1341878 九、發明說明： 【發明所屬之技術領域】 % 且特別是有關於含奈米碳 本發明係有關於一種纖維 S之聚醋纖维。 【先前技術】 在工業纖維之應用 „ ’聚醋纖維是常用的重要材料。1341878 IX. Description of the invention: [Technical field to which the invention pertains] % and particularly relating to nanocarbon-containing carbon The present invention relates to a polyester fiber of a fiber S. [Prior Art] In industrial fiber applications „ ‘polyvinyl acetate fiber is an important material commonly used.
布0曰几應用面很廣，例如輪胎簾子線、傳輸帶、蓬帆 工、=、帳棚等等。這些應用所用之纖維需具有高強 度、低伸度、及耐磨耗等性質。 為了進#提升聚酉旨纖維的品質與應用面，需設法辦 力口聚_維之強度與耐隸雜，並減低其伸度。除此: 外’還需設法提升聚S旨纖維的玻璃轉換溫度與冷卻結晶溫 度。玻璃轉換溫度的提升有助於提高聚自旨纖維的熱穩定 性，使其應用產品能適用於溫度較高之環境而不軟化，增 力:應用蛇圍。冷卻結晶溫度的提升，可促使聚g旨纖維在製 程:於較高溫度便開始結晶，可使結晶速度加快並可獲得 結晶相較多的聚酯纖維，有助於增強纖維的強度。 除了上述低伸度纖維之應用，業界亦有較高伸度之耐 熱纖維的需求。 因此’業界亟需高熱穩定性的聚酯纖維及其製法，且 聚酯纖維之強度、伸度、及耐磨度還要能輕易地變動以符 合各種不同應用之需求。 【發明内容】 5 1341878 -. 本發明提供一種纖維，包括聚酯纖維，以及分散於聚酯 纖維中之複數個奈米碳管，其中奈米碳管大抵順向排列於 聚酯纖維之延伸方向。 本發明另提供一種形成纖維的方法，包括提供聚酯粒， 提供複數個奈米碳管，對奈米碳管與聚酯粒進行混煉，以 及對於混煉後之奈米碳管及聚酯粒進行熔融抽絲而獲得聚 酯纖維，其中奈米碳管大抵順向排列於聚酯纖維中。 • 為讓本發明之上述和其他目的、特徵、和優點能更明顯 易懂，下文特舉出較佳實施例，並配合所附圖式，作詳細 說明如下： 【實施方式】 本發明在此提供一種聚酯纖維及其製法。主要是將奈 米碳管（carbon nanotube，CNT)導入聚g旨纖維中而增加聚酉旨 纖維的熱穩定性。並可透過不同的奈米碳管添加量來調節 纖維之強度、耐磨性、及伸度以符合各種應用之需求，增 鲁加其應用範圍。 本發明所提供之聚酯纖維應用範圍很廣，例如可用於 輪胎簾子線、傳輸帶、蓬帆布、風帆布、帳棚、或各種紡 織用纖維等。特別是關於需有高強度、高耐磨、低伸度、 及高熱穩定度之應用。此外，本發明之部分實施例還可獲 得具有高熱穩定度及高伸度之纖維。可例如用作較高溫度 環境下之彈性纖維。 為了改善聚酯纖維的各項性質，本發明將奈米碳管導 6 1341878 入聚酯纖維中，利用混煉方式，使奈米碳管與聚酯粒充分 混合。接著對所得聚酯粒/奈米碳管混合酯粒進行熔融分散 抽絲，而獲得聚酯/奈米碳管纖維。透過適當選用奈米碳管 之種類與添加量，並配合適當的製程條件，奈米碳管大抵 沿著聚酯纖維的延伸方向順向排列，可克服抽絲時奈米碳 管聚集而產生斷絲無法成型的問題。利用奈米碳管之小尺 寸、高強度、高韌性、高導電性、高徑長比等特性，可有 效地增加聚酯纖維的強度，並使其耐磨性及熱穩定性大幅 提升。 以下，提供本發明實施例之纖維的形成方法。首先提 供用以形成聚酯纖維的聚酯粒，聚酯粒的材質可包括聚對 笨二曱酸乙二醇醋（卩〇1>^11>^116 16代卩111；113以6,?£1[)、聚對 苯二曱酸丁二醇酉旨（polybutylene terephthalate，PBT)、聚對 苯二曱酸丙二醋（polypropylene terephthalate，PPT)、聚芳香 酯（Polyarylate，PAR)、聚對苯二曱酸乙二醇酯（Glycol modified polyethylene terephthalate PETG)等、或前述之組 合。接著，可透過習知各種適合的方法將聚酯粒與微量的 奈米碳管均勻混合。例如可採用雙螺桿混煉機、單螺桿混 煉機、單螺桿押出機、雙螺桿押出機、萬馬力機、連續混 煉機、或前述之組合來將聚酯粒與奈米碳管充分混合並形 成聚酯/奈米碳管之混合聚酯粒。奈米碳管的添加量相對於 聚酉旨粒可為約0.05phr至約1 phr。適合的奈米碳管之直徑 可為約10奈米至約40奈米，而適合的長度可為約1微米 至約25微米。適合的奈米碳管還可具有各種程度不同的繞 7 1341878 曲結構。 接著，對混煉後之酯粒進行熔融抽絲而可獲得聚酯/奈 米碳管纖維。例如，可將混煉後之酯粒放入加熱的紡絲反 應室（spinning chamber)並透過喷絲頭噴出或流出，喷絲頭 中可例如具有數個直徑約0.005英吋至約0.030英吋之孔洞 以供纖維由孔洞喷出或流出而成型。纖維成型的過程中可 使用例如加壓空氣氣流將所喷出融炫態的聚酷/奈米碳管 纖維快速冷卻至其玻離轉化溫度以下而硬化成絲。所形成 之聚酯/奈米碳管纖維可利用一捲繞滾筒收集。捲繞滾筒之 捲繞速度可例如約1000公尺/分鐘至約6000公尺/分鐘。熔 融抽絲所採用之溫度可例如為約200°C至約300°C之間。酯 粒經融熔抽取成絲的過程中，可能會對聚酯纖維及其内部 的奈米碳管形成順著纖維沿伸方向的拉伸應力（例如空氣 氣流的拉力及磨擦力在纖維冷卻硬化的過程所造成之應 力），此拉伸應力可能會促使奈米碳管大抵沿著纖維之沿伸 方向順向排列。 本發明實施例之聚酯/奈米碳管纖維之耐熱溫度（即玻 璃轉換溫度）可大於約86°C，強度可提昇約12%，伸度小 於約27.9%，耐磨耗強度可提昇約41%。此外，本發明實 施例之聚酯/奈米碳管纖維可連續抽絲而使其長度可大於 約100公尺以上。例如，可以每分鐘800公尺之速度連續 抽絲5分鐘而獲得長度約4000公尺之聚酯/奈米碳管纖 維。可視需要以不同的抽絲速度來獲得所需長度之聚酯/ 奈米碳管纖維。 8 1341878 所導入奈米碳管的尺寸、型態、及添加量對聚酯/奈米 碳管纖維之性質影響很大。本發明透過導入具有繞曲結構 之奈米碳管於聚酯纖維中，可顯著地增加聚酯纖維的耐熱 性質。本發明一實施例之聚酯/奈米碳管纖維採用繞曲程度 較大而管徑較小之奈米碳管，可較使用繞曲程度較低而管 徑較大之奈米碳管的纖維有更高的熱穩定度。透過控制奈 米碳管之添加量可使奈米碳管大抵順向排列於聚酯纖維之 延伸方向，而可順利抽絲成型。適當的奈米碳管添加量可 使聚酯纖維強度提升而伸度下降。添加量較少之聚酯纖維 可具有較高之伸度與不錯的财熱性。此外，奈米碳管繞曲 的程度或其尺寸（包括管徑與長度）亦可視需要作調整。所 導入之奈米碳管亦不一定僅限於一種結構或形式，例如可 導入兩種以上具有不同直徑、不同長度、不同繞曲度、或 不同添加量之奈米碳管於纖維中。以下，將列舉本發明之 實施例來作說明。 實施例1 取 PET 酯粒約 3000 克並與 0.15g、0.3g、0_5g、lg 的 奈米碳管混合，透過雙螺桿混煉將奈米碳管（CNT)與PET 酯粒充分均勻混合並形成PET/CNT之混合聚酯粒。此實施 例中，所用雙螺桿混煉機之螺桿直徑為約45 0，其長徑比 (L/D)為約30，螺桿轉速為約200rpm。共採用十段溫度來 進行雙螺桿混煉，分別是180°C、210°C、230°C、240°C、 250°C、250°C、260°C、260°C、260°C、及 250°C。在此實 施例中，所採用的奈米碳管屬繞曲式，其SEM照片顯示於 9 1341878 第1圖中，其直徑為約20 nm，其長度為約1微米至約25 微米，且其結構是實質繞曲的。奈米碳管的添加量相對於 PET酯粒分別為約Ophr至約lphr。接著，對雙螺桿混煉後 之PET/CNT酯粒進行熔融抽絲（熔融抽絲溫度為約270°C 至約280°C)而獲得PET/CNT纖維。 第2a圖顯示PET/CNT纖維之SEM照片，而第2b圖 顯示放大倍率較高之PET/CNT纖維之SEM照片。如第2a 圖及第2b圖所示，奈米碳管大抵順向排列於PET纖維的 延伸方向，且仍部分保有其繞曲結構。經由適當選用奈米 碳管之尺寸、控制奈米碳管之添加量、以及製程參數的控 制，所得PET/CNT纖維大抵順向排列於纖維之延伸方向而 不容易斷絲，並可順利抽絲成形。例如以800公尺/分鐘之 速度抽絲5分鐘，而獲得長度大於約4000公尺之纖維。表 一列出此實施例中具有不同繞曲式奈米碳管添加量之 PET/CNT纖維的各項材料性質，並同時列出不含奈米碳管 之PET纖維的各項性質以供比較。 繞曲式 CNT含量 Tm (°C) Tg (°C) Tcc (°C) 細度 (den) 磨耗 (%) 強度 (R/d) 伸度（％) PET(blank) 250 70 186 612 0.161 1.74±0.4 67.2 士 31.9 0.15 phr 259 86 209 577 1.32 士 0.3 102.8±46.1 0.3 phr 258 85 207 583 _ 1.53 土 0.08 100.2 士 3.6 0.5 phr 260 84 206 560 0.103 1.95±0.12 33.8±4.9 1 phr 258 83 211 _ 0.096 麵 1341878 如表一所示，可看出繞曲式奈米碳管之導入可顯著地 提升PET纖維的熱穩定性。PET/CNT纖維之玻璃轉換溫度 (Tg)相較於PET(blank)纖維可提升至少約l〇°C以上’可提 高纖維的耐熱溫度（大於約70。〇，使能應用於較高溫之環 境。除了玻璃轉換溫度之外，PET/CNT纖維之冷卻結晶溫 度（Tcc)相較於PET(blank)纖維亦提升了約20°C以上。冷卻 結晶溫度之提升可促使熔融抽絲纖維於較高冷卻溫度便開 始結晶，可使結晶速度加快並獲得結晶相較多的纖維，有 助於提升纖維的強度。PET/CNT纖維冷卻結晶溫度提升的 原因目前尚不清楚，不排除是因為繞曲式奈米碟管的添加 形成了許多的CNT/PET界面，PET較易於界面附近產生異 質成核，使結晶較早發生，因而提高了冷卻結晶溫度。當 繞曲式奈米碳管之添加量增加至〇.5phr時，PET/CNT纖維 之強度開始大於PET(blank)纖維之L74士〇.4g/d而達到約 l‘95±〇.12g/d ’且其伸度相較於pET(blank)纖維之 67.2±31_9%大幅縮減至33.8±4.9%。其中，CNT含量約 〇.15phr至約0.3phr之纖維具有較佳的熱穩定性，但其強度 卻較低而伸度較高’其原因目前尚不清楚。這些較耐熱且 伸度較高之纖維，仍可有許多其他應用，例如可作為較高 溫度環境下之彈性纖維。表一還列出部分PET/CNT纖維之 耐磨耗檢驗結果，其顯示各纖維在相同的磨耗條件下，被 磨耗之重量百分比（比之磨耗前），可從表一發現，隨著奈 米碳f添加量的提升，可有效減少pET/CNT纖維之磨耗量 (減少約35%以上），提升其耐磨耗度。其中，cnt含量為 1341878 0.5phr與O.lphr之PET/CNT纖維在相同磨耗條件下，其磨 耗量比之？£丁〇13111〇分別減少了 35.627%與40.277%，更有 助於PET/CNT纖維在較高磨耗環境下之應用。 實施例2 以相同於實施例1之方式來準備實施例2中之 PET/CNT纖維，僅將實施例中之繞曲式奈米碳管替換為繞 曲程度較低且直徑較大的低繞曲奈米碳管。此實施例中所 用的低繞曲奈米碳管之SEM照片顯示於第3圖中，其直徑 為約30 nm至約90 nm，而其長度為約1微米至約2微米。 所得之PET/CNT纖維之各項性質列於表二中。 表二 低繞曲 Tm Tg Tcc CNT含量 (°C) (°C) (°C) PET(blank) 250 70 186 0.3 phr 222 72 175 1 phr 246 78 195 如表二所示，導入低繞曲奈米碳管之PET/CNT纖維的 熱穩定性亦可獲得提升。隨著低繞曲奈米碳管之添加量增 加至lphr時，其玻璃轉換溫度(Tg)可增加至約78°C，而其 冷卻結晶溫度（Tcc)可增加至約195°C。比較表一與表二可 看出添加低繞曲奈米碳管之PET/CNT纖維的玻璃轉換溫 1341878 度或冷卻結晶溫度所提升的幅度明顯小於添加繞曲式$ $ 碳管之PET/CNT纖維。其原因目前尚不清楚，不挪除=^ 為實施例2中所用之奈米碳管比之實施例1中所用 碳管有較大的直徑與較不繞曲的結構，較大直徑與|交 曲之奈米碳管與周圍PET纖維之接觸界面的面積較小，= 此PET與奈米碳管間異質成核的成核點較少，造成冷卻妹 晶溫度增加的幅度小於採用奈米碳管之直徑較小且幸交绝= 之PET/CNT纖維。The cloth has a wide range of applications, such as tire cords, conveyor belts, sailors, =, tents, and so on. The fibers used in these applications are required to have high strength, low elongation, and abrasion resistance. In order to improve the quality and application of the fiber, it is necessary to try to strengthen the strength and resistance of the squad, and reduce its elongation. In addition to this: It is necessary to try to improve the glass transition temperature and cooling crystallization temperature of the poly-S fiber. The increase in glass transition temperature helps to improve the thermal stability of the fiber, so that the application can be applied to a higher temperature environment without softening, and the force is applied: the snake circumference is applied. The increase in the cooling crystallization temperature promotes the polymerization of the fibers in the process: crystallization starts at a higher temperature, the crystallization speed is increased, and a polyester fiber having a larger crystal phase is obtained, which contributes to the strength of the fiber. In addition to the above applications of low elongation fibers, the industry also has a need for higher elongation heat resistant fibers. Therefore, the industry needs high heat stability polyester fiber and its preparation method, and the strength, elongation, and abrasion resistance of the polyester fiber can be easily changed to meet the needs of various applications. SUMMARY OF THE INVENTION 5 1341878 - The present invention provides a fiber comprising a polyester fiber, and a plurality of carbon nanotubes dispersed in the polyester fiber, wherein the carbon nanotubes are arranged substantially in the direction in which the polyester fibers extend. . The invention further provides a method for forming a fiber, comprising providing polyester pellets, providing a plurality of carbon nanotubes, kneading the carbon nanotubes with the polyester pellets, and mixing the carbon nanotubes and the polyester The pellets are melt-spun to obtain polyester fibers in which the carbon nanotubes are arranged substantially in the forward direction in the polyester fibers. The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the invention. A polyester fiber and a process for the preparation thereof are provided. Mainly, carbon nanotubes (CNTs) are introduced into the fibers of the polyg to increase the thermal stability of the fibers. The strength, wear resistance, and elongation of the fibers can be adjusted through different amounts of carbon nanotubes to meet the needs of various applications, increasing the range of applications. The polyester fiber provided by the present invention has a wide range of applications, for example, for tire cords, conveyor belts, tarpaulins, wind canvas, tents, or various textile fibers. Especially for applications requiring high strength, high wear resistance, low elongation, and high thermal stability. Further, some embodiments of the present invention can also obtain fibers having high heat stability and high elongation. It can be used, for example, as an elastic fiber in a higher temperature environment. In order to improve various properties of the polyester fiber, the present invention introduces a carbon nanotube guide 6 1341878 into a polyester fiber, and mixes the carbon nanotube with the polyester pellet by a kneading method. Next, the obtained polyester pellet/carbon nanotube mixed ester pellet was subjected to melt dispersion spinning to obtain a polyester/carbon nanotube fiber. By appropriately selecting the type and amount of carbon nanotubes and the appropriate process conditions, the carbon nanotubes are arranged along the direction in which the polyester fibers extend, which can overcome the accumulation of carbon nanotubes during spinning. The problem that silk can't be formed. By utilizing the characteristics of small size, high strength, high toughness, high electrical conductivity, and high diameter to length ratio of the carbon nanotubes, the strength of the polyester fiber can be effectively increased, and the wear resistance and thermal stability are greatly improved. Hereinafter, a method of forming a fiber of an embodiment of the present invention is provided. First, a polyester granule for forming a polyester fiber is provided. The material of the polyester granule may include polyparaphenyl phthalate (卩〇1>^11>^116 16 卩111; 113 to 6,? £1[), polybutylene terephthalate (PBT), polypropylene terephthalate (PPT), polyarylate (PAR), poly pair Glycol modified polyethylene terephthalate PETG, or the like, or a combination thereof. Next, the polyester granules can be uniformly mixed with a trace amount of carbon nanotubes by various suitable methods. For example, a twin-screw kneader, a single-screw kneader, a single-screw extruder, a twin-screw extruder, a 10,000-mass machine, a continuous mixer, or a combination thereof can be used to thoroughly mix the polyester particles with the carbon nanotubes. And a mixed polyester pellet of a polyester/nanocarbon tube is formed. The carbon nanotubes may be added in an amount of from about 0.05 phr to about 1 phr relative to the polycapsule. Suitable carbon nanotubes can range from about 10 nanometers to about 40 nanometers in diameter, and suitable lengths can range from about 1 micron to about 25 microns. Suitable carbon nanotubes can also have varying degrees of winding 7 1341878 curved structures. Next, the kneaded ester particles are melt-spun to obtain polyester/carbon nanotube fibers. For example, the kneaded ester granules can be placed in a heated spinning chamber and spouted or vented through a spinneret, which can have, for example, a plurality of diameters from about 0.005 inches to about 0.030 inches. The holes are formed by the fibers being ejected or flowed out of the holes. During the fiber forming process, for example, a pressurized air stream can be used to rapidly cool the sprayed condensed poly/carbon nanotube fibers to below their glass transition temperature to harden the filaments. The formed polyester/carbon nanotube fibers can be collected using a winding drum. The winding speed of the winding drum can be, for example, from about 1000 meters/minute to about 6000 meters/minute. The temperature employed for melt spinning can be, for example, between about 200 ° C and about 300 ° C. During the process of melting and extracting the ester particles into filaments, the polyester fibers and the inner carbon nanotubes inside thereof may form tensile stress along the extending direction of the fibers (for example, the tensile force and frictional force of the air flow in the fiber cooling hardening) The stress caused by the process), which may cause the carbon nanotubes to align along the direction along which the fibers extend. The heat-resistant temperature (ie, glass transition temperature) of the polyester/carbon nanotube fiber of the embodiment of the invention may be greater than about 86 ° C, the strength may be increased by about 12%, the elongation is less than about 27.9%, and the abrasion resistance strength may be increased. 41%. In addition, the polyester/carbon nanotube fibers of the embodiments of the present invention can be continuously drawn to a length greater than about 100 meters. For example, a polyester/nanocarbon tube fiber having a length of about 4000 meters can be obtained by continuously drawing for 5 minutes at a speed of 800 meters per minute. Polyester/carbon nanotube fibers of the desired length can be obtained at different spinning speeds as desired. 8 1341878 The size, type, and amount of carbon nanotubes introduced have a significant effect on the properties of the polyester/nanocarbon tube fibers. The present invention can significantly increase the heat resistance of the polyester fiber by introducing a carbon nanotube having a winding structure into the polyester fiber. The polyester/nanocarbon tube fiber according to an embodiment of the present invention adopts a carbon nanotube having a large degree of curvature and a small diameter, and can be used in comparison with a carbon nanotube having a lower degree of winding and a larger diameter. Fibers have a higher thermal stability. By controlling the amount of carbon nanotubes added, the carbon nanotubes can be aligned in the direction in which the polyester fibers extend, and can be smoothly drawn. The proper amount of carbon nanotubes added can increase the strength of the polyester fiber and decrease the elongation. The polyester fiber added in a small amount can have a high elongation and a good finer. In addition, the extent to which the carbon nanotubes are twisted or their dimensions (including tube diameter and length) can also be adjusted as needed. The introduced carbon nanotubes are not necessarily limited to one structure or form. For example, two or more types of carbon nanotubes having different diameters, different lengths, different degrees of curvature, or different addition amounts may be introduced into the fibers. Hereinafter, an embodiment of the present invention will be described. Example 1 Approximately 3000 g of PET ester particles were taken and mixed with 0.15 g, 0.3 g, 0-5 g, lg of carbon nanotubes, and the carbon nanotubes (CNT) and PET ester particles were uniformly mixed and formed by twin-screw kneading. PET/CNT mixed polyester pellets. In this embodiment, the twin-screw kneader used had a screw diameter of about 50,000, an aspect ratio (L/D) of about 30, and a screw rotation speed of about 200 rpm. A total of ten stages of temperature are used for twin-screw mixing, which are 180 ° C, 210 ° C, 230 ° C, 240 ° C, 250 ° C, 250 ° C, 260 ° C, 260 ° C, 260 ° C, And 250 ° C. In this embodiment, the carbon nanotubes are used in a curved form, and the SEM photograph thereof is shown in Fig. 1 of 1 1341878, which has a diameter of about 20 nm and a length of about 1 μm to about 25 μm, and The structure is essentially curved. The amount of carbon nanotubes added is from about 0 phr to about 1 phr, respectively, relative to the PET ester granules. Next, the PET/CNT ester pellets after the twin-screw kneading were melt-spun (melt spinning temperature was about 270 ° C to about 280 ° C) to obtain PET/CNT fibers. Fig. 2a shows an SEM photograph of the PET/CNT fiber, and Fig. 2b shows a SEM photograph of the PET/CNT fiber with a higher magnification. As shown in Fig. 2a and Fig. 2b, the carbon nanotubes are arranged substantially in the direction in which the PET fibers extend, and still partially retain their winding structure. Through proper selection of the size of the carbon nanotubes, the control of the amount of carbon nanotubes, and the control of the process parameters, the obtained PET/CNT fibers are arranged in the direction in which the fibers extend in a direction that is not easy to break, and can be smoothly drawn. Forming. For example, the yarn is drawn at a speed of 800 meters per minute for 5 minutes to obtain fibers having a length of more than about 4000 meters. Table 1 lists the material properties of PET/CNT fibers with different amounts of twisted carbon nanotubes added in this example, and also lists the properties of PET fibers without carbon nanotubes for comparison. . Winding CNT content Tm (°C) Tg (°C) Tcc (°C) Fineness (den) Abrasion (%) Strength (R/d) Elongation (%) PET(blank) 250 70 186 612 0.161 1.74 ±0.4 67.2 ± 31.9 0.15 phr 259 86 209 577 1.32 ± 0.3 102.8 ± 46.1 0.3 phr 258 85 207 583 _ 1.53 Soil 0.08 100.2 ± 3.6 0.5 phr 260 84 206 560 0.103 1.95 ± 0.12 33.8 ± 4.9 1 phr 258 83 211 _ 0.096 Face 1341878 As shown in Table 1, it can be seen that the introduction of the wrapped carbon nanotubes can significantly improve the thermal stability of the PET fibers. The glass transition temperature (Tg) of PET/CNT fiber can be increased by at least about 10 °C or higher compared to PET (blank) fiber, which can increase the heat resistance temperature of the fiber (greater than about 70 〇, enabling application to higher temperature environments). In addition to the glass transition temperature, the cooling crystallization temperature (Tcc) of PET/CNT fibers is also increased by about 20 ° C compared to PET (blank) fibers. The increase in cooling crystallization temperature can promote the melting of the drawn fibers at a higher temperature. The cooling temperature begins to crystallize, which can accelerate the crystallization rate and obtain more fibers with a crystal phase, which helps to increase the strength of the fiber. The reason for the increase of the cooling crystallization temperature of PET/CNT fiber is still unclear, and it is not excluded because of the winding mode. The addition of nano-disc tube forms a lot of CNT/PET interface. PET is more prone to heterogeneous nucleation near the interface, which causes crystallization to occur earlier, thus increasing the cooling crystallization temperature. When the amount of the twisted carbon nanotube is increased At 5 phr, the strength of PET/CNT fibers begins to be greater than that of PET (blank) fibers by L74 ± 4 g/d and reaches about l'95 ± 〇 12.12 g / d ' and its elongation is compared to pET (blank) ) 67.2±31_9% of fiber is greatly reduced to 33.8±4 9%. Among them, fibers having a CNT content of about 1515 phr to about 0.3 phr have better thermal stability, but their strength is lower and the elongation is higher. The reason is still unclear. These are more heat resistant and stretched. Higher grade fibers can still be used in many other applications, such as elastic fibers in higher temperature environments. Table 1 also lists the wear resistance test results for some PET/CNT fibers, which show the same wear of each fiber. Under the condition, the weight percentage of wear (before abrasion) can be found from Table 1. With the increase of the amount of nano carbon f, the wear of pET/CNT fiber can be effectively reduced (about 35% or less). Improve the wear resistance. Among them, the cnt content of 1341878 0.5phr and O.lphr PET/CNT fiber under the same wear condition, the wear amount is reduced by 35.627% and 40.277%, respectively. It is more conducive to the application of PET/CNT fiber in a higher wear environment. Example 2 The PET/CNT fiber of Example 2 was prepared in the same manner as in Example 1, and only the twisted nephew in the example was prepared. The carbon tube is replaced by a low winding with a low degree of curvature and a large diameter. The SEM photo of the low-revolution carbon nanotube used in this example is shown in Figure 3, having a diameter of from about 30 nm to about 90 nm, and a length of from about 1 micron to about 2 Micron. The properties of the obtained PET/CNT fiber are listed in Table 2. Table 2 Low Winding Tm Tg Tcc CNT Content (°C) (°C) (°C) PET(blank) 250 70 186 0.3 phr 222 72 175 1 phr 246 78 195 As shown in Table 2, the thermal stability of PET/CNT fibers introduced into low-roughness carbon nanotubes can also be improved. As the amount of the low-turned carbon nanotubes is increased to 1 phr, the glass transition temperature (Tg) can be increased to about 78 ° C, and the cooling crystallization temperature (Tcc) can be increased to about 195 ° C. Comparing Table 1 and Table 2, it can be seen that the glass transition temperature of the PET/CNT fiber with low-revolution carbon nanotubes is increased by 1,341,878 degrees or the cooling crystallization temperature is significantly smaller than that of the PET/CNT with the addition of the curved carbon tube. fiber. The reason for this is still unclear, and it is not removed = ^ is the carbon nanotube used in the embodiment 2 has a larger diameter and a less curved structure than the carbon tube used in the embodiment 1, the larger diameter and | The area of the contact interface between the carbon nanotubes and the surrounding PET fibers is small, = the nucleation point of the heterogeneous nucleation between the PET and the carbon nanotubes is less, and the increase in the temperature of the cooling crystal is smaller than that of the nanometer. The diameter of the carbon tube is small and the PET/CNT fiber is fortunately replaced.
由實施例1及實施例2可知奈米碳管之型式（如繞曲矛呈 度）、尺寸大小、及添加量影響聚酯纖維之性質甚鉅，可透 過奈米碳管之選用與添加來調整聚酯纖維之各項性質。 綜上所述，本發明透過導入具有繞曲結構之奈米碳管 於聚酯纖維中，可顯著地增加聚酯纖維的耐熱性質。透過 奈米碳管之添加還可控制聚酯/奈米碳管纖維之強度、耐磨 耗度、及伸度以符合各種應用之需求。其中，添加〇.5phr 較繞曲奈米碳管之PET/CNT纖維具有84°C之玻璃轉換溫 度（較 PET blank 高出 14°C)、1·95士0.12g/d 之強度（較 PET blank高出約12%)、及約33%之伸度（約為PET blank伸度 的一半）。此外，PET/CNT纖維之耐磨耗度還會隨著奈米碳 管添加量的增加而提高，有助於PET/CNT纖維於較高磨耗 環境下之應用。 雖然本發明已以數個較佳實施例揭露如上，然其並非 用以限定本發明，任何所屬技術領域中具有通常知識者， 在不脫離本發明之精神和範園内，當可作任意之更動與潤 1341878 飾，因此本發明之保護範圍當視後附之申請專利範圍所界 定者為準。It can be seen from the first embodiment and the second embodiment that the type of the carbon nanotube (such as the degree of the spear), the size and the amount of the carbon fiber affect the properties of the polyester fiber, and can be selected and added through the carbon nanotube. Adjust the properties of polyester fiber. In summary, the present invention can significantly increase the heat resistance of the polyester fiber by introducing a carbon nanotube having a winding structure into the polyester fiber. The addition of carbon nanotubes also controls the strength, wear resistance, and elongation of the polyester/carbon nanotube fibers to meet a variety of applications. Among them, the addition of 〇.5phr is higher than that of the modified carbon nanotubes. The PET/CNT fiber has a glass transition temperature of 84 ° C (14 ° C higher than PET blank) and a strength of 1.95 ± 0.12 g / d (more than PET). The blank is about 12% higher, and about 33% of the elongation (about half of the PET blank's elongation). In addition, the wear resistance of PET/CNT fibers increases with the addition of carbon nanotubes, which contributes to the application of PET/CNT fibers in higher wear environments. The present invention has been disclosed in the above preferred embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the present invention. It is intended to cover the scope of the invention as defined in the appended claims.
14 1341878 【圖式簡單說明】 第1圖顯示一種繞曲式奈米碳管之SEM照片。 第2a-2b圖為一實施例中PET/CNT纖維之SEM照片。 第3圖為一種低繞曲奈米碳管之SEM照片。 【主要元件符號說明】 無。14 1341878 [Simple description of the diagram] Figure 1 shows an SEM photograph of a curved carbon nanotube. Figures 2a-2b are SEM photographs of PET/CNT fibers in one embodiment. Figure 3 is a SEM photograph of a low-revolution carbon nanotube. [Main component symbol description] None.
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