112058192A (en) * 2020-09-04 2020-12-11 湖南大学 Continuous flow micro-reactor, manufacturing method and application
CN112373014A (en) * 2020-10-09 2021-02-19 青岛大学 Method for preparing magnetoelectric composite material based on magnetic field assisted 3D printing technology

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Application publication date: 20170929