TWI644787B - 多孔金屬複合結構 - Google Patents
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- 239000002905 metal composite material Substances 0.000 title claims abstract description 41
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 66
- 229910052751 metal Inorganic materials 0.000 claims abstract description 49
- 239000002184 metal Substances 0.000 claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 59
- 239000002041 carbon nanotube Substances 0.000 claims description 36
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 22
- 239000010931 gold Substances 0.000 claims description 19
- 210000003041 ligament Anatomy 0.000 claims description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000007769 metal material Substances 0.000 claims description 11
- 238000005411 Van der Waals force Methods 0.000 claims description 6
- 239000002071 nanotube Substances 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005452 bending Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 description 33
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- 229910001316 Ag alloy Inorganic materials 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
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- 239000010409 thin film Substances 0.000 description 8
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Abstract
本發明涉及一種多孔金屬複合結構,包括多孔金屬結構和一奈米碳管結構,該奈米碳管結構固定在所述多孔金屬結構的表面,所述奈米碳管結構包括多根奈米碳管,所述多孔金屬複合結構包括多個褶皺部。
Description
本發明涉及一種多孔金屬複合結構。
近年來,奈米多孔金屬材料在擁有高比表面積、比模量等特性的同時,還兼具金屬材料的高導熱率、高導電率等優異性能,從而在生物傳感、催化、能量轉化與存儲、消音吸振、遮罩、熱交換、電化學等領域中有著廣闊的應用前景。
然而,如圖1所示,現有的皺縮的奈米多孔金屬材料中,奈米多孔金屬存在韌帶連接不完整等現象,因此,該皺縮的奈米多孔金屬材料的韌性不好,容易發生脆斷,從而影響該皺縮的奈米多孔金屬材料的應用。
有鑑於此,確有必要提供一種韌性較好的多孔金屬複合結構。
一種多孔金屬複合結構,包括多孔金屬結構和一個奈米碳管結構,該奈米碳管結構固定在所述多孔金屬結構的表面,所述奈米碳管結構包括多根奈米碳管,所述多孔金屬複合結構包括多個褶皺部。
與先前技術相比較,本發明提供的多孔金屬複合結構中奈米碳管固定於所述多孔金屬結構的表面,且由於奈米碳管具有良好的韌性,因此所述多孔金屬複合結構具有良好的韌性,發生皺縮時不容易脆斷。
圖1是先前技術中褶皺的奈米多孔金膜在高倍鏡下的掃描電鏡圖。
圖2是本發明實施例提供的多孔金屬複合結構在低倍鏡下的掃描電鏡圖。
圖3是本發明實施例提供的多孔金屬複合結構在高倍鏡下的掃描電鏡圖。
圖4是本發明實施例提供的多孔金屬複合結構的掃描電鏡圖。
圖5是本發明實施例圖3中褶皺部的結構示意圖。
圖6是本發明實施例提供的多孔金屬複合結構製備方法的流程示意圖。
圖7是本發明實施例提供的多孔金屬複合結構中奈米多孔金膜的掃描電鏡表徵圖。
圖8是本發明實施例提供的多孔金屬複合結構中第二複合結構的掃描電鏡表徵圖。
圖9是本發明實施例提供的多孔金屬複合結構中第二複合結構的掃描電鏡圖。
下面根據說明書圖式並結合具體實施例對本發明的技術方案進一步詳細表述。
請參閱圖2及圖3,本發明實施例提供一種多孔金屬複合結構,該多孔金屬複合結構包括多孔金屬結構和一個奈米碳管結構,該奈米碳管結構固定在所述多孔金屬結構的表面,所述奈米碳管結構包括多根奈米碳管,所述多孔金屬複合結構包括多個褶皺部。
所述多孔金屬結構可以為多孔金屬膜、多孔金屬奈米片等任意結構。所述多孔金屬結構呈三維網狀,所述多孔金屬結構包括多個韌帶,該多個韌帶之間形成多個孔,所述多個孔可以呈規則分佈,如三維雙連續網路形式分佈,也可以呈不規則分佈。所述韌帶的材料為金、銀、鉑中的任意一種。該多個孔的孔徑為奈米級,優選的,所述多個孔的孔徑小於1000nm。
所述奈米碳管結構可以通過一連接材料固定於所述多孔金屬結構表面。具體地,所述奈米碳管結構中的奈米碳管與所述多孔金屬結構中的韌帶接觸形成多個接觸面,該接觸面周圍設置有連接材料,使奈米碳管結構不容易脫離多孔金屬結構的表面。優選的,所述連接材料將所述接觸面包裹住。所述連接材料可以為有機粘結材料或金屬材料。所述有機粘結材料可以為萘酚等具有粘結作用的材料,所述金屬材料可以為Au、Ag、Cu等。優選的,所述金屬材料與
所述多孔金屬結構的材料相同,減小金屬材料與多孔金屬結構中韌帶的接觸電阻。
請參閱圖4及圖5,所述多個褶皺部100相互連接形成一連續結構。該褶皺部100由多孔金屬結構110和奈米碳管結構120共同彎折構成。這一點也可以從上述圖3中看出。在所述褶皺部100處,奈米碳管結構120的褶皺處的奈米碳管可以沿同一方向延伸。具體的,奈米碳管之間通過凡得瓦力首尾相連且沿同一方向排列。可以理解,奈米碳管結構的排列方向也可以不限。
所述褶皺部為不可逆轉的變形。由於奈米碳管具有良好的韌性,奈米碳管橫穿所述褶皺部,起到加固所述褶皺部的作用,奈米碳管結構與所述多孔金屬結構固定形成的多孔金屬複合結構具有良好的韌性,褶皺部不容易發生斷裂,該多孔金屬複合結構具備自支持的性能。
請參閱圖6,本發明實施例進一步提供一種多孔金屬複合結構的製備方法,其包括以下步驟:
步驟S20,提供一基板;該基板的材料選擇受熱能夠收縮的材料。優選的,所述基板為塑膠板,該塑膠板的材料為聚苯乙烯、聚丙烯、聚對苯二甲醇乙二酯等。本實施例中,該塑膠板的材料為聚苯乙烯。
步驟S30,在所述基板的表面固定多孔金屬結構,形成第一複合結構;所述固定的方法不限,在某個實施例中,可以通過加熱所述基板,使基板稍微熔化從而粘住所述多孔金屬結構,優選的,將基板與多孔金屬結構在80℃的溫度下加熱30min~60min;在另外一個實施例中,通過在所述基板與所述多孔金屬結構的接觸面周圍生長金屬,具體的,將所述第一複合結構轉移到含有Au+、Ag+、Cu+等任意一種金屬離子溶液中,在所述含有金屬離子的溶液中添加還原劑形成金屬顆粒,該金屬顆粒通過化學鍍的方式沉積在所述多孔金屬結構中韌帶與奈米碳管結構中奈米碳管的接觸處周圍,從而使多孔金屬結構固定在基板的表面。本實施例中,將基板與多孔金屬結構在80℃的溫度下加熱30min,加熱過程中所述基板的表面稍微發生熔融,多孔金屬結構粘合在所述基板的表面。
所述多孔金屬結構的獲取方法不限,可以為目前市場上售賣的各種多孔金屬,也可以自行製備。本實施例中,所述多孔金屬結構為奈米多孔金膜,該奈米多孔金膜通過化學腐蝕的方法製備得到,具體方法如下:
S31,提供一Au-Ag合金薄膜。
該Au-Ag合金薄膜為表面光滑的薄膜材料,具有銀白色的光澤,其厚度範圍為50nm-200nm。該Au-Ag合金薄膜的尺寸不限,可以根據需要任意選擇。本實施例中,所述Au-Ag合金薄膜的厚度為100nm,該Au-Ag合金薄膜中所述金原子的百分比為35%,銀的原子百分比為65%。
S32,將所述Au-Ag合金薄膜放置於濃硝酸溶液中,直到該Au-Ag合金薄膜由銀白色變成棕紅色,形成奈米多孔金膜。
所述濃硝酸的濃度範圍可為50%-80%。通過玻璃片靜電吸附將該Au-Ag合金薄膜轉移到所述濃硝酸溶液中。本實施例中,所述濃硝酸的濃度為70%。所述Au-Ag合金中的Ag與濃硝酸進行反應,當Ag與濃硝酸反應完全後,所述Au-Ag合金薄膜變成棕紅色,此時,所述Au-Ag合金薄膜的表面形成多個不規則的孔,從而形成奈米多孔金膜。
請參閱圖7,所述奈米多孔金膜具有多個孔,多個孔之間通過韌帶連接,該多個孔的孔徑及韌帶尺寸與所述Au-Ag合金薄膜腐蝕的時間、濃硝酸濃度等因素有關。
S33,將所述奈米多孔金膜放置于去離子水中進行清洗。
採用玻璃片將所述形成的奈米多孔金膜轉移到去離子水中浸泡清洗,在浸泡過程中不斷更換去離子水,使殘留在所述米多孔金膜韌帶上的硝酸徹底清洗掉。
步驟S40,在所述第一複合結構中多孔金屬結構的表面固定一個奈米碳管結構,形成第二複合結構;請參閱圖8及圖9,所述奈米碳管結構可以機械平鋪在所述多孔金屬結構的表面,該奈米碳管結構可以為線狀結構,如奈米碳管線,或可以為一奈米碳管膜狀結構。
所述奈米碳管線可以為一條或多條,當所述奈米碳管線為多條時,該多條奈米碳管線可以並排設置成束狀結構,也可以交叉設置成網狀結構,或者將該多條奈米碳管線相互扭轉形成一相互纏繞的絞線結構。
所述奈米碳管線可以為一非扭轉的奈米碳管線或扭轉的奈米碳管線。
該非扭轉的奈米碳管線包括多個沿該非扭轉的奈米碳管線長度方向排列的奈米碳管,該多個奈米碳管基本相互平行,且該奈米碳管的軸向基本平行於該奈米碳管線的長度方向。具體地,該非扭轉的奈米碳管線中的沿非扭轉奈米碳管線軸向上的相鄰的奈米碳管通過凡得瓦力首尾相連。該非扭轉的奈米碳管線長度不限,直徑為0.5奈米~100微米。進一步地,該非扭轉的奈米碳管線可以用有機溶劑處理。
所述扭轉的奈米碳管線包括多個繞該扭轉的奈米碳管線軸向螺旋排列的奈米碳管。該扭轉的奈米碳管線可採用一機械力將所述非扭轉的奈米碳管線兩端沿相反方向扭轉獲得。
上述扭轉的奈米碳管線和非扭轉的奈米碳管線均由於其中的奈米碳管之間通過凡得瓦力緊密結合而使得該扭轉的奈米碳管線和非扭轉的奈米碳管線均具有自支撐結構。所述自支撐為奈米碳管線不需要大面積的載體支撐,而只要相對兩邊提供支撐力即能整體上懸空而保持自身線狀狀態,即將該奈米碳管線置於(或固定於)間隔一定距離設置的兩個支撐體上時,位於兩個支撐體之間的奈米碳管線能夠懸空保持自身線狀狀態。
所述奈米碳管膜狀結構可以為奈米碳管拉膜、奈米碳管絮化膜或奈米碳管碾壓膜中任意一種膜狀結。兩種以上膜狀結構的組合。當該奈米碳管膜狀結構為兩種以上膜狀結構,該兩種以上膜狀結構可以為共面設置或層疊設置,當該兩種以上膜狀結構層疊設置時,相鄰兩層奈米碳管膜狀結構中奈米碳管之間的夾角可以為0°≦α≦90°。
所述奈米碳管拉膜可以為一層或多層,當奈米碳管拉膜為多層時,該多層奈米碳管拉膜可以為共面設置或層疊設置。本實施例中,所述奈米碳管結構為奈米碳管拉膜,由於該奈米碳管拉膜中的奈米碳管通過凡得瓦力首尾相連且沿同一方向延伸,能夠減小所述多孔金屬複合結構的內部阻抗,提高其導電性。
所述奈米碳管拉膜為由若干奈米碳管組成的自支撐結構。所述若干奈米碳管基本沿同一方向擇優取向排列,所述擇優取向排列是指在奈米碳管拉膜中大多數奈米碳管的整體延伸方向基本朝同一方向。而且,所述大多數奈米碳管的整體延伸方向基本平行于奈米碳管拉膜的表面。進一步地,所述奈米碳管
拉膜中大多數奈米碳管是通過凡得瓦力首尾相連。具體地,所述奈米碳管拉膜中基本朝同一方向延伸的大多數奈米碳管中每一奈米碳管與在延伸方向上相鄰的奈米碳管通過凡得瓦力首尾相連。當然,所述奈米碳管拉膜中存在少數隨機排列的奈米碳管,這些奈米碳管不會對奈米碳管拉膜中大多數奈米碳管的整體取向排列構成明顯影響。
所述奈米碳管碾壓膜可以為一層或多層,當奈米碳管碾壓膜為多層時,該多層奈米碳管碾壓膜可以為共面設置或層疊設置。
所述奈米碳管碾壓膜包括均勻分佈的奈米碳管,該奈米碳管無序,沿同一方向或不同方向擇優取向排列。優選地,所述奈米碳管碾壓膜中的奈米碳管基本沿同一方向延伸且平行於該奈米碳管碾壓膜的表面。所述奈米碳管碾壓膜中的奈米碳管相互交疊,從而使所述奈米碳管碾壓膜的表面較為粗糙。所述奈米碳管碾壓膜中奈米碳管之間通過凡得瓦力相互吸引並形成多個間隙。該奈米碳管碾壓膜具有很好的柔韌性,可以彎曲折疊成任意形狀而不破裂。所述奈米碳管絮化膜可以為一層或多層,當奈米碳管絮化膜為多層時,該多層奈米碳管絮化膜可以為共面設置或層疊設置。
所述奈米碳管絮化膜包括相互纏繞的奈米碳管。該奈米碳管之間通過凡得瓦力相互吸引、纏繞形成網狀結構,從而使所述奈米碳管絮化膜的表面較為粗糙。所述奈米碳管絮化膜中的奈米碳管為均勻分佈,無規則排列。
所述固定奈米碳管結構的方法有兩種:(一)通過有機粘結材料來固定:在所述第一複合結構中奈米碳管結構的表面滴加有機粘結材料,該有機粘結材料通過所述奈米碳管中的間隙進入所述多孔金屬結構,該有機粘結材料將所述多孔金屬結構和奈米碳管結構的接觸面包裹住;(二)通過金屬材料固定:將所述第二複合結構轉移到含有Au+、Ag+、Cu+等任意一種金屬離子溶液中,在所述含有金屬離子的溶液中添加還原劑形成金屬顆粒,該金屬顆粒通過化學鍍的方式沉積在所述多孔金屬結構中韌帶與奈米碳管結構中奈米碳管的接觸處周圍,從而使多孔金屬結構和奈米碳管結構結合在一起。本實施例中,將第一複合結構轉移到含有Au+溶液中,採用水合肼對Au+進行還原生成Au,生成的Au包裹所述韌帶與奈米碳管的接觸面周圍。
步驟S50,使所述第二複合結構發生皺縮,形成一多孔金屬複合結構。
該第二複合結構發生皺縮的方法不限,只要能夠使所述基板、多孔金屬結構及奈米碳管結構形成的第二複合結構發生褶皺即可。本實施例中,將所述第二複合結構在160℃的溫度下加熱2min,該基板發生皺縮,由於所述多孔金屬結構固定在所述基板表面,奈米碳管結構固定在所述多孔金屬結構表面,因此所述基板發生皺縮的過程中會帶動所述多孔金屬結構與所述奈米碳管膜一起發生皺縮,此時所述多孔金屬結構不容易斷裂,形成的多孔複合結構具有良好的韌性。
本發明實施例提供的多孔金屬複合結構及其製備方法具有以下優點:其一,奈米碳管具有良好的韌性,提高了多孔金屬複合結構的韌性,使多孔金屬複合結構不容易發生脆斷;其二,由於奈米碳管具有良好的導電性,從而提高了多孔金屬複合結構的導電性。
綜上所述,本發明確已符合發明專利之要件,遂依法提出專利申請。惟,以上所述者僅為本發明之較佳實施例,自不能以此限制本案之申請專利範圍。舉凡習知本案技藝之人士援依本發明之精神所作之等效修飾或變化,皆應涵蓋於以下申請專利範圍內。
Claims (10)
- 一種多孔金屬複合結構,包括多孔金屬結構和一個奈米碳管結構,該奈米碳管結構固定在所述多孔金屬結構的表面,所述奈米碳管結構包括多根奈米碳管,所述多根奈米碳管的延伸方向平行於所述固定有奈米碳管結構的多孔金屬複合結構的表面,所述多孔金屬複合結構包括多個褶皺部。
- 如請求項第1項所述的多孔金屬複合結構,其中,所述褶皺部由多孔金屬結構和奈米碳管結構共同彎折構成。
- 如請求項第2項所述的多孔金屬複合結構,其中,所述褶皺部處的奈米碳管通過凡得瓦力首尾相連且沿同一方向延伸。
- 如請求項第1項所述的多孔金屬複合結構,其中,所述多個褶皺部相互連接形成一連續結構。
- 如請求項第1項所述的多孔金屬複合結構,其中,所述多孔金屬結構包括多個韌帶,該多個韌帶之間形成多個孔。
- 如請求項第5項所述的多孔金屬複合結構,其中,所述韌帶的材料為金、銀、鉑中的任意一種。
- 如請求項第1項所述的多孔金屬複合結構,其中,所述多孔金屬複合結構進一步包括一連接材料,該連接材料用於將奈米碳管結構固定在所述多孔金屬結構的表面。
- 如請求項第7項所述的多孔金屬複合結構,其中,所述連接材料包裹所述多孔金屬結構與奈米碳管結構形成的接觸面。
- 如請求項第7項所述的多孔金屬複合結構,其中,所述連接材料為有機粘結材料或金屬材料。
- 如請求項第1項所述的多孔金屬複合結構,其中,所述奈米碳管結構包括多根沿同一方向延伸的奈米碳管。
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JP2019002072A (ja) | 2019-01-10 |
US20180354228A1 (en) | 2018-12-13 |
CN109019563B (zh) | 2021-02-26 |
JP6703041B2 (ja) | 2020-06-03 |
CN109019563A (zh) | 2018-12-18 |
US10919261B2 (en) | 2021-02-16 |
TW201902693A (zh) | 2019-01-16 |
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