1373874 六、發明說明： ^ 【發明所屬之技術領域】 、轉明侧於-種纽性碳化基材及其製財法與料；特定 •言之’本發明尤其關於-種可製造用作燃料電池中之氣體擴散層 材料之多孔性碳化基材的方法及由此所提供之多孔性碳化基材。 【先前技術】 近年來，由於能源短缺及地球溫室效應等因素，氣供系統之燃 鲁料電池（fudcell)的發展引起人們的注意；蓋燃料電池非但益非 充電電池用完即丟棄所導致之環保上的問題，亦可免除傳統充電 電池所需耗時充電程序的缺點；同時，燃料電池的排放物（例如 水）對環境亦無危害。 在各種燃料電池中，因質子交換膜燃料電池（pr〇t〇n exchange membrane fuel cel 卜 PEMFC )及直接甲醇燃料電池（direct methan〇1 fuel cell，DMFC)可在低溫下操作，又可產生高電流密度，故被 廣泛地應用在車輛、聯合發電系統及各類3C產品（如筆記型電 • 腦、手機等）的電源設備中。 以PEMFC為例’其每一個單電池的主要構件包括膜電極組 (membrane-electrode assembly，MEA)及具有氣體流道的雙極板 (bipolar plates)。一般而言’ MEA係由一質子交換膜（通常為一 高分子膜，作為電解質）、分別位於該質子交換膜兩侧之兩個觸媒 層、及分別置於該兩個觸媒層外側之兩個氣體擴散層（另可稱為 「氣體擴散電極」）所組成。其中，氣體擴散層之主要功能係藉由 其多孔性結構’將氣體均勻地擴散及分布在觸媒層上，與觸媒進 行電池反應’因此氣體擴散層必須具備適當的多孔性及良好的導 1373874 電性。此外，為避免氣體擴散層之孔洞被電池反應所產生之水所 佔據，阻礙反應氣體的傳送，氣體擴散層亦須具備良好的疏水性， •，以確保反應氣體及水能順利進出氣體擴散層。為提高疏水性，目 •刖常使用疏水劑（如聚四氟乙烯）對氣體擴散層進行疏水處理。 目前所用的氣體擴散層有兩種’一種是碳布（carl>〇n cloth)，另 種是碳紙（carbon paper )。其中’瑞·纸之製造方法係將纖維與例 如聚乙烯醇相混合後，利用造紙技術製成纖維紙，之後將該纖維 紙含浸一定量之樹脂後，再進行碳化熱處理而製传，碳布則係利 ® 用紡織技術，將纖維先紡製成紗後’再進行織布工程製成織布， 其後進行碳化熱處理。 於碳化過程中，以PAN纖維為例，PAN纖維所含之非碳元素係 以小分子化合物的形式（如H20、HCN、NH3、C02、N2)釋出， 使得纖維内部逐漸形成碳基本平面（carbon basal plane )。其中纖 維内之碳層結構係沿纖維軸向堆疊排列，可用X光繞射儀來量測 碳層結構之結晶寬（La )及結晶高（Lc )大小，La及Lc之值係 φ 隨碳化溫度升高而變大。根據J.B. Donnet及R.C. Bansal所述（參 考 Carbon Fibers, Marcel Dekker，Inc.，1990, ISBN: 0-8247-7865-0, • Page 34-36)，當碳化溫度達到1300°C時，PAN纖維所製得之碳纖維 的組成除仍有約2重量％至3重量％的氮元素外，其餘全是碳元素。τ.η.Κο 的研究亦顯示類似的結果，即在1300°C下碳化所得到的碳纖維，其碳元素 含量在 95 重量％以上（Influence of continuom stabilization on physical properties and microstructure of PAN-based carbon fibers, Journal of Applied Polymer Science, Vol. 42, 1949-1957,（1991)) 〇 上述J.B. Donnet及R.C. Bansal之研究並指出，為提高所製得 1373874 碳纖維強度、獲知較佳之碳層結構（即較大的La/Lc值），必須於 碳化過程中使小分子化合物緩慢地釋出，因此在碳化開始進行 ，時，必須用較慢之升溫速率進行熱處理（例如每分鐘所提高之熱 處理溫度小於10。〇然而長時間的高溫碳化過程，不僅耗時更必 須消耗大量的能源》 本案發明人經不斷研究發現，可在不影響多孔性碳化基材強 度、及使用效月b的情況下，快速製造所欲之多孔性碳化基材，所 製知之多孔性兔化基材具有尚空孔率、高疏水性高含氧率、及 南含氮率等利於作為例如燃料電池之氣體擴散層的特性。此外， 依此方法所製得之多孔性碳化基材之收縮率較小，故在原料相同 的情況下，能提供更大的產量。 【發明内容】 本發明之一目的，在於提供一種多孔性碳化基材其含氧量為j 重量/〇至13重量％且含氮量為2重量％至16重量％，以基材總重 计。該夕孔性碳化基材可作為燃料電池之氣體擴散層材料。 本發明之另一目的，在於提供一種製造上述多孔性碳化基材之 方法，包含： 提供一纖維基材，其包含氧化纖維及聚醯胺纖維之至少一 者；以及 於一惰性氣體氛圍中熱處理該纖維基材，其中該熱處理係 i括^以50 C/分鐘至300°C/分鐘之速率加熱該惰性氣體氛圍炱 〇〇 C至2〇〇〇 〇c之熱處理溫度。 為讓本發明之上述目的、技術特徵及優點能更明顯易懂，下文 1373874 係以部分具體實施態樣進行詳細說明。 【實施方式】 d 以下將具體地描述根·據本發明之部分具體實施態樣；惟，在不 •背離本發明之精神下，本發明尚可以多種不同形式之態樣來實 踐’不應將本發明保護範圍解釋為限於說明書所陳述者。 本發明之多孔性碳化基材，以基材總重計，其含氧量為1重量％至 13重量％且含氮量為2重量％至16重量％»習知碳化基材之碳層 φ 結構中，幾乎不含氧元素、僅含少量之氮元素，其餘均為碳元素， 一般而言，過低的氮元素、或氧元素含量過低（如氮元素小於2 重量％、氧元素小於1重量％)’將形成完整的碳基本平面，使得 績才不具多孔性；若氮元素、或氧元素含量過高，則碳基本平面 又過於紛亂，將影響其導電性。 本發明多孔性碳化基材可用於燃料電池中作為氣體擴散層之材 料，其厚度一般為0.1毫米至1.0毫米’較佳為0.2毫米至〇5毫 φ 米。此外，本發明多孔性碳化基材之碳層結構令，其結晶高（Lc)較佳 為2.0奈米至4.0奈米。 如前所述，就燃料電池之氣體擴散層材料而言，所用之碳化基 材必須具備適當的多孔性及良好的導電性。經發現，若碳化基材 之空孔率小於15%或單位面積重量大於800公克/平方公尺，表示 其結構過於緊密，不利於氣體擴散，若空孔率大於6〇%或單位面 積重量小於20公克/平方公尺，則材料強度過於鬆散，耐用度恐不 佳且徒增後續加工的困難度。當使用於燃料電池作為氣體擴散層 材料時，為提供良好的透氣性’供氣體交換進行電池反應，本發 1373874 明之多孔性碳化基材之空孔率較佳為15%至60%，以18%至40% • 尤佳，且其單位面積重量較佳為20公克/平方公尺至800公克/平 -.方公尺，40公克/平方公尺至500公克/平方公尺尤佳。 . 如後附實施例所示，本發明之多孔性碳化基材具有相當優異的 疏水性，能避免氣體擴散層之孔洞被電池反應所產生之水所佔 據，阻礙反應氣體的傳送。即本發明多孔性碳化基材無需如先前 技術般地先進行疏水性處理，即可直接應用於燃料電池（尤其是 | PEMFC及DMFC)，作為氣體擴散層。 本發明亦關於一種製造上述多孔性碳化基材之方法，其能快速 製造上述多孔性碳化基材，該方法包含： 提供一纖維基材，其包含氧化纖維及聚醯胺纖維之至少一 者；以及 於一惰性氣體氛圍中熱處理該纖維基材，其中該熱處理係 包括以50°C/分鐘至300°C/分鐘之速率加熱該惰性氣體氛圍至 700 °C至2000 °C之熱處理溫度。 ® 其中，於本發明方法之較佳態樣中，所製得之多孔性碳化基材的 面積收縮率係小於3 %。 於本發明方法中，為避免纖維於熱處理過程中灰化，該熱處理 步驟宜於惰性氣體保護下進行。舉例言之，可採用選自以下群組 之惰性氣體以進行碳化處理：氮氣、氦氣、氬氣、及其組合。視 需要地，可於無張力狀態下（即纖維基材未受到外力拉伸或固定 的情況下）進行該熱處理。 該熱處理步驟係包含一升溫階段及一視需要之實質持溫階段， 1373874 該升溫階段係以50°C/分鐘至300°C/分鐘、較佳150°C/分鐘至 * 300°C/分鐘之速率，加熱該惰性氣體氛圍，至一預設之熱處理溫 •.度。其後，視需要進行一實質持溫階段，即維持該熱處理溫度大 致不變一段時間，以完成纖維基材之碳化。其中該熱處理溫度一 般為700°C至2000 °C，較佳為800 °C至1700 °C。該實質持溫階 段，當採用時，係歷時約1秒至約15分鐘之時間。例如，於本發 明之部分實施態樣中，採用包含以150°C/分鐘至300°C/分鐘速度 升溫之升溫階段以及歷時約10分鐘之持溫階段的熱處理步驟。 • 使用於本發明之纖維基材可為一織物或非織物（如不織布、 氈）。舉例言之，可經由以下步驟提供一適用於本發明之織物： (i) 若同時使用氧化纖維及聚醯胺纖維時，先混合該氧化纖維與 該聚醯胺纖維，以提供一纖維混合物，若僅使用單一氧化纖維或 聚醯胺纖維則可直接進行步驟(ii); (ii) 將該纖維或纖維混合物加以紡紗，以提供一（混）紡紗， 紗線支數較佳在NE 4至50之間，5至40尤佳，過高的紗線支數 B 會增加織布工程難度；以及 (iii) 將該（混）紡紗加以織布，以提供該（混）紡織物。 於上述操作中，可先將氧化纖維及/或聚醯胺纖維裁切成短纖維 後再加以紡紗。該紡紗步驟可採一次完成或利用一粗紡工程與一 細紡工程而實施。以後者為例，先將纖維混合物進行3至10倍的 牵伸以得到粗紗；再將所得粗紗進行10至15倍的牵伸以得到細 紗。之後，可視需要對細紗進行併線工程，將兩股細紗併線而提 1373874 供雙股形式之紗線。 • 讀，可·任何合宜之織布技術進行織布工程，以提供混纺 織布。舉例言之’可採用梭織法'針織法、或其組合；其中當 j用梭織法時"Tk供具平紋編織或斜紋編織之紡織布，當利用 針織法時’可提供具針織結構之纺織布。在使帛本發％碳化織物 作為氣體聽層㈣之情況τ，因氣體擴散層必須均句地讓燃料 氣體擴散’同時與觸媒層之間通常須有較平滑的接觸面故較佳 _ 係採用透職織法所提供之紡織布以提供本發明之多孔性碳化基 材。 可於本發明方法採用任何合宜之聚醯胺纖維。舉例言之，該聚 酿胺纖維可為^知聚醯胺（aromatic polyamide)纖維，其特定之 實施態樣如杜邦公司生產之Normex或Kevlar、帝人公司生產之 Technora、及 Teijin Twaron 公司生產之 Twaron 等。 可使用任何適合之氧化纖維於本發明方法，一般而言，該氧化 φ 纖維可經由熱處理一選自以下群組之纖維所提供：聚丙烯腈 (polyacrylonitrile，PAN)纖維、瀝青纖維、酚醛纖維、纖維素纖 維、及其組合，於本發明之部分實施態樣中係使用聚丙烯腈 (polyacrylonitrile，PAN )纖維。舉例言之，可經由在空氣中、於 200至300°C之溫度下熱處理PAN纖維而提供該氧化纖維。於此， 亦可直接使用市售可得之防火纖維為本發明方法中之氧化纖維， 例如SGL Carbon Group公司出產之Panox、Toho Tenax公司出產 之Pyromex、Zoltek公司出產之Pyron及Asahi Kasei公司出產之1373874 VI. Description of the invention: ^ [Technical field to which the invention pertains], illuminating the side of the carbonized substrate and its manufacturing method and material; specific • the invention of the invention is particularly useful for the manufacture of fuel A method of porous carbonized substrate of a gas diffusion layer material in a battery and a porous carbonized substrate provided thereby. [Prior Art] In recent years, due to energy shortages and the global warming effect, the development of gas-fired systems (fudcells) has attracted attention; the cover fuel cells are not only caused by the disposal of disposable batteries. Environmental problems can also eliminate the shortcomings of the time-consuming charging procedures required for traditional rechargeable batteries. At the same time, fuel cell emissions (such as water) are not harmful to the environment. Among various fuel cells, proton exchange membrane fuel cells (PEMFC) and direct methan〇1 fuel cells (DMFC) can be operated at low temperatures and can be produced at high temperatures. Current density is widely used in power supplies for vehicles, cogeneration systems, and various 3C products (such as notebook computers, mobile phones, etc.). Taking PEMFC as an example, the main components of each of the unit cells include a membrane-electrode assembly (MEA) and bipolar plates having a gas flow path. In general, 'MEA is composed of a proton exchange membrane (usually a polymer membrane as an electrolyte), two catalyst layers respectively located on both sides of the proton exchange membrane, and respectively disposed outside the two catalyst layers. Two gas diffusion layers (also referred to as "gas diffusion electrodes") are composed. Among them, the main function of the gas diffusion layer is to uniformly diffuse and distribute the gas on the catalyst layer by its porous structure, and perform a battery reaction with the catalyst. Therefore, the gas diffusion layer must have appropriate porosity and good conductivity. 1373874 Electrical. In addition, in order to prevent the pores of the gas diffusion layer from being occupied by the water generated by the reaction of the battery and hinder the transmission of the reaction gas, the gas diffusion layer must also have good hydrophobicity, so as to ensure that the reaction gas and water can smoothly enter and exit the gas diffusion layer. . In order to improve the hydrophobicity, the gas diffusion layer is often subjected to a hydrophobic treatment using a hydrophobic agent such as polytetrafluoroethylene. There are two types of gas diffusion layers currently used: one is carbon cloth (carl > 〇n cloth), and the other is carbon paper. The manufacturing method of 'Rui Paper> is to mix fiber with, for example, polyvinyl alcohol, and then make fiber paper by papermaking technology, and then impregnate the fiber paper with a certain amount of resin, then carry out carbonization heat treatment to transfer, carbon cloth Then, we use the textile technology to spin the fiber into a yarn, then weaving it into a woven fabric, followed by carbonization heat treatment. In the carbonization process, taking PAN fiber as an example, the non-carbon elements contained in the PAN fiber are released in the form of small molecular compounds (such as H20, HCN, NH3, C02, N2), so that the carbon interior plane is gradually formed inside the fiber ( Carbon basal plane ). The carbon layer structure in the fiber is arranged in the fiber axial direction, and the crystal width (La) and the crystal height (Lc) of the carbon layer structure can be measured by an X-ray diffractometer, and the values of La and Lc are φ with carbonization. The temperature increases and becomes larger. According to JB Donnet and RC Bansal (refer to Carbon Fibers, Marcel Dekker, Inc., 1990, ISBN: 0-8247-7865-0, • Page 34-36), when the carbonization temperature reaches 1300 ° C, PAN fiber The composition of the obtained carbon fiber is all carbon except that it is still about 2% by weight to 3% by weight of nitrogen. The τ.η.Κο study also showed similar results, that is, the carbon fiber obtained by carbonization at 1300 ° C has a carbon content of more than 95% by weight (Influence of continuom stabilization on physical properties and microstructure of PAN-based carbon fibers). , Journal of Applied Polymer Science, Vol. 42, 1949-1957, (1991)) 〇JB Donnet and RC Bansal study and pointed out that in order to improve the strength of the produced 1373874 carbon fiber, better carbon layer structure is known (ie larger The La/Lc value) must be slowly released during the carbonization process, so that at the beginning of carbonization, heat treatment must be performed at a slower temperature increase rate (for example, the heat treatment temperature per minute is increased by less than 10. However, the long-term high-temperature carbonization process not only consumes a lot of energy, but also consumes a large amount of energy. The inventors of the present invention have found through continuous research that they can quickly manufacture without affecting the strength of the porous carbonized substrate and the use efficiency b. The porous carbonized substrate to be prepared has a porous porosity, high hydrophobicity and high oxygen content. And the south nitrogen content rate is advantageous as a gas diffusion layer of, for example, a fuel cell. Further, the porous carbonized substrate obtained by the method has a small shrinkage ratio, so that the raw material can provide a larger amount of the same material. SUMMARY OF THE INVENTION An object of the present invention is to provide a porous carbonized substrate having an oxygen content of from j wt/〇 to 13 wt% and a nitrogen content of from 2 wt% to 16 wt% to a substrate. The total weight of the porous carbonized substrate can be used as a gas diffusion layer material for a fuel cell. Another object of the present invention is to provide a method for producing the above porous carbonized substrate, comprising: providing a fibrous substrate, And comprising at least one of an oxidized fiber and a polyamide fiber; and heat treating the fiber substrate in an inert gas atmosphere, wherein the heat treatment comprises heating the inert gas at a rate of 50 C/min to 300 ° C/min. The heat treatment temperature of the atmosphere 炱〇〇C to 2〇〇〇〇c. In order to make the above objects, technical features and advantages of the present invention more obvious and easy to understand, the following 1373874 is detailed in some specific embodiments. [Embodiment] d Hereinafter, a part of the specific embodiment of the present invention will be specifically described; however, the present invention can be practiced in various different forms without departing from the spirit of the present invention. The scope of protection of the present invention should be construed as being limited to the specification. The porous carbonized substrate of the present invention has an oxygen content of 1% by weight to 13% by weight and a nitrogen content of 2% by weight based on the total weight of the substrate. Up to 16% by weight of the carbon layer φ structure of the conventional carbonized substrate, almost no oxygen, only a small amount of nitrogen, the rest are carbon, in general, too low nitrogen, or oxygen content Too low (such as less than 2% by weight of nitrogen and less than 1% by weight of oxygen) will form a complete carbon basic plane, so that the performance is not porous; if the nitrogen or oxygen content is too high, the carbon base plane is Too much chaos will affect its conductivity. The porous carbonized substrate of the present invention can be used as a material for a gas diffusion layer in a fuel cell, and has a thickness of usually 0.1 mm to 1.0 mm', preferably 0.2 mm to 毫5 mφm. Further, the carbon layer structure of the porous carbonized substrate of the present invention has a high crystallinity (Lc) of preferably from 2.0 nm to 4.0 nm. As described above, in the case of the gas diffusion layer material of the fuel cell, the carbonized substrate used must have appropriate porosity and good electrical conductivity. It has been found that if the porosity of the carbonized substrate is less than 15% or the weight per unit area is more than 800 g/m 2 , it means that the structure is too tight, which is not conducive to gas diffusion, and if the porosity is greater than 6〇% or the weight per unit area is less than At 20 g/m2, the material strength is too loose, the durability is not good, and the difficulty of subsequent processing is increased. When used in a fuel cell as a gas diffusion layer material, in order to provide a good gas permeability for gas exchange for battery reaction, the porosity of the porous carbonized substrate of the present invention 1373874 is preferably 15% to 60%, to 18 % to 40% • Especially preferred, and its basis weight is preferably from 20 g/m2 to 800 g/m-. square meters, preferably 40 g/m2 to 500 g/m2. As shown in the appended Examples, the porous carbonized substrate of the present invention has a relatively excellent hydrophobicity, and it is possible to prevent the pores of the gas diffusion layer from being occupied by water generated by the reaction of the battery and hinder the transfer of the reaction gas. That is, the porous carbonized substrate of the present invention can be directly applied to a fuel cell (especially | PEMFC and DMFC) as a gas diffusion layer without first performing hydrophobic treatment as in the prior art. The present invention also relates to a method of producing the above porous carbonized substrate, which is capable of rapidly producing the above porous carbonized substrate, the method comprising: providing a fibrous substrate comprising at least one of an oxidized fiber and a polyamide fiber; And heat treating the fibrous substrate in an inert gas atmosphere, wherein the heat treatment comprises heating the inert gas atmosphere at a rate of from 50 ° C / minute to 300 ° C / minute to a heat treatment temperature of from 700 ° C to 2000 ° C. ® wherein, in a preferred aspect of the process of the invention, the resulting porous carbonized substrate has an area shrinkage of less than 3%. In the method of the present invention, in order to avoid ashing of the fibers during the heat treatment, the heat treatment step is preferably carried out under the protection of an inert gas. For example, an inert gas selected from the group consisting of nitrogen, helium, argon, and combinations thereof may be employed. The heat treatment can be carried out in a tension-free state (i.e., in the case where the fibrous substrate is not stretched or fixed by an external force) as needed. The heat treatment step comprises a temperature rising phase and a substantial temperature holding phase as needed. 1373874 The temperature rising phase is 50 ° C / min to 300 ° C / min, preferably 150 ° C / min to * 300 ° C / min. The rate of heating the inert gas atmosphere to a predetermined heat treatment temperature. Thereafter, a substantial temperature holding phase is carried out as needed, i.e., the heat treatment temperature is maintained for a substantial period of time to complete the carbonization of the fibrous substrate. The heat treatment temperature is generally from 700 ° C to 2000 ° C, preferably from 800 ° C to 1700 ° C. The substantial temperature-holding phase, when employed, takes from about 1 second to about 15 minutes. For example, in some embodiments of the present invention, a heat treatment step comprising a temperature rise phase at a rate of from 150 ° C/min to 300 ° C/min and a temperature hold period of about 10 minutes is employed. • The fibrous substrate used in the present invention may be a woven or non-woven fabric (e.g., non-woven fabric, felt). For example, a fabric suitable for use in the present invention can be provided by the following steps: (i) if both oxidized fibers and polyamide fibers are used, the oxidized fibers and the polyamide fibers are first mixed to provide a fiber mixture. If only a single oxidized fiber or polyamide fiber is used, step (ii) may be directly carried out; (ii) the fiber or fiber mixture is spun to provide a (mixed) spinning yarn, preferably having a yarn count of NE Between 4 and 50, preferably 5 to 40, too high a yarn count B will increase the difficulty of the weaving process; and (iii) weave the (mixed) yarn to provide the (mixed) textile . In the above operation, the oxidized fiber and/or the polyamide fiber may be first cut into short fibers and then spun. The spinning step can be carried out in one operation or using a woollen project and a fine spinning process. In the latter case, the fiber mixture is first drawn 3 to 10 times to obtain a roving; the resulting roving is further drawn 10 to 15 times to obtain a spun yarn. After that, the spun yarns can be joined in parallel, and the two spun yarns can be combined to provide 1373874 yarn in a double-strand form. • Read, any suitable weaving technique for weaving to provide a blended fabric. For example, 'weaving method' can be used for knitting, or a combination thereof; when j is woven, "Tk is provided with plain weave or twill weave, when knitted, it can provide a knitted structure Textile cloth. In the case where the carbon fiber woven fabric is used as the gas listening layer (4), since the gas diffusion layer must uniformly diffuse the fuel gas, it is generally necessary to have a smooth contact surface with the catalyst layer. A woven fabric provided by a transmissive weave is used to provide the porous carbonized substrate of the present invention. Any suitable polyamide fiber can be employed in the process of the invention. For example, the polyamine fiber may be an aromatic polyamide fiber, and specific embodiments thereof include Normex or Kevlar manufactured by DuPont, Technora manufactured by Teijin, and Twaron manufactured by Teijin Twaron. Wait. Any suitable oxidized fiber may be used in the process of the invention. Generally, the oxidized φ fiber may be provided by heat treatment of a fiber selected from the group consisting of polyacrylonitrile (PAN) fibers, pitch fibers, phenolic fibers, Cellulose fibers, and combinations thereof, use polyacrylonitrile (PAN) fibers in some embodiments of the invention. For example, the oxidized fiber can be provided by heat-treating the PAN fiber in air at a temperature of 200 to 300 °C. Here, it is also possible to directly use the commercially available fire-retardant fiber as the oxidized fiber in the method of the present invention, such as Panox produced by SGL Carbon Group, Pyrox produced by Toho Tenax, Pyron and Asahi Kasei produced by Zoltek.
Lastan ° t S1 10 1373874 本發明方法所提供之多孔性碳化基材尤其適用於燃料電池中， 如PEMFC及DMFC，作為氣體擴散層，即燃料電池中之陽極與陰 極。其中’燃料電池中各元件之材料與結構，係此技術領域中具 有通常知識者所熟知者。舉例言之，可參見中華民國專利第 1272739號及美國專利公開第2007/0117005A1號，其所揭露内容 均倂於此處以供參考。 茲以下列具體實施態樣以進一步例示說明本發明，其中，所採 用之量測儀器及方法分別如下： (A) 锈氣唐量測方法 透氣度量測儀：Gurley Model 4320 測量規範：ASTM D726-58 透氣度用圓捅容量：300 cc 透氣度用圓桶重量：5盎司 量測面積：1平方英吋 實驗前’確定透氣度用圓桶位於指定位置。取一試樣，面積大 於1平方英吋，並將試樣置入透氣度量測儀之支架上。根據 ASTM D726-58測試標準程序操作軟體，確認無誤後，將透氣 度用圓桶輕輕放下，待透氣度用圓桶完成整個程序，獲得一數 值。其中，所測得數值越低代表試樣之透氣度越高，反之越低。 (B) 雷池性能詈測方法 電池測 s式機台.FCEDPD50 Asia Fuel Cell Technologies，Ltd. 電子負載機型號：Chroma 63103 1373874 測試條件： . 陽極燃料：氫氣（純度99.999%)，流速500 cc/分鐘 . 陰極燃料：工業用氧氣，流速500 cc/分鐘 陽極陰極增濕溫度：40 °C 增濕瓶出口相對溼度：95%Lastan ° t S1 10 1373874 The porous carbonized substrate provided by the method of the present invention is particularly suitable for use in fuel cells, such as PEMFC and DMFC, as a gas diffusion layer, i.e., an anode and a cathode in a fuel cell. The materials and structures of the various elements in the fuel cell are well known to those of ordinary skill in the art. For example, reference is made to the Republic of China Patent No. 1272739 and the U.S. Patent Publication No. 2007/0117005 A1, the disclosure of which is incorporated herein by reference. The invention will be further illustrated by the following specific embodiments in which the measuring instruments and methods are as follows: (A) Gas Measure Method Gas Permeability Meter: Gurley Model 4320 Measurement Specification: ASTM D726 -58 Capacity for air permeability: 300 cc Drum capacity for air permeability: 5 ounces Measurement area: 1 square inch before the experiment 'Determining the air permeability with the drum at the specified position. A sample was taken with an area greater than 1 square inch and the sample was placed on a stent of a gas permeability meter. Operate the software according to the ASTM D726-58 test standard procedure. After confirming the correctness, gently lower the air permeability in a drum and wait for the air permeability to complete the entire procedure in a drum to obtain a value. Among them, the lower the measured value, the higher the gas permeability of the sample, and vice versa. (B) Thunder cell performance measurement method Battery test s-type machine. FCEDPD50 Asia Fuel Cell Technologies, Ltd. Electronic loader model: Chroma 63103 1373874 Test conditions: . Anode fuel: hydrogen (purity 99.999%), flow rate 500 cc / min Cathode fuel: Industrial oxygen, flow rate 500 cc / min Anode cathode humidification temperature: 40 °C Humidification bottle outlet relative humidity: 95%
電池測試溫度：40°C 電池組裝扭力：40公斤重-公分（kgf-cm) φ 電池反應面積：25平方公分 將所製得之試樣裁切為5公分x5公分之大小後，不須經任何 疏水處理或整平處理，再將其與美國Dupont公司所生產之觸 媒塗覆膜（catalyst coated membrane ’ CCM，型號：DupontTM， type NRE-211 )，以40公斤重-公分的扭力組合成膜電極組 (membrane-electrode assembly，MEA )。使用具有蛇紋狀 (serpentine-type grooved)溝渠之石墨板作為雙極板。然後， φ 再利用不銹鋼板及聚四氟乙烯襯墊（Teflon Gasket)作最後封 裝成為一個燃料電池。在陽極端的氣體流速（氫氣）為500 cc/ 分鐘，而在陰極端的氣體流速（氧氣）為500 cc/分鐘，壓力 為1 kg/cm2,溫度則是設定在40°C。於此條件下測試電池性能。 (C)碳層結椹玱疊戽唐（即結晶高Lc)量測方法 儀器：X 光繞射儀（型號 MXP-3 X-ray Diffraction) 測試方法：將試樣以X光繞射儀進行量測’其中掃描角度為 10度至60度，謝勒常數（Scherrer constant ’ K)為0.9 ’繞射 12 1373874 線之繞射波長（λ)為0.1543奈米 . (D)元素分析量測方法Battery test temperature: 40 °C Battery assembly torque: 40 kg weight-cm (kgf-cm) φ Battery reaction area: 25 square centimeters After cutting the prepared sample to a size of 5 cm x 5 cm, no need to pass Any hydrophobic treatment or leveling treatment, and then combined with the catalyst coated membrane (CCM, model: DupontTM, type NRE-211) produced by Dupont Company of the United States, with a torque of 40 kg-cm. Membrane-electrode assembly (MEA). A graphite plate having serpentine-type grooved trenches was used as the bipolar plate. Then, φ is finally sealed into a fuel cell by using a stainless steel plate and a Teflon Gasket. The gas flow rate (hydrogen) at the anode end was 500 cc/min, and the gas flow rate (oxygen) at the cathode end was 500 cc/min, the pressure was 1 kg/cm2, and the temperature was set at 40 °C. Battery performance was tested under these conditions. (C) Carbon layer junction stacking (ie, high crystallization Lc) measurement method Instrument: X-ray diffractometer (model MXP-3 X-ray Diffraction) Test method: the sample is X-ray diffractometer Measurement 'Where the scanning angle is 10 to 60 degrees, the Scherrer constant 'K' is 0.9 'The diffraction wavelength (λ) of the diffraction line 12 1373874 is 0.1543 nm. (D) Elemental analysis measurement method
* - 儀器：德國Elemental·公司之元素分析儀（Universal CHNOS . Elemental Analyzer Vario EL III 型） 將試樣於1150°C之溫度下，以純氧燃燒成二氧化碳及氧化 氮，接著以純銅還原成燒成二氧化碳及氮氣後，通入氣相層析 儀中，檢測碳及氮之重量百分比。 • (E)空孔率量測方法 儀器：天平（量測精密度至0.0001克）、烘箱 測試標準：ASTM D-570測試法 將試樣置入120°C (±5°C)之烘箱，持續烘乾24小時。取出 後秤重，得一數值W,。將烘乾後的試樣浸潰於逆滲透水24小 時後，取出栻乾表面，秤重得一數值W2。利用下列公式算出 試樣之空孔率： # [(W2-W,)/W!] X 100% =空孔率（％) (F)面精收縮率量測方法 . 儀器：游標尺 於碳化處理前，以游標尺量測未經碳化之纖維的長寬並計算其 面積，得一數值A,，待碳化完成後，再以游標尺量測經碳化 後之纖維的長寬，同樣計算其面積，得一數值A2。利用下列 公式算出試樣之面積收縮率： [(ArAG/AJxlOO%:面積收縮率（％) ί S3 13' 1373874 (G)接觸角量測方法 ' 儀器：法國 GBX model D-S Instruments •- 一般常以待測基材表面與液滴之接觸點的接觸角，作為評量待 . 測基材之疏水性能的依據，其中接觸角係指液滴與固體基材表 面之接觸點所做的切線與固-液界面之夹角。其中，接觸角係 根據楊氏方程式（Young’s equation)計算而得。 實施例1 ^ 採用由美國Zoltek公司生產之短纖狀氧化纖維，將該氧化纖維 裁成63毫米長度後，經過粗紡機的延伸，形成粗紗；再經過細紗 機的再次延伸，得到細紗。接著將所得之紗線（所用之紗線支數 為NE 6.7)以平紋方式編織成一厚度為0.8毫米且重量為460公 克/平方公尺之紡織布。 將所得之紡織布於氮氣保護下，以190°C/分鐘之升溫速率，加熱 至1300°C，維持該溫度約10分鐘後，以同樣190°C/分鐘之速率降 • 至室溫。獲得厚度為0.58毫米，重量為251公克/平方公尺之多孔 性碳化基材。以前述方式對該多孔性碳化基材進行測試，並將結 果記錄於表一。如表一所示，其空孔率為24.7%，面積收縮率為 0.2%，氮含量為13.42重量％，氧含量為11·79重量％。 隨後使用該多孔性碳化基材組裝一燃料電池，並進行燃料電池 效能之測試，將結果同樣記錄於表一。如表一所示，在0.5伏特下， 所測得之電流密度為1017毫安培/平方公分，最大功率密度為566 毫瓦/平方公分。 1373874 實施例2 ' 使用與實施例1相同之紡織布及方式製造多孔性碳化基材，惟升溫及降 • ‘溫速率均提高至220°(：/分鐘。獲得厚度為0.60毫米，重量為243公克/平 •方公尺之多孔性碳化基材。以前述方式對該多孔性碳化基材進行測試，並 將結果記錄於表一。如表一所示，其空孔率為23.0%，面積收縮率為 0.5%，氮含量為13.65重量％，氧含量為12.95重量％ » 使用該多孔性碳化基材組裝一燃料電池，並進行燃料電池效能 之測试，結果兄錄於表一。如表一所不’在0.5伏特下，所測得之 電流密度為978毫安培/平方公分，最大功率密度為541毫瓦/平方 公分。 實施例3 使用與實施例1相同之紡織布及方式製造多孔性碳化基材，惟升溫及降 温速率均提高至250°C/分鐘。獲得厚度為0.57毫米，重量為237公克/平 方公尺之多孔性碳化基材。以前述方式對該多孔性碳化基材進行測試，並 φ 將結果記錄於表一。如表一所示，其空孔率為37.0%，面積收縮率為 2.5% ’敗含量為13.81重量％，氧含量為ι〇·19重量％。 使用該多孔性碳化基材組裝一燃料電池，並進行燃料電池效能 之測試，結果記錄於表一。如表一所示，在0.5伏特下，所測得之 電流密度為1132毫安培/平方公分，最大功率密度為625毫瓦/平 方公分。 實施例4 使用與實施例1相同之紡織布及方式製造多孔性碳化基材，惟升溫及降 I S3 15 1373874 溫速率均提高至28〇°C/分鐘。獲得厚度為0.61毫米，重量為232公克/平 方公尺之多孔性碳化基材。以前述方式對該多孔性碳化基材進行測試，並 1將結果記錄於表―。如表—所示，纟空孔率為32.G%，面積收縮率為 2.8% ’氮含量為u 98重量％，氧含量為7 49重量％。 使用該多孔性碳化基材組裝一燃料電池，並進行燃料電池效能 之測試，結果同樣記錄於表一。如表一所示，在0.5伏特下，所測 得之電机达度為1丨28毫安培/平方公分，最大功率密度為633毫瓦 /平方公分。 比較實施例1* - Instrument: Elemental Analyzer Vario EL III from Germany Elemental· The sample is burned to carbon dioxide and nitrogen oxide at a temperature of 1150 ° C, then reduced to pure copper. After carbon dioxide and nitrogen, they are passed through a gas chromatograph to measure the weight percentage of carbon and nitrogen. • (E) Porosity measurement method Instrument: Balance (measurement precision to 0.0001 g), oven test standard: ASTM D-570 test method The sample is placed in an oven at 120 ° C (± 5 ° C). Continue to dry for 24 hours. After taking it out, weigh it and get a value W. After the dried sample was immersed in reverse osmosis water for 24 hours, the dried surface was taken out and weighed to obtain a value W2. Calculate the porosity of the sample using the following formula: # [(W2-W,)/W!] X 100% = porosity (%) (F) Surface shrinkage measurement method. Instrument: vernier scale on carbonization Before processing, the length and width of the uncarbonized fiber are measured by a vernier scale and the area is calculated to obtain a value A. After the carbonization is completed, the length and width of the carbonized fiber are measured by a vernier scale, and the same is calculated. The area is given a value of A2. The area shrinkage of the sample was calculated using the following formula: [(ArAG/AJx100%: area shrinkage (%) ί S3 13' 1373874 (G) Contact angle measurement method] Instrument: France GBX model DS Instruments •- The contact angle between the surface of the substrate to be tested and the contact point of the droplet is used as a basis for measuring the hydrophobic properties of the substrate to be tested, wherein the contact angle refers to the tangent and solidification of the contact point between the droplet and the surface of the solid substrate. The angle between the liquid interfaces, wherein the contact angle is calculated according to the Young's equation. Example 1 ^ Using a short-fiber oxidized fiber produced by Zoltek, USA, the oxidized fiber is cut to a length of 63 mm. Thereafter, the roving is extended to form a roving; the roving is further extended by the spinning machine to obtain a spun yarn. Then, the obtained yarn (the yarn count used is NE 6.7) is woven into a thickness of 0.8 mm and weight in a plain pattern. The woven fabric of 460 g/m 2 . The obtained woven fabric was heated to 1300 ° C at a heating rate of 190 ° C / min under nitrogen protection, and maintained at this temperature for about 10 minutes, at the same 190 ° C. / The rate of the clock is lowered to room temperature. A porous carbonized substrate having a thickness of 0.58 mm and a weight of 251 g/m 2 is obtained. The porous carbonized substrate is tested in the manner described above, and the results are reported in Table 1. As shown in Table 1, the porosity is 24.7%, the area shrinkage is 0.2%, the nitrogen content is 13.42% by weight, and the oxygen content is 11.79% by weight. Subsequently, the porous carbonized substrate is used to assemble a fuel cell. And test the fuel cell performance, the results are also recorded in Table 1. As shown in Table 1, at 0.5 volts, the measured current density is 1017 mA / cm ^ 2, the maximum power density is 566 mW / 1373874 Example 2 'A porous carbonized substrate was produced using the same woven fabric and method as in Example 1, except that the temperature rise and the temperature were increased to 220° (:/min. The obtained thickness was 0.60 mm, A porous carbonized substrate having a weight of 243 g/m2 and a square meter. The porous carbonized substrate was tested in the manner described above, and the results are reported in Table 1. As shown in Table 1, the porosity was 23.0. %, area The rate was 0.5%, the nitrogen content was 13.65 wt%, and the oxygen content was 12.95 wt%. » A fuel cell was assembled using the porous carbonized substrate, and the fuel cell performance test was performed. The results are shown in Table 1. The current density measured at 0.5 volts was 978 mA/cm 2 and the maximum power density was 541 mW/cm 2 . Example 3 Porousness was produced using the same woven fabric and method as in Example 1. Carbonized substrate, but the heating and cooling rates were increased to 250 ° C / min. A porous carbonized substrate having a thickness of 0.57 mm and a weight of 237 g/m2 was obtained. The porous carbonized substrate was tested in the manner described above, and the results are reported in Table 1. As shown in Table 1, the porosity was 37.0%, the area shrinkage was 2.5%, the yield was 13.81% by weight, and the oxygen content was 〇19.9% by weight. A fuel cell was assembled using the porous carbonized substrate, and the fuel cell performance was tested. The results are shown in Table 1. As shown in Table 1, at 0.5 volts, the measured current density was 1132 mA/cm 2 and the maximum power density was 625 mW/cm 2 . Example 4 A porous carbonized substrate was produced using the same woven fabric and method as in Example 1, except that the temperature was raised to 28 ° C/min. A porous carbonized substrate having a thickness of 0.61 mm and a weight of 232 g/m2 was obtained. The porous carbonized substrate was tested in the manner described above, and the results were recorded in Table--. As shown in the table, the open porosity was 32. G%, the area shrinkage was 2.8%, the nitrogen content was u 98% by weight, and the oxygen content was 749% by weight. A fuel cell was assembled using the porous carbonized substrate, and fuel cell performance tests were conducted. The results are also reported in Table 1. As shown in Table 1, at 0.5 volts, the measured motor reached 1 丨 28 mA/cm 2 and the maximum power density was 633 mW/cm 2 . Comparative Example 1
使用與實施例1相同之纟機布製造多孔性碳化基材，其巾係制習知慢 速升溫之方式’以2〇c/分鐘之升溫速率加熱至13〇〇〇c，維持該溫度約 1〇分鐘後’以同樣2〇C/分鐘之速率降至室溫。獲得厚度為0.57毫米， 重量為240公克/平方公尺之多孔性碳化基材。以前述方式對該多孔性碳化 基材進订測式’並將結果記錄於表一如表—所示，其空孔率為^ 6%， 面積收縮率為8.7%，氮含量為135重量％，氧含量為〇重量％。 使用該多孔性碳化美 、 基材道裝一燃料電池，並進行燃料電池效能 之測試，結果同樣記錄於表一。 .θ . φ ^ . 如表一所示，在0.5伏特下，所測 侍之電流岔度為1172毫安谇/ 、 千方Α为’最大功率密度為628毫瓦 比較實施例2 使用與實施例1相同之妨敏太 溫速率均提高至”。。。讀二製造乡錄碳化祕，惟升溫及降 又得厚度為G.59毫米，重量為218公克/平 1373874 方公尺之多孔性碳化基材。以前述方式對該多孔性碳化基材進行測試，並 將結果記錄於表一。如表一所示，其空孔率為16.1%，面積收縮率為 3.2%，氮含量為16.44重量％，氧含量為12.24重量％。 使用該多孔性碳化基材組裝一燃料電池，並進行燃料電池效能 之測試，結果同樣記錄於表一。如表一所示，在0.5伏特下，所測 得之電流密度為401毫安培/平方公分，最大功率密度為208毫瓦/ 平方公分。 氮含 量 ( 重 量％) 氡含 量 (重 量％) 空孔 率（％) 面積 收縮 率 (%) 碳層結 構 (Lc， 奈米） 接觸 角 (度） ‘電流 密度 (毫 安培/ 平方 公分） 最大功 率密度 (毫瓦 /平方 公分） 實施 例1 13.42 11.79 24.7 0.2 2.55 125 1017 566 實施 例2 13.65 12.95 23.0 0.5 2.56 108 978 541 實施 例3 13.81 10.19 37.0 2.5 2.53 100 1132 625 實施 例4 15.98 7.49 32.0 2.8 2.54 <90 1128 633 I S1 17 1373874 - 比較 實施 例1 1.35 0 12.6 8.7 2.57 135 1172 628 比較 實施 16.44 12.24 16.1 3.2 1.94 <90 401 208 例2 —_ 電流密度係於G.5伏特之電壓下所測得β 由表結果可知’本發明實施例1至4所製得之多孔性碳化基 材”有旦虽的氮及氧含量，相較於比較實施例1所製得之碳化 基材，具有較佳的空孔率’且由接觸角觀之，可知本發明多孔性 石反化基材亦具有良㈣疏水性能，上述優點均有助於其作為燃料 電池之氣體擴散層時，提供較佳的透氣性及疏水性。比較電流密 度及最大功率密度可知，本發明方法不僅能快速製得所欲之多孔 性碳化基材，且㈣本發明纽性基材之燃料電池具有堪與習知 燃料電池相匹配之電池效能。 此外，實施例1至4所製得之多孔性碳化基材之碳層結構（參 :^值）與吨實蘭1㈣狀碳化歸錢有_差異，顯 ^:明之方法並沒有先前技術所云，以高升溫速率進行碳化處 理會破壞碳層結構之情事。 另由面積收縮率可知，依本發明方法所製得之碳化基材（實施 例】至4),其面積收縮率明顯小於以習知技術所製得者（比較實 施例1)，亦即在使料量原料崎心，本發明之方 18A porous carbonized substrate was produced using the same woven cloth as in Example 1, and the method of heating at a temperature increase rate of 2 〇c/min was carried out to a temperature of 2 〇c/min to maintain the temperature. After 1 minute, 'reduced to room temperature at the same rate of 2 〇C/min. A porous carbonized substrate having a thickness of 0.57 mm and a weight of 240 g/m 2 was obtained. The porous carbonized substrate was subjected to the measurement formula 'in the foregoing manner, and the results are shown in Table 1. The porosity was ^6%, the area shrinkage was 8.7%, and the nitrogen content was 135% by weight. The oxygen content is 〇% by weight. A fuel cell was mounted on the substrate using the porous carbonized product, and the fuel cell performance was tested. The results are also reported in Table 1. .θ . φ ^ . As shown in Table 1, at 0.5 volts, the measured current mobility is 1172 mA / , and the square power is 'maximum power density 628 mW. Comparative Example 2 Use and Implementation In Example 1, the same temperature and temperature rate were increased to “...”. The second method of manufacturing was to record the carbonization secret, but the thickness and temperature were G.59 mm, and the weight was 218 g/flat 1373874 m. Carbonized substrate. The porous carbonized substrate was tested in the manner described above, and the results are reported in Table 1. As shown in Table 1, the porosity was 16.1%, the area shrinkage was 3.2%, and the nitrogen content was 16.44. % by weight, oxygen content was 12.24% by weight. A fuel cell was assembled using the porous carbonized substrate, and the fuel cell performance test was performed. The results are also reported in Table 1. As shown in Table 1, at 0.5 volts, the measured The current density is 401 mA/cm 2 and the maximum power density is 208 mW/cm 2 . Nitrogen content (% by weight) 氡 content (% by weight) Porosity (%) Area shrinkage (%) Carbon layer structure (Lc, nano) contact angle (degrees) 'current density Degree (milliamps per square centimeter) Maximum power density (milliwatts per square centimeter) Example 1 13.42 11.79 24.7 0.2 2.55 125 1017 566 Example 2 13.65 12.95 23.0 0.5 2.56 108 978 541 Example 3 13.81 10.19 37.0 2.5 2.53 100 1132 625 Example 4 15.98 7.49 32.0 2.8 2.54 <90 1128 633 I S1 17 1373874 - Comparative Example 1 1.35 0 12.6 8.7 2.57 135 1172 628 Comparative Implementation 16.44 12.24 16.1 3.2 1.94 <90 401 208 Example 2 -_ Current Density System The β measured at a voltage of G. 5 volts shows that the porous carbonized substrate obtained in Examples 1 to 4 of the present invention has a nitrogen and oxygen content as compared with Comparative Example 1. The carbonized substrate obtained has a better porosity> and is observed from the contact angle. It is known that the porous stone reversal substrate of the present invention also has good (four) hydrophobic properties, and the above advantages are all beneficial to the fuel cell. The gas diffusion layer provides better gas permeability and hydrophobicity. Comparing the current density and the maximum power density, the method of the present invention not only rapidly produces a desired porous carbonized substrate, but (4) the fuel cell of the novel substrate of the present invention has battery performance compatible with conventional fuel cells. In addition, the carbon layer structure (parameter: value) of the porous carbonized substrate prepared in Examples 1 to 4 is different from the carbonized material of the Tengshilan 1 (four) shape, and the method of the invention is not clouded by the prior art. Carbonization at a high heating rate will destroy the carbon layer structure. Further, from the area shrinkage ratio, the carbonized substrate (Examples to 4) obtained by the method of the present invention has an area shrinkage ratio significantly smaller than that obtained by a conventional technique (Comparative Example 1), that is, Making the raw material raw material, the party of the invention 18
I SJ 1373874 速製得所欲之多孔性碳化基材，且其產率亦明顯優於習知技術。 比較實施例2雖亦使用快速升溫之方式製造碳化基材，然所使 * '用之升溫速率過高，以致於所製得之碳化基材的碳層結構被破壞 .(參照Lc值），如文獻所記載，且當用於燃料電池中時，電池效 能不彰。 综上所述，本發明之方法能快速獲得所欲之多孔性碳化基材， 且所製得之多孔性碳化基材不會有如文獻記載之碳層結構不佳之 φ 問題，具有良好的多孔性及疏水性，當應用於燃料電池中作為氣 體擴散層時，更能提供與習知碳化基材至少相匹配之效能。 上述實施例僅為例示性說明本發明之原理及其功效，並闡述本 發明之技術特徵，而非用於限制本發明之保護範疇。任何熟悉本 技術者在不違背本發明之技術原理及精神下，可輕易完成之改變 或安排，均屬本發明所主張之範圍。因此，本發明之權利保護範 圍係如後附申請專利範圍所列。 ^ 【圖式簡單說明】 (無） 【主要元件符號說明】 (無） I S3 19I SJ 1373874 produces a porous carbonized substrate at a desired rate, and its yield is also significantly better than conventional techniques. Although Comparative Example 2 also used a rapid heating method to manufacture a carbonized substrate, the rate of temperature increase was too high, so that the carbon layer structure of the obtained carbonized substrate was destroyed (refer to the Lc value). As described in the literature, and when used in a fuel cell, the battery performance is not good. In summary, the method of the present invention can quickly obtain a desired porous carbonized substrate, and the obtained porous carbonized substrate does not have a problem of a poor carbon layer structure as described in the literature, and has good porosity. And hydrophobicity, when applied as a gas diffusion layer in a fuel cell, can provide at least a matching performance with a conventional carbonized substrate. The above embodiments are merely illustrative of the principles and effects of the present invention, and are illustrative of the technical features of the present invention and are not intended to limit the scope of the present invention. Any changes or arrangements that can be easily made by those skilled in the art without departing from the technical principles and spirit of the invention are within the scope of the invention. Therefore, the scope of the invention is set forth in the appended claims. ^ [Simple description of the diagram] (none) [Explanation of main component symbols] (none) I S3 19