TW201637828A - 藉由噴霧的飛行中固化之三維結構的製造技術 - Google Patents
藉由噴霧的飛行中固化之三維結構的製造技術 Download PDFInfo
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Abstract
一種用於製造三維結構之方法。加熱或UV照射正噴射至標的表面之飛行中的噴霧液滴,可改變其等之特性。UV光至少部分地固化光聚合物液滴,或選擇性地使溶劑基奈米粒子分散物之液滴在飛行中快速地乾燥,以及增加該噴霧液滴之黏度之結果,促進自立三維結構之形成。此3D製造可使用各式各樣的光聚合物、奈米粒子分散物以及複合材料進行。所產生的3D形狀可為自立的,在無支撐物之情況下製得的,且可藉由相對於標的基材操縱列印噴嘴,獲得任意形狀。
Description
本申請案請求於2015年2月10日提申之美國臨時專利申請案第62/114,354號,標題“MICRO 3D PRINTING”之優先權以及權益,其之說明書以及申請專利範圍在此併入本案以為參考。
本發明有關藉由噴霧射出的奈米粒子以及聚合物墨水的飛行中固化之3D電氣以及機械結構、微結構以及奈米結構之製造。
注意,下列討論會參考許多公開以及參考文獻。在此,此等公開文獻之討論,係為提供更完整的科學理論之背景知識,而不應被解釋成承認此公開文獻為在決定專利性質時之先前技術。
三維列印是一個快速發展的技術,其有可能徹底改變增量製造(additive manufacturing)。利用3D列印,可在不需要切削機械加工或蝕刻步驟之情況下,將各種諸如塑
膠以及金屬之結構材料,製成淨形結構。極少的材料浪費以及減少製程步驟,使3D列印可能成為符合成本效益之綠色技術。許多3D列印技術是目前可得的,簡單地比較此等技術與本發明會很有用。
立體微影技術是一種增量製造方法,其操作是藉由將紫外線(UV)雷射聚焦於光聚合物樹脂槽上。在電腦輔助製造或電腦輔助設計(CAM/CAD)軟體之幫助下,用UV雷射在光聚合物槽之表面上繪製一預編程設計或形狀。因為光聚合物在紫外線下是光敏性的,受到照射的樹脂固化而形成所欲的3D物件中之單一層。針對設計的每一層重複此方法,直到3D物件完成。層解析度典型地50-150μm,橫向尺寸接近10μm。此方法一般而言限於光聚合物材料以及需要犧牲結構來支撐懸垂部分。
噴墨技術典型地用於以2D方式列印石墨以及顏料墨水。近來的材料發明,使得噴墨列印能夠噴射聚合以及金屬奈米粒子墨水。一般而言,噴墨列印中使用之墨水必須具有相對低的黏度,意思是墨水在列印後會大幅地擴散,因此限制了列印特徵之最小特徵尺寸以及縱橫比。墨水噴射器沒有接觸到基材,但很靠近(小於mm)。
擠出技術在熱塑性聚合物之3D列印方面很受歡迎。此情況下是將噴嘴中之熱性塑料加熱至熔點,然後擠至基材上。塑料在接觸的基材上快速地冷卻以及固化,以及可維持三維形狀。3D部分典型地是一層一層製造的,各層包含擠出細絲之光柵圖案。懸垂部分可藉由擠出犧牲支
撐材料,之後溶解或以機械方式移除該支撐結構而製成。典型地特徵尺寸為數百微米,而材料很大程度被限制至熱塑性以及少數的熱固性聚合物,以及導電膠。nScrypt工具能夠利用自動CAD/CAM控制定位噴嘴,在3D表面上列印。
本發明是一種用於在基材上製造三維結構之方法,該方法包含將噴霧液滴從一沉積頭推至該基材上,部分地改變在飛行中之噴霧液滴的特性以及當該噴霧液滴沉積成為該三維結構之一部分時,完全改變其等之特性。改變特性任擇地包含使用電磁輻射之固化,例如,紫外線(UV)固化或硬化。在此具體例中,噴霧液滴較佳地包含光可固化聚合物,以及所製得的三維結構包含固化的聚合物。該噴霧液滴任擇地包含分散在光可固化聚合物中之固態粒子,而所製得的三維結構包含固化的聚合物,其包含包埋的固態粒子。該固態粒子任擇地包括陶瓷、金屬、纖維或矽。在另一具體例中,該噴霧液滴包含溶劑,而改變特性包含使溶劑蒸發。此等噴霧液滴任擇地包含金屬奈米粒子,在此情況下,該方法較佳地另外包含用UV輻射照射該噴霧液滴、加熱該金屬奈米粒子以及充分地加熱該噴霧液滴至至少部分地使該溶劑蒸發。該方法較佳地另外包含在其等已經沉積之後,持續照射該金屬奈米粒子,從而至少部份地燒結該金屬奈米粒子。
該方法任擇地包含相對於該基材傾斜或移動該
沉積頭。該方法任擇地包含在不需要犧牲支撐物或傾斜該沉積頭或該基材之情況下,製造懸垂結構。該沉積頭與該基材間之噴射距離,較佳地至少1mm,更佳地至少2mm。該方法較佳地包含增加該噴霧液滴在飛行中之黏度,以及較佳地包含用電磁輻射照射在飛行中以及在該噴霧液滴已經沉積後之噴霧液滴,任擇地在飛行中,從超過一個方向照射。該方法任擇地包含用電磁輻射加熱在飛行中以及在該噴霧液滴已經沉積後之噴霧液滴。製得的三維結構任擇地包含選自於由下列所構成之群組之結構:微米量級之表面紋理、機械中介層、精密墊片、包含包埋電連接器之機械中介層、封閉中空結構、機械支架以及功能性電線。
本發明之目的、優點以及新穎特徵,以及適用性之進一步範疇,有些將在下面詳細的說明中,結合所附之圖式作說明,而有些對在檢視下列或從本發明實例中學習後之熟悉此技藝之人士而言,將變得顯而易見。憑藉附加的申請專利範圍中指出之手段以及組合,可理解以及獲得本發明之目的以及優點。
所附的圖式,其併入本發明並形成本發明說明書之一部分,舉例說明數個本發明之具體例,且加上說明,用於解釋本發明之原理。該等圖式僅供例示說明本發明之較佳具體例之目的,不能被解釋為本發明之限制。在圖式中:
圖1是描述噴霧噴射三維列印之機制之示意圖。
圖2A-2C是依照本發明之具體例列印之聚合物柱陣列之影像。圖2D是顯示柱建造速率之圖。
圖3是複合柱陣列之影像。
圖4A以及4B分別是依照本發明之具體例列印之中介層之透視圖以及頂視圖。
圖5A顯示使用圖1中所示之偏移方法列印之三維似鐵叉(jack-like)結構。圖5B顯示開放錐結構。
圖6A以及6B顯示具有沿著長度之開放內部之封閉通道。圖6C顯示墨水在通道之內部流動。
圖7A以及7B分別顯示具有L形列印柱之個別的天線以及天線之陣列。圖7C以及7D是列印在微晶片上之3D電氣組件之影像。
圖8A顯示列印時藉由傾斜列印頭製得之自立聚合物彈簧。圖8B顯示支撐一塊體之彈簧。
圖9A是顯示銀奈米粒子之光學密度之圖。圖9B顯示用原位照射方法列印之3D銀線陣列。
圖10A-10F是使用UV聚合物以及飛行中固化列印的各種3D形狀之影像。
本發明是一種使用噴霧以及墨水的飛行中固化來製造三維結構,諸如包含高縱橫比特徵之結構之方法,以及直接列印液態材料以製造三維、自立的複合結構之方法。明確而言,本發明之具體例結合了諸如在美國專利案
第7,674,671號、第7,938,079號以及第7,987,813號中所述之獲得專利的噴霧噴射分配技術以及飛行中之材料加工機制,其使得液態液滴在沉積於表面上之前部分地固化。在飛行中加工之後,液滴可沉積下來形成自立的結構。此方法之一些優點包括超高解析度三維(3D)列印,特徵尺寸降至10微米,橫向特徵解析度至1微米,以及垂直解析度至100nm。該自立結構之縱橫比可超過100,且可藉由操縱列印頭相對於該等表面之傾斜度以及位置,在幾乎任何表面以及表面幾何形狀上列印該結構。懸垂以及閉孔可直接列印,不須使用犧牲支撐材料。金屬與絕緣材料均可加工,其使得能夠共沉積用於製造3D電路之電子材料。此外,可列印複合材料,此容許定制3D結構之機械與電氣特性。紫外線(UV)聚合物可在其等正撞擊至標的之飛行中固化,以及低燒結溫度使能夠在塑料表面金屬化。使用噴霧噴射方法,實際上任何類型之材料和/或溶劑均可列印。此方法中,與基材間大的噴射距離(典型地幾毫米),使在無任何z-軸移動之情況下之高縱橫比列印成為可能。亞10微米的噴霧噴射聚焦,使製造超細特徵成為可能。
噴霧噴射列印是一種非接觸式、噴霧基的噴射技術。起始墨水是配製成低黏度(0.5至1000cP),且在典型的方法中,其等先被霧化成1-5μm直徑液滴之細液滴分散物。較佳地氮氣帶著液滴以及透過細噴嘴(0.1-1mm內徑),將其等推至供沉積之標的基材。併流,較佳地氮鞘氣,會將液滴噴射聚焦縮小至10μm直徑,其容許列印具此大小之特徵。
在噴嘴以及基材間之大噴射距離(數mm)、細解析度(特徵寬10μm)、體積分配精準度(10毫微微升)以及廣泛的材料相容性方面,噴射技術是值得注意的。因為噴射距離大,所以在液滴飛行至基材期間,乾燥和/或以其它方式固化液滴係可能的。在這情況下,液滴之黏度可能增加遠遠的超過起始黏度。在較高的黏度下,列印的墨水可自我支撐,且可堆積成自立管柱以及其它高縱橫比特徵。為了增加黏度,較佳地在噴嘴出口與標的基材間之間隙區域,施用從燈管或UV LED而來之UV光,如圖1所示。假如起始墨水包含具吸收帶與UV發出光譜重疊之光聚合物,則該UV光可完全或部分地固化在飛行中之光聚合物液滴,從而增加黏度。
圖1是描述噴霧噴射3D列印之機制之示意圖。微3D結構較佳地係使用噴霧噴射相容的低黏度光可固化樹脂製得,其較佳地係使用噴霧噴射技術列印。電磁輻射,在此例子中是紫外線,照射以及部分地固化飛行中之液滴。該部分固化會增加液滴的黏度,其反過來限制基材上之沉積物的擴散。液滴在標的基材上合成一體,然後完全固化。上示意圖顯示液滴垂直堆疊。下示意圖顯示液滴在基材於列印頭下平移時堆積懸垂結構。示範高達45度之懸垂結構,然而可達到甚至更大的角度。
圖2A是用Loctite 3104丙烯酸胺基甲酸酯以及同時UV LED固化列印之直立聚合物柱之照片。入射UV功率為0.65mW,UV波長為385nm以及容積列印速率為7.5nL/s。該等柱可從標的基材實質上延伸至噴霧噴射噴嘴之出口。
圖2B是柱陣列之放大影像;柱之高度為1.0mm,高度變異為1%,間隔為0.5mm以及直徑為90μm。圖2C是柱陣列之頂表面之影像。各柱之頂部形狀是圓的,近半球形。圖2D是顯示所測得之單柱建造速率之圖。發現,當列印噴嘴固定在一指定位置時,柱高度與時間成正比。高度之變異大約為1%,或選擇性地對1.0mm高之柱而言,大約10μm。
在飛行中之加工方法,在固態粒子,諸如陶瓷、金屬或纖維,分散於光聚合物墨水中之情況下亦是可能的。在此情況下中,固化的光聚合物作為固態粒子之3D機械支撐物。此複合材料之機械與電氣特性,可因,例如,提供耐磨性以及形成3D電導體而得到最佳化。圖3是複合柱陣列之影像。將具粒徑小於500nm之矽粉,以7重量%之濃度分散於UV光聚合物樹脂中。之後將該複合分散物列印以及在飛行中固化,產生包埋矽之固化樹脂的實心柱。柱直徑為120μm,高度為1.1mm。複合材料對最佳化3D結構之機械以及電氣特性是有利的。在此例子中,該複合材料對UV光而言夠透明,所以即使單邊照射UV,亦可完全固化。在更高的濃度以及具有高度吸收性粒子之情況下,複合樹脂可能無法使入射光透過。在此情況下,需要從反側照射列印區域,或用環燈照射沉積物。只要在3D結構之外表面附近的UV樹脂固化,則有足夠的機械支撐力容許結構在垂直方向上建造。在柱加工步驟中,可任擇地藉由,例如加熱該3D結構至超過該光聚合物之蒸發或分解點,任擇地移除光聚合物。
圖4顯示列印的機械中介層之影像,其是可提供結構支撐以及二個分開的組件間之精密間隔之元件。該中介層是經由堆疊數層UV樹脂之列印而成,可見圖4A之透視圖。圖4B顯示頂表面網格圖案。在一些具體例中,中介層可在元件之間或連接至另一個之間,提供電氣或流體通路,在此情況下,該間隙間隔可充填導電材料或流體。
圖5A顯示使用圖1所示之偏移方法列印之三維似鐵叉(jack-like)結構。下面4個腳是列印頭在x以及y方向上移動至頂點列印而成。柱相對於基材大約傾斜45度。頂腳是列印頭移動離開頂點列印而成。總高度是4mm,個別柱直徑為60μm。圖5B顯示開放圓錐體結構。此係利用將平台以漸增半徑重複環狀移動列印而得。需要時,可藉由連續環狀移動以及將半徑減少至0而封閉此圓錐體。
圖6A以及6B顯示具有沿著長度之開放內部之密閉管道。該管道之各側壁,是藉由堆疊光可固化聚合物之線以及連續地偏移大約線寬的½列印而得。此方法在偏移方向上產生一傾斜大約45度之壁。以相反方向偏移,壁會在中間點接觸。圖6C描述一滴放置在管道入口附近之染色墨水,其似乎因表面張力而被拉通過管道。此證明,管道沿著長度是封閉的,但端至端是完全開放的。
圖7A顯示一種作為電氣組件之機械支撐物之光固化柱。聚合物柱是使用圖1中之方法製得,其大約1mm高,0.1mm寬。藉由使列印頭對每一個傾斜45度,將銀墨水列印在柱以及基材之側壁上。在列印期間,銀墨水具低黏度,
因此在基材上會慢慢擴散。因為提供了機械支撐,可沿著支撐物之表面三維列印銀墨水。列印後,在烤箱中以150℃熱燒結該銀墨水60分鐘。所產生的導電圖案用作為自立、毫米波偶極天線。圖7B顯示微天線之陣列。圖7C以及7D是列印在微晶片上之3D電氣組件之影像。本發明之方法排除需以其它方式建構於組件中之複雜的連結以及導波管。此例子顯示諸如3D電氣組件之功能性元件(例如,加熱器、天線以及連接線),可直接列印在驅動晶片上。
圖8A顯示利用列印期間傾斜列印頭製造之自立聚合物彈簧。在建構各個彈簧期間,列印頭從0°傾斜至-30°,然後回到0°。圖8B描述一個顯示該彈簧陣列可支撐一機械塊體之示範。與之前所述之立柱相反,彈簧在二個表面之間提供可撓性中介層連接。
在諸如金屬奈米粒子分散物之溶劑基墨水之例子方面,液滴黏度可藉由飛行期間部分或完全乾燥而增加。因為已知金屬奈米粒子會高度吸收UV光,所以將液滴曝露於UV照射可加熱奈米粒子以及加速溶劑蒸發。圖9顯示此一原位固化方法延伸至非光可固化材料。圖9A是顯示在UV波長下銀奈米粒子之光學密度(即,吸收光譜),隨著粒徑減少而增加之圖。曲線在410nm附近有一強大的峰值,但吸收邊緣延伸至可見光,使得用一般的UV LED以及水銀燈來進行飛行中之方法成為可能。因此包含銀奈米粒子分散於溶劑中之墨水液滴,可因吸收近400nm波長之UV光而被加熱。若在飛行中加熱,溶劑會大量地蒸發,因而當撞擊在表面
上時,產生高度濃縮的銀滴。金屬奈米粒子液滴可保留其等之3D形狀,因為攜帶溶劑被蒸發了,亦因為粒子部分被燒結了。可以用和光聚合物之堆疊相似之方式,進行現在較高黏度銀液滴之3D堆疊。列印後進一步的照射,會將奈米粒子加熱超過將溶劑蒸發所需之程度,使奈米粒子部分地燒結而變成導體。圖9B顯示用原位照射方法列印之3D銀線陣列。線寬為40μm,高為0.8mm。該等線稍微的彎曲,因為事實上僅使用單側照射,此使照射側上之線得到較多的加熱,導致不對稱收縮。
圖10A-10F是使用UV聚合物以及飛行中固化列印之各種3D形狀之影像。圖10A顯示柱狀(0.1mm間距,0.25mm高)。圖10B顯示扭曲薄片(0.5mm寬,2mm高)。圖10C顯示盒狀(1mm長,0.25mm高,0.03mm壁)。圖10D顯示帽狀(0.5mm直徑,0.5mm高)。圖10E顯示錐狀(0.5mm直徑,0.5mm高)。圖10F顯示泡泡狀(0.5mm直徑,1mm高)。
在本發明之具體例中,UV照射是用於修改噴霧液滴在其等被噴射至標的表面時之特性。明確而言,UV光至少部分地固化光聚合物液滴,以及所導致之黏度的增加,促進自立結構之形成。UV光任擇地會引起溶劑基奈米粒子分散物之液滴於飛行中快速地乾燥,同樣地使能夠3D製造。此3D製造可使用廣泛的光聚合物、奈米粒子分散物以及複合材料進行。所產生的3D形狀可為自立的、不需要支撐,且可藉由相對於標的基材操縱列印噴嘴,獲得任意形狀。特徵尺寸主要由噴射方法決定,可縮小至10μm或甚至更
小。
雖然本發明是參考所揭示的具體例來進行詳細的說明,但其它具體例亦可達到相同的結果。本發明之變化以及修飾對熟悉此技藝之人士而言是顯而易見的,且其意圖涵蓋所有此等修飾以及相等物。以上所引述之所有專利以及公開案之完整揭示內容,均在此併入本案以為參考。
Claims (18)
- 一種用於在基材上製造三維結構之方法,該方法包含:將噴霧液滴從一沉積頭推至該基材上;部分地改變在飛行中之噴霧液滴的特性;以及當該噴霧液滴沉積成為該三維結構之一部分時,完全改變其等之特性。
- 如請求項1之方法,其中改變特性包含使用電磁輻射之固化或硬化。
- 如請求項2之方法,其中固化包含紫外線(UV)固化。
- 如請求項2之方法,其中該噴霧液滴包含光可固化聚合物,且所製得的三維結構包含固化的聚合物。
- 如請求項4之方法,其中該噴霧液滴包含分散在該光可固化聚合物中之固態粒子,而所製得的三維結構包含固化的聚合物,其包含包埋的固態粒子。
- 如請求項5之方法,其中該固態粒子包含陶瓷、金屬、纖維或矽。
- 如請求項1之方法,其中該噴霧液滴包含溶劑,而改變特性包含使該溶劑蒸發。
- 如請求項7之方法,其中該噴霧液滴包含金屬奈米粒子,該方法另外包含:用UV輻射照射該噴霧液滴;加熱該金屬奈米粒子;以及充分地加熱該噴霧液滴至至少部分地使該溶劑蒸 發。
- 如請求項8之方法,其另外包含在其等已經沉積之後,持續照射該金屬奈米粒子,從而至少部份地燒結該金屬奈米粒子。
- 如請求項1之方法,其另外包含相對於該基材傾斜或移動該沉積頭。
- 如請求項1之方法,其包含在不需要犧牲支撐物或傾斜該沉積頭或該基材之情況下,製造懸垂結構。
- 如請求項1之方法,其中該沉積頭與該基材間之噴射距離為至少1mm。
- 如請求項12之方法,其中該沉積頭與該基材間之噴射距離為至少2mm。
- 如請求項1之方法,其包含增加該噴霧液滴在飛行中之黏度。
- 如請求項1之方法,其包含用電磁輻射照射在飛行中之噴霧液滴以及在該噴霧液滴已經沉積後之噴霧液滴。
- 如請求項15之方法,其包含在飛行中,用電磁輻射從超過一個方向照射。
- 如請求項1之方法,其包含用電磁輻射加熱在飛行中之噴霧液滴以及在該噴霧液滴已經沉積後之噴霧液滴。
- 如請求項1之方法,其中該製得的三維結構包含選自於由下列所構成之群組之結構:微米量級之表面紋理、機械中介層、精密墊片、包含包埋電連接器之機械中介層、封閉中空結構、機械支架以及功能性電線。
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WO2016130709A1 (en) | 2016-08-18 |
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CN107548346A (zh) | 2018-01-05 |
EP3256308A1 (en) | 2017-12-20 |
TWI735425B (zh) | 2021-08-11 |
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