TW202302322A - In-situ precipitation 3D printing device capable of printing a thin film or a structure for manufacturing an ionic crystal, particularly with regard to printing a regular ionic crystal structure - Google Patents

In-situ precipitation 3D printing device capable of printing a thin film or a structure for manufacturing an ionic crystal, particularly with regard to printing a regular ionic crystal structure Download PDF

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TW202302322A
TW202302322A TW110124190A TW110124190A TW202302322A TW 202302322 A TW202302322 A TW 202302322A TW 110124190 A TW110124190 A TW 110124190A TW 110124190 A TW110124190 A TW 110124190A TW 202302322 A TW202302322 A TW 202302322A
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TWI777644B (en
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林清彬
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淡江大學學校財團法人淡江大學
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

This invention provides an in-situ precipitation 3D printing device. The 3D printing device comprises six parts including a computer control and 3D movement system, an etching solution supply system, a printing pen, a forming solution supply system, a forming solution recovery system and a printing platform system. The equipment of this invention is composed of the above-mentioned systems, and an in-situ precipitation 3D printing method is further proposed. The 3D printing method can be used to print a thin film or a structure for manufacturing an ionic crystal, particularly with regard to printing a regular ionic crystal structure.

Description

原位析出3D列印設備與方法In-situ precipitation 3D printing equipment and method

本發明屬於一種3D列印技術,特別指一種採取原位析出(in situ precipitation)的3D列印設備與方法。The invention belongs to a 3D printing technology, in particular to a 3D printing device and method using in situ precipitation.

目前有關於離子晶體的陶瓷3D列印製程,大致包括有:熔融沉積成型(fused deposition modeling ; FDM),直接墨水書寫(direct ink writing ; DIW),光固化成型(stereolithography ; SL100),選擇性雷射燒結(selective laser sintering ; SLS),直接能量沉積(directed energy deposition ; DED),雷射陶瓷沈積(laser ceramic deposition ; LMD),粉體熔化成型(powder bed fusion ; PBF),選擇性雷射熔化成型(selective laser melting ; SLM),直接雷射燒結(direct laser sintering DLS),黏合劑噴射成型(binder jetting ; BJ),熔絲製造(fus ed filament fabrication ; FFF),Titomic動力熔融(Titomic kinetic fusion ; TKF),數位光固化(digital light processing ; DLP),雙光子聚合(two photon polymerization ; TPP),噴墨列印 (inkjet printing ; IJP),層壓實體製造(laminated object manufacturing ; LOM)。這些陶瓷3D列印除了Titomic動力熔融與層壓實體製造外,其他製程會面臨一些製程的困難,以列印氯化銀離子晶體為例,說明如下。Currently, there are ceramic 3D printing processes for ionic crystals, which roughly include: fused deposition modeling (FDM), direct ink writing (DIW), stereolithography (SL100), selective laser Selective laser sintering (SLS), direct energy deposition (directed energy deposition; DED), laser ceramic deposition (laser ceramic deposition; LMD), powder bed fusion (PBF), selective laser melting Forming (selective laser melting; SLM), direct laser sintering (direct laser sintering DLS), binder jetting (binder jetting; BJ), fuse manufacturing (fus ed filament fabrication; FFF), Titomic kinetic fusion (Titomic kinetic fusion ; TKF), digital light processing (DLP), two photon polymerization (TPP), inkjet printing (inkjet printing; IJP), laminated object manufacturing (LOM). In addition to Titomic power fusion and laminated entity manufacturing, these ceramic 3D printing processes will face some process difficulties. Taking the printing of silver chloride ion crystals as an example, the description is as follows.

直接墨水書寫: 1.直接墨水書寫含有奈米氯化銀顆粒的懸浮液(墨水)必須能順利通過微米級圓柱狀噴嘴,形成線形流體及迅速固化以保持列印形狀,甚至在成型含有跨度或懸空梁(無支撐)的結構時,需能保持其形狀而不會發生坍塌或斷裂現象; 2.高含量奈米氯化銀顆粒不易分散在溶液體系及保持長時間的穩定,若是使用低含量,分散較好的奈米氯化銀顆粒懸浮液,列印結構在乾燥和燒結過程中,容易產生大量收縮或引起開裂及變形; 3.高含量奈米氯化銀顆粒懸浮液通過噴嘴時易發生堵塞; 4.無剪切作用固化時,在無支撐條件下不易保持原有形狀; 5.列印好的生胚經燒結後,一些為了分散在溶液體系的有機物接枝及空間位阻的長鏈高分子,若無法有效從奈米氯化銀光觸媒表面清除乾淨,會降低銀原子簇的產生及光催化活性。 Direct Ink Writing: 1. Direct ink writing The suspension (ink) containing nano-silver chloride particles must be able to pass through the micron-sized cylindrical nozzle smoothly, form a linear fluid and solidify quickly to maintain the printing shape, even when the molding contains spans or suspended beams (without support), it must be able to maintain its shape without collapsing or breaking; 2. High-content nano-silver chloride particles are not easy to disperse in the solution system and remain stable for a long time. If you use a low-content, well-dispersed nano-silver chloride particle suspension, the printed structure will be in the process of drying and sintering. It is easy to produce a large amount of shrinkage or cause cracking and deformation; 3. The suspension of high-content nano-silver chloride particles is prone to clogging when passing through the nozzle; 4. When solidified without shearing, it is not easy to maintain the original shape under unsupported conditions; 5. After the printed green embryo is sintered, some long-chain polymers that are grafted with organic matter and sterically hindered in the solution system, if they cannot be effectively removed from the surface of the nano-silver chloride photocatalyst, the silver atoms will be reduced. Cluster formation and photocatalytic activity.

光固化成型與數位光固化: 1.使用含有低含量奈米氯化銀顆粒的感光性樹脂,列印好的生胚經脫脂及燒結後,會產生較大的體積收縮和強度較差的低密度結構; 2.使用高含量的奈米氯化銀顆粒不易均勻分散於感光性樹脂中,因而會列印出不均質的結構; 3.奈米氯化銀顆粒在感光性樹脂會產生光散射的遮蔽效應,這樣的散射不利於光的穿透,進而會影響大尺寸結構的固化及尺寸精度; 4.列印的生胚經熱脫脂及燒結後,若光觸媒表面無法有效將有機物清除乾淨,會降低氯化銀光觸媒銀原子簇的產生及光催化活性。 Light curing molding and digital light curing: 1. Use a photosensitive resin containing low-content nano-silver chloride particles. After the printed green embryo is degreased and sintered, it will produce a large volume shrinkage and a low-density structure with poor strength; 2. Using a high content of nano-silver chloride particles is not easy to disperse evenly in the photosensitive resin, so it will print an inhomogeneous structure; 3. Nano-silver chloride particles will produce a light-scattering shielding effect in the photosensitive resin. Such scattering is not conducive to the penetration of light, which in turn will affect the curing and dimensional accuracy of large-scale structures; 4. After the printed green embryo is thermally degreased and sintered, if the surface of the photocatalyst cannot be effectively cleaned of organic matter, the production of silver clusters and the photocatalytic activity of the silver chloride photocatalyst will be reduced.

選擇性雷射燒結,直接能量沉積,選擇性雷射熔化成型,雷射陶瓷沈積及直接雷射燒結: 1.高能量的雷射燒結或熔化奈米氯化銀顆粒時,會產生較大的熱應力或熱震會使多孔性氯化銀光觸媒結構產生裂縫或熱變形; 2.雷射的熱量傳遞到奈米氯化銀顆粒進行燒結或熔化時,在光觸媒結構強度要求下的雷射功率與掃描速率,一些高斯分布能量較高的掃描區域會產生過熱,使奈米氯化銀顆粒產生熱還原變成氧化銀或氧化銀在與環境中的水氣反應形成氫氧化銀,因而失掉奈米氯化銀光觸媒的光催化效果。 Selective Laser Sintering, Direct Energy Deposition, Selective Laser Melting, Laser Ceramic Deposition and Direct Laser Sintering: 1. When high-energy laser sintering or melting nano-silver chloride particles, large thermal stress or thermal shock will cause cracks or thermal deformation of the porous silver chloride photocatalyst structure; 2. When the heat of the laser is transferred to the nano-silver chloride particles for sintering or melting, the laser power and scanning rate under the requirements of the photocatalyst structure strength, some scanning areas with high Gaussian distribution energy will overheat, making the nano Silver chloride particles are thermally reduced to silver oxide or silver oxide reacts with moisture in the environment to form silver hydroxide, thus losing the photocatalytic effect of the nano-silver chloride photocatalyst.

黏合劑噴射成型: 1.黏合劑噴射列印成型時,使用熱固性黏合劑黏合奈米氯化銀顆粒時,生胚的熱固性黏合劑需能有效完全移除,否則會降低銀原子簇的產生及光催化效果; 2.黏合劑噴射列印生胚的初始密度(green density)較低,經過熱脫脂及燒結後,最終多孔性氯化銀光觸媒結構的相對密度及強度也較差; 3.雖然使用低黏滯係數的熱固性黏合劑,還是不容易完全滲透到奈米氯化銀顆粒的間隙,造成生胚的結構強度大大降低或破壞。 Binder Injection Molding: 1. When using a thermosetting adhesive to bond nano-silver chloride particles during the binder jet printing molding, the thermosetting adhesive of the green embryo must be effectively and completely removed, otherwise the generation of silver clusters and the photocatalytic effect will be reduced; 2. The initial green density of the binder jet printing green body is low, and after thermal degreasing and sintering, the relative density and strength of the final porous silver chloride photocatalyst structure are also poor; 3. Although a thermosetting adhesive with a low viscosity coefficient is used, it is still not easy to completely penetrate into the gaps of the nano-silver chloride particles, which will greatly reduce or destroy the structural strength of the green embryo.

熔絲製造(或熔融沉積成型): 1.熔絲製造列印多孔性氯化銀光觸媒結構時,首先需製造列印線,列印線的製造係將體積含率約60%-80%的奈米氯化銀顆粒與體積含率約20%-40%的有機接著劑、蠟及硬脂酸等助劑均勻混練後進行造粒,再藉由押出成形製得直徑約1.75mm或3mm的列印線。高含量的奈米氯化銀顆粒不易均勻分散於有機接著劑中,所以先前實驗進行連續押出成型時,列印線容易產生脆斷或不易將列印線捲曲到捲線盤; 2.含有團聚奈米氯化銀顆粒的溶膠易在噴嘴處產生堵塞; 3.列印好的生胚經脫脂及燒結後,若有機物無法有效清除乾淨,會降低氯化銀光觸媒銀原子簇的產生及光催化活性。 Fused Filament Fabrication (or Fused Deposition Modeling): 1. When manufacturing and printing the porous silver chloride photocatalyst structure of the fuse, it is first necessary to manufacture the printing line. About 20%-40% of organic adhesives, waxes, stearic acid and other additives are uniformly mixed and granulated, and then extruded to make printing lines with a diameter of about 1.75mm or 3mm. The high content of nano-silver chloride particles is not easy to disperse evenly in the organic adhesive. Therefore, when the continuous extrusion molding was carried out in the previous experiment, the printing line was easy to be brittle or it was difficult to curl the printing line to the winding reel; 2. The sol containing agglomerated nano-silver chloride particles is prone to clogging at the nozzle; 3. After the printed green embryo is degreased and sintered, if the organic matter cannot be effectively removed, it will reduce the production of silver clusters and the photocatalytic activity of the silver chloride photocatalyst.

雙光子聚合: 1.需要進一步研發雙光子聚合的感光性樹脂,因為商業用的感光性樹脂,大都採用對紫外光較敏感的光起始劑,由於這類光起始劑具有較小的雙光子吸收截面,而表現出較低的起始活性,通常需要再增加激發能量或增加曝光時間,才能讓感光性樹脂發生光聚合,因此容易超過破壞閾值而導致結構的缺陷產生; 2.奈米氯化銀顆粒在感光性樹脂會產生光散射的遮蔽效應,這樣的散射不利於光的穿透而會影響大尺寸結構的光固化及尺寸精度; 3.較高含量的奈米氯化銀顆粒不易均勻分散在感光性樹脂中,若使用較低含量的奈米氯化銀顆粒時,生胚經脫脂及燒結後會增加體積收縮和產生強度較低的結構; 4.生胚經脫脂及燒結後,若有機物無法有效清除乾淨,會降低氯化銀光觸媒銀子簇的產生及光催化效果。 Two-photon polymerization: 1. It is necessary to further develop photosensitive resins for two-photon polymerization, because commercial photosensitive resins mostly use photoinitiators that are sensitive to ultraviolet light. Since such photoinitiators have a smaller two-photon absorption cross section, However, if the initial activity is low, it is usually necessary to increase the excitation energy or increase the exposure time to allow the photopolymerization of the photosensitive resin, so it is easy to exceed the destruction threshold and cause structural defects; 2. Nano-silver chloride particles will produce a light-scattering shielding effect in the photosensitive resin. Such scattering is not conducive to light penetration and will affect the photocuring and dimensional accuracy of large-scale structures; 3. Higher content of nano-silver chloride particles is not easy to disperse evenly in the photosensitive resin. If a lower content of nano-silver chloride particles is used, the green embryo will increase volume shrinkage and produce lower strength after degreasing and sintering. low structure; 4. After the green embryo is degreased and sintered, if the organic matter cannot be effectively removed, the generation of silver clusters and the photocatalytic effect of the silver chloride photocatalyst will be reduced.

由此觀之,顯見習用技術不易製造多孔性氯化銀光觸媒結構,且會劣化光催化效果,隨然習用技術係以多孔性氯化銀離子晶體為例,其他離子晶體的薄膜及結構列印均會遇到相同的問題。故仍存有極大的問題而並非完善的製程,亟待業界研究加以解決。From this point of view, it is obvious that the conventional technology is not easy to manufacture the porous silver chloride photocatalyst structure, and will deteriorate the photocatalytic effect. However, the conventional technology is based on the porous silver chloride ion crystal as an example, and the thin films and structures of other ion crystals are listed. Printing will have the same problem. Therefore, there are still huge problems rather than a perfect manufacturing process, which urgently need to be solved by industry research.

為克服上述缺點,本發明的目的在於提供一種解決習知技術不易製造離子晶體的薄膜及結構的缺點,可以利用原位析出(in situ precipitation)技術進行3D列印離子晶體暨其結構和產品者。In order to overcome the above-mentioned shortcomings, the object of the present invention is to provide a method that solves the shortcomings of the prior art that it is difficult to manufacture ionic crystal films and structures, and can use in situ precipitation (in situ precipitation) technology to 3D print ionic crystals and its structure and products. .

本發明的另一目的在於提供一種原位析出3D列印設備與方法,其製程較為簡單,減少3D列印離子晶體的成本,且製程中避免污染而影響產品特性,也助於提高品質。Another object of the present invention is to provide an in-situ precipitation 3D printing device and method, which has a relatively simple manufacturing process, reduces the cost of 3D printing ion crystals, and avoids pollution during the manufacturing process that affects product characteristics, and also helps to improve quality.

為了達到以上目的,本發明採用的技術方案是提供一種原位析出3D列印設備,是由六個部分所組成,包括有:電腦控制與3D移動系統、析出反應溶液供液系統、列印筆、成型溶液供液系統、列印平台系統和成型溶液回收系統,其中, 該電腦控制與3D移動系統將3D列印結構的成型移動路徑指令傳遞給該列印筆,精確控制該列印筆到指定的列印路徑; 該 析出反應溶液(I)供液系統包括有儲存桶,用來將析出反應溶液(I)注入到該列印筆; 該列印筆可以定量供應該析出反應溶液(I)且不會產生滲漏,利用固定供液的泵送壓力、重力和複數槽道的毛細管作用力,直接持續將定量的該析出反應溶液(I)從筆頭流出進行連續列印,列印時找到適當的列印角度和壓力,隨該電腦控制與3D移動系統的成型移動路徑指令精確進行列印; 該析出反應溶液(II)供液系統設置有裝置在中空桶體內具有高精度調控高度的供液活塞,該中空桶體內裝滿析出反應溶液(II),該供液活塞上方的該中空桶體表面設置含有孔洞陣列的供液平台,該供液平台上方設置一個可以左右平移及調控與該供液平台間隙的刮刀; 該析出反應溶液(II)回收系統設置有裝置在中空桶體內的回收活塞,該回收活塞上方的該中空桶體表面設置含有孔洞陣列的回收平台; 該列印平台系統設有高精度控制器調控高度的列印活塞與冷卻劑槽,使該冷卻劑槽上方以活動式固定設置有列印平台,該列印平台鄰接該供液平台,該冷卻劑槽內充填液態氮,該列印平台系統兩端鄰接該成型溶液供液系統與該析出反應溶液(II)回收系統,並使該冷卻劑槽緊鄰密接該中空桶體並共享桶壁。 In order to achieve the above objectives, the technical solution adopted by the present invention is to provide an in-situ precipitation 3D printing equipment, which is composed of six parts, including: computer control and 3D moving system, precipitation reaction solution supply system, printing pen , forming solution supply system, printing platform system and forming solution recovery system, wherein, The computer control and 3D moving system transmits the forming movement path command of the 3D printing structure to the printing pen, and precisely controls the printing pen to the designated printing path; The precipitation reaction solution (I) liquid supply system includes a storage tank for injecting the precipitation reaction solution (I) into the printing pen; The printing pen can quantitatively supply the precipitation reaction solution (I) without leakage, and directly and continuously deliver the quantitative precipitation reaction solution ( I) Continuous printing is carried out from the tip of the pen, and the appropriate printing angle and pressure are found during printing, and the printing is carried out precisely according to the computer control and the forming movement path command of the 3D moving system; The precipitation reaction solution (II) liquid supply system is provided with a liquid supply piston with a high-precision control height in the hollow barrel body, the hollow barrel body is filled with the precipitation reaction solution (II), and the hollow barrel body above the liquid supply piston A liquid supply platform containing an array of holes is arranged on the surface, and a scraper that can translate left and right and adjust the gap with the liquid supply platform is arranged above the liquid supply platform; The precipitation reaction solution (II) recovery system is provided with a recovery piston installed in the hollow barrel, and the surface of the hollow barrel above the recovery piston is provided with a recovery platform containing a hole array; The printing platform system is equipped with a high-precision controller to adjust the height of the printing piston and the coolant tank, so that the printing platform is movable and fixed above the coolant tank, and the printing platform is adjacent to the liquid supply platform. The coolant tank is filled with liquid nitrogen, the two ends of the printing platform system are adjacent to the forming solution supply system and the precipitation reaction solution (II) recovery system, and the coolant tank is closely adjacent to the hollow barrel and shares the barrel wall.

如請求項10所述的原位析出3D列印設備,其中,該析出反應溶液(II)為氯化鈉水溶液,該析出反應溶液(I)為硝酸銀水溶液,該冷卻劑為液態氮。The in-situ precipitation 3D printing device according to claim 10, wherein the precipitation reaction solution (II) is an aqueous solution of sodium chloride, the precipitation reaction solution (I) is an aqueous solution of silver nitrate, and the coolant is liquid nitrogen.

根據前述的設備,本發明進一步提出一種原位析出3D列印的製程方法,包括有: 於列印平台塗佈一層析出反應溶液(II),形成析出反應溶液(II)薄膜,並在該列印平台下方的冷卻劑槽注入冷卻劑,間接冷卻該析出反應溶液(II)薄膜,使冷卻凝固的該析出反應溶液(II)薄膜用來當作之後脫模用的犧牲層; 將析出反應溶液(I)注入列印筆,使該列印筆以適當的壓力及角度接觸到凝固的該成型溶液薄膜進行列印書寫,當常溫的該析出反應溶液(I)接觸到凝固的該該析出反應溶液(II)薄膜時,該析出反應溶液(I)的溫度會溶解凝固的該析出反應溶液(II)薄膜,析出反應形成該析出反應溶液(I)的列印線; 將列印完成後的該析出反應溶液(II)薄膜下降,塗佈下一層的該析出反應溶液(II),同樣進行冷卻凝固、該列印筆的列印書寫過程,反覆進行直到成型整個3D列印結構;最後對該3D列印結構進行燒結,使用適當溶劑將未產生析出反應的固體反應物給予溶解,最後從基板3D列印基板脫模成型。 According to the aforementioned equipment, the present invention further proposes a process method for in-situ precipitation 3D printing, including: Coating a layer of precipitation reaction solution (II) on the printing platform to form a thin film of precipitation reaction solution (II), and injecting a coolant into the coolant tank below the printing platform to indirectly cool the precipitation reaction solution (II) film, so that The precipitated reaction solution (II) film which is cooled and solidified is used as a sacrificial layer for demoulding afterwards; Inject the precipitation reaction solution (I) into the printing pen, and make the printing pen touch the solidified forming solution film at an appropriate pressure and angle for printing and writing. When the precipitation reaction solution (I) at normal temperature touches the solidified film When the precipitation reaction solution (II) film, the temperature of the precipitation reaction solution (I) will dissolve the solidified precipitation reaction solution (II) film, and the precipitation reaction forms the printing line of the precipitation reaction solution (I); After the printing is completed, the film of the precipitation reaction solution (II) is lowered, and the next layer of the precipitation reaction solution (II) is coated, and the process of cooling and solidification, and the printing and writing process of the printing pen are repeated until the entire 3D is formed. Print the structure; finally, sinter the 3D printed structure, use an appropriate solvent to dissolve the solid reactant that has not produced a precipitation reaction, and finally release the mold from the substrate 3D printed substrate.

本發明的原位析出3D列印設備與方法,與現有技術相較之下,具有下列特點與功效: 1.本發明可以直接製造離子晶體薄膜或晶體結構,而沒有任何汙染物形成其中或表面而劣化其性質,這些離子晶體薄膜或晶體結構不易直接或使用傳統的溶膠凝膠(sol-gel)或目前發展的陶瓷3D列印製造,尤其是不易直接使用原位析出製造規則性孔洞的離子晶體薄膜或晶體結構; 2.本發明原位析出3D列印可以用於會產生析出反應的離子晶體薄膜或晶體結構製造,只要調製好反應物的濃度,大於溶度積(K SP)時即可以一邊析出一邊列印成形,而反應物可以有多樣的選擇,例如要原位析出3D列印規則性氯化銀,可以使用硝酸銀水溶液和氯化鈉水溶液作析出反應,或可以使用硝酸銀水溶液和鹽酸水溶液作析出反應; 3.本發明原位析出3D列印離子晶體薄膜或晶體結構,可以將要功能性摻雜(doping)的元素,直接先溶解於反應物的溶液中,列印完後參雜元素會直接形成於離子晶體薄膜或晶體結構中,不需要作二次摻雜處理,且摻雜元素可以均勻分布於離子晶體薄膜或晶體結構中; 4.本發明原位析出3D列印離子晶體薄膜或晶體結構時,可以將兩種離子晶體共同列印,例如可以使用兩種列印筆,例如硝酸銀水溶液及硝酸鎳(Ni(NO 3) 2·6H 2O)水溶液,分別在適當位置與氫氧化鈉(NaOH)水溶液產生氫氧化銀(Ag(OH))與氫氧化鎳(Ni(OH)),經加熱後形成氧化銀(Ag 2O)與一氧化鎳(NiO)共析出離子晶體薄膜或晶體結構者; 5.由於離子晶體結構不易加工成所需的形狀,本發明原位析出3D列印可以直接列印出所需形狀的離子晶體結構。 Compared with the prior art, the in-situ precipitation 3D printing equipment and method of the present invention have the following characteristics and effects: 1. The present invention can directly manufacture ionic crystal films or crystal structures without any pollutants forming in or on the surface To degrade its properties, these ionic crystal films or crystal structures are not easy to be directly manufactured by traditional sol-gel (sol-gel) or the currently developed ceramic 3D printing, especially it is not easy to directly use in-situ precipitation to create regular holes. Crystal film or crystal structure; 2. The in-situ precipitation 3D printing of the present invention can be used in the manufacture of ion crystal film or crystal structure that will produce precipitation reaction, as long as the concentration of the reactant is adjusted well, it will be greater than the solubility product (K SP ) It can be printed and shaped while being precipitated, and there are various choices of reactants. For example, if you want to precipitate 3D printing regular silver chloride in situ, you can use silver nitrate aqueous solution and sodium chloride aqueous solution for the precipitation reaction, or you can use silver nitrate aqueous solution and Hydrochloric acid aqueous solution for precipitation reaction; 3. The present invention precipitates 3D printing ionic crystal film or crystal structure in situ, and the elements to be functionally doped (doping) can be directly dissolved in the solution of reactants first, and can be added after printing. Impurity elements will be directly formed in the ionic crystal film or crystal structure, no secondary doping treatment is required, and the doping elements can be uniformly distributed in the ionic crystal film or crystal structure; 4. In situ precipitation of 3D printing ions In the case of crystal film or crystal structure, two kinds of ionic crystals can be printed together. For example, two kinds of printing pens can be used, such as silver nitrate aqueous solution and nickel nitrate (Ni(NO 3 ) 2 ·6H 2 O) aqueous solution. With sodium hydroxide (NaOH) aqueous solution to produce silver hydroxide (Ag(OH)) and nickel hydroxide (Ni(OH)), after heating to form silver oxide (Ag 2 O) and nickel monoxide (NiO) co-precipitated ions Crystal film or crystal structure; 5. Since the ionic crystal structure is not easy to process into the desired shape, the in-situ precipitation 3D printing of the present invention can directly print the ionic crystal structure of the desired shape.

下面結合附圖對本發明的較佳實施例進行詳細闡述,以使本發明的優點和特徵能更易於被本領域技術人員理解,從而對本發明的保護範圍做出更為清楚明確的界定。 [實施例一] The preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings, so that the advantages and features of the present invention can be more easily understood by those skilled in the art, so as to define the protection scope of the present invention more clearly. [Example 1]

請參閱圖1至圖4所示,為本發明所稱之原位析出3D列印設備,主要用來製造多孔性AgCl光觸媒結構。該原位析出3D列印系統由六個部分所組成,包括:電腦控制與3D移動系統(100)、硝酸銀(AgNO 3)水溶液供液系統(B)、列印筆300、氯化鈉(NaCl)水溶液供液系統400、列印平台系統500和氯化鈉水溶液回收系統600,以下分別說明。 Please refer to Figures 1 to 4, which are the in-situ deposition 3D printing equipment referred to in the present invention, which is mainly used to manufacture porous AgCl photocatalyst structures. The in-situ precipitation 3D printing system consists of six parts, including: computer control and 3D moving system (100), silver nitrate (AgNO 3 ) aqueous solution supply system (B), printing pen 300, sodium chloride (NaCl ) The aqueous solution supply system 400, the printing platform system 500 and the sodium chloride aqueous solution recovery system 600 are described below respectively.

該電腦控制與3D移動系統(100)主要通過安裝在X軸和Y軸的線形電機和編碼器及Z軸的高精度控制器來控制列印成型的路徑,該系統通過C100D設計所需的3D列印結構800,將列印結構成型移動路徑轉化為相關指令代碼,並通過3D運動平台系統的控制器,將成型移動路徑指令傳遞給列印筆300,在3D方向作自由移動,從而精確控制列印筆300到指定的列印路徑。The computer control and 3D moving system (100) mainly controls the path of printing and forming through the linear motors and encoders installed on the X-axis and Y-axis and the high-precision controller of the Z-axis. The printing structure 800 converts the forming movement path of the printing structure into relevant instruction codes, and transmits the forming movement path instruction to the printing pen 300 through the controller of the 3D motion platform system, and moves freely in the 3D direction, thereby precisely controlling Print the pen 300 to the designated printing path.

該硝酸銀水溶液供液系統(B)提供硝酸銀或等效溶液作為3D列印的析出反應溶液(I),其包括儲存桶210,桶內填充硝酸銀水溶液220,利用微流體蠕動幫浦230(可微量調控供液的流量與速率)及中空列印管240,中空列印管240出口端面再密封設置列印筆300,硝酸銀水溶液供液系統(B)與電腦控制與3D移動系統(100)設置,使其在列印時,兩個系統是同步連動,藉由微流體蠕動幫浦230提供動力在穩定速率下將定量硝酸銀水溶液220輸送到中空列印管240,再注入到列印筆300。The silver nitrate aqueous solution supply system (B) provides silver nitrate or an equivalent solution as the precipitation reaction solution (I) for 3D printing, which includes a storage barrel 210 filled with an aqueous silver nitrate solution 220, and uses a microfluidic peristaltic pump 230 (traceable Regulate the flow and rate of the liquid supply) and the hollow printing tube 240, the outlet end of the hollow printing tube 240 is sealed and the printing pen 300 is installed, the silver nitrate aqueous solution supply system (B) and the computer control and 3D mobile system (100) are set, When printing, the two systems operate synchronously, and the microfluidic peristaltic pump 230 provides power to transport the quantitative silver nitrate aqueous solution 220 to the hollow printing tube 240 at a stable rate, and then injects it into the printing pen 300 .

列印筆300作為3D列印的塑型工具,在預備實驗時,發明人使用馬克筆頭當列印筆300時,由於筆頭是由人造纖維束所組成,再藉由毛細管作用力將硝酸銀水溶液220從筆頭滲出,因為硝酸銀水溶液220的黏滯係數很低,所以筆頭會滲漏硝酸銀水溶液220及累積形成大顆水滴而影響列印的品質,另外,在列印完後,若筆頭沒有清洗乾淨,當水溶液蒸發後會在纖維間隙析出硝酸銀顆粒而阻塞後續的供液;The printing pen 300 is used as a modeling tool for 3D printing. In the preparatory experiment, the inventor used a marker pen tip as the printing pen 300. Since the pen tip is composed of man-made fiber bundles, the silver nitrate aqueous solution 220 Seepage from the tip of the pen, because the viscosity coefficient of the silver nitrate aqueous solution 220 is very low, so the silver nitrate aqueous solution 220 will leak from the pen tip and accumulate to form large water droplets, which will affect the printing quality. In addition, after printing, if the pen tip is not cleaned, When the aqueous solution evaporates, silver nitrate particles will be precipitated in the fiber gap and block the subsequent liquid supply;

因此,本發明另外製作一款可以定量供液且不能產生滲漏的列印筆300,其設計是將列印筆300與中空列印管240密封螺接,列印筆300的結構係在筆桿一端部以低摩擦係數鐵氟龍(teflon)為材質,筆桿設置具複數條柱狀導流凸緣相互束結且螺旋延伸的筆頭,該複數導流凸緣之延伸端部呈一個漸縮的筆尖部,因此複數導流凸緣之間自然會形成凹型的槽道,筆尖部使用火燄加熱使筆尖部端表面因內聚力作用而收縮呈光滑的圓弧面,使其能滑順列印,可以藉由圓弧面的大小改變列印寬度,複數槽道的加工精度要高,每個槽道的末端連接一個孔,用於空氣流動以平衡壓力,由於硝酸銀水溶液220與列印筆300連通,因此藉由固定供液的泵送壓力、重力和複數槽道的毛細管作用力,可以直接持續將定量硝酸銀水溶液220從筆頭流出進行連續列印,列印時找到適當的列印角度和壓力,列印筆300隨電腦控制與3D移動系統(100)按成型移動路徑的指令精確進行列印,不列印時需使用密封筆蓋將鐵氟龍筆桿與筆頭封住防止水溶液流失及硝酸銀顆粒的析出,列印前將鐵氟龍筆桿與筆頭浸泡到蒸餾水中,將殘留在複數槽道的硝酸銀顆粒溶解,使後續的供液順暢,使用蒸餾水的理由是由於自來水中的礦物質含量太高會阻塞槽道。Therefore, the present invention makes another printing pen 300 that can supply liquid quantitatively without leakage. Its design is to seal and screw the printing pen 300 with the hollow printing tube 240. One end is made of low-friction Teflon (teflon), and the pen holder is provided with a plurality of columnar diversion flanges that are bound together and extend spirally. The extended ends of the plurality of diversion flanges are tapered At the tip of the pen, concave grooves will naturally be formed between the plurality of diversion flanges. The tip of the pen is heated by a flame so that the surface of the tip of the nib shrinks due to the cohesive force and becomes a smooth arc surface, so that it can be printed smoothly. The printing width is changed by the size of the arc surface, and the processing accuracy of the multiple channels is high. The end of each channel is connected with a hole for air flow to balance the pressure. Since the silver nitrate aqueous solution 220 is connected with the printing pen 300, the By fixing the pumping pressure, gravity and the capillary force of multiple channels, the quantitative silver nitrate aqueous solution 220 can be directly and continuously flowed out from the pen tip for continuous printing. When printing, find the appropriate printing angle and pressure, and print The pen 300 is controlled by the computer and the 3D moving system (100) to accurately print according to the instructions of the forming movement path. When not printing, it is necessary to use a sealed pen cap to seal the Teflon pen holder and the pen tip to prevent the loss of aqueous solution and the precipitation of silver nitrate particles. Before printing, soak the Teflon pen holder and nib in distilled water to dissolve the silver nitrate particles remaining in the multiple channels, so that the subsequent liquid supply is smooth. The reason for using distilled water is that the mineral content in tap water is too high to block the channels. road.

該氯化鈉水溶液供液系統400提供氯化鈉水溶液或等效溶液作為3D列印析出反應溶液(II),氯化鈉水溶液供液系統400包括裝置在鐵氟龍中空桶體420內並設有高精度調控高度的鐵氟龍供液活塞410,鐵氟龍供液活塞410上方的鐵氟龍中空桶體420表面設置含有孔洞陣列430及表面平整的鐵氟龍供液平台440,鐵氟龍供液平台440上方設置一個可以左右平移及可高精度調控與鐵氟龍供液平台440間隙的刮刀450,鐵氟龍中空桶體420內裝滿氯化鈉水溶液460,為了防止氯化鈉水溶液460的滲漏,鐵氟龍供液活塞410設置一固體潤滑材料的活塞環470與鐵氟龍中空桶體420壁密接,使用固體潤滑材料可以讓鐵氟龍供液活塞410順暢上下滑移,當鐵氟龍供液活塞410以一定高度向上時,氯化鈉水溶液460會以一定量從孔洞陣列430滲出,再藉由刮刀450調整與鐵氟龍供液平台440間隙,將溢出的氯化鈉水溶液460塗佈到列印平台500的有效列印區域。The sodium chloride aqueous solution supply system 400 provides sodium chloride aqueous solution or an equivalent solution as the 3D printing precipitation reaction solution (II). The sodium chloride aqueous solution supply system 400 includes a device in a Teflon hollow barrel 420 and There is a Teflon liquid supply piston 410 with high-precision height adjustment, and the surface of the Teflon hollow barrel 420 above the Teflon liquid supply piston 410 is provided with a hole array 430 and a Teflon liquid supply platform 440 with a flat surface. A scraper 450 is set above the dragon liquid supply platform 440, which can translate left and right and can adjust the gap with the Teflon liquid supply platform 440 with high precision. The Teflon hollow barrel 420 is filled with an aqueous sodium chloride solution 460. For the leakage of the aqueous solution 460, the Teflon liquid supply piston 410 is provided with a piston ring 470 of solid lubricating material in close contact with the wall of the Teflon hollow barrel 420, and the solid lubricating material can make the Teflon liquid supply piston 410 slide up and down smoothly , when the Teflon liquid supply piston 410 is raised at a certain height, the sodium chloride aqueous solution 460 will seep out from the hole array 430 in a certain amount, and then the gap between the Teflon liquid supply platform 440 and the Teflon liquid supply platform 440 is adjusted by the scraper 450, and the overflowing chlorine The sodium chloride aqueous solution 460 is applied to the effective printing area of the printing platform 500 .

該氯化鈉水溶液回收系統600設置有裝置在中空桶體內的鐵氟龍回收活塞640,該鐵氟龍回收活塞640上方的鐵氟龍中空桶體420表面設置含有孔洞陣列630的鐵氟龍回收平台620,將塗佈到列印平台500而多餘的氯化鈉水溶液610推移到氯化鈉水溶液回收系統600的鐵氟龍回收平台620,讓多餘的氯化鈉水溶液610從鐵氟龍回收平台620的孔洞陣列630流到鐵氟龍中空桶體420中,為了防止氯化鈉水溶液610的滲漏,鐵氟龍回收活塞640設置一固體潤滑材料作成的活塞環650與鐵氟龍中空桶體420壁密接。The sodium chloride aqueous solution recovery system 600 is provided with a Teflon recovery piston 640 installed in the hollow barrel body, and the Teflon hollow barrel body 420 above the Teflon recovery piston 640 is provided with a Teflon recovery element containing a hole array 630 on the surface. The platform 620 is to transfer the excess sodium chloride aqueous solution 610 applied to the printing platform 500 to the Teflon recovery platform 620 of the sodium chloride aqueous solution recovery system 600, allowing the excess sodium chloride aqueous solution 610 to recover from the Teflon recovery platform The hole array 630 of 620 flows into the Teflon hollow barrel 420. In order to prevent the leakage of the sodium chloride aqueous solution 610, the Teflon recovery piston 640 is provided with a piston ring 650 made of solid lubricating material and the Teflon hollow barrel. 420 wall tight.

該列印平台系統500包括設有高精度控制器調控高度的鐵氟龍列印活塞510與鐵氟龍冷卻劑槽520設置在一起,使該鐵氟龍冷卻劑槽520上方以活動式固定設置一個具有鏡面及超親水(superhydrophilic)銅質的列印平台540,鐵氟龍冷卻劑槽520內充填液態氮530,且在鐵氟龍冷卻劑槽520設置一注入孔與鎖蓋用以補充液態氮530。The printing platform system 500 includes a Teflon printing piston 510 with a high-precision controller to adjust the height and a Teflon coolant tank 520, so that the upper part of the Teflon coolant tank 520 is movable and fixed. A printing platform 540 with a mirror surface and superhydrophilic copper, the Teflon coolant tank 520 is filled with liquid nitrogen 530, and an injection hole and a lock cover are set in the Teflon coolant tank 520 to replenish the liquid Nitrogen 530.

經由前述各系統整合得完成本發明原位析出3D列印系統的建置,其中,該鐵氟龍冷卻劑槽520與氯化鈉水溶液供液系統400與氯化鈉水溶液回收系統600的鐵氟龍中空桶體420需緊鄰密接及共享桶壁,刮刀450在塗佈氯化鈉水溶液460時,氯化鈉水溶液460從氯化鈉水溶液供液系統400的鐵氟龍供液平台440到列印平台540時,兩者的平台必須是共平面。在平移的路徑,刮刀450與兩者平台的間隙要一致,刮刀450平移到氯化鈉水溶液回收系統600的鐵氟龍回收平台620,需能作下壓將讓多餘的氯化鈉水溶液610擠入氯化鈉水溶液回收系統600的鐵氟龍中空桶體420,為了防止刮刀450在全程的平移路徑,氯化鈉水溶液460與多餘的氯化鈉水溶液610從四周溢出,這三個系統需等高共平面設置在一起,四邊周圍再設置一個相對矮的圍牆700。Through the integration of the aforementioned systems, the construction of the in-situ precipitation 3D printing system of the present invention is completed, wherein the Teflon coolant tank 520, the Teflon water supply system 400 and the sodium chloride aqueous solution recovery system 600 The dragon hollow barrel body 420 needs to be close to and share the barrel wall. When the scraper 450 is coating the sodium chloride aqueous solution 460, the sodium chloride aqueous solution 460 is from the Teflon liquid supply platform 440 of the sodium chloride aqueous solution supply system 400 to the printing When platform 540 is used, the platforms of both must be coplanar. In the path of translation, the gap between the scraper 450 and the two platforms should be consistent, and the scraper 450 should be moved to the Teflon recovery platform 620 of the sodium chloride aqueous solution recovery system 600, and it needs to be able to press down to squeeze the excess sodium chloride aqueous solution 610 Into the Teflon hollow barrel 420 of the sodium chloride aqueous solution recovery system 600, in order to prevent the scraper 450 from moving in the whole process, the sodium chloride aqueous solution 460 and the excess sodium chloride aqueous solution 610 overflow from the surroundings. These three systems need to wait The high coplanar planes are set together, and a relatively low wall 700 is set around the four sides.

請結合圖5所示,藉由前述原位析出3D列印系統,發明人進一步提出一種原位析出3D列印的製程方法: 5-1.首先由氯化鈉水溶液供液系統400的鐵氟龍供液活塞410以預定高度向上,此時一定量的氯化鈉水溶液460會從孔洞陣列430溢出,即時使用刮刀450調整適當的間隙,平移將溢出的氯化鈉水溶液460均勻塗佈在列印平台540,均勻塗上一層很薄的氯化鈉水溶液460,由於列印平台540具有鏡面與超親水性,所以在表面可以形成一層厚度很小的NaCI水溶液460薄膜,接著注入液態氮530到列印平台540下方鐵氟龍冷卻劑槽520內作為冷卻劑,間接冷卻列印平台540表面上的氯化鈉水溶液460薄膜,氯化鈉水溶液460薄膜會立即凝固,凝固的氯化鈉水溶液薄膜810是用來當作之後脫模用的犧牲層; 5-2.接著微流體蠕動幫浦230提供動力將定量硝酸銀水溶液220輸送到中空列印管240,再注入直到列印筆300,列印筆300以適當的壓力及角度接觸到凝固的氯化鈉水溶液薄膜(Hl)進行列印書寫,當常溫的硝酸銀水溶液220與凝固氯化鈉水溶液薄膜810接觸時,硝酸銀水溶液220的溫度會溶解凝固氯化鈉水溶液薄膜810,此時水溶液薄膜中的銀離子與氯離子的溶度積(K sp)若大於氯化銀,會立即析出反應形成氯化銀的列印線820; 5-3.此時再給予紫外燈900照射氯化銀列印線820因為光還原產生銀原子簇,轉為黑色的列印線820,使用列印筆300的筆頭寬度約2mm; 5-4.精確地列印出第一層結構後,鐵氟龍列印活塞510下降一適當高度,再次使氯化鈉水溶液供液系統400的鐵氟龍供液活塞410高度上升,將一定量的氯化鈉水溶液460會從孔洞陣列430溢出,並即時使用刮刀450調整適當的間隙,間隙的大小與鐵氟龍列印活塞510下降的高度相當,還要考慮凝固收縮的問題,平移將溢出的氯化鈉水溶液460均勻塗佈到第一層已列印的氯化鈉水溶液薄膜810上,即時將第二層的氯化鈉水溶液460再次給予凝固,適當厚度的氯化鈉水溶液凝固層是要減少凝固層收縮產生的表面不平整,接著再次使用列印筆300書寫列印及紫外燈900照射,重復以上同樣方式的列印,直至整個該3D列印結構800完成成型; 5-5.列印完後,將鐵氟龍列印活塞510向上頂出,超過圍牆700的高度,移出列印平台540,並將列印平台540放置到烘箱進行乾燥處理後,再將列印平台540移入燒結爐內,在適當的燒結溫度及加溫速率進行燒結,用以增加氯化銀光觸媒結構的強度,最後將燒結後的列印平台540浸入到去離子水中,使用去離子水溶解氯化鈉顆粒及硝酸銀顆粒的殘留物830,同時溶解氯化鈉水溶液薄膜810形成的犧牲層,最後將列印結構與列印平台540順利給予脫模。 [實施例二] Please combine with Figure 5, with the aforementioned in-situ precipitation 3D printing system, the inventor further proposes a process method for in-situ precipitation 3D printing: 5-1. The dragon liquid supply piston 410 goes up at a predetermined height, at this time a certain amount of sodium chloride aqueous solution 460 will overflow from the hole array 430, immediately use the scraper 450 to adjust the appropriate gap, and spread the overflowing sodium chloride aqueous solution 460 evenly on the column The printing platform 540 is evenly coated with a very thin layer of sodium chloride aqueous solution 460. Since the printing platform 540 has a mirror surface and super-hydrophilicity, a layer of NaCl aqueous solution 460 film with a small thickness can be formed on the surface, and then liquid nitrogen 530 is injected to The Teflon coolant tank 520 below the printing platform 540 is used as a coolant to indirectly cool the sodium chloride aqueous solution 460 film on the surface of the printing platform 540, and the sodium chloride aqueous solution 460 film will solidify immediately, and the solidified sodium chloride aqueous solution film 810 is used as a sacrificial layer for subsequent demoulding; 5-2. Then the microfluidic peristaltic pump 230 provides power to transport the quantitative silver nitrate aqueous solution 220 to the hollow printing tube 240, and then inject it until the printing pen 300, printing The pen 300 touches the solidified sodium chloride aqueous solution film (H1) at an appropriate pressure and angle for printing and writing. When the normal temperature silver nitrate aqueous solution 220 contacts the solidified sodium chloride aqueous solution film 810, the temperature of the silver nitrate aqueous solution 220 will dissolve and solidify. Sodium chloride aqueous solution film 810, if the solubility product (K sp ) of silver ions and chloride ions in the aqueous solution film is greater than silver chloride, it will immediately precipitate and react to form a printing line 820 of silver chloride; 5-3. At this time, the UV lamp 900 is used to irradiate the silver chloride printing line 820 to produce silver atom clusters due to photoreduction, which turns into a black printing line 820, and the width of the tip of the printing pen 300 is about 2mm; 5-4. Accurately list After the first layer of structure is printed, the Teflon printing piston 510 is lowered to an appropriate height, and the height of the Teflon liquid supply piston 410 of the sodium chloride aqueous solution supply system 400 is raised again, and a certain amount of sodium chloride aqueous solution 460 It will overflow from the hole array 430, and immediately use the scraper 450 to adjust the appropriate gap. The size of the gap is equivalent to the height of the Teflon printing piston 510, and the problem of solidification and shrinkage should also be considered. The sodium chloride aqueous solution 460 that will overflow Apply evenly on the first layer of the printed sodium chloride aqueous solution film 810, and immediately solidify the second layer of sodium chloride aqueous solution 460. The appropriate thickness of the sodium chloride aqueous solution solidified layer is to reduce the shrinkage of the solidified layer The surface of the 3D printing structure 800 is uneven, then use the printing pen 300 to write and print and irradiate with the ultraviolet lamp 900, and repeat the above printing in the same way until the entire 3D printing structure 800 is formed; 5-5. After printing, put The Teflon printing piston 510 is pushed out upwards, exceeding the height of the enclosure wall 700, and the printing platform 540 is moved out, and the printing platform 540 is placed in an oven for drying treatment, and then the printing platform 540 is moved into the sintering furnace. The sintering temperature and heating rate are sintered to increase the strength of the silver chloride photocatalyst structure. Finally, the sintered printing platform 540 is immersed in deionized water, and the residual sodium chloride particles and silver nitrate particles are dissolved in deionized water. object 830, while dissolving the sacrificial layer formed by the sodium chloride aqueous solution film 810, and finally the printing structure and the printing platform 540 are successfully released from the mold. [Example 2]

列印規則性多孔性溴化銀(AgBr)離子晶體,使用溴化鈉(NaBr)水溶液取氯化鈉水溶液,溴化銀離子晶體光還原後形成銀/溴化銀,同時可以具有紫外光即可見光的光催化效果,可用於工業染料廢水及飲用水殺菌的效果,本發明3D列印製造規則性多孔性100g/100gCl的光觸媒結構,除了多孔性可以增加光催化的表面積外,同時可以解決光觸媒顆粒的固著及可以重複使用的問題。 [實施例三] Print regular porous silver bromide (AgBr) ion crystals, use sodium bromide (NaBr) aqueous solution to obtain sodium chloride aqueous solution, silver bromide ion crystals are photoreduced to form silver/silver bromide, and at the same time can have ultraviolet light that is The photocatalytic effect of visible light can be used to sterilize industrial dye wastewater and drinking water. The 3D printing of the present invention produces a photocatalyst structure with regular porosity of 100g/100gCl. In addition to the porosity can increase the surface area of photocatalysis, it can also solve the problem of photocatalyst Particle fixation and reusability issues. [Embodiment three]

列印規則性多孔性一氧化鎳(NiO)離子晶體,使用硝酸鎳(Ni(NO 3) 2·6H 2O)水溶液取代硝酸銀水溶液,氫氧化鈉(NaOH)水溶液取代氯化鈉水溶液析出反應,規則性多孔性一氧化鎳用於超電容器的電極材料,其比電容、大功率性能和迴圈穩定性均較使用碳材料、過渡金屬氧化物和導電聚合物優異。 Print regular porous nickel monoxide (NiO) ionic crystals, use nickel nitrate (Ni(NO 3 ) 2 6H 2 O) aqueous solution instead of silver nitrate aqueous solution, sodium hydroxide (NaOH) aqueous solution instead of sodium chloride aqueous solution for precipitation reaction, Regular porous nickel monoxide is used as an electrode material for supercapacitors, and its specific capacitance, high-power performance and cycle stability are all superior to carbon materials, transition metal oxides and conductive polymers.

以上實施方式只為說明本發明的技術構思及特點,其目的在於讓熟悉此項技術的人瞭解本發明的內容並加以實施,並不能以此限制本發明的保護範圍,凡根據本發明精神實質所做的等效變化或修飾,都應涵蓋在本發明的保護範圍內。The above embodiments are only to illustrate the technical concept and characteristics of the present invention. All equivalent changes or modifications shall fall within the protection scope of the present invention.

100:電腦控制與3D移動系統 200:硝酸銀水溶液供液系統 210:儲存桶 220:硝酸銀水溶液 230:微流體蠕動幫浦 240:中空列印管 300:列印筆 400:氯化鈉水溶液供液系統 410:供液活塞 420:中空桶體 430:孔洞陣列 440:供液平台 450:刮刀 460:氯化鈉水溶液 470:活塞環 500:列印平台系統 510:列印活塞 520:冷卻劑槽 530:液態氮 540:列印平台 600:氯化鈉水溶液回收系統 610:氯化鈉水溶液 620:回收平台 630:孔洞陣列 640:回收活塞 650:活塞環 700:圍牆 800:3D列印結構 810:氯化鈉水溶液薄膜 820:列印線 830:殘留物 900:紫外燈 100: Computer control and 3D moving system 200: Silver nitrate aqueous solution supply system 210: storage bucket 220: Silver nitrate aqueous solution 230:Microfluidic peristaltic pump 240: hollow printing tube 300: printing pen 400: Sodium chloride aqueous solution supply system 410: liquid supply piston 420: hollow barrel 430: Hole array 440: liquid supply platform 450: scraper 460: Sodium chloride aqueous solution 470:piston ring 500:Print platform system 510:Print Piston 520: Coolant tank 530: liquid nitrogen 540: printing platform 600: Sodium chloride aqueous solution recovery system 610: Sodium chloride aqueous solution 620: Recycling platform 630:hole array 640: Recovery Piston 650:piston ring 700: wall 800: 3D Printed Structures 810: Sodium chloride aqueous solution film 820: Printing line 830: Residue 900: UV lamp

圖1為本發明的原位析出3D列印設備的結構立體圖; 圖2為該原位析出3D列印設備的結構平面圖; 圖3為該原位析出3D列印設備所完成3D列印結構的結構示意圖; 圖4該3D列印結構經燒結、脫模後的結構示意圖;以及 圖5該原位析出3D列印設備的實施流程圖。 Fig. 1 is a perspective view of the structure of the in-situ precipitation 3D printing device of the present invention; Fig. 2 is a structural plan view of the in-situ precipitation 3D printing equipment; Fig. 3 is a structural schematic diagram of the 3D printing structure completed by the in-situ precipitation 3D printing device; Fig. 4 is a schematic structural diagram of the 3D printing structure after sintering and demoulding; and Fig. 5 is an implementation flow chart of the in-situ deposition 3D printing device.

100:電腦控制與3D移動系統 100: Computer control and 3D moving system

200:硝酸銀水溶液供液系統 200: Silver nitrate aqueous solution supply system

210:儲存桶 210: storage bucket

220:硝酸銀水溶液 220: Silver nitrate aqueous solution

230:微流體蠕動幫浦 230:Microfluidic peristaltic pump

240:中空列印管 240: hollow printing tube

300:列印筆 300: printing pen

400:氯化鈉水溶液供液系統 400: Sodium chloride aqueous solution supply system

410:供液活塞 410: liquid supply piston

420:中空桶體 420: hollow barrel

430:孔洞陣列 430: Hole array

440:供液平台 440: liquid supply platform

450:刮刀 450: scraper

460:氯化鈉水溶液 460: Sodium chloride aqueous solution

470:活塞環 470:piston ring

500:列印平台系統 500:Print platform system

510:列印活塞 510:Print Piston

520:冷卻劑槽 520: Coolant tank

530:液態氮 530: liquid nitrogen

540:列印平台 540: printing platform

600:氯化鈉水溶液回收系統 600: Sodium chloride aqueous solution recovery system

610:氯化鈉水溶液 610: Sodium chloride aqueous solution

620:回收平台 620: Recycling platform

630:孔洞陣列 630:hole array

640:回收活塞 640: Recovery Piston

650:活塞環 650:piston ring

700:圍牆 700: wall

800:3D列印結構 800: 3D Printed Structures

810:氯化鈉水溶液薄膜 810: Sodium chloride aqueous solution film

900:紫外燈 900:UV lamp

Claims (25)

一種原位析出3D列印方法,包括有: 於列印平台塗佈一層析出反應溶液(II),形成析出反應溶液(II)薄膜,並在該列印平台下方的冷卻劑槽注入冷卻劑或使用致冷晶片,間接冷卻該成型溶液薄膜,使冷卻凝固的該析出反應溶液(II)薄膜用來當作之後脫模用的犧牲層; 將析出反應溶液(I)注入列印筆,使該列印筆以適當的壓力及角度接觸到凝固的該析出反應溶液(I)薄膜進行列印書寫,當常溫的該析出反應溶液(I)接觸到凝固的該析出反應溶液(II)薄膜時,該析出反應溶液(I)的溫度會溶解凝固的該析出反應溶液(II)薄膜,析出反應形成列印線; 將列印完成後的該析出反應溶液(II)薄膜下降,塗佈下一層的該析出反應溶液(II),同樣進行冷卻凝固、該列印筆的列印書寫過程,反覆進行直到成型整個3D列印結構; 對該3D列印結構進行燒結、使用適當溶劑將未產生析出反應的固體反應物給予溶解,最後從基板3D列印基板脫模成型。。 An in-situ precipitation 3D printing method, including: Coating a layer of precipitation reaction solution (II) on the printing platform to form a thin film of precipitation reaction solution (II), and injecting a coolant into the coolant tank under the printing platform or using a cooling chip to indirectly cool the forming solution film, The precipitation reaction solution (II) film that makes cooling and solidification is used as a sacrificial layer for demoulding afterwards; Inject the precipitation reaction solution (I) into the printing pen, and make the printing pen touch the solidified precipitation reaction solution (I) film at an appropriate pressure and angle for printing and writing. When the precipitation reaction solution (I) at room temperature When contacting the solidified precipitation reaction solution (II) film, the temperature of the precipitation reaction solution (I) will dissolve the solidified precipitation reaction solution (II) film, and the precipitation reaction forms a printing line; After the printing is completed, the film of the precipitation reaction solution (II) is lowered, and the next layer of the precipitation reaction solution (II) is coated, and the process of cooling and solidification, and the printing and writing process of the printing pen are repeated until the entire 3D is formed. print structure; The 3D printing structure is sintered, and the solid reactant that does not produce a precipitation reaction is dissolved using an appropriate solvent, and finally the 3D printing substrate is released from the substrate for molding. . 如請求項1所述的原位析出3D列印方法,其中,該析出反應溶液(II)為氯化鈉水溶液,該析出反應溶液(I)為硝酸銀水溶液。The in-situ precipitation 3D printing method according to claim 1, wherein the precipitation reaction solution (II) is an aqueous sodium chloride solution, and the precipitation reaction solution (I) is an aqueous silver nitrate solution. 如請求項1所述的原位析出3D列印方法,其中,該析出反應溶液(II)為溴化鈉(NaBr)水溶液,該析出反應溶液(I)為硝酸銀水溶液。The in-situ precipitation 3D printing method according to claim 1, wherein the precipitation reaction solution (II) is an aqueous solution of sodium bromide (NaBr), and the precipitation reaction solution (I) is an aqueous solution of silver nitrate. 如請求項1所述的原位析出3D列印方法,其中,該析出反應溶液(II)為氫氧化鈉(NaOH)水溶液,該析出反應溶液(I)為硝酸鎳(Ni(NO 3) 2·6H 2O)水溶液。 The in-situ precipitation 3D printing method as described in Claim 1, wherein the precipitation reaction solution (II) is sodium hydroxide (NaOH) aqueous solution, and the precipitation reaction solution (I) is nickel nitrate (Ni(NO 3 ) 2 • 6H 2 O) aqueous solution. 如請求項1所述的原位析出3D列印方法,其中,該冷卻劑為液態氮。The in-situ precipitation 3D printing method as described in Claim 1, wherein the coolant is liquid nitrogen. 如請求項1所述的原位析出3D列印方法,其中,該冷卻劑為致冷晶片。The in-situ deposition 3D printing method according to claim 1, wherein the coolant is a cooling wafer. 如請求項1所述的原位析出3D列印方法,其中,該3D列印結構首先經過C100D設計,並轉化為成型移動路徑相關指令代碼,通過一電腦控制與3D移動系統將成型移動路徑指令傳遞給該列印筆,精確控制列該印筆3D方向作自由移動到指定的列印路徑。The in-situ precipitation 3D printing method as described in claim item 1, wherein the 3D printing structure is firstly designed by C100D, and converted into instruction codes related to the molding movement path, and the molding movement path instruction is transmitted through a computer control and 3D movement system Pass it to the printing pen, and precisely control the 3D direction of the printing pen to move freely to the specified printing path. 如請求項1所述的原位析出3D列印方法,其中,該析出反應溶液(II)是先流到該列印平台一側的供液平台,藉由刮刀調整與該供液平台間隙,將該析出反應溶液(II)塗佈到該列印平台的有效列印區域,同時將多餘的該析出反應溶液(II)推移到該列印平台另一側的回收平台進行回收, 此時該供液平台、該列印平台與該回收平台需維持等高共平面。The in-situ precipitation 3D printing method as described in Claim 1, wherein the precipitation reaction solution (II) first flows to the liquid supply platform on one side of the printing platform, and the gap with the liquid supply platform is adjusted by a scraper, apply the precipitation reaction solution (II) to the effective printing area of the printing platform, and at the same time push the excess precipitation reaction solution (II) to the recovery platform on the other side of the printing platform for recovery, at this time the The liquid supply platform, the printing platform and the recovery platform must maintain the same height and coplanarity. 如請求項1所述的原位析出3D列印方法,其中,該列印平台塗佈每一層該析出反應溶液(II)時,需要考慮凝固收縮的問題,以提供適當厚度的該析出反應溶液(II)薄膜,減少凝固收縮產生的表面不平整。The in-situ precipitation 3D printing method as described in Claim 1, wherein, when the printing platform coats each layer of the precipitation reaction solution (II), the problem of solidification shrinkage needs to be considered to provide the precipitation reaction solution with an appropriate thickness (II) Thin film, reducing surface unevenness caused by solidification shrinkage. 如請求項1所述的原位析出3D列印方法,其中,對該3D列印結構進行燒結、脫模的程序,先將該列印平台移入燒結爐進行燒結,增加該3D列印結構的強度,最後將燒結後的該列印平台浸入到去離子水中,溶解該成型溶液及該蝕刻溶液顆粒的殘留物,以及溶解該成型溶液薄膜形成的犧牲層,最後將該3D列印結構與列印平台進行脫模。The in-situ precipitation 3D printing method as described in Claim 1, wherein, in the process of sintering and demolding the 3D printing structure, first move the printing platform into a sintering furnace for sintering, increasing the 3D printing structure Strength, finally immerse the sintered printing platform into deionized water, dissolve the residue of the forming solution and the etching solution particles, and dissolve the sacrificial layer formed by the forming solution film, and finally combine the 3D printing structure with the array Printing platform for demoulding. 一種原位析出3D列印設備,包括有:電腦控制與3D移動系統、蝕刻溶液供液系統、列印筆、成型溶液供液系統、列印平台系統和成型溶液回收系統,其中, 該電腦控制與3D移動系統將3D列印結構的成型移動路徑指令傳遞給該列印筆,精確控制該列印筆到指定的列印路徑; 該析出反應溶液(I)供液系統包括有儲存桶,用來將析出反應溶液(I)注入到該列印筆; 該列印筆可以定量供應該析出反應溶液(I)且不會產生滲漏,利用固定供液的泵送壓力、重力和複數槽道的毛細管作用力,直接持續將定量的該蝕刻溶液從筆頭流出進行連續列印,列印時找到適當的列印角度和壓力,隨該電腦控制與3D移動系統的成型移動路徑指令精確進行列印; 該成型溶液供液系統設置有裝置在中空桶體內具有高精度調控高度的供液活塞,該中空桶體內裝滿成型溶液,該供液活塞上方的該中空桶體表面設置含有孔洞陣列的供液平台,該供液平台上方設置一個可以左右平移及調控與該供液平台間隙的刮刀; 該析出反應溶液(II)回收系統設置有裝置在中空桶體內的回收活塞,該回收活塞上方的該中空桶體表面設置含有孔洞陣列的回收平台; 該列印平台系統設有高精度控制器調控高度的列印活塞與冷卻劑槽,使該冷卻劑槽上方以活動式固定設置有列印平台,該列印平台鄰接該供液平台,該冷卻劑槽內充填液態氮,或冷卻劑為致冷晶片。該列印平台系統兩端鄰接該成型溶液供液系統與該成型溶液回收系統,並使該冷卻劑槽緊鄰密接該中空桶體並共享桶壁。 An in-situ precipitation 3D printing equipment, including: computer control and 3D moving system, etching solution supply system, printing pen, forming solution supply system, printing platform system and forming solution recovery system, wherein, The computer control and 3D moving system transmits the forming movement path command of the 3D printing structure to the printing pen, and precisely controls the printing pen to the designated printing path; The precipitation reaction solution (I) liquid supply system includes a storage tank for injecting the precipitation reaction solution (I) into the printing pen; The printing pen can quantitatively supply the precipitation reaction solution (I) without leakage, and directly and continuously transfer the quantitative etching solution from the pen head by utilizing the pumping pressure, gravity and the capillary force of the fixed liquid supply. Flow out for continuous printing, find the appropriate printing angle and pressure during printing, and print accurately with the computer control and 3D moving system's forming movement path instructions; The forming solution liquid supply system is provided with a liquid supply piston with high-precision height control in the hollow barrel, the hollow barrel is filled with forming solution, and the surface of the hollow barrel above the liquid supply piston is provided with a liquid supply with an array of holes A platform, above the liquid supply platform, a scraper that can translate left and right and adjust the gap with the liquid supply platform; The precipitation reaction solution (II) recovery system is provided with a recovery piston installed in the hollow barrel, and the surface of the hollow barrel above the recovery piston is provided with a recovery platform containing a hole array; The printing platform system is equipped with a high-precision controller to adjust the height of the printing piston and the coolant tank, so that the printing platform is movable and fixed above the coolant tank, and the printing platform is adjacent to the liquid supply platform. Liquid nitrogen is filled in the agent tank, or the coolant is a cooling chip. Both ends of the printing platform system are adjacent to the forming solution supply system and the forming solution recovery system, and the coolant tank is closely adjacent to the hollow barrel and shares the barrel wall. 如請求項11所述的原位析出3D列印設備,其中,該析出反應溶液(II)為氯化鈉水溶液,該蝕刻溶液為硝酸銀水溶液。The in-situ deposition 3D printing device according to claim 11, wherein the deposition reaction solution (II) is an aqueous solution of sodium chloride, and the etching solution is an aqueous solution of silver nitrate. 如請求項11所述的原位析出3D列印設備,其中,該析出反應溶液(II)為溴化鈉水溶液,該蝕刻溶液為硝酸銀水溶液。The in-situ deposition 3D printing device according to claim 11, wherein the deposition reaction solution (II) is an aqueous solution of sodium bromide, and the etching solution is an aqueous solution of silver nitrate. 如請求項11所述的原位析出3D列印設備,其中,該析出反應溶液(II)為氫氧化鈉溶液,該蝕刻溶液為硝酸鎳水溶液。The in-situ deposition 3D printing device according to claim 11, wherein the deposition reaction solution (II) is a sodium hydroxide solution, and the etching solution is a nickel nitrate aqueous solution. 如請求項11所述的原位析出3D列印設備,其中,該冷卻劑為液態氮。The in-situ deposition 3D printing device as claimed in claim 11, wherein the coolant is liquid nitrogen. 如請求項11所述的原位析出3D列印設備,其中該冷卻劑為致冷晶片The in-situ precipitation 3D printing device as described in claim 11, wherein the coolant is a cooling wafer 如請求項11所述的原位析出3D列印設備,其中,該電腦控制與3D移動系統在X軸和Y軸安裝有線形電機和編碼器,以及Z軸上的高精度控制器,來控制該3D列印結構的成型移動路徑。The in-situ deposition 3D printing device as described in claim 11, wherein the computer control and 3D moving system is equipped with linear motors and encoders on the X-axis and Y-axis, and a high-precision controller on the Z-axis to control The molding movement path of the 3D printed structure. 如請求項11所述的原位析出3D列印設備,其中,該析出反應溶液(I)供液系統的該儲存桶,設置有微流體蠕動幫浦及中空列印管,該中空列印管出口端面連接該列印筆,該蝕刻溶液供液系統與該電腦控制與3D移動系統同步連動,使該微流體蠕動幫浦提供動力在穩定速率下將定量的該蝕刻溶液經該中空列印管輸送到該列印筆。The in-situ precipitation 3D printing equipment as described in claim 11, wherein, the storage tank of the precipitation reaction solution (I) liquid supply system is provided with a microfluidic peristaltic pump and a hollow printing tube, and the hollow printing tube The outlet end is connected to the printing pen, and the etching solution supply system is synchronized with the computer control and 3D moving system, so that the microfluidic peristaltic pump provides power to pass a quantitative amount of the etching solution through the hollow printing tube at a stable rate sent to the pen. 如請求項11所述的原位析出3D列印設備,其中,該列印筆與該中空列印管密封螺接,該列印筆在筆桿一端部以低摩擦係數鐵氟龍(teflon)為材質,該筆頭則以具複數條柱狀導流凸緣相互束結且螺旋延伸形成,並使該複數導流凸緣之延伸端部呈一個漸縮的筆尖部,因此該複數導流凸緣之間自然會形成凹型的槽道,該筆尖部使用火燄加熱使筆尖部端表面因內聚力作用而收縮呈光滑的圓弧面,使其能滑順列印,並以該圓弧面的大小改變列印寬度,複數的該槽道的加工精度要高,各該槽道的末端連接一個孔,用於空氣流動以平衡壓力,由於該蝕刻溶液與該列印筆連通。The in-situ precipitation 3D printing device as described in claim item 11, wherein the printing pen is sealed and screwed to the hollow printing tube, and the printing pen is made of low friction coefficient Teflon (teflon) at one end of the pen holder. Material, the nib is formed by a plurality of columnar guide flanges that are mutually bound and spirally extended, and the extension end of the plurality of guide flanges is a tapered nib, so the plurality of guide flanges A concave groove will naturally be formed between them. The nib is heated by a flame so that the surface of the nib shrinks into a smooth arc surface due to the cohesive force, so that it can be printed smoothly, and the column is changed according to the size of the arc surface. Printing width, the processing accuracy of the plurality of channels is high, and the end of each channel is connected with a hole for air flow to balance the pressure, because the etching solution communicates with the printing pen. 如請求項11所述的原位析出3D列印設備,其中,該列印筆設置有密封筆蓋,以在不列印時將該筆桿與該筆頭封住,列印前將筆桿與筆頭浸泡到蒸餾水中去除殘留物,以維持後續的供液順暢。The in-situ deposition 3D printing device as described in claim 11, wherein the printing pen is provided with a sealing pen cap to seal the pen holder and the pen head when not printing, and soak the pen holder and the pen head before printing Remove the residue in distilled water to keep the subsequent liquid supply smooth. 如請求項11所述的原位析出3D列印設備,其中,該列印平台為具有鏡面及超親水銅質的結構。The in-situ deposition 3D printing device according to claim 11, wherein the printing platform has a mirror surface and super-hydrophilic copper structure. 如請求項11所述的原位析出3D列印設備,其中,該列印平台系統的該冷卻劑槽設置有注入孔與鎖蓋,用以補充該冷卻劑。The in-situ deposition 3D printing device as claimed in claim 11, wherein the coolant tank of the printing platform system is provided with an injection hole and a locking cover for replenishing the coolant. 如請求項11所述的原位析出3D列印設備,其中,該供液活塞與該回收活塞設置固體潤滑材料的活塞環而與該中空桶體壁密接,以提供順暢上下滑移,避免該成型溶液的滲漏。The in-situ precipitation 3D printing device as described in claim 11, wherein the liquid supply piston and the recovery piston are provided with piston rings of solid lubricating materials to closely contact with the wall of the hollow barrel to provide smooth up and down sliding and avoid the Leakage of forming solution. 如請求項11所述的原位析出3D列印設備,其中,該供液平台、該列印平台與該回收平台為等高共平面,以利於塗佈該成型溶液。The in-situ deposition 3D printing device according to claim 11, wherein the liquid supply platform, the printing platform and the recovery platform are of the same height and coplanar, so as to facilitate coating of the forming solution. 如請求項24所述的原位析出3D列印設備,其中,該供液平台、該列印平台與該回收平台周圍設置有圍牆。The in-situ deposition 3D printing device according to claim 24, wherein walls are set around the liquid supply platform, the printing platform and the recycling platform.
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