TWI558660B - Composite reinforcing material and manufacturing method thereof - Google Patents
Composite reinforcing material and manufacturing method thereof Download PDFInfo
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- TWI558660B TWI558660B TW104129806A TW104129806A TWI558660B TW I558660 B TWI558660 B TW I558660B TW 104129806 A TW104129806 A TW 104129806A TW 104129806 A TW104129806 A TW 104129806A TW I558660 B TWI558660 B TW I558660B
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- graphite
- graphene
- reinforcing material
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- based carbon
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Description
本發明係有關於複合強化素材及其製造方法。
近年來,在各種領域中,正以小型輕量化等為目的,研究各式各樣奈米材料的添加技術。尤其,因環境或資源等問題,石墨烯、CNT(奈米碳管)及富勒烯等碳素材係作為非金屬之奈米材料而備受矚目,為能提高樹脂的物性(抗張強度、彈性係數等),已有人提出一種將強化素材(填料)分散於樹脂中而成的樹脂複合強化素材。
例如,已揭示一種在聚烯烴等熱可塑性樹脂中添加薄片化石墨等碳素材而成的樹脂複合強化素材(專利文獻1)。又,已揭示一種添加薄片化石墨與無機填料以謀求改善物性(張力彈性係數、剛性、耐衝撃性)的複合強化素材(專利文獻2、專利文獻3)。
其中尤其是石墨烯,其在性能方面自不待言,從量產性及操作性等方面來看亦較其他碳素材更為優秀,而在各種領域中頗受期待,惟,為能在將石墨烯等強化素材與樹脂混練時獲得充分之物性改善效果,必須使強化素材均勻
分散。
為能獲得具石墨層數少等特性之高品質石墨烯,目前已在研討如下方法:在溶劑(NMP)中對天然石墨長時間(7~10小時)施加弱超音波後,去除底部沈澱的大塊體,然後將上清液離心分離並予以濃縮,藉此獲得石墨烯分散液,其分散有約0.5g/L之下述石墨材料:單層小片佔20%以上,2層或3層小片佔40%以上,10層以上小片則低於40%的石墨材料(專利文獻4)。
專利文獻1:日本特開2010-254822號公報([0032]-[0038])。
專利文獻2:日本特開2014-201676號公報([0048]-[0064])。
專利文獻3:日本特開2014-210916號公報([0043])
專利文獻4:國際公開第2014/064432號(第19頁第4行-第9行)。
專利文獻5:日本特開2013-79348號公報([0083])。
專利文獻6:日本特開2009-114435號公報([0044])。
非專利文獻1:石墨伴隨研磨而生之結構變化;著作者:稻垣道夫、麥島久枝、細川健次;1973年2月1日(受理)。
非專利文獻2:概率P1,PABA,PABC伴隨碳加熱處理所生
之變化;著作者:野田稻吉、岩附正明、稻垣道夫;1966年9月16日(受理)。
非專利文獻3:來自印度東高止山脈活動帶之流體沈積菱面體石墨的光譜及X射線繞射研究(Spectroscopic and X-ray diffraction studies on fluid deposited rhombohedral graphite from the Eastern Ghats Mobile Belt,India);G.Parthasarathy,Current Science,Vol.90,No.7,10 April 2006.
非專利文獻4:固體碳材料之分類及各自之結構特徵;名古屋工業大學 川崎晉司。
然而,在專利文獻1、2及3所揭方法中,由於使用市售的薄片化石墨而薄片化石墨發生凝集故僅以混練無法分散,薄片化石墨所致效果並未充分發揮。又,即便將專利文獻4所示方法製得的石墨材料(單層小片20%以上、2層或3層小片40%以上且10層以上小片低於40%)混合於溶劑中,分散在溶劑中的石墨烯分散量仍低,只能獲得稀薄的石墨烯分散液。又,雖也可考慮收集上清液來進行濃縮,但反覆進行收集上清液並濃縮的步驟在處理上耗費時間,會有石墨烯分散液的生產效率不彰的問題。如同專利文獻4所揭,即便對天然石墨進行長時間超音波處理,仍僅有表面較脆弱之部分發生剝離,其他大部分則無助於剝
離,獲剝離之石墨烯量甚低,可想見此即成為問題。
又,雖說為了提升機械強度而在聚合物等母材中添加強化素材為一般作法,但視所添加之強化素材量而而定,有時也會對聚合物的原有性狀(外觀)帶來影響(專利文獻5)。
上述專利文獻2、3係添加強化素材而使彈性係數或耐衝撃性等有助於剛性(硬度)的物性提升。本說明書之實施例5(在本申請案以前未公開之發明)亦有相同的結果。
又,為了提高抗拉強度(抗張強度),添加強化素材乃是現行作法(例如專利文獻1)。為了提升抗拉強度,一般而言,諸如碳纖維或玻璃纖維、纖維素纖維等繩狀素材適合作為強化素材(填料)。另外,亦有人提出,為使繩狀素材不易從母材脫落,使用相溶化劑以提高抗張降伏應力(專利文獻6)。但是,現已獲得單只添加繩狀素材並無法充分提升抗張強度等機械強度等之知識見解。吾人認為此係由於母材柔軟而致使繩狀素材連同母材一併脫落之故。
如上所述,一般而言,即便將天然石墨直接處理,所剝離的石墨烯量仍少而成為問題。然而,經戮力研究的結果,對欲成為材料的石墨施以預定的處理,從而獲得了易於剝離成石墨烯並且能使其高濃度化或高分散化的石墨系碳素材(石墨烯前驅物)。該石墨烯前驅物會經由超音波或攪拌、混練而部份或全部剝離,成為從石墨烯前驅物乃至於石墨烯皆有之混存物「類石墨烯石墨」。由於類石墨烯石墨會依石墨烯前驅物的添加量或加工時間等而在
尺寸及厚度等上會有所變化,故雖未予以限定,惟以更呈薄片化者為宜。亦即,換言之,可藉由既存的攪拌或混練製程或裝置而易於剝離、分散成類石墨烯石墨的石墨即是石墨系碳素材(石墨烯前驅物)。
吾人發現,可藉由將該類石墨烯石墨與強化素材一起少量分散於母材中來提高機械強度,諸如彎曲彈性係數、壓縮強度、抗張強度、楊格係數等,且與習知方法相較無須大幅變更製造方法即可製出該複合強化素材。
本發明即著眼於此等問題點而作成者,目的在於提供一種機械強度優良的複合強化素材及其製造方法。
此外,目的在於提供一種複合強化素材,其即便是分散、混合於母材中之類石墨烯石墨量較少,仍可達成所欲性狀。
次又,目的在於使用習知製程來提供機械強度優良的複合強化素材。
為解決前述課題,本發明之複合強化素材,是於母材中至少分散有剝離自石墨系碳素材之類石墨烯及強化素材的複合強化素材;並且,前述石墨系碳素材具有菱面晶系石墨層(3R)與六方晶系石墨層(2H),且前述菱面晶系石墨層(3R)與前述六方晶系石墨層(2H)利用X射線繞射法以下列(式1)定義之比率Rate(3R)為31%以上:Rate(3R)=P3/(P3+P4)×100....(式1)
在此,P3為菱面晶系石墨層(3R)利用X射線繞射法所
得(101)面之峰強度,P4為六方晶系石墨層(2H)利用X射線繞射法所得(101)面之峰強度。
依據此項特徵,複合素材具有優良的機械強度。推測其係歸因於:類石墨烯石墨分散於母材中,而使令母材本身彈性係數提升的作用與令強化素材變得難以脫落的作用得以相乘發揮之故。又,機械強度可舉如彎曲彈性係數、壓縮強度、抗張強度、楊格係數等,例如具有優異抗張強度。
作為特徵的是,前述強化素材係繩狀、線狀或薄片狀的微粒子。
依據此項特徵,微粒子的周圍有類石墨烯石墨存在,可使微粒子所具強化機能充分發揮。
作為特徵的是,前述微粒子的縱橫比為5以上。
依據此項特徵,可使微粒子所具強化機能進一步充份發揮。
作為特徵的是,前述石墨系碳素材與前述類石墨烯石墨相對於前述強化素材的合計重量比為1/100以上且低於10。
依據此項特徵,可使強化素材所具強化機充份發揮。
作為特徵的是,前述母材為聚合物。
依據此項特徵,可獲得機械強度優良的複合強化素材。
作為特徵的是,前述母材為無機材料。
依據此項特徵,可獲得機械強度優良的複合強化素
材。
作為特徵的是,成形材料使用了前述複合強化素材。
依據此項特徵,可獲得機械強度優良且供用於諸如3D列印等的成形材料。
1‧‧‧天然石墨材料
2‧‧‧加料斗
3‧‧‧文氏噴嘴
4‧‧‧噴射磨機
5‧‧‧壓縮機
6‧‧‧槽
7‧‧‧電漿產生裝置
8‧‧‧噴嘴
9‧‧‧氣體
10‧‧‧高壓電源
11‧‧‧線圈
12‧‧‧電漿
13‧‧‧配管
14‧‧‧集塵器
15‧‧‧收集容器
16‧‧‧用作石墨烯前驅物之石墨系碳素材
17‧‧‧鼓風機
20‧‧‧球磨機
21‧‧‧微波產生器、微波產生裝置(磁控管)
22‧‧‧導波管
23‧‧‧微波流入口
24‧‧‧介質
25‧‧‧天然石墨材料
26‧‧‧收集容器
27‧‧‧過濾器
28‧‧‧用作石墨烯前驅物之石墨系碳素材
30‧‧‧使用試料5的石墨烯分散液
31‧‧‧使用試料1的石墨烯分散液
33‧‧‧小片
34‧‧‧計算區域
40‧‧‧燒杯
41‧‧‧石墨烯分散液
42‧‧‧微波產生裝置的腔室
43‧‧‧微波產生裝置
44‧‧‧超音波產生裝置、超音波產生器
44A‧‧‧超音波振動子
圖1係一顯示石墨結晶構造之圖,其中(a)為六方晶的結晶構造,(b)為菱面體晶的結晶構造。
圖2係一顯示一般天然石墨的X射線繞射圖譜之圖。
圖3係一用以說明實施例1中使用噴射研磨與電漿之製造裝置A的圖。
圖4係一用以說明實施例1中使用球磨機與磁控管之製造裝置B的圖,其中(a)為說明粉碎狀態的圖,(b)為說明石墨系碳素材(前驅物)收集狀態的圖。
圖5係一顯示試料5之石墨系碳素材X射線繞射圖譜的圖,該試料5係以實施例1之製造裝置B製得。
圖6係一顯示試料6之石墨系碳素材X射線繞射圖譜的圖,該試料6係以實施例1之製造裝置A製得。
圖7係一顯示試料1的石墨系碳素材X射線繞射圖譜之圖,該試料1的石墨系碳素材表示比較例。
圖8係一顯示分散液製作裝置之圖,該裝置使用石墨系碳素材作為前驅物來製作分散液。
圖9係一顯示分散液之分散狀態的圖,該分散液係使
用試料1(表示比較例)與試料5(實施例1之製造裝置B所製出)的石墨系碳素材製作而成者。
圖10(a)、(b)為已分散於分散液中之石墨系碳素材(石墨烯)的TEM相片。
圖11係一顯示石墨系碳素材之分佈狀態之圖,該石墨系碳素材已被分散在使用試料5之石墨系碳素材(前驅物)所製出之分散液中,其中(a)為顯示平均尺寸分佈之圖,(b)為顯示層數分佈之圖。
圖12係一顯示石墨系碳素材之分佈狀態之圖,該石墨系碳素材已分散於使用試料1(其表示比較例)之石墨系碳素材(前驅物)所製出的分散液中,其中(a)為顯示平均尺寸分佈之圖,(b)為顯示層數分佈之圖。
圖13係一顯示石墨系碳素材之層數分佈之圖,該石墨系碳素材已分散於將試料1至7用作前驅物而製出的分散液中。
圖14係一顯示已分散於分散液中之10層以下之石墨烯相對於菱面體晶含有率之比率的圖。
圖15係一顯示石墨分佈狀態之圖,其已變更實施例2之使用試料5之石墨系碳素材(前驅物)來製作分散液的條件,其中(a)為顯示併用超音波處理與微波處理時之分佈的圖,(b)則是一顯示已施行超音波處理時之層數分佈的圖。
圖16係一顯示使實施例3之石墨系碳素材分散於導電性墨水時之阻抗值之圖。
圖17係一顯示將實施例4之石墨系碳素材混練於樹脂
時之抗張強度之圖。
圖18係一顯示將實施例5之石墨系碳素材混練於樹脂時之抗張強度之圖。
圖19係一顯示分散液中石墨碳系素材之分佈狀態之圖,該分散液係為了補充說明實施例5之分散狀態而分散於N-甲基吡咯啶酮(NMP)者,其中(a)為顯示試料12之分佈狀態之圖,(b)為顯示試料2之分佈狀態之圖。
圖20係一顯示實施例6試驗片之抗張強度及彎曲彈性係數之圖。
圖21係一石墨烯前驅物之SEM照相圖(平面圖)。
圖22係一石墨烯前驅物之SEM照相圖(側面圖)。
圖23係一已分散有類石墨烯石墨之樹脂的SEM照相圖(剖面圖)。
圖24係圖23中類石墨烯石墨的側SEM照相圖(側面圖)。
圖25係一顯示實施例7試驗片之抗張強度及彎曲彈性係數之圖。
圖26係一顯示實施例8之改變了強化素材形狀時試驗片之抗張強度及彎曲彈性係數之圖。
圖27係用於說明實施例8之強化素材形狀的示意圖,(a)為玻璃纖維、碳纖維之形狀,(b)滑石之形狀,(c)為氧化矽之形狀。
圖28係一顯示實施例9之石墨烯前驅物對強化素材之混合比率改變時的試驗片抗張強度及彎曲彈性係數之圖。
本發明係著眼於石墨的結晶構造,故先說明該結晶構造的相關事項。已知天然石墨依據層之重疊方式而被區分為六方晶、菱面體晶及無規等三種結晶構造。如圖1所示,六方晶為層以ABABAB...之順序積層而成的結晶構造,菱面體晶則為層以ABCABCABC...之順序積層而成的結晶構造。
天然石墨於掘出階段幾乎不存有菱面體晶,但在純化階段時則會進行破碎等步驟,因此,在一般的天然石墨系碳素材中,菱面體晶約存在14%左右。又,已知即便在純化時進行長時間的破碎步驟,菱面體晶的比率仍將匯聚在約30%左右(非專利文獻1及2)。
又,除了破碎等之物理力以外,亦知有經由加熱使石墨膨張以進行薄片化的方法,但即便對石墨施以1600K(攝氏約1300度)之熱來進行處理,菱面體晶的比率仍在約25%左右(非專利文獻3)。即便進一步施以超高溫之攝氏3000度的熱,也僅止於約30%左右(非專利文獻2)。
如此這般,雖有可能以物理力或熱來對天然石墨進行處理藉此使菱面體晶的比率增加,但其上限約為30%。
天然石墨所多量含有的六方晶(2H)是非常安定的,其石墨烯與石墨烯彼此間之層間凡得瓦力係以(式3)表示(專利文獻2)。藉由提供超過該力的能量,石墨烯會剝離。由於剝離所需能量與厚度的3次方呈反比,故在重疊
有無數層之厚體狀態下非常微弱,以超音波等之微弱物理力石墨烯即會剝離,但要從薄至一定程度之石墨剝離時,就需要非常大的能量。亦即,即便將石墨進行長時間處理,仍僅有表面較脆弱之部分會剝離,其大部分會維持未剝離之狀態。
Fvdw=H.A/(6π.t3)....(式3)
Fvdw:凡得瓦力
H:Hamaker常數
A:石墨或石墨烯的表面積
t:石墨或石墨烯的厚度
本案發明人等藉由對天然石墨施以如下述所示之預定處理,使得利用粉碎或超高溫加熱之處理也僅能增加到約30%的菱面體晶(3R)比率成功增加到30%以上。一旦石墨系碳材料的菱面體晶(3R)含有率變得更多,尤其是在31%以上的含有率時,則藉由將該石墨系碳素材作為前驅物使用,會有容易剝離成石墨烯的傾向,而可簡單地獲得高濃度化、高分散度化的石墨烯溶液等,上述事項係一以實驗/研究結果之形式而獲得之知識見解。此可想見是因對菱面體晶(3R)施加剪切等力時,層間發生歪曲,亦即石墨構造整體的歪曲變大,因而不再依賴凡得瓦力而變得容易剝離。因此,於本發明中,將可藉由對天然石墨施加預定處理而讓石墨烯輕易剝離進而可使石墨烯高濃度化或高度分散的石墨系碳素材稱為「石墨烯前驅物」,以下,於後述實施例中依序說明:顯示預定處理之石墨烯前驅物
之製造方法、石墨烯前驅物之結晶構造、使用了石墨烯前驅物之石墨烯分散液。
在此,於本說明書中,石墨烯係指平均尺寸為100nm以上的結晶(非為平均尺寸數nm~數十nm的微結晶)且層數為10層以下的薄片狀或片狀的石墨烯。
另外,由於石墨烯為平均尺寸100nm以上的結晶,屬天然石墨以外之非晶質(微結晶)碳素材的人造石墨、碳黑即便是將其等進行處理仍無法獲得石墨烯(非專利文獻4)。
又,本說明書中,石墨烯複合體意味著使用本發明之可用作石墨烯前驅物之石墨系碳素材,即Rate(3R)在31%以上之石墨系碳素材(例如後述之實施例1試料2-7、實施例5試料2、21...)而作成的複合體。
以下,就用以實施本發明之複合強化素材及成形材料的實施例進行說明。
<關於可用作石墨烯前驅物之石墨系碳素材的製造>
就利用圖3所示使用噴射研磨與電漿的製造裝置A來獲得可用作石墨烯前驅物之石墨系碳素材的方法予以說明。製造裝置A係以下述情況為例:施加電漿來作為利用電磁波力之處理,並且使用噴射研磨作為利用物理力之處理。
圖3中,元件符號1為5mm以下粒子的天然石墨材料(日本石墨工業製,鱗片狀石墨ACB-50);2為容納天然石墨材料1的加料斗(hopper);3為將天然石墨材料1從加料斗2
噴射出的文氏噴嘴(Venturi nozzle);4為噴射磨機,其噴射從壓縮機5被分成8處加壓送出的空氣而使天然石墨材料藉噴射之噴流而在腔室內碰撞;7為電漿產生裝置,其係從槽6將氧、氬、氮、氫等氣體9自噴嘴8噴射出,同時自高壓電源10對捲繞在噴嘴8外圍的線圈11施加電壓而使電漿產生在噴射磨機4的腔室內,該電漿產生裝置係在腔室內設有4處。13為連接噴射磨機4與集塵器14的配管;14為集塵器;15為收集容器;16為石墨系碳素材(石墨烯前驅物);17為鼓風機。
接著就製造方法予以說明。噴射磨機及電漿的條件係如下所述。
噴射磨機的條件如下。
壓力:0.5MPa
風量:2.8m3/min
噴嘴內直徑:12mm
流速:約410m/s
電漿的條件如下。
輸出功率:15W
電壓:8kV
氣體種類:Ar(純度99.999Vol%)
氣體流量:5L/min
吾人認為,利用文氏噴嘴3而投入到噴射磨機4之腔室內的天然石墨材料1會在腔室內加速到音速以上,因天然石墨材料1彼此對撞或撞擊內壁的衝撃而粉碎,在此同
時,電漿12經由對天然石墨材料1放電或激發而對原子(電子)直接作用,增加結晶的歪曲並促進粉碎。天然石墨材料1一旦到達一定程度粒徑(1~10μm左右)而成為微粉,則因質量減少、離心力減弱,將會從連接腔室中心的配管13吸出。
混有已自配管13流入集塵器14腔室之圓筒容器中的石墨系碳素材(石墨烯前驅物)的氣體會成為旋轉流,而使碰撞容器內壁的石墨系碳素材16落到下方的收集容器15中,在此同時,因腔室下方的錐狀容器部而在腔室中心發生上昇氣流,氣體從鼓風機17排氣(所謂的旋風作用)。若以本實施例中的製造裝置A而言,可從原料之1kg天然石墨材料1獲得約800g的可用作石墨烯前驅物之石墨系碳素材(石墨烯前驅物)16(回收效率:8成左右)。
接著,就利用圖4所示使用球磨機與微波的製造裝置B來獲得可用作石墨烯前驅物之石墨系碳素材的方法予以說明。製造裝置B係以下述情況為例:施加微波作為利用電磁波力之處理,並且使用球磨機作為利用物理力之處理。
於圖4(a)及(b)中,符號20為球磨機;21為微波產生裝置(磁控管);22為導波管;23為微波流入口;24為介質;25為5mm以下粒子之天然石墨材料(日本石墨工業製,鱗片狀石墨,ACB-50);26為收集容器;27為過濾器;28為石墨系碳素材(石墨烯前驅物)。
接著就製造方法予以說明。球磨機及微波產生裝置的條件係如下述。
球磨機的條件如下。
轉速:30rpm
介質尺寸:φ5mm
介質種類:氧化鋯珠
粉碎時間:3小時
微波產生裝置(磁控管)的條件如下。
輸出功率:300W
頻率:2.45GHz
照射方法:斷續式
於球磨機20的腔室內投入1kg的天然石墨系碳原料25及800g的介質24,關閉腔室並以30rpm的轉速處理3小時。在該處理中對腔室斷續照射(每隔10分鐘照射20秒)微波。可想見的是,經由該微波的照射,可直接對原料的原子(電子)作用而增加結晶的歪曲。處理後,以過濾器27除去介質24,可藉此將10μm程度粉體的石墨系碳素材(前驅物)28收集於收集容器26中。
<關於石墨系碳素材(前驅物)的X射線繞射圖譜>
參照圖5至圖7,就製造裝置A、B所製得之石墨系天然材料(試料6、試料5)以及僅使用製造裝置B之球磨機所得10μm程度粉體之石墨系天然材料(試料1:比較例)的X射線繞射圖譜和結晶構造予以說明。
X射線繞射裝置的測定條件如下。
射線源:Cu K α線
掃描速度:20°/min
管電壓:40kV
管電流:30mA
若利用X射線繞射法(Rigaku公司製試料水平型多功能X射線繞射裝置,Ultima IV),各試料會分別在六方晶2H的面(100)、面(002)、面(101)及菱面體晶3R的面(101)顯示出峰強度P1、P2、P3及P4,因此就其等予以說明。
在此,X射線繞射圖譜的測定,近年無論日本國內外均使用所謂標準化值。該Rigaku公司製試料水平型多目的X射線繞射裝置Ultima IV是一種可按照JIS R 7651:2007「碳材料之晶格參數及微晶尺寸的測定方法」來測定X射線繞射圖譜的裝置。此外,Rate(3R)是以Rate(3R)=P3/(P3+P4)×100求得的繞射強度之比,即便繞射強度的值有所變化,Rate(3R)的值也不會發生變化。亦即,繞射強度之比業已規格化,為了避免以絕對值鑑定物質,其已獲得汎用,該值與測定裝置不具相依性。
施加球磨機之處理與微波處理的製造裝置B所製出的試料5係如圖5及表1所示,峰強度P3及峰強度P1之強度比率高,表示P3相對於P3與P4之和的比率且以(式1)定義的Rate(3R)為46%。又,強度比P1/P2為0.012。
Rate(3R)=P3/(P3+P4)×100....(式1)
在此,P1為六方晶系石墨層(2H)利用X射線繞射法所得(100)面之峰強度,P2為六方晶系石墨層(2H)利用X射線繞射法所得(002)面之峰強度,P3為菱面晶系石墨層(3R)利用X射線繞射法所得(101)面之峰強度,P4為六方晶系石墨層
(2H)利用X射線繞射法所得(101)面之的峰強度。
同樣地,施加噴射磨機處理與電漿處理的製造裝置A所製出的試料6係如圖6及表2所示,峰強度P3及峰強度P1之強度比率高,Rate(3R)為51%。又,強度比P1/P2為0.014。
表2
又,試料1(其表示僅以球磨機製出之比較例)係如圖7及表3所示,峰強度P3相較於試料5和6,其比率較小,Rate(3R)為23%。又,強度比P1/P2為0.008。
如此,以實施例1之製造裝置B所製出的試料5及實施例1之製造裝置A所製出的試料6而言,Rate(3R)各為
46%及51%,相較於圖2所示之天然石墨或表示比較例之試料1,表現出在40%以上或50%以上的情況。
接著,使用上述製出的石墨烯前驅物製作石墨烯分散液,並比較石墨烯的剝離容易性。
<關於石墨烯分散液>
參照圖8,就石墨烯分散液的作成方法予以說明。圖8中係以下述情況為例:製作石墨烯分散液時,於液中併用超音波處理與微波處理。
(1)於燒杯40中加入可用作石墨烯前驅物之石墨系碳素材0.2g及分散液之N-甲基吡咯啶酮(NMP)200ml。
(2)將燒杯40放入微波產生裝置43的腔室42中,從上方將超音波產生器44的超音波振動子44A插入分散液41中。
(3)使超音波產生器44啟動,連續賦予3小時之20kHz(100W)超音波。
(4)在上述使超音波產生器44啟動的期間,使微波產生裝置43啟動而斷續地(每隔5分鐘照射10秒)賦予微波2.45GHz(300W)。
圖9係上述般製出之石墨烯分散液經過24小時的模樣。
使用製造裝置B所製出之試料5的石墨烯分散液30雖有部份沉澱,但已確認整體呈現黑色。可以想見這是因為,用作石墨烯前驅物之石墨系碳素材中有許多是在已剝離成石墨烯的狀態下呈分散。
已確認使用試料1(其表示比較例)之分散液31中石墨系
碳素材幾乎都已沉澱,分散液之一部份係以上清液之形式浮出。可由此想見,僅有極少部份剝離成石墨烯並作為上清液浮出。
又,將如上述般製出之石墨烯分散液於試料台(TEM網環)上稀釋成可觀察的濃度並塗佈後使其乾燥,經由穿透式電子顯微鏡(TEM)之如圖10所示的相片,觀察石墨烯的尺寸及層數。此外,試料1則使用將上清液稀釋、塗佈而成者。例如,在圖10的情況下,尺寸從圖10(a)觀察出其為小片33之最大長度L,約600nm;層數則從圖10(b)觀察小片33之端面並計數石墨烯層之重疊數,求出為6層(符號34所指區域)。如此測定各小片(令小片數為N)的尺寸及層數,求得圖11及圖12所示之石墨烯層數與大小。
參照圖11(a),實施例1之製造裝置B所製出之試料5(Rate(R3)為46%)之石墨烯分散液所含薄片狀之小片的粒度分佈(尺寸分佈)係以0.5μm為尖峰的分佈。又,於圖11(b)中,層數係以3層為尖峰且呈10層以下之石墨烯佔68%的分佈。
參照圖12,比較例之試料1(Rate(R3)為23%)的分散液所含薄片狀小片的粒度分佈(尺寸分佈)係以0.9μm為尖峰的分佈。又,層數係以30層以上者佔大部分且呈10層以下之石墨烯佔10%的分佈。
從該結果得知,製造裝置B所製出之試料5之物在用作石墨烯前驅物時以10層以下的石墨烯居多,石墨烯的分散性優良,且可獲得高濃度的石墨烯分散液。
接著,參照圖13,就石墨烯前驅物的比率Rate(3R)與石墨烯分散液中層數的關係予以說明。圖13中的試料1、5及6係如上述。試料2、3及4係施加球磨機之處理與微波處理的製造裝置B所製出者,且是使用令微波照射時間較試料5更短而製出之石墨烯前驅物來製作石墨烯分散液。又,試料7係以施行噴射磨機之處理與電漿處理的製造裝置A所製出者,且是使用賦予較試料6更高輸出功率之電漿而製出之石墨烯前驅物來製作石墨烯分散液。
從圖13來看,Rate(3R)為31%及38%的試料2及3之層數分佈形狀呈現與在13層前後具有尖峰之正規分佈近似的形狀(使用了試料2、3的分散液)。Rate(3R)在40%以上的試料4至7之層數分佈形狀則呈現在數層(薄石墨烯)部份具有尖峰的所謂對數正規分佈之形狀。另一方面,Rate(3R)為23%的試料1則呈現在層數達30層以上之部份具有尖峰的形狀(使用試料1的分散液)。亦即,可知有下述傾向:Rate(3R)一旦在31%以上則層數分佈形狀會與低於31%時不同,且一旦Rate(3R)進一步達40%以上,層數分佈的形狀會與低於40%時有明顯差異。又,就10層以下之石墨烯的比率而言,使用試料3之分散液的Rate(3R)為38%,相對來說,使用試料4之分散液的Rate(3R)為62%,可知Rate(3R)一旦達40%以上,10層以下之石墨烯的比率驟增。
由此等現象可以想見,Rate(3R)為31%以上時容易剝離成10層以下的石墨烯,更進一步來說,隨著Rate(3R)逐步增多為40%、50%、60%,會變得更容易剝離成10層以
下的石墨烯。又,若著眼於強度比P1/P2,則試料2至試料7呈現相對狹隘之0.012~0.016之範圍內的數值,超過被認為結晶構造會發生歪曲而容易剝離成石墨烯的0.01,因此無論何者均甚理想。
進行Rate(3R)與含有10層以下石墨烯之比率的對比,將結果進一步顯示於圖14。一旦參照圖14即可明瞭,Rate(3R)若在25%以上,10層以下之石墨烯自31%附近開始增加(成為朝右斜上傾斜),此外,10層以下之石墨烯在40%前後驟增(就10層以下之石墨烯的比率而言,使用試料3之分散液的Rate(3R)為38%,相對於此,使用試料4之分散液的Rate(3R)為62%,因Rate(3R)增加4%,10層以下之石墨烯的比率急速增加,增加24%),並且,佔於全體內之10層以下之石墨烯達50%以上。此外,圖14中的黑四方形之點為各別不同的試料,包含上述試料1至7,亦包含其等以外的其他試料。
據此,若將Rate(3R)在31%以上的試料用作石墨烯前驅物並製作石墨烯分散液,10層以下之石墨烯分散的比率會開始增加,若進一步將Rate(3R)在40%以上的試料用作石墨烯前驅物並製作石墨烯分散液,則10層以下之石墨烯會生成50%以上。亦即,可獲得石墨烯呈高濃度且高分散化的石墨烯分散液。又,如上所述,由於該分散液所含石墨系碳素材(前驅物)幾乎不會沈澱,可簡單獲得濃石墨烯分散液。藉由該方法,也可在未進行濃縮下成功製出石墨烯濃度超過10%的石墨烯分散液。尤其是從10層以下之石
墨烯發生分散的比率會驟增至50%以上的觀點來看,Rate(3R)為40%以上較佳。
由上述可知,當Rate(3R)為31%以上(宜40%以上,更宜50%以上)時,分離成10層以下之石墨烯及10層前後之薄層石墨系碳素材的比率高,將此等石墨系碳素材用作石墨烯前驅物時,石墨烯的分散性優良,而且可獲得高濃度的石墨烯分散液。又,因後述之實施例5,Rate(3R)為31%以上時石墨系碳素材作為石墨烯前驅物係有用一事已臻明確。
又,雖認為Rate(3R)之上限毋須特別規定,但從製作分散液等時容易分離成石墨烯一事來考量,則以能同時滿足強度比R1/R2在0.01以上者為宜。此外,在使用製造裝置A、B之製造方法的情況下,從容易製造石墨烯前驅物的觀點來看,上限為70%程度。又,從容易得到Rate(3R)較高之物的觀點來看,以併用製造裝置A之利用噴射磨機之處理與電漿處理的方法更佳。此外,只要併用物理力之處理與電磁波力之處理使Rate(3R)成為31%以上即可。
實施例1係針對製得石墨烯分散液時併用超音波處理與微波處理的情況予以說明,但實施例2僅進行超音波處理而未作微波處理,其他條件則與實施例1相同。
圖15(b)顯示石墨烯分散液的層數分佈,該石墨烯分散液係使用製造裝置B所製出之試料5(Rate(3R)=46%)的石墨烯前驅物並施加超音波處理而獲得者。此外,圖15(a)與
實施例1之製造裝置B所製出之試料5的圖11(b)所示分佈相同。
結果,層數分佈的傾向大致相同,惟10層以下之石墨烯的比率為64%,較實施例1的68%稍低。由此明瞭,製作石墨烯分散液時以同時進行物理力與電磁波力之處理的方式較有效果。
實施例3係針對用於導電墨水之例予以說明。
將實施例1的試料1(Rate(3R)=23%)、試料3(Rate(3R)=38%)、試料5(Rate(3R)=46%)及試料6(Rate(3R)=51%)作為石墨烯前驅物,於水與作為導電性賦予劑之碳數3以下之醇的混合溶液中,調整成導電性墨水所用濃度並製作出INK1、INK3、INK5及INK6,比較各自的電阻值。從結果來看,呈現了電阻值隨著Rate(3R)變高而降低的結果。
實施例4係就混練至樹脂之例予以說明。
在製作分散有石墨烯之樹脂片材時,因添加玻璃纖維者之抗張強度非常良好而調查其原因,而獲得了下述知識見解:與玻璃纖維同時添加的相溶化劑有助於前驅物進行石墨烯化。於是,針對將分散劑與相溶化劑混至樹脂中者進行研討。
將實施例1之試料5(Rate(3R)=46%)作為前驅物,直接添加1wt%於LLDPE(聚乙烯)中,以捏合機或雙軸混練機(擠壓機)等,一邊施加剪切(剪切力)一邊進行捏合。
由於石墨系碳素材一旦在樹脂中石墨烯化並高度分散,抗張強度就會增加一事已屬習知,而可藉由測定樹脂之抗張強度來推測石墨烯化與分散之程度。抗張強度係以島津製作所公司製之桌上型精密萬能試驗機(AUTOGRAPH AGS-J)在試驗速度500mm/min的條件下測得者。
又,為能比較有無添加劑所致之石墨烯化與分散性,而進行了下述(a)、(b)、(c)之3種比較。
(a)無添加劑
(b)一般的分散劑(硬脂酸鋅)
(c)相溶化劑(接枝改質聚合物)
參照顯示測定結果之圖17並就結果加以說明。另外,圖17中,圓印為使用比較例之試料1的樹脂材料,方形印為使用實施例1之試料5的樹脂材料。
在(a)之未加入添加劑的情況下,抗張強度的差距小。
在(b)之已添加分散劑的情況下,可知試料5之石墨烯前驅物之石墨烯化受到一定程度的促進。
在(c)之已添加相溶化劑的情況下,可知試料5之石墨烯前驅物之石墨烯化受到相當程度的促進。這被認為是因為,相溶化劑除了有使石墨烯分散的效果外,亦使石墨烯層結合體與樹脂相結合,在此狀態下若施加剪切力,就會以將石墨烯層結合體拉開之形式發揮作用。
分散劑雖以硬脂酸鋅為例予以說明,但選擇配合化合物性質之物即可。分散劑可舉例如陰離子(anion)界面
活性劑、陽離子(cation)界面活性劑、兩性離子界面活性劑、非離子(nonion)界面活性劑。對石墨烯而言,尤以陰離子界面活性劑及非離子界面活性劑為佳。更宜為非離子界面活性劑。非離子界面活性劑是一種氧伸乙基或羥基、葡萄糖苷等之糖鏈等不會解離成離子而與水之氫鍵結因此呈現出親水性的界面活性劑,因此雖然不具如同離子性界面活性劑般之親水性強度,但有可在非極性溶劑中使用的優勢。而且,可藉由改變其親水基鏈長而使其性質在親油性至親水性之間自由變化。以陰離子界面活性劑來說,宜為X酸鹽(X酸諸如膽酸、去氧膽酸),例如SDC:去氧膽酸鈉、磷酸酯等。又,以非離子界面活性劑來說,宜為丙三醇脂肪酸酯、去水山梨醇脂肪酸酯、脂肪醇乙氧化物、聚氧伸乙基烷基苯基醚、烷基醣苷等。
為了進一步驗證已於實施例1說明之「使Rate(3R)在31%以上則作為石墨烯前驅物係有用」之事實,實施例5係使用混練至樹脂之例進一步加以說明。即,將包含實施例1之試料1~7且Rate(3R)值已繪於圖14之石墨系碳素材作為前驅物使用,針對如此所得的樹脂成形品之彈性係數予以說明。
(1)將上述石墨系碳素材作為前驅物,並將LLDPE(聚乙烯:普瑞曼聚合物公司製20201J)5wt%與分散劑(非離子系界面活性劑)1wt%一同混入離子交換水中,將上述圖8之裝置以相同條件驅動,獲得石墨烯乃至於石墨系
碳素材為5wt%的石墨烯分散液。
(2)使用捏合機(森山股份有限公司製,加壓型捏合機WDS7-30)將(1)所得之石墨烯分散液0.6kg立刻混練至樹脂5.4kg中並製作顆粒。捏合條件則如後述。此外,樹脂與分散液的混合比率係以使石墨烯乃至於石墨系碳素材的添加量最終會呈現0.5wt%之方式選定。
(3)將(2)所製出的顆粒以射出成型機製作成試驗片JIS K7161 1A形(全長165mm,幅寬20mm,厚度4mm)。
(4)依據JIS K7161,以島津製作所股份有限公司製之桌上型精密萬能試驗機(AUTOGRAPH AGS-J)在試驗速度:500mm/min的條件下,測定由(3)製作出之試驗片的彈性係數(Mpa)。
混練條件如下。
混練溫度:135℃
轉子轉速:30rpm
混練時間:15分鐘
爐內加壓:開始後10分鐘為0.3MPa,10分鐘過後釋壓至大氣壓力
在此,就上述(2)之石墨烯分散液對樹脂的分散而言,由於一般來說樹脂之熔點在100℃以上,若在大氣中水會蒸發,但加壓捏合機則可使爐內加壓。在爐內提高水的沸點並使分散液維持液體原狀,可藉此獲得分散液與樹脂的乳濁液。經預定時間加壓後緩緩釋除壓力,水的沸點下降,水不斷蒸發。此時原被封閉在水中的石墨烯會殘留在
樹脂中。可以想見樹脂中之石墨烯石墨系碳素材係因此而高分散化。
又,由於石墨烯分散液有石墨烯石墨系碳素材隨著時間經過而發生沈降的傾向,宜在獲得石墨烯分散液後隨即混練至樹脂中。
另外,獲得分散液與樹脂之乳濁液的手段除了加壓捏合機以外,化學推進器(chemical thruster)、旋渦混合器、均勻混合器(homomixer)、高壓均質機、水力剪切器(hydroshear)、噴流混合器、濕式噴射磨機、超音波產生器等亦可。
又,分散液之溶劑除了水以外,亦可使用2-丙醇(IPA)、丙酮、甲苯、N-甲基吡咯啶酮(NMP)、N,N-二甲基甲醯胺(DMF)等。
於表4中顯示Rate(3R)為30%左右時Rate(3R)與樹脂成形品之彈性係數的關係。此外,表4中的試料00係未混練前驅物的空白試料,試料11及12為Rate(3R)在試料1與試料2之間之試料,試料21則為Rate(3R)在試料2與試料3之間的試料。
從圖18及表4明瞭,相對於試料00(空白試料)之彈
性係數差距(彈性係數的增加比率),至Rate(3R)達31%為止大致在10%前後而略呈定值,以Rate(3R)為31%為界,該差距驟增至32%,Rate(3R)從31%跨42%時該差距單調遞增至50%,Rate(3R)在42%以後該差距係微增乃至於匯聚在60%左右。如此,一旦Rate(3R)在31%以上,即可獲得彈性係數優良的樹脂成形品。又,由於樹脂成形品所含石墨烯乃至於石墨系碳素材為0.5wt%而甚少量,對樹脂原有性狀造成的影響並不多。
咸認此種傾向蓋因Rate(3R)係以31%為界,與樹脂接觸之包含10層以下石墨烯的薄層石墨系碳素材驟增之故。在此,實施例5中,因用以使其分散於水中之分散劑的影響,即便以TEM觀察仍無法確認石墨烯的層數。因此,作為參考,基於表4所示之分散於NMP時的石墨系碳素材層數分佈來研討上述驟增的理由。若對比試料12與試料2,則石墨烯(層數10層以下)均為25%。另一方面,如圖19所示,試料2中低於15層之薄層比率較試料12更高,亦即可以想見,這是因為作為前驅物而令其分散之石墨系碳素材的表面積甚廣,與樹脂接觸的面積急遽擴大之故。
如此,經由實施例5明確顯示了下述傾向:一旦Rate(3R)在31%以上,用作石墨烯前驅物之石墨系碳素材會分離成10層以下之石墨烯乃至於薄層之石墨系碳素材。
實施例5僅使類石墨烯石墨分散,然而只有彈性係數提昇,而幾乎未見抗張強度的提昇。
因此,進行在樹脂中添加依上述方法製得之石墨烯前驅物與玻璃纖維的實驗。
<各條件>
樹脂:PP(聚丙烯)普瑞曼聚合物製J707G;
相溶化劑:KAYABRID(KAYAKUAKZO公司製006PP馬來酸酐改性PP);
玻璃纖維(GF):Central玻璃纖維公司製ECS03-631K(直徑13μm,長度3mm);
石墨系碳素材:石墨烯前驅物(由上述方法製造);
混合機:轉鼓混合機(SEIWA技研社製)。
<混合條件1:旋轉數25rpm×1分>
混練機:2軸擠壓機(神戶製鋼社製HYPERKTX 30);
<混練條件1:管柱溫度180℃,轉子旋轉數100rpm,吐出量8kg/h>
試驗片:JIS K7139(170mm×20mm×t4mm);
測定裝置:島津製作所製 桌上型精密萬能試驗機AUTOGRAPH AGS-J。
<實驗順序>
步驟1. 事先以混合條件1在轉鼓混合機中混合玻璃纖維(GF)40wt%、相溶化劑4wt%與樹脂56wt%,然後利用2軸擠壓機(押出機)以混練條件1進行混練,製得母料1。
步驟2. 事先以混合條件1在轉鼓混合機中混合表5所示Rate(3R)各異之石墨烯前驅物12wt%與樹脂88wt%,然後
利用2軸擠壓機(押出機)以混練條件1進行混練,製得母料2。
步驟3. 事先以混合條件1於轉鼓混合機中混合25wt%之母料1、25wt%之母料2、50wt%之樹脂,然後利用2軸擠壓機(押出機)以混練條件1進行混練。
步驟4. 將在步驟3混練而成之物以射出成型機成型為試驗片,根據JIS K7139,以試驗速度500mm/min觀察機械強度的變化。
為了確認類石墨烯石墨的影響,依表5所示混合比率,以Rate(3R)為23%(試料1)、31%(試料2)、35%(試料21)及42%(試料4)進行實驗。
由表5及圖20觀察到,實施例6-2、6-3及6-4的抗張強度較實施例6-1、比較例6-1、6-2及6-3更高。尤其是觀察到,一旦石墨烯前驅物的比率Rate(3R)在31%以上,相較於0%(比較例6-2)及23%(實施例6-1)時,抗張強度提高30%以上此一值得特別述及的傾向。另外,不含GF的比較例6-1及6-3並未作圖於圖20中。
又,彎曲彈性係數與抗張強度相同,可觀察到實
施例6-2、6-3及6-4較實施例6-1、比較例6-1、6-2及6-3更高。尤其,觀察到一旦石墨烯前驅物的比率Rate(3R)在31%以上,相較於0%(比較例6-2)及23%(實施例6-1)彎曲彈性係數提高40%以上此一值得特別述及的傾向。
一旦將Rate(3R)在31%以上(實施例6-2、6-3、6-4)的石墨烯前驅物與GF併用,抗張強度及彎曲彈性係數就會變高。推測此現象是因PP間分散有厚度為0.3~數十nm、大小為數nm~1μm的類石墨烯石墨而使得PP本身的彈性係數上升,同時因相容化劑而迫使GF密著於PP上變得不易脫落,與此GF接觸的類石墨烯石墨會令所謂的楔塞作用發生,而因PP本身彈性係數上升的作用與楔塞作用的加乘效果,抗張強度及彎曲彈性係數分別上升。若舉例來說,附有倒勾的樁子即便扎在泥濘地面也容易拔除,但在經踏實的地面則不易拔出,這與上述是一樣的情形。又,推測下述者亦是成因之一:因相溶化劑的添加,類石墨烯石墨等從石墨系碳素材剝離的情況受到促進,而有甚薄的類石墨烯石墨大量存在。
此外,Rate(3R)低於31%時(實施例6-1),分散的類石墨烯石墨數量較少,可想見添加石墨烯前驅物產生之效果未能充份發揮。
又,一旦Rate(3R)在35%以上(實施例6-3及6-4),則彎曲彈性係數及抗張強度較Rate(3R)低於該值時更為良好。可想見這是相較於Rate(3R)為31%(實施例6-2)時,會使PP彈性係數提高的類石墨烯石墨數量增加之故。
為供參考而就石墨烯前驅物之掃描式電子顯微鏡(SEM)照相圖予以說明。實施例1所得之石墨烯前驅物是長7μm厚度0.1μm之薄層石墨積層體,如同圖21及22所示一般。
又,分散於樹脂的類石墨烯石墨可藉由將已成形之試驗片以精密高速切斷機(ALLIED公司製TechCut5)等切斷而以掃描式電子顯微鏡(SEM)等進行觀察。例如,圖23顯示了已分散有奈米碳管與類石墨烯石墨之樹脂的剖面,線狀部分為奈米碳管,白斑狀部分為類石墨烯石墨。舉例來說,該類石墨烯石墨係如圖24所示般為厚度3.97nm之薄層石墨的積層體。
使用上述方法所製石墨烯前驅物進行製得樹脂成形品的實驗。
<各條件>
樹脂:PA66(耐綸66)旭化成製1300S;
相溶化劑:KAYABRID 006PP(KAYAKUAKZO公司製馬來酸酐改性PP);
玻璃纖維(GF):Central玻璃纖維社製ECS03-631K(直徑13μm,長度3mm);
石墨系碳素材:石墨烯前驅物(由上述方法製造);
混合機:轉鼓混合機(SEIWA技研社製);
<混合條件1:旋轉數25rpm×1分>
混練機:2軸擠壓機(神戶製鋼社製HYPERKTX
30);
<混練條件2:管柱溫度280℃,轉子旋轉數200rpm,吐出量12kg/h>
試驗片:JIS K7139(170mm×20mm×t4mm);
測定裝置:島津製作所製 桌上型精密萬能試驗機AUTOGRAPH AGS-J。
<實驗順序>
步驟1. 事先以轉鼓混合機將玻璃纖維(GF)40wt%、相溶化劑4wt%及樹脂56wt%依混合條件1予以混合,然後以2軸擠壓機(押出機)依混練條件2進行混練,獲得母料1。
步驟2. 事先以轉鼓混合機將表6所示Rate(3R)各異之石墨烯前驅物12wt%與樹脂88wt%依混合條件1予以混合,然後以2軸擠壓機(押出機)依混練條件2進行混練,獲得母料2。
步驟3. 事先以轉鼓混合機將37.5wt%之母料1、25wt%母料2及37.5wt%樹脂依混合條件1予以混合,然後以2軸擠壓機(押出機)依混練條件2進行混練。
步驟4. 依據JIS K7139,將步驟3混練之物以射出成型機成型為試驗片,在試驗速度500mm/min下觀察機械強度的變化。
為了確認類石墨烯石墨的影響,依表6所示之混合比率,以Rate(3R)為23%(試料1)、31%(試料2)、35%(試料21)及42%(試料4)進行實驗。
表6
從表6及圖25觀察到,實施例7-2、7-3及7-4抗張強度較實施例7-1、比較例7-1、7-2及7-3來得高。尤其是觀察到,一旦石墨烯前驅物的比率Rate(3R)在31%以上,相較於0%(比較例7-2)、23%(實施例7-1)時,抗張強度提高20%以上此一值得特別述及之傾向。此外,不含GF的比較例7-1及7-3並未繪圖於圖25中。
又,觀察到彎曲彈性係數與抗張強度相同,均是實施例7-2、7-3及7-4較實施例7-1、比較例7-1、7-2及7-3來得高。尤其,觀察到值得特別述及的傾向,即一旦石墨烯前驅物的比率Rate(3R)在31%以上,相較於0%(比較例7-2)、23%(實施例7-1)時彎曲彈性係數提高20%。
抗張強度及彎曲彈性係數提升的理由,可想見與實施例6中的說明相同。
由實施例6及7觀察到,一旦添加GF,則不拘母材的樹脂,抗張強度及彎曲彈性係數皆提升。茲就與GF一起添加石墨烯前驅物的情形予以說明。已然觀察到,將Rate(3R)為23%者(實施例6-1,7-1)用作石墨烯前驅物時,不拘母材之樹脂,抗張強度及彎曲彈性係數與未添加石墨烯前驅物者(比較例6-2,比較例7-2)相較僅些微提高而已,惟一
旦使用Rate(3R)為31%以上者作為石墨烯前驅物,抗張強度及彎曲彈性係數皆急劇提高(提升10%以上)。
進行將上述方法所製石墨烯前驅物與強化素材添加於樹脂中之實驗。
實施例8係使用玻璃纖維(GF)、碳纖維(CF)、滑石、氧化矽作為強化素材來確認強化素材的形狀所致影響。強化素材以外的實驗條件等與實施例6相同。
如圖27所示,就強化素材而言,GF及CF呈直徑數十μm且長度數百μm的繩狀乃至於線狀。滑石呈代表長度數~數十μm且厚度數百nm之薄片狀,氧化矽呈直徑數十nm~數μm的粒狀。
如表7及圖26所示,相較於未添加強化素材的比較例6-1,添加了強化素材之任一者的抗張強度及彎曲彈性係數均有提升。若將添加了強化素材及石墨烯前驅物者(實施例6-2、8-1、8-2、8-3)與僅添加強化素材者(比較例6-2、
8-1、8-2、8-3)相較,則與石墨烯前驅物一同添加的強化素材為GF時,抗張強度與彎曲彈性係數分別為1.4倍及1.4倍(實施例6-2相對於比較例6-2的增減率)。同樣地,強化素材為CF時為1.3倍、1.3倍;滑石時為1.3倍、1.1倍;氧化矽時則為1.0倍、2.0倍。由此可知,若將石墨烯前驅物與繩狀、線狀或薄片狀的強化素材併用,抗張強度及彎曲彈性係數將上升10%以上,甚為理想。可以推測,繩狀、線狀或薄片狀的奈米強化素材因其形狀使然,每單位質量的表面積較廣,而使抗張強度提升的效果強且能夠使彎曲彈性係數提高,與類石墨烯石墨的相性良好。又進一步確知,強化素材就繩狀、線狀或薄片狀的形狀而言,以縱橫比在5以上者尤佳。相反地,如同氧化矽般縱橫比在5以下的強化素材變成僅使彎曲彈性係數提高的結果。此外,薄片狀素材的縱橫比僅需求出平均厚度對最長部分的比即可。在此所謂之縱橫比可由記載於強化素材產品型錄等之直徑或厚度的平均值與長度的平均值來求得。在未特別有型錄等的情況,則以SEM等電子顯微鏡觀察任意個數,從其長度與厚度的平均值求出。
接著,使用上述方法所製石墨烯前驅物,進行獲得樹脂成形品的實驗。
將Rate(3R)為31%之石墨烯前驅物對強化素材的混合比率以表8所示條件進行實驗。實驗條件等與實施例6相同。
表8
如表8及圖28所示,石墨烯前驅物對強化素材的混合比率一旦變得比1(實施例9-4)還大,則抗張強度或彎曲彈性係數就會變成大致相同之數值,而觀察到特性已臻飽和。又,一旦石墨烯前驅物的混合比率在10以上,對母材性狀的影響就會變大。另一方面,觀察到混合比率為1/100(實施例9-8)之物較不添加石墨烯前驅物的比較例6-2抗張強度增加4%以上,彎曲彈性係數則增加10%以上。又,觀察到抗張強度是在該混合比率1/10(實施例6-2)以上時急劇增加,彎曲彈性係數則是在該混合比率1/3(實施例9-1)以上時急劇增加。
據此,混合比率下限為1/100以上且宜為1/10以上,上限為10以下且宜為1以下。
此外,不含GF的比較例6-1未繪圖於圖28中。
於此,由於實施例6-9是以電波力處理及/或物理力處理方式來製造石墨烯前驅物,故毋須進行氧化、還原處理。進一步來說,於製造試驗片時,由於毋須還原處理
故無需令其呈高溫,試驗片的製造甚為容易。
以上,雖利用圖表來說明本發明的實施例,惟具體構成並不受限於該等實施例,即使在未逸脫本發明要旨的範圍內有所變更或追加,仍包含於本發明之中。
舉例來說,就用以使強化素材與石墨系碳素材分散的母材而言,可舉如下列物質。惟,母材之比率亦可較強化素材或石墨系碳素材等更小。又,使用時也會有因燃燒、氧化、氣化、蒸發等而消失的情況。舉例來說,在塗佈劑等母材為揮發性溶劑的情況,則如同C/C複合材料般使母材燃燒而使其碳化等。
樹脂方面可列舉如聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)、聚氯乙烯(PVC)、ABS樹脂(ABS)、聚乳酸(PLA)、丙烯酸樹脂(PMMA)、聚醯胺/尼龍(PA)、聚縮醛(POM)、聚碳酸酯(PC)、聚對苯二甲酸乙二酯(PET)、環狀聚烯烴(COP)、聚伸苯硫(PPS)、聚四氟乙烯(PTFE)、聚碸(PSF)、聚醯胺醯亞胺(PAI)、熱可塑性聚醯亞胺(PI)、聚醚醚酮(PEEK)、液晶聚合物(LCP)等熱可塑性樹脂。又,於合成樹脂中,作為熱硬化性樹脂或紫外線硬化樹脂,可列舉環氧樹脂(EP)、苯酚樹脂(PF)、三聚氰胺樹脂(MF)、聚胺甲酸乙酯(PUR)、不飽和聚酯樹脂(UP)等;導電性高分子方面為PEDOT、聚噻吩、聚乙炔、聚苯胺、聚吡咯等;纖維狀的尼龍、聚酯、壓克力、維尼綸、聚烯烴、聚胺甲酸乙酯、嫘縈等纖維;作為彈性體之異戊二烯橡膠(IR)、丁二烯橡膠(BR)、苯乙烯丁二烯橡膠(SBR)、氯丁二烯橡膠
(CR)、腈橡膠(NBR)、聚異丁烯橡膠/丁基橡膠(IIR)、乙烯丙烯橡膠(EPM/EPDM)、氯磺化聚乙烯(CSM)、壓克力橡膠(ACM)、表氯醇橡膠(CO/ECO)等;作為熱硬化性樹脂系彈性體,可列舉如一部分的胺甲酸乙酯橡膠(U)、聚矽氧橡膠(Q)、氟橡膠(FKM)等;熱可塑性彈性體則可列舉如苯乙烯系、烯烴系、聚氯乙烯系、胺甲酸乙酯系、醯胺系之彈性體。
無機材料可舉如,混凝土、陶瓷、石膏、金屬粉末等。
強化素材可列舉如下述物質。
以金屬材料而言,有銀奈米粒子、銅奈米粒子、銀奈米線、銅奈米線、鱗片狀銀、鱗片狀銅、鐵粉、氧化鋅、纖維狀金屬(硼、鎢、氧化鋁、碳化矽)等。
碳素材有碳黑、碳纖維、CNT、石墨、活性碳等。
碳以外的非金屬材料有玻璃纖維、奈米纖維素、奈米黏土(蒙脫土等黏土礦物)、芳綸纖維、聚乙烯纖維等。
又,就供用以製造用作石墨烯前驅物之石墨系碳素材的天然石墨而言,雖是以5mm以下粒子之天然石墨材料(日本石墨工業製,鱗片狀石墨,ACB-50)為例予以說明,但從取得容易的觀點來看,天然石墨以下述者為佳:屬於鱗片狀石墨且已粉碎至5mm以下,Rate(3R)低於25%,且強度比P1/P2低於0.01者。經由近年的技術開發,已可以人造方式合成出如同天然石墨之石墨(結晶重疊為層狀之物),因此石墨烯及類石墨烯石墨的原料不限於天
然石墨(礦物)。對於需要控制金屬含量的用途而言,使用純度高的人造石墨較為理想。又,只要Rate(3R)為31%以上,亦可為以上述物理力處理或電波力處理以外的方式所得之人造石墨。
此外,雖然用作石墨烯前驅物的石墨系碳素材一般而言被稱為石墨烯、石墨烯前驅物、石墨烯奈米微片(GNP)、少層石墨烯(FLG)及奈米石墨烯等,但並無特別限定。
本發明是以具有強度之複合強化素材作為對象,而不問其應用領域。此外,就本發明而言,例如有下述各種領域。
(1)母材為有機材料(樹脂,塑膠)之例
(1-1)運載工具
飛行機、自動車(乘用車、貨車、巴士等)、船舶、遊具等之框體或構件等構造部材(構造部材為複合樹脂、改質樹脂、纖維強化樹脂等)。
(1-2)汎用品
家具、家電、家庭用品、玩具等的框體及構件等構造部材。
(1-3)3D列印機
用於熱溶解積層成形法(FDM)、光成形法(SLA)、粉末固著、粉末燒結成形法(SLS)、多噴頭(Multi-jet)成形法(MLM、噴墨成形法)之樹脂纖絲、UV硬化樹脂等各種成
形材料。
(1-4)塗佈劑
與樹脂一同分散於有機溶劑中,以噴塗或塗裝等方式塗佈而將表面被覆。除了提升強度外,有撥水、防銹、耐紫外線等效果。用途為建築物(橋脚、建物、壁、道路等)、自動車、飛行機等的表面及內部塗裝,盔罩,保護層等的樹脂成型物等。
(2)母材為無機材料之例
水泥(混凝土、灰泥)、石膏板、陶瓷、C/C複合材料(碳纖維強化碳複合材料)等纖維強化構造部材。將該等無機材料作為母材並使類石墨烯石墨及強化素材分散而成者。
(3)母材為金屬材料
鋁、不銹鋼、鈦、黃銅、青銅、軟鋼、鎳合金、碳化鎢等構造部材。(構造部材為纖維強化金屬等)。將該等金屬材料作為母材並使類石墨烯石墨及強化素材分散而成者。
Claims (8)
- 一種複合強化素材之製造方法,其特徵在於該方法包括下述步驟:將至少石墨系碳素材與強化素材混練至母材中,前述石墨系碳素材具有菱面晶系石墨層(3R)與六方晶系石墨層(2H),且前述菱面晶系石墨層(3R)與前述六方晶系石墨層(2H)利用X射線繞射法以下列(式1)定義之比率Rate(3R)為31%以上;Rate(3R)=P3/(P3+P4)×100....(式1)於此,P3為菱面晶系石墨層(3R)利用X射線繞射法所得(101)面之峰強度,P4為六方晶系石墨層(2H)利用X射線繞射法所得(101)面之峰強度。
- 如請求項1之複合強化素材之製造方法,其中前述強化素材為繩狀、線狀或薄片狀的微粒子。
- 如請求項2之複合強化素材之製造方法,其中前述微粒子之縱橫比為5以上。
- 如請求項1或2之複合強化素材之製造方法,其中前述石墨系碳素材對前述強化素材之重量比為1/100以上且低於10。
- 如請求項1之複合強化素材之製造方法,其中前述母材為聚合物。
- 如請求項5之複合強化素材之製造方法,其係於前述步驟中使用相溶化劑。
- 如請求項1之複合強化素材之製造方法,其中前述母材為無機材料。
- 一種複合強化素材,其特徵在於:該複合強化素材係將至少石墨系碳素材與強化素材混練至母材中而使前述石墨系碳素材部份或全部剝離而獲得者,並且,前述石墨系碳素材具有菱面晶系石墨層(3R)與六方晶系石墨層(2H),且前述菱面晶系石墨層(3R)與前述六方晶系石墨層(2H)利用X射線繞射法以下列(式1)定義之比率Rate(3R)為31%以上;Rate(3R)=P3/(P3+P4)×100....(式1)於此,P3為菱面晶系石墨層(3R)利用X射線繞射法所得(101)面之峰強度,P4為六方晶系石墨層(2H)利用X射線繞射法所得(101)面之峰強度。
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PCT/JP2015/055977 WO2016002254A1 (ja) | 2014-09-09 | 2015-02-27 | グラフェン前駆体として用いられる黒鉛系炭素素材及びその製造方法 |
PCT/JP2015/058331 WO2015198657A1 (ja) | 2014-09-09 | 2015-03-19 | 複合強化素材及び造形材料 |
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