TWI425071B - 通電加熱固化奈米碳管及環氧樹脂複合膠料以接合構件的方法 - Google Patents

通電加熱固化奈米碳管及環氧樹脂複合膠料以接合構件的方法 Download PDF

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TWI425071B
TWI425071B TW100136440A TW100136440A TWI425071B TW I425071 B TWI425071 B TW I425071B TW 100136440 A TW100136440 A TW 100136440A TW 100136440 A TW100136440 A TW 100136440A TW I425071 B TWI425071 B TW I425071B
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carbon nanotube
epoxy resin
compound
paper
resin compound
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TW100136440A
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TW201315791A (zh
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Shih Chin Chang
Ping Cheng Sung
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Nat Univ Tsing Hua
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Priority to TW100136440A priority Critical patent/TWI425071B/zh
Priority to US13/344,645 priority patent/US20130087278A1/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C65/00Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • B29C65/34Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement"
    • B29C65/3404Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the type of heated elements which remain in the joint
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    • B29C65/3472Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the composition of the heated elements which remain in the joint
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    • B29C65/3492Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the composition of the heated elements which remain in the joint being non-metallic being carbon
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29C65/34Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement"
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    • B29C65/3496Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the composition of the heated elements which remain in the joint being non-metallic with a coating, e.g. a metallic or a carbon coating
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    • B29C65/4835Heat curing adhesives
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    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C65/5007Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like characterised by the structure of said adhesive tape, threads or the like
    • B29C65/5014Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like characterised by the structure of said adhesive tape, threads or the like being fibre-reinforced
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29C65/5057Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding using adhesive tape, e.g. thermoplastic tape; using threads or the like positioned between the surfaces to be joined
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/01General aspects dealing with the joint area or with the area to be joined
    • B29C66/05Particular design of joint configurations
    • B29C66/10Particular design of joint configurations particular design of the joint cross-sections
    • B29C66/11Joint cross-sections comprising a single joint-segment, i.e. one of the parts to be joined comprising a single joint-segment in the joint cross-section
    • B29C66/112Single lapped joints
    • B29C66/1122Single lap to lap joints, i.e. overlap joints
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/40General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/43Joining a relatively small portion of the surface of said articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00General aspects of processes or apparatus for joining preformed parts
    • B29C66/70General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29C66/9161Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux
    • B29C66/91651Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux by controlling or regulating the temperature, the heat or the thermal flux by controlling or regulating the heat or the thermal flux, i.e. the heat flux by controlling or regulating the heat generated by Joule heating or induction heating
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B29C66/00General aspects of processes or apparatus for joining preformed parts
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    • B29C66/919Measuring or controlling the joining process by measuring or controlling the temperature, the heat or the thermal flux characterised by specific temperature, heat or thermal flux values or ranges
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J5/00Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16BDEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
    • F16B11/00Connecting constructional elements or machine parts by sticking or pressing them together, e.g. cold pressure welding
    • F16B11/006Connecting constructional elements or machine parts by sticking or pressing them together, e.g. cold pressure welding by gluing
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    • B29C65/3468Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using heated elements which remain in the joint, e.g. "verlorenes Schweisselement" characterised by the means for supplying heat to said heated elements which remain in the join, e.g. special electrical connectors of windings
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    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites

Description

通電加熱固化奈米碳管及環氧樹脂複合膠料以接合構件的方 法
本發明涉及一種加熱固化奈米碳管及環氧樹脂複合膠料以接合構件的方法,尤其是涉及一種通電加熱奈米碳管紙,以固化奈米碳管及環氧樹脂複合膠料,達成接合構件的方法。
習知技術中,將兩個或以上之構件黏著之方式有許多種,可透過聚合物、樹脂、焊接等方式進行黏著,然而,黏著劑之種類不同,以及基板表面特性不同,會決定黏著之時間以及成效。
環氧樹脂是被廣泛應用在工業修補的材料,使用環氧樹脂做接合相較於機械鉚釘修補具有製程簡單、無應力集中、無接合縫之滲水、鏽蝕等問題。而高強度的環氧樹脂其固化則需要在高溫環境下進行。
傳統的加熱固化是利用加熱板、加熱毯、紅外光或是高溫爐等方式。然而這些方式的熱是由外部部件經由傳導或輻射到膠料處,使膠料升溫固化,因此需要較長的固化時間,並造成大部分熱能的散失浪費。為了能夠縮短固化的時間,有在環氧樹脂膠體中佈入銅網,並且利用電磁感應之電流加熱銅網,而使環氧樹脂得以高溫固化。此方法雖可以大幅縮短固化時間,但是由於銅網受限於銅線直徑為一百五十微米(現今最細銅線直徑至少為數十微米),無法縮小至奈米級,使其與膠料的結合效果不佳,形成應力集中易於破裂,削弱了接合的強度。
曾有使用微波加熱奈米碳管及環氧樹脂的複合膠料,此製程 雖能大幅縮短加熱固化時間,且可高度提升接合強度,然而以微波加熱固化的方式卻有許多限制,即其所需使用之微波設備較為昂貴、複雜,且有效接合面積受限於微波能穩定照射的區域。而且此方式因為是使用微波加熱,僅能使用在接合不會反射或吸收微波的基材上,而不適用於可反射或吸收材料的接合。
由於奈米碳管具有導電特性,因此通以電流可快速加熱奈米碳管。將奈米碳管加入環氧樹脂中形成的奈米碳管及環氧樹脂複合膠料,當奈米碳管加入量超過一導通量(percolation threshold)後,奈米碳管及環氧樹脂複合膠料將有相當之導電性,可通以電流快速加熱。但由於奈米碳管具有溫度越高電阻越低的特性,又稱為導電度-溫度的正回饋效應,若使用一般的通電方式加熱奈米碳管及環氧樹脂複合膠料,由於碳管膠料的電阻依然很高,若要產生足夠大的功率以加熱膠料,需要施加非常大的電壓。在這樣的情形下,最初會有少量的電流通過一部分電阻較低的區域,初始導電的路徑會因溫度上升而電阻更為降低,形成導電度-溫度的正回饋,使得更多的電流流經這區域,而會導致膠料沿初始導電的路徑局部的過熱燒毀,而其餘部分則尚未加溫固化。
爰此之故,申請人有鑑於習知技術之缺失,乃思一較習知更為新穎之黏著方法,不但所耗費之黏著時間短亦較省能,且黏著強度佳,簡單設備即可以完成,進而發明出本案「通電加熱固化奈米碳管及環氧樹脂複合膠料以接合構件的方法」,用以改善上述習用手段之缺失。
本發明的目的即在提出一種構件接合的方法,其係使用奈米碳管所製程之奈米碳管紙,以真空過濾法將奈米碳管及環氧樹脂複合膠料滲透於奈米碳管紙中,以形成具有奈米碳管及環氧樹脂複合膠料之奈米碳管紙,將其置於欲接合構件之間,並於奈米碳管紙施以電流加熱,達奈米碳管及環氧樹脂複合膠料固化反應溫度,即可固化奈米碳管及環氧樹脂複合膠料,達成接著構件之效果。
為達前述目的,本發明提供一種導電材料接合的方法,包含下列步驟(a)備製一奈米碳管紙及一奈米碳管及環氧樹脂複合膠料;(b)將該奈米碳管及環氧樹脂複合膠料塗佈於該奈米碳管紙上;(c)將塗有該奈米碳管及環氧樹脂複合膠料的該奈米碳管紙黏置於欲接合的複數個構件接合面之間;以及(d)於該奈米碳管紙之二端分別設置一電極,調整電源功率以通一電流加熱該奈米碳管及環氧樹脂複合膠料,使該奈米碳管紙均勻導熱以達一固化溫度以固化該奈米碳管及環氧樹脂複合膠料。
根據上述構想,其中步驟(a)該奈米碳管及環氧樹脂複合膠料含有0~6%重量百分比之奈米碳管。
根據上述構想,其中步驟(a)該奈米碳管及環氧樹脂複合膠料係一已添加硬化劑之高溫固化型環氧樹脂。
根據上述構想,其中步驟(c)更包含步驟(c1)對該複數個構件施加適度壓力。
根據上述構想,其中步驟(d)該電流之大小視該奈米碳管紙之大小及環氧樹脂複合膠料之固化溫度而調整。
因此,本發明使用簡單的設備,以通電加熱方式,因奈米碳管 紙具優良導熱性,可快速且均勻地加熱環氧樹脂或奈米碳管及環氧樹脂複合膠料,使其固化,達成接著之效果。此方法不受環境影響,不限構件類別,有效減少固化環氧樹脂所耗費之能源及時間,並且進一步達成強化效果,深具產業價值之構件接合方法。
本案將可由以下的實施例說明而得到充分瞭解,使得熟習本技藝之人士可據以完成,然本案之實施並非可由下列實施例而被限制其實施型態。
請參見第1圖:其顯示本發明一實施例之製作流程圖。首先備製一奈米碳管紙及一奈米碳管及環氧樹脂複合膠料11,其中該奈米碳管紙係由奈米碳管所製成的一片薄膜,於本實施例中,該奈米碳管及環氧樹脂複合膠料中含有介於0~6%重量百分比之奈米碳管,且該奈米碳管及環氧樹脂複合膠料係一已添加硬化劑之高溫固化型環氧樹脂;接著,將該奈米碳管及環氧樹脂複合膠料塗佈於該奈米碳管紙上12;同時以真空過濾法將該奈米碳管及環氧樹脂複合膠料均勻滲入該奈米碳管紙13;隨後,將塗有該奈米碳管及環氧樹脂複合膠料的該奈米碳管紙黏置於欲接合的複數個構件接合面之間14;緊接著,對該複數個構件施加適度壓力15;最後,於該奈米碳管紙之二端分別設置一電極,通一電流加熱該奈米碳管及環氧樹脂複合膠料,使達一固化溫度以固化該奈米碳管及環氧樹脂複合膠料16,其中該電流之大小視該奈米碳管紙之大小而調整,其固化溫度則視所使用之環氧樹脂材料而定,固化所需時間少於20分鐘。於一實施例中,使用一個一平方厘米的奈米碳管紙 結合環氧樹脂複合膠料,當以功率3.76W通電加熱該環氧樹脂複合膠料時,可在8分鐘內升溫至150℃,若增加功率至4.58W通電,加熱時間可以進一步縮短到4分鐘,欲達環氧樹脂複合膠料完全固化,維持固化溫度約僅需費時20分鐘。因此,以通電加熱奈米碳管紙以固化環氧樹脂複合膠料的方法,比微波加熱需時30分鐘或傳統加熱所需的60分鐘明顯短少。且由於幾乎所有的應用電能是在固化時消耗,此過程比任何其他習知加熱過程所耗的能量少,且經估算,本實施例中,固化1厘米×1厘米×110微米之奈米碳管紙結合環氧樹脂複合膠料,其於接著構件過程所耗費的能量小於7.5K焦耳。
請參見第2圖,其顯示本發明一實施例之示意圖。由圖示可知,於二纖維強化高分子複合材料(FRP)21及22之接合處黏置一滲有奈米碳管及環氧樹脂複合膠料之奈米碳管紙25,且於該奈米碳管紙25之兩端分別設置二電極23及24,當通一電流加熱時,該電流即由一電極23或24,流經該含有奈米碳管及環氧樹脂複合膠料奈米碳管紙25,再流通至另一電極24或23。隨後,該奈米碳管及環氧樹脂複合膠料25即因此電流而加熱,達固化溫度後,該二纖維強化高分子複合材料(FRP)21及22即完成黏合效果。
請參見第3圖,其顯示本發明一實施例之剖面圖。由圖示可知,於二纖維強化高分子複合材料(FRP)31及32之接合處黏置一滲有奈米碳管及環氧樹脂複合膠料33之奈米碳管紙34,當通一電流加熱時,該電流即及在奈米碳管紙34流動以加熱固化奈米碳管及環氧樹脂複合膠料33。
請參見第4圖,其顯示五種不同奈米碳管含量的膠料分別以三 種不同加熱方式所呈現之接著強度比較圖,橫軸代表多層奈米碳管重量百分比,縱軸代表各膠料經測試的接著強度,其中各膠料分別以三種不同的加熱方式進行測試,並以不同顏色A、B及C分別表示微波加熱、傳統加熱及電子加熱等方式。由圖示可知,本發明通電加熱方法的優點是,通電加熱的粘合強度高於傳統或微波的加熱方式。以傳統加熱固化環氧樹脂的單面膠料樣品的接著強度為15.9MPa,而以通電加熱固化奈米碳管紙是17.0MPa(增加7%)。對於有0.5wt%奈米碳管含量之膠料樣品,其以傳統、微波及通電固化膠料的接著強度分別是18.1MPa、22.5MPa和26.7MPa,可知以通電固化膠料的接著強度增加48%。
綜上所述,本發明提出了一種新穎之黏著方法,其可無須受限於欲黏著物之大小及特性而進行黏合。於功效上,本發明方法之黏著時間不但較習知短,且黏著材料之製作簡單,亦節省成本及材料製作時間,更可增加接著強度,提昇兩構件之黏著品質及效率。
以上所述之實施例僅為說明本發明之最佳實施例原理及其功效,而非用以限制本發明。因此,熟悉本技藝之人士可在不違背本發明之精神對上述實施例進行修改及變化,然皆不脫如附申請專利範圍所欲保護者。
11~16‧‧‧步驟
21‧‧‧纖維強化高分子複合材料(FRP)
22‧‧‧纖維強化高分子複合材料(FRP)
23‧‧‧電極
24‧‧‧電極
25‧‧‧奈米碳管紙
31‧‧‧纖維強化高分子複合材料(FRP)
32‧‧‧纖維強化高分子複合材料(FRP)
33‧‧‧奈米碳管及環氧樹脂複合膠料
34‧‧‧奈米碳管紙
第1圖:顯示本發明一實施例之製作流程圖。
第2圖:顯示本發明一實施例之示意圖。
第3圖:顯示本發明一實施例之剖面圖。
第4圖:顯示五種不同奈米碳管含量的膠料分別以三種不同加 熱方式所呈現之接著強度比較圖。
21‧‧‧纖維強化高分子複合材料(FRP)
22‧‧‧纖維強化高分子複合材料(FRP)
23‧‧‧電極
24‧‧‧電極
25‧‧‧奈米碳管紙

Claims (7)

  1. 一種通電加熱固化奈米碳管及環氧樹脂複合膠料以接合構件的方法,包含下列步驟:(a)備製一具導電性之奈米碳管紙及一奈米碳管及環氧樹脂複合膠料;(b)將該奈米碳管及環氧樹脂或環氧樹脂複合膠料塗佈於該具導電性之奈米碳管紙上;(c)將塗有該奈米碳管及環氧樹脂複合膠料的該具導電性之奈米碳管紙黏置於欲接合的複數個構件接合面之間;以及(d)於該具導電性之奈米碳管紙之二端分別設置一電極,調整電源功率以通一電流加熱該奈米碳管及環氧樹脂複合膠料,使該具導電性之奈米碳管紙均勻導熱以達一固化溫度以固化該奈米碳管及環氧樹脂複合膠料。
  2. 如申請專利範圍第1項之方法,其中步驟(a)該具導電性之奈米碳管紙係由奈米碳管所製成的薄膜。
  3. 如申請專利範圍第1項之方法,其中步驟(a)該奈米碳管及環氧樹脂複合膠料含有0~6%重量百分比之奈米碳管。
  4. 如申請專利範圍第1項之方法,其中步驟(a)該奈米碳管及環氧樹脂複合膠料係一已添加硬化劑之高溫固化型環氧樹脂。
  5. 如申請專利範圍第1項之方法,其中步驟(b)更包含步驟(b1)以真空過濾法將該奈米碳管及環氧樹脂複合膠料均勻滲入該具導電性之奈米碳管紙。
  6. 如申請專利範圍第1項之方法,其中步驟(c)更包含步驟(c1)對該複數個構件施加適度壓力。
  7. 如申請專利範圍第1項之方法,其中步驟(d)該電流之大小視該具導電性之奈米碳管紙之大小及環氧樹脂複合膠料之固化溫度而調整。
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