CN109483872A - Application of the expendable material in the printing of micro-structure 3D photocuring - Google Patents

Application of the expendable material in the printing of micro-structure 3D photocuring Download PDF

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Publication number
CN109483872A
CN109483872A CN201811196663.XA CN201811196663A CN109483872A CN 109483872 A CN109483872 A CN 109483872A CN 201811196663 A CN201811196663 A CN 201811196663A CN 109483872 A CN109483872 A CN 109483872A
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China
Prior art keywords
resin
printing
film
scraper
micro
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Pending
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CN201811196663.XA
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Chinese (zh)
Inventor
夏春光
黄立
赵�卓
贺晓宁
方绚莱
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Wuxi Mofang Precision Technology Co Ltd
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Wuxi Mofang Precision Technology Co Ltd
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Priority to CN201811196663.XA priority Critical patent/CN109483872A/en
Publication of CN109483872A publication Critical patent/CN109483872A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/106Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20Apparatus for additive manufacturing; Details thereof or accessories therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/205Means for applying layers
    • B29C64/214Doctor blades
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE 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
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00Apparatus for additive manufacturing; Details thereof or accessories therefor

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)

Abstract

The present invention provides application of the expendable material in the printing of micro-structure 3D photocuring, comprise the following steps: step A: by the image projection on DLP to film and resin contact surface, resin monomer occurs photochemical reaction and is cross-linked into solid the projection lens in more micro- stereolithography systems of material;Step B: system is provided with two scrapers arranged side by side, walks preceding scraper and strikes off old resin, walks posterior scraper and smears resin backward;Step C: system changes liquid film;Step D: above step is repeated to different materials, successively completes the printing of 3D sample.The beneficial effects of the present invention are: being provided using more file printing systems how in minute yardstick printing suspension and movable part, to realize the full 3D printing of minute yardstick.It also proposed a kind of formula for being used as the photosensitive resin for sacrificing mechanism in 3D printing simultaneously, also optimize application of the sacrificial resin in support construction on this basis.

Description

Application of the expendable material in the printing of micro-structure 3D photocuring
Technical field
The present invention relates to a kind of 3D printing fields more particularly to a kind of expendable material in the printing of micro-structure 3D photocuring Using.
Background technique
With the development of 3D printing technique, application range is also constantly expanding, and from Structural Engineering, material engineering is arrived Biology and medical engineering;From macro smooth scale (more than centimetres) to micro-scale (below millimeter).But the skill of traditional 3D printing The defect of art also starts to present, such as more materials, high-precision (less than 50 microns), suspended structure and bascule etc..In macro light Scale, in order to print suspended structure and bascule, existing method is to print support construction simultaneously, and the later period, artificial mechanism was gone again Except support construction.These support constructions are often some fine columnar groups.For micro-scale, artificial mechanism removes support construction Have been changed to it is unrealistic, or even can not because in microstructure, during mechanical removal first to the requirement of tool extremely It is harsh and expensive, followed by easily damage the structure of needs.For this purpose, Cabrera most proposed projecting micro- solid early in 1998 Suspended structure is made with sacrificial layer material in photoetching, but the work of early period is due to the limitation of photoetching technique, is all to pass through craft Inefficient switching resin is realized, some flat structures are made;Although proposing later summer spring scenery in 2009 and side are gorgeous Realized in project stereoscopic photoetching technique using the same resin of low gradation exposure sacrifice structure production, but this method for Different resins has different effects, even requires different etchant solutions to different resins.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of expendable material answering in the printing of micro-structure 3D photocuring With.
Specifically, the present invention provides a kind of micro- stereolithography system of more materials, including set gradually ray machine, film, scrape Knife structure, resin delivery, container molding and control computer;The ray machine includes micro display chip, and the micro display chip is adopted With reflective liquid crystal screen LCOS or DLP.
Most important component is micro display chip in ray machine, it can be reflective liquid crystal screen LCOS either Texas Instrument Digital optical demodulator (DLP), LCOS is considered the brightness and contrast for having better image than traditional transflective liquid crystal screen Its each pixel can adjust the polarization state of reflected light according to the voltage of application.Therefore one piece of polaroid is added in the optical path can The reflected light of corresponding polarization pixel is allowed to pass through to form image.DLP technology was invented in 1987 by Texas Instrument, with liquid crystal The principle that screen changes the polarization state of reflected light is different, and each pixel of DLP is a small reflective mirror.It passes through deflected micromirror Face controls the whereabouts of reflected light.Deflectable ± the 10o. of each eyeglass bright pixel is exactly that reflected light enters camera lens, opposite It is exactly dark pixel.The gray scale of image is controlled by the frequency of eyeglass deflection.DLP chip has better than liquid crystal chip We using the resolution of DLP chip are 1920X1080 in this invention by ultraviolet light compatibility and higher contrast, Each micro mirror chip size is that 7.6 um X, 7.6 um. optical source wavelength is the optical section that 405 nanometers of opticators include ray machine Part, the camera of a spectroscope and printing surface monitoring.One projection lens connects the image projection on DLP to film and resin Contacting surface, resin monomer occurs photochemical reaction and is cross-linked into solid there.
The present invention provides a kind of Method of printing using expendable material in the printing of micro-structure 3D photocuring, including following several A step:
Step A: the projection lens in the micro- stereolithography system of material sets the image projection on DLP to film and resin contact surface Alicyclic monomer occurs photochemical reaction and is cross-linked into solid;
Step B: system is provided with two scrapers arranged side by side, walks preceding scraper and strikes off old resin, walks posterior scraper backward Smear resin;
Step C: system changes liquid film;
Step D: above step is repeated to different materials, successively completes the printing of 3D sample.
Preferably, the step C including the following steps:
Step C1: at the uniform velocity moving scraper to the side of film, while scraper spues new resin to the opposite direction of movement, coated membrane table Face;
Step C2: scraper and film are detached from, and sample stage rises to after designated position, and image is projected on film.
Preferably, the material of the film uses PDMS or PFA, and thickness uses 25 microns to 100 microns.
Preferably, the step of step C1 are as follows:
It printing interlayer and switches resin, the second resin is printed upon on the first resin, after scraper is painted with the second resin on film, sample quilt It is moved to apart from the corresponding thickness of film, then the second resin layer is exposed.
Preferably, the step of step C1 are as follows:
Switch resin in layer, the second resin is printed upon in the first resin layer, and after scraper is painted with the second resin on film, sample can be returned To the position tangent with film, by the second resin squeeze into same layer need to fill the space of the second resin then to the second resin according to When the exposure of layer picture, step can be repeated before exposure when needing: applying the second resin, and the first resin of extruding is multiple, thus Avoid the mixing of the second resin and the first resin.
Preferably, first resin is target material resin, and second resin is that can sacrifice light-sensitive material resin.
Wherein, target material resin may is that acrylate, acrylamide and silicone-acrylate, difunctional or The one or more of multi-functional alkyl acrylate, alkoxy acrylic ester or glycols acrylate.
Preferably, it is described sacrifice light-sensitive material the preparation method comprises the following steps: DMMA(N, N- dimethylacrylamide, CAS: 2680-03-7) monomer and its 819 photoinitiator of mixed solution and Igacure are mixed by the weight ratio of 100:2-100:6 Body is prepared at room temperature, while the modes such as mechanical stirring (> 800 revs/min), ultrasonic vibration can be used and accelerate photoinitiator Dissolution.
The present invention also provides a kind of method for releasing of the expendable material of the bascule in 3D printing, comprising the following steps: It is impregnated needing the device for carrying out expendable material release to be put into the buffer solution or water of pH=3.0, solution rate is greater than 150 Micro- m/h.Release solution is also possible to water.
The beneficial effects of the present invention are: how being provided using more file printing systems in minute yardstick printing suspension and activity Component, to realize the full 3D printing of minute yardstick.It also proposed a kind of light for being used as sacrifice mechanism in 3D printing simultaneously The formula of quick resin also optimizes application of the sacrificial resin in support construction on this basis.
Detailed description of the invention
Fig. 1 is the micro- stereoprojection lithography system of the more material faces of inventive film coating.
Fig. 2 is a kind of embodiment of the double scraper coating structures of present system
Fig. 3 is that present system changes liquid film flow diagram.
Fig. 4 is two kinds of interlayer switching resin schematic diagrames of the present invention.
Fig. 5 is that the suspended structure and action result sample, arrow in 3D printing of the present invention represent Print direction.
Fig. 6 is the application that the present invention projects expendable material in micro- stereolithography printing, and arrow represents Print direction.
Fig. 7 be in MCSL of the present invention expendable material to the optimization figure of support structure designs.
Specific embodiment
With reference to the accompanying drawing, preferably embodiment of the invention is described in further detail:
Embodiment 1
As shown in Figure 1, more micro- stereolithography systems of material include: that ray machine 10, electronics (penetrate) beam splitter 20, detergent 31, tree Rouge delivers 30, projecting lens 40, scraper 50, film 60 and container 70.
Embodiment 2
A kind of Method of printing using expendable material in the printing of micro-structure 3D photocuring, comprises the following steps:
The lower surface that one projection lens contacts the image projection on DLP to film and resin, light occurs for resin monomer there It chemically reacts and is cross-linked into solid.Here the material of film can be PDMS, PFA or other transparent films, thickness from 25 microns to 100 microns.The system has two scrapers arranged side by side (Fig. 2), to strike off resin, 0.5 millimeters deep of scraper teleblem.Often Scraper is ined succession two kinds of resins.Preceding scraper is walked when work and strikes off old resin, is walked posterior scraper and is smeared resin backward, such as Scheme (3).In MCSL, the switching of resin in two kinds of situation (Fig. 4), first is that printing interlayer switches resin, a kind of printing of resin On another resin, after scraper is painted with new resin on film, sample is moved to apart from the corresponding thickness of film, to new tree The exposure of rouge layer;Second is that switching resin in layer, a kind of resin is printed upon in another resin layer, and in this case, scraper is on film After being painted with new resin, sample can return to the position tangent with film, and new resin is squeezed into the sky that same layer needs to fill new resin Between then to new resin according to when layer picture exposure.
Fig. 3, system change liquid apply membrane process: 1,0.5 millimeter of double scraper teleblems;2, at the uniform velocity move scraper to the other side of film, Scraper smears film surface to the new resin of the opposite direction of movement discharge simultaneously;3, scraper and film are detached from, and sample stage rises to finger After positioning is set, image is projected on film.Above step is repeated to different materials, successively completes the printing of 3D sample.
Here suspended structure is relative to 3 D-printing direction, and such as Fig. 5, arrow represents Print direction.Suspended structure exists It is printed before connection structure, so if in printing, it is floated not as support construction, position is indefinite, and causes most It can not form eventually;Bascule cannot have any adhesion with adjacent structure again, therefore also must have support construction could be final Molding.As previously mentioned, filament support construction traditional in micro-scale is no longer applicable in.Applicant proposes a kind of new side Method, such as Fig. 6 print support with the degradable photosensitive sacrificial resin of gas or liquid in the micro- stereolithography system of more materials simultaneously Structure.Sample after printing is placed in corrosion in gas (plasma, acid, alkalinity) or solution (acid, alkalinity) again Support construction is sacrificed in removal.This gas and solution have the corrosion of very strong (10 times or more) to select structural material and expendable material Property.This method without entire support construction all use can sacrificial resin, traditional support construction application in, pillar or needle-shaped Support is finally to be broken support construction from junction by mechanical means to remove.Therefore in fact, we are only permitted in support machine The junction of structure and practical application structure introduces degradable resin it is ensured that the chemistry of support construction removes (Fig. 7).It is this Method has not only saved the consumption of expendable material, and will greatly improve print speed, because the major part of support construction can With with same structural material, and do not have to frequently switch to expendable material.
It can sacrifice there are many kinds of light-sensitive materials, functional structure may have corresponding drop to solution of different nature or gas Solution performance, such as the DMMA(N of here, N- dimethylacrylamide, CAS:2680-03-7) monomer and its mixing it is molten By the weight ratio mixture of 100:2 or so, we are prepared for three kinds of solution, formula point for liquid and 819 photoinitiator of Igacure It is not 1:73.5% DMAA monomer, 24.5%H2O, 2% Igacure 819;It is formulated 2:73.5%DMAA monomer, 24.5% poly- second two Alcohol (MW200), 2% Igacure 819;It is formulated 3:98%DMAA monomer, 2% Igacure 819, curing molding situation is investigated, acid Dissolubility tests (being put into the acid solution of PH=3 after solidification), and observation print dissolves situation within every 1 hour.As a result such as table 1.
The acid dissolution speed of 1 difference DMMA of table formula
Formula Solidification energy At type hardness tester Print thickness Dissolution time Solution rate
1 4.4J/cm2 65 Shore A 1.03mm 4h 257.5um/h
2 4.4J/cm2 40 Shore A 0.87mm 1h 870.0 um/h
3 4.4J/cm2 80 Shore A 0.66mm 2h 330.0 um/h
It is anti-that data show that acid-soluble monomer DMAA can carry out photocuring under conditions of photoinitiator Igacure 819 is added It answers, he can also be miscible with water, polyethylene glycol (PEG molecular weight 200), and carries out photocuring reaction.DMMA monomer light is solid It can be dissolved in the buffer solution of PH=3 after change, rate of dissolution 330um/h, the water of certain proportion (25%) is added not in formula Stereolithography is influenced, but its acid dissolution rate can be reduced to 257.5 um/h;Certain proportion (mass concentration is added in formula 25%) PEG(200) Stereolithography is not influenced, and its acid dissolution rate can be promoted to 870um/h.
Wherein, buffer solution uses the buffer solution of PH=3, using sodium dihydrogen phosphate-citric acid solution, citric acid-hydrogen-oxygen Change one of sodium-hydrochloric acid solution, citric acid-sodium citrate solution, phthalic acid-hydrochloric acid solution.
In the present invention, it using the side of rubbing (BMF) more file printing systems, provides and how to print suspension in minute yardstick and live Dynamic component, to realize the full 3D printing of minute yardstick.We also proposed one kind for being used as sacrifice machine in 3D printing simultaneously The formula of the photosensitive resin of structure also optimizes application of the sacrificial resin in support construction on this basis.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that Specific implementation of the invention is only limited to these instructions.For those of ordinary skill in the art to which the present invention belongs, exist Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to of the invention Protection scope.

Claims (10)

1. a kind of micro- stereolithography system of more materials, ray machine, optical path, film, scraper, resin including setting gradually are delivered, are formed Container and control computer;The ray machine includes micro display chip, the micro display chip using reflective liquid crystal screen LCOS or DLP。
2. a kind of Method of printing using expendable material in the printing of micro-structure 3D photocuring, comprises the following steps:
Step A: projection lens in more micro- stereolithography systems of material as described in claim 1 is by the image projection on DLP To film and resin contact surface, resin monomer occurs photochemical reaction and is cross-linked into solid;
Step B: system is provided with two scrapers arranged side by side, walks preceding scraper and strikes off old resin, walks posterior scraper backward Smear resin;
Step C: system changes liquid film;
Step D: above step is repeated to different materials, successively completes the printing of 3D sample.
3. method according to claim 2, which is characterized in that the step C including the following steps:
Step C1: at the uniform velocity moving scraper to the side of film, while scraper spues new resin to the opposite direction of movement, coated membrane table Face;
Step C2: scraper and film are detached from, and sample stage rises to after designated position, and image is projected on film.
4. Method of printing as claimed in claim 2, which is characterized in that the material of the film use PDMS, PFA or other Transparent film, thickness use 25 microns to 100 microns.
5. Method of printing as claimed in claim 3, which is characterized in that the step of the step C1 are as follows:
It printing interlayer and switches resin, the second resin is printed upon on the first resin, after scraper is painted with the second resin on film, sample quilt It is moved to apart from the corresponding thickness of film, then the second resin layer is exposed.
6. Method of printing as claimed in claim 3, which is characterized in that the step of the step C1 are as follows:
Switch resin in layer, the second resin is printed upon in the first resin layer, and after scraper is painted with the second resin on film, sample can be returned To the position tangent with film, by the second resin squeeze into same layer need to fill the space of the second resin then to the second resin according to When layer picture exposes, alternatively, repeating step before exposure: the second resin is applied, and it is multiple to squeeze the first resin, to avoid the The mixing of two resins and the first resin.
7. such as Method of printing described in claim 5 or 6, which is characterized in that first resin is target material resin, described Second resin is that can sacrifice light-sensitive material resin.
8. Method of printing as claimed in claim 2, which is characterized in that it is described sacrifice light-sensitive material the preparation method comprises the following steps: DMMA monomer and 819 photoinitiator of Igacure are mixed by the weight ratio of 100:2-100:6.
9. a kind of method for releasing of the expendable material of the bascule in 3D printing, which comprises the following steps: need to The device for carrying out expendable material release, which is put into the buffer solution or water of pH=3.0, to be impregnated, solution rate be greater than 330 microns/ Hour.
10. a kind of method for releasing of the expendable material of the bascule in 3D printing, which is characterized in that the buffer solution is adopted With: sodium dihydrogen phosphate-citric acid solution, citric acid-sodium hydroxide-hydrochloric acid solution, citric acid-sodium citrate solution, adjacent benzene two Formic acid-hydrochloric acid solution.
CN201811196663.XA 2018-10-15 2018-10-15 Application of the expendable material in the printing of micro-structure 3D photocuring Pending CN109483872A (en)

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Cited By (7)

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CN109970450A (en) * 2019-03-28 2019-07-05 天津大学 A kind of light sensitive ceramics liquid and its ceramic member for 3D printing
CN110027210A (en) * 2019-05-29 2019-07-19 吴振行 Multiple material sunk type photocuring Method of printing
CN111168995A (en) * 2020-01-03 2020-05-19 深圳摩方新材科技有限公司 Multi-material photocuring 3D printing equipment for film coating and using method thereof
CN111531881A (en) * 2020-04-03 2020-08-14 湖南大学 Multimode multi-material 3D printing equipment
US20210299952A1 (en) * 2020-03-25 2021-09-30 Bmf Material Technology Inc. Roller-membrane layering micro stereolithography
CN114364508A (en) * 2019-09-11 2022-04-15 Bae系统信息和电子系统集成有限公司 3D printing of high stiffness to weight ratio reflective optics
WO2022151539A1 (en) * 2021-01-18 2022-07-21 青岛理工大学 3d printing device and method for integrated manufacturing of functionally gradient material and three-dimensional structure

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CN109970450A (en) * 2019-03-28 2019-07-05 天津大学 A kind of light sensitive ceramics liquid and its ceramic member for 3D printing
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CN110027210A (en) * 2019-05-29 2019-07-19 吴振行 Multiple material sunk type photocuring Method of printing
CN114364508A (en) * 2019-09-11 2022-04-15 Bae系统信息和电子系统集成有限公司 3D printing of high stiffness to weight ratio reflective optics
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CN111168995A (en) * 2020-01-03 2020-05-19 深圳摩方新材科技有限公司 Multi-material photocuring 3D printing equipment for film coating and using method thereof
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CN111531881A (en) * 2020-04-03 2020-08-14 湖南大学 Multimode multi-material 3D printing equipment
WO2022151539A1 (en) * 2021-01-18 2022-07-21 青岛理工大学 3d printing device and method for integrated manufacturing of functionally gradient material and three-dimensional structure
US12083745B2 (en) 2021-01-18 2024-09-10 Qingdao university of technology 3D printing device and method for integrated manufacturing of functionally gradient materials and three-dimensional structures

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