TWI611892B - 積層製造３ｄ列印物品的方法 - Google Patents

積層製造３ｄ列印物品的方法 Download PDF

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TWI611892B
TWI611892B TW105139918A TW105139918A TWI611892B TW I611892 B TWI611892 B TW I611892B TW 105139918 A TW105139918 A TW 105139918A TW 105139918 A TW105139918 A TW 105139918A TW I611892 B TWI611892 B TW I611892B
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printing
item
patent application
slurry
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TW105139918A
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TW201726344A (zh
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王志光
何美泠
潘力誠
傅尹志
陳崇桓
張瑞根
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高雄醫學大學
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Abstract

本發明提供一種積層製造3D列印物品的方法，包含(a)以3D印表機列印沉積一或多層漿體，其中該漿體包含一陶瓷粉末的組合物；(b)進一步注入一油於該一或多層漿體周圍，其中注入的油的高度低於該漿體的高度；(c)重複步驟(a)和(b)直到得到一具有所需幾何形狀的本體；及(d)藉由加熱燒結該本體以得到該3D列印物品，其中該3D印表機的列印載座溫度為30至80℃。

Description

積層製造3D列印物品的方法
本發明係關於一種積層製造3D列印物品的方法。
原料是3D列印的核心技術之一，目前塑膠、金屬、陶瓷是3大主流，不過放眼未來，多元材料的列印將成必然。
相對於塑膠的早期運用，金屬則是在3D列印發展較後期才出現，早期仍以塑膠為主原料的時代，3D列印不被視為機器製造的技術，直到金屬列印技術被開發出來，此一看法才逐漸扭轉。目前金屬3D列印主要有兩種方法，一種是先將金屬粉末鋪平(或塗敷熱敏塑膠黏合劑)，直接用雷射使之選擇性的燒熔或黏合，後者黏合成形後在於熱爐中燒結，另一種則是透過列印噴頭擠出融化金屬，依照設計檔移動噴射頭，使噴出之金屬精準成形。過去消費性3D印表機只能使用塑膠材質，不過隨著印表機與原料技術的進步，目前已有部分消費用機台可使用特殊材質的原料，像是將金屬粉末與凝膠混合，至於純金屬的3D印表機，目前的價格仍然偏高，並不屬於消費端層次。
除了塑膠與金屬外，陶瓷與玻璃也是3D列印原料之一，不過這兩種原料的應用都有其侷限，陶瓷列印目前常見約有兩種方式，一種 是陶瓷粉末是以列印頭噴灑加入加凝結劑或加光硬化樹脂的方式，另一種則是列印頭擠出泥條，形成粗胚後再進爐燒製，不管是那一種方式，陶瓷列印都需要2階段以上的製程，列印後再施釉窯燒，而且容易有變形、坯體乾燥時間長及膨脹係數控制的問題。目前陶瓷列印的最主要應用之一是在醫療領域，用以製作如假牙、骨骼等人體部位，陶瓷列印在此處的應用是先以斷層掃描出齒模或骨骼形狀，再以3D列印出陶瓷植入物，以期降低製作成本、加速癒合時間、達到客製化產品或縮小手術時間等困擾。
雖然市場上已有一些多孔性磷酸鹽生物陶瓷植入物，但是機械性大多不好，且不易開發精密與複雜形狀的骨材，導致開發成本太高，無進一步促進骨癒合治療功能。本發明已利用新式的負溫感水膠均壓收縮技術開發多孔性雙相磷酸鹽(HAp/TCP)生物陶瓷製程，不僅具有微孔洞且可達較佳的機械應力，經成份與燒結條件控制亦可能不同雙相磷酸鹽(HAp/TCP)比例之生物陶瓷。若配合現今3D生物列印技術預期可客制化精密與複雜形狀的多孔性骨材。進一步，可攜帶促進骨生長之藥物，預計其能成為兼具骨引導與骨傳導作用的前瞻性骨材。
3D列印早在1980年代就已經出現了，當時稱作「積層製造」或「快速成型」，其應用在工業上大量製造前開模設計校正之用。直到近年這些技術專利陸續到期，加上工業發展基礎的進步，將此技術漸漸普遍應用在生活上。此技術發展讓過往再設計獨特或客製化需求不再限制於成本上的問題，轉而透過此項技術讓可以簡單呈現，大大降低時間跟成本之間的限制，讓客製化這名詞連帶成為熱門發展方向。由平面的二維結構轉化為三維立體呈現。目前就發明人所知，除發明人已具有以負溫感水膠均壓 收縮系統(p(NiPPAm)、p(NiPAAm-MMA)等等)來製作多孔陶瓷的專利與文獻。其他尚無類似文獻。此外，本發明是以發展可3D列印的陶瓷材料列印技術，即利用負溫感水膠均壓收縮系統來列印標準化與客製化陶瓷成品，並且利用疏水性液油控溫與協助陶瓷燒結過程有更好收縮緻密化功能。可應用在傳統陶瓷、生醫陶瓷、電子與結構性陶瓷等等市場價值均具有高的潛力。
本發明3D陶瓷列印專利主要是以負溫感水膠可均壓收縮之模板來簡化製程，並可獲得良好雙連續相之互穿性孔洞通道、良好控制的收縮率，此外高緻密化使得陶瓷支架機械性甚佳等好處是本發明可以有機會得到專利技術的方向。相對應的3D列印材料系統，唯獨陶瓷材料尚在研究開發的初始階段。雖然同樣類型技術已有數種，然而本技術具高特異性與高緻密燒結的特性，在傳統陶瓷、玻璃、精密陶瓷與金屬等等市場價值均具有高的潛力。此外，尤其在醫療器材的植入性生物陶瓷植體與牙科用氧化鋯、氧化鋁等牙冠陶瓷材料等更是好的目標。
例如：可應用在人工生物陶瓷植體的標準化與客製化製程。無論如何多孔性生物陶瓷之孔隙率與尺寸控制/要利於骨細胞生長與藥物控制範圍，多孔質可吸收性生物陶瓷製作方法/多孔性陶瓷製作技術雖然已廣為生醫業界應用，然而其應用的發泡技術或以高分子粒殘留法達成時，往往應用的材料種類並不一定能用在磷酸鈣生物陶瓷的多孔性製作上，原因是材料是否有適當的機械性與無毒性，再者要達到雙連續相之互有聯通的 通道孔洞也是另一種要解決的問題。
本發明之目的係將具負溫感性水膠/陶瓷材料，透過3D列印技術(積層製造)成型技術製作成型。方法是利用負溫感性水膠系統(p(NiPAAm)、p(NiPAAm-MMA)等等)的逆溫感特性與生物陶瓷粉末攪拌使用，再透過3D列印設備製作成型。負溫感性水膠溶液依陶瓷粉末的不同，調整其黏度、濃度及添加比例。負溫感性水膠溶液可控制溫度來有效提高陶瓷粉末間均勻收縮，可取代大多陶瓷製作上需透過機械力擠壓定型的成本與時間。因負溫感性水膠特性，擺脫模具限制，提升其成型方式與樣式的多元，跟進3D列印技術發展腳步，利用負溫感性水膠逆溫感特性，控制溫度列印成型，使其型態上可不具限制，且具有規則性的互穿孔洞，突破傳統生物陶瓷製作上的限制。
因此，本發明提供一具負溫感性可均壓收縮水膠混合陶瓷粉末系統可進行3D列印陶瓷結構，其包含負溫感性水膠使用，該負溫感性水膠可為例如：N-異丙基丙烯醯胺聚合物(poly(N-isopropylacrylamide；p(NiPAAm))、N-異丙基丙烯醯胺-甲基丙烯酸共聚合物(poly(N-isopropylacrylamide-co-methacrylic acid；p(NiPAAm-MAA))及其類似負溫感化合物；該生物陶瓷材料可為氫氧基磷灰石(HA)、磷酸三鈣(TCP)、高密度氧化鋁(Al2O3)、氧化鋯(ZrO2)、生物活性玻璃(Biogiass；BG)其類似生物陶瓷材料；該3D列印生物陶瓷列印技術可為沉積成型(FDM；Fused Deposition Modeling)、層狀物體製造(LDP；Digital Light Processing)、立體平版列印(SLA)及其相關3D列印技術。
本發明具有以下技術優勢：
(1)負溫感水膠在溫度上升時會有均壓收縮的能力，讓燒結粉體能夠緻密化，其原理猶如粉末冷均壓(cold isostatic pressing；CIP)成型技術，可均勻收縮，減低收縮時內應力，故不需經緩慢耗時收乾過程，可立即進行燒結過程，且易得到不龜裂地燒結體與較佳機械性質。
(2)負溫感水膠的黏性可以經均勻攪拌氣孔入泥狀胚體，經燒結後可留下孔洞，也可真空攪拌除氣以利3D列印，成為3D列印墨水材料，進行複雜形狀與互穿性孔洞的基層列印產品。
(3)3D列印過程控制參數：a.機台的各種溫度、壓力、速度、列印孔徑等等。b.陶瓷列印墨水材料粉粒大小、固液比、黏度、水膠濃度。c.列印槽基板需以液體油相來浸置，逐漸控制油高度可一方面來可控制列印材料的溫度，二來可將水相泥狀混合列印材料以油包覆，可更利後續高溫收縮燒結過程，達成陶瓷燒節高緻密化結果。
負溫感水膠應用在3D列印上可添加光固化起始劑，使其可以透過UV光的照射進行固化成型，此項固化方式可以提高列印精細度及較複雜形狀製作。
本發明提供一種積層製造3D列印物品的方法，包含：(a)以一3D印表機列印沉積一或多層漿體，其中該漿體包含一陶瓷粉末的組合物；(b)進一步注入一油於該一或多層漿體周圍，其中注入的油的高度低於該漿體的高度；(c)重複步驟(a)和(b)直到得到一具有所需幾何形狀的本體；及(d)藉由加熱燒結該本體以得到該3D列印物品，其中該3D印表機的列印載座溫度為30至80℃。
在一較佳實施例中，該漿體為一組合物，其包含陶瓷粉末、玻 璃粉末或金屬粉末。在另一較佳實施例中，該油包含但不限於合成油品(如聚二醇、矽油、氟化油、磷酸酯、聚醚…等)、礦物油品(如石蠟、十二烷基醇…等)、植物油(如橄欖油、大豆油…等)、烴礦物油、液體石蠟或合成烴。在另一較佳實施例中，該陶瓷粉末包含但不限於氫氧基磷灰石(HA)、磷酸三鈣(TCP)、高密度氧化鋁(Al2O3)、氧化鋯(ZrO2)、生物活性玻璃(Biogiass；BG)、碳化物系陶瓷材料(如碳化矽(Silicon carbide)…等)、氮化物系陶瓷材料(如氮化矽(Silicon nitride)…等)、矽酸鋁(aluminium silicate)、硼化物陶瓷材料或矽化物陶瓷材料。
在一較佳實施例中，該漿體的黏度範圍在100至900cP之間，該3D印表機的噴嘴的大小範圍在19至30G之間，而該3D印表機的列印速度範圍在0.1至5cm/s之間。
在一較佳實施例中，該加熱包含以下四個階段：第一階段：在2小時內緩慢加熱至600℃~650℃(3~6℃/min)，並維持該溫度30至60分鐘；第二階段：在20~30分鐘內快速將溫度上升至1150℃至1250℃(15~25℃/min)，並維持該溫度10~30分鐘；第三階段：在10~30分鐘內緩慢加熱至1250℃~1350℃(3~6℃/min)，並維持該溫度1至3小時；及第四階段：藉由冷卻緩慢將溫度降至25℃。
在一較佳實施例中，該漿體由以下步驟製備：(a)合成聚(N-異丙基丙烯醯胺)(p(NiPAAm))或聚(N-異丙基丙烯醯胺-共聚-甲基丙烯酸)(p(NiPAAm-MAA))；(b)將一分散劑與羥磷灰石混合；(c)將步驟(a) 的該p(NiPAAm)或該p(NiPAAm-MAA)與水混合以得到一水凝膠溶液；(d)將步驟(c)的該水凝膠溶液與步驟(b)的產物混合以產生一混合物；及(e)攪拌步驟(d)的該混合物以產生該漿體。在另一較佳實施例中，該聚合物顆粒包含但不限於聚乙烯。
在另一較佳實施例中，步驟(b)的該羥磷灰石與該分散劑是以重量百分比範圍25：1至25：5的比例混合。步驟(b)的該分散劑可為聚丙烯酸(PAA)、聚甲基丙烯酸(PMA)或聚乙烯醇(PVA)及其類似物；步驟(b)的該羥磷灰石或磷酸鈣鹽係在混合前於高溫爐中燒結至700℃~900℃；步驟(c)的該p(NiPAAm-MAA)與水是以體積比範圍1：10至2：1的比例混合；步驟(e)的大分子顆粒具有與步驟(d)的混合物的總體積的5%~50%相等的體積。
在另一較佳實施例中，該方法進一步添加一光固化起始劑於步驟(c)的水凝膠溶液，使該漿體可經UV照射而光固化成型。即負溫感水膠UV光固化成型。該光固化起始劑的種類包含游離基型光固化起始劑或陽離子型光固化起始劑。該游離基型光固化起始劑包含但不限於丙烯酸或不飽和聚酯，該陽離子型光固化起始劑包含但不限於環氧、氧雜環丁烷或乙烯醚。
在一較佳實施例中，該多孔陶瓷組合物具有奈米孔或微米孔，且可用作生物材料支架(biomaterial scaffold)；該生物材料支架是部份生物可吸收的。在一較佳實施例中，該生物材料支架被用作人工骨，並與刺激骨生成的物質混合，其中該刺激骨生成的物質選自由骨髓、BMP生長因子、血管生成因子、史他汀類藥物(statin drugs)、雙膦酸鹽藥物、骨細 胞、幹細胞及其藥物載體所組成的群組。在另一較佳實施例中，該生物材料支架被用作治療劑的載體。在一較佳實施例中，該治療劑為一抗生素藥物。
本發明提供一具負溫感性水膠混合陶瓷粉末系統可進行3D列印陶瓷結構，其包含負溫感性水膠使用，該負溫感性水膠可為例如：氮-異丙基丙烯醯胺聚合物(poly(N-isopropylacrylamide；PNIPAAM)、氮-異丙基丙烯醯胺-甲基丙烯酸共聚合物(poly(N-isopropylacrylamide-co-methacrylic acid；PNIPAAM-MAA)其類似溫感化合物；該生物陶瓷材料可為氫氧基磷灰石(HA)、磷酸三鈣(TCP)、高密度氧化鋁(Al2O3)、氧化鋯(ZrO2)、生物活性玻璃(Biogiass；BG)及其類似生物陶瓷材料；該3D列印生物陶瓷列印技術可為沉積成型(FDM；Fused Deposition Modeling)、層狀物體製造(LDP；Digital Light Processing)、立體平版列印(SLA)其及相關3D列印技術。
圖1為3D列印生物用水膠陶瓷材料條件參數。
圖2為3D列印技術可有效控制生物陶瓷孔洞大小、間距、圖案。
圖3為均勻收縮與強化燒結密度的實施例。
圖4為磷酸鹽陶瓷有無含油收縮率比較。
圖5為氧化鋯陶瓷有無含油收縮率比較。
圖6為3D列印具互穿性孔洞磷酸鈣鹽生物陶瓷複合性材料 支架(scaffold)。
圖7為UV光固化成型3D列印磷酸鈣鹽生物陶瓷複合性材料支架(scaffold)。
圖8為UV光固化成型陶瓷磷酸鹽陶瓷含油收縮率比較。
圖9為不均勻收縮後的陶瓷裂紋的示意圖示。(乾燥太快造成樣本因不均勻收縮導致彎曲或裂縫)。
圖10為不含油膜乾燥的乾燥粉末收縮的示意圖。不加熱過程中，生胚外圍水膠會先收縮，但升溫過程，其外圍水分也會散失，導致外部顆粒不易再具有高度收縮緻密化。內部粉末在後續升溫過程易發生孔隙。
圖11為含油膜乾燥的乾燥粉末收縮的示意圖。加熱過程中，生胚外圍因為油膜包覆，整體水膠會利於收縮進行，水往外圍排出，故易具有較高收縮率幫助燒結緻密化。內部粉末在後續升溫過程，其孔隙度因高溫燒結擴散，會下降許多。
以下實施例非用於限定而僅是本發明的各個態樣與特徵的代表。
本發明係關於3D列印技術成型(積層製造)製作生物陶瓷，即為生醫陶瓷(Bioceramics)。關於溫感水膠製備含多孔性陶瓷組合物的方法可參考美國專利US8940203。本發明利用溫感性水膠及3D列印技術結合製備多孔性陶瓷。故本發明目標有(1)調整負溫感性水膠/陶瓷粉末最佳 3D列印成型條件範圍之比例。(2)3D列印製作過程中最佳控制條件範圍。(3)3D列印製作生物陶瓷(HAp/β-TCP)/負溫感性水膠(p(NiPAAm-MMA))，並檢測分析。(4)3D列印製作含油(如矽油)生物陶瓷(HAp/β-TCP)/溫感性水膠(p(NiPAAm-MMA))，並檢測分析。(5)3D列印製作生物陶瓷(氧化鋯，ZrO2)/負溫感性水膠(p(NiPAAm-MMA))，並檢測分析。(6)3D列印製作含油(如矽油)生物陶瓷(氧化鋯，ZrO2)/負溫感性水膠(p(NiPAAm-MMA))，並檢測分析。(7)負溫感水膠陶瓷添加UV光固化起始劑，進行光固化列印。其中負溫感性水膠溶液與陶瓷粉墨混合攪拌比例，以負溫感性水膠溶液的重量百分比濃度(wt%)及陶瓷粉末重量克重。3D列印負溫感性水膠/生物陶瓷條件，以負溫感性水膠溫度敏感特性設計，調整列印載座上溫度控制使其負溫感性水膠相轉變收縮，讓陶瓷粉末間緊密，達成型效果。其他列印控制條件有列印頭推擠出料器壓、列印速度、列印出料端針頭口徑大小。3D列印製作生物陶瓷成型後以有無添加油品(驗證中以矽油為範例)覆蓋陶瓷進行高溫燒結動作作為對照組別，檢測其燒結前後及有無添加油品覆蓋的收縮大小比例進行比較。在以兩種不同的陶瓷粉末驗證負溫感性水膠系統及3D列印技術結合適用於不同陶瓷粉末。初步結果顯示，負溫感性水膠與生物陶瓷混合攪拌後其膠體黏度需達約100~900cP符合3D列印機台氣體推動出料之50~200,000mPa.s範圍。依照生物陶瓷粉末之顆粒大小及列印線條粗細，其適用選擇列印針頭之大小範圍19~30G進行製作。3D列印製作列印頭移動速度決定線條粗細因素之一，經實際測試最佳列印速度範圍0.1~5(cm/s)為最佳。比較3D列印製作有無含油類(矽油、碳氫礦物油、液體 石蠟、石蠟、合成烴等等)生物陶瓷(HAp/β-TCP)/負溫感性水膠(p(NiPAAm-MMA)或p(NiPAAm))燒結前後收縮率，其中以含油覆蓋組具較高收縮比例，最高達27.9%的收縮率。比較不同生物陶瓷粉末比較，3D列印製作有無含油生物陶瓷(氧化鋯，ZrO2)/負溫感性水膠(p(NiPAAm-MMA))，燒結前後收縮率，同樣含油覆蓋組具較高收縮比例，最高達36%的收縮率。目前將燒結後陶瓷以掃描式電子顯微鏡(SEM)觀察，可由正面觀察到孔洞大小約500μm大小，再由側面觀察其表面型態，可看見由3D列印成型特有條狀交錯的堆疊型態。本發明成功製備一適用於3D列印生物陶瓷的系統，此系統負溫感性水膠可與多項生物陶瓷材料很合使用，並由3D列印設備以溫控方式列印多元型態，其中負溫感性水膠與油相溶液結合使用進一步提升生物陶瓷收縮之效果。
1、負溫感性水膠溶液與陶瓷粉末混合攪拌比例，以負溫感性水膠溶液的重量百分比濃度(wt%)及陶瓷粉末重量克重，最佳實例會依陶瓷粉末的特性差異進行調整。以下為實際實施比例：
(1)磷酸鈣(β-TCP)陶瓷粉末為1mL 15%的負溫感水膠溶液添加2.0g磷酸鈣陶瓷粉末真空攪拌混合8分鐘，得可列印之漿體。
(2)氧化鋯(ZrO2)陶瓷粉末為1mL 10%的負溫感水膠溶液添加1.8g氧化鋯陶瓷粉真空攪拌混合8分鐘，得可以列印之漿體。
(3)氫氧基磷灰石(HAp)陶瓷粉末為1mL 15%的負溫感水膠溶液添加2.0g氫氧基磷灰石陶瓷粉末真空攪拌混合8分鐘，得可列印之漿體。
2、3D列印負溫感性水膠/生物陶瓷條件，以負溫感性水膠 溫度敏感特性設計，調整列印載座上溫度控制使其負溫感性水膠相轉變收縮，讓陶瓷粉末間緊密，達成型效果。其他列印控制條件有列印頭推擠出料器壓、列印速度、列印出料端針頭口徑大小。
(1)3D列印製作列印頭移動速度決定線條粗細因素之一，經實際測試最佳列印速度範圍0.1~5(cm/s)為最佳。
(2)3D列印製作列印頭出料速度決定線條粗細因素之一，經實際測試最佳初料速度23G針頭(內徑25mm)為主，氣動推送出料所需氣壓為±4.5bar。
(3)3D列印製作負溫感水膠固化成型條件，透過載座提升溫度使得負溫感性水膠相轉化收縮，其溫度±40℃。在另一較佳實施例中，列印載座的溫度加溫至30至80℃。
3、3D列印負溫感性水膠/生物陶瓷製作，將列印完成後進行燒結動作前，以油品包覆列印完成之陶瓷，而後送入高溫爐中燒結。以下為有無油品包覆收縮差異及陶瓷燒結溫度：
(1)將上述攪拌混合之氫氧基磷灰石漿體，進行列印成形，列印直徑約14mm*高3mm的物件，分別其中之一以矽油包覆，送至高溫爐中以±1250℃之梯度溫度進行燒結6~8小時。完成後進行直徑與高度測量，得其收縮率(如圖4)，未添加矽油之陶瓷塊燒結後收縮比例：直徑10%、高11.0%；矽油滴附之陶瓷塊燒結後收縮比例：直徑27.9%、高21.3%。
(2)將上述攪拌混合之氧化鋯漿體，進行列印成形，列印直徑約18.10mm的物件，分別其中之一以矽油包覆，送至高溫爐中以±1400℃之梯度溫度進行燒結6~8小時。完成後進行直徑與高度測量，得其收縮 率(如圖5)，未添加矽油之陶瓷塊燒結後收縮比例：直徑23.4%；矽油滴附之陶瓷塊燒結後收縮比例：直徑36.08%。
4、負溫感性水膠/生物陶瓷3D列印成型技術：
先前固化技術使用溫度控制進行列印製作，但是負溫感水膠具有光固化機制的官能基結構，可以透過添加光固化起始劑，即可轉換為光固化成形方式進行列印。
光固化列印實施案例，將15%負溫感水膠添加1~5%光固化起始劑I2959(UV吸收波長為365mm)攪拌1~2天，而後與氫氧基磷灰石(HAp)陶瓷粉末攪拌，以1mL 15%的負溫感水膠溶液添加2.0g氫氧基磷灰石陶瓷粉末真空攪拌混合8分鐘，得可列印之漿體。進行列印時透過UV模組的設定給與光固化之路徑及相關照射時間使得固化成形(如圖7)，列印一直徑15mm*高5mm的陶瓷並滴附矽油包覆，送至高溫爐中以±1250℃之梯度溫度進行燒結6~8小時。完成後進行直徑與高度測量，得燒結後尺寸，直徑為11.26mm、高3.88mm的陶瓷塊，其收縮比率分別為直徑25%、高22.4%。(如圖8)
結果：
上述實驗結果中可確認：
(1)本發明所使用之負溫感水膠混合攪拌陶瓷粉進行3D列印成型之技術為可行之3D成形技術。
(2)3D列印成型過程，列印之參數可調整，漿體出料速率、列印頭移動速率、載台溫度、列印針頭之內徑…等，相關之參數控制進行製作。
(3)負溫感水膠系統可與多數陶瓷粉末一起混合攪拌，進行製作燒結，可透過負溫感水膠相轉化收縮之特性，固化成形進行列印，並再燒結過程中溫度提高進而加大收縮力，類似傳統陶瓷工藝上類均壓的工法，如同上述實驗結果所示，可達10~20%的收縮率。
(4)本發明實驗中提出透過油品的滴附在列印完成之陶瓷物件進行包覆之動作，此項步驟可有效提升陶瓷燒結時收縮之效果，如同上述實驗結果所示，可達20~40%的收縮率，較未滴附油品之陶瓷具有較大的收縮率。
(5)本發明所用負溫感水膠材料可添加光固化起始劑，使之轉化為具有光固化能力膠體材料，在列印上可透過UV光的照射達到固化效果，且收縮之能力不變。

Claims (15)

  1. 一種積層製造3D列印物品的方法，包含：(a)以一3D印表機列印沉積一或多層漿體，其中該漿體包含一陶瓷粉末的組合物；(b)進一步注入一油於該一或多層漿體周圍，其中注入的油的高度低於該漿體的高度；(c)重複步驟(a)和(b)直到得到一具有所需幾何形狀的本體；及(d)藉由加熱燒結該本體以得到該3D列印物品，其中該3D印表機的列印載座溫度為30至80℃。
  2. 如申請專利範圍第1項所述的方法，其中該漿體為一組合物，其包含陶瓷粉末、玻璃粉末或金屬粉末。
  3. 如申請專利範圍第2項所述的方法，該陶瓷粉末包含氫氧基磷灰石、磷酸三鈣、高密度氧化鋁、氧化鋯、生物活性玻璃、碳化物系陶瓷材料、氮化物系陶瓷材料、矽酸鋁、硼化物陶瓷材料或矽化物陶瓷材料。
  4. 如申請專利範圍第1項所述的方法，其中該油包含聚二醇、矽油、氟化油、磷酸酯、聚醚、石蠟、十二烷基醇、橄欖油、大豆油、烴礦物油、液體石蠟或合成烴。
  5. 如申請專利範圍第1項所述的方法，其中該漿體的黏度範圍在100至900cP之間。
  6. 如申請專利範圍第1項所述的方法，其中該3D印表機的噴嘴的大小範圍在19至30G之間。
  7. 如申請專利範圍第1項所述的方法，其中該3D印表機的列印速度範圍在0.1至5cm/s之間。
  8. 如申請專利範圍第1項所述的方法，其中該漿體由以下步驟製備：(a)合成聚(N-異丙基丙烯醯胺)(p(NiPAAm))或聚(N-異丙基丙烯醯胺-共聚-甲基丙烯酸)(p(NiPAAm-MAA))；(b)將一分散劑與羥磷灰石混合；(c)將步驟(a)的該p(NiPAAm)或該p(NiPAAm-MAA)與水混合以得到一水凝膠溶液；(d)將步驟(c)的該水凝膠溶液與步驟(b)的產物混合以產生一混合物；及(e)攪拌步驟(d)的該混合物以產生該漿體。
  9. 如申請專利範圍第8項所述的方法，其進一步包含在步驟(e)之前將聚合物顆粒加入步驟(d)的該混合物。
  10. 如申請專利範圍第8項所述的方法，其中步驟(b)的該羥磷灰石與該分散劑是以重量百分比範圍25：1至25：5的比例混合。
  11. 如申請專利範圍第8項所述的方法，其中步驟(b)的該分散劑為聚丙烯酸(PAA)、聚甲基丙烯酸(PMA)或聚乙烯醇(PVA)。
  12. 如申請專利範圍第8項所述的方法，其中步驟(c)的該p(NiPAAm-MAA)與水是以體積比範圍1：10至2：1的比例混合。
  13. 如申請專利範圍第8項所述的方法，其進一步添加一光固化起始劑於步驟(c)的水凝膠溶液，使該漿體可經UV照射而光固化成型。
  14. 如申請專利範圍第13項所述的方法，其中該光固化起始劑為游離基型光固化起始劑或陽離子型光固化起始劑。
  15. 如申請專利範圍第14項所述的方法，其中該游離基型光固化起始劑包含丙烯酸或不飽和聚酯，該陽離子型光固化起始劑包含環氧、氧雜環丁烷或乙烯醚。
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