201221491 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種管道，其由鉑或Pt合金製成且經保護 而免於在氧化氛圍中在>1，20(TC之溫度下使用時遭受汽化 損失。 ' 【先前技術】 定義 術語鉑應理解為意謂可含有工業中常見之其他元素部分 之舶材料。此尤其關於不可避免之雜質。 術語鉑合金及鉑基材料應理解為意謂具有鉑作為主要部 分，尤其具有超過80°/。鉑之合金。除不可避免之雜質以 外’其餘部分較佳為铑及/或銥。 術語汽化率應理解為意謂材料損失發生之速率。其可表 示為每單位操作時間之質量損失。 技術背景 高品質玻璃（諸如用於例如製造平板螢幕之極薄（約〇 8 mm)榮幕）在極高溫度（通常>16〇(Γ(：)下熔融及澄清 (refine)，主要以消除會引起小氣泡形成之微少痕量氣體。 該等處理通常在由Pt材料（通常為氧化物分散硬化ptRh合 金）製成之「進料系統」中進行。該等組件通常由多個垂 直且大部分水平管道組成，該等管道藉由直接通電而經電 加熱。個別管道區段經由凸緣密封，該等凸緣不僅以機械 方式穩定結構，且亦充當電力連接器。該等組件之典型使 用哥命達數年。 159215.doc 201221491 始組件由高熔點耐火材料（通常基於氧化鋁）環繞，該等 兩溶點耐火材料以固體石料之形式以及以大塊顆粒或纖維 塾形式使用《耐火材料之目的為向組件提供機械支撐及熱 絕緣。 在南溫下Pt材料與含氧氛圍接觸會導致pt氧化物形成。 特疋5之’二氧化鉑pt〇2具揮發性。即使在超過1，2〇〇乞之 溫度下’由Pt氧化及氧化物汽化所致之貴金屬損失亦會造 成相當大之經濟損失。隨著溫度升高，汽化損失如此顯著 以致壁厚度大幅減小且組件之機械穩定性受損。 有趣的是，實際使用中所觀察到之汽化損失遠不及實驗 至實驗中所觀察到之速率水準。關於對以及pt族金屬之汽 化損失之科學研究的綜述已由Jehn(Hermann Jehn， 「High201221491 VI. Description of the Invention: [Technical Field] The present invention relates to a pipe made of platinum or a Pt alloy and protected from being used in an oxidizing atmosphere at a temperature of >1,20 (TC) It suffers from vaporization losses. ' [Prior Art] Definition The term platinum should be understood to mean a material that can contain other elements of the common elements in the industry. This is especially true for unavoidable impurities. The term platinum alloy and platinum-based materials should be understood as meaning. It is said that platinum has a main part, especially an alloy of more than 80°/platinum. The remainder is preferably 铑 and/or 除 except for unavoidable impurities. The term vaporization rate is understood to mean the rate at which material loss occurs. It can be expressed as a mass loss per unit of operation time.Technical Background High quality glass (such as the extremely thin (about 8 mm) curtain used to make, for example, a flat screen screen) is at very high temperatures (usually >16〇(Γ( :) Melting and refining, mainly to eliminate traces of gas that can cause small bubbles to form. These treatments are usually performed by Pt materials (usually oxide dispersion hardening ptRh Gold) is made in a "feed system". These components are usually composed of a plurality of vertical and most horizontal pipes which are electrically heated by direct energization. Individual pipe sections are sealed via flanges, The flanges not only mechanically stabilize the structure, but also act as power connectors. The typical use of these components has been for many years. 159215.doc 201221491 The starting assembly is surrounded by a high melting point refractory material (usually based on alumina). The two melting point refractories are used in the form of solid stone and in the form of large particles or fiber rafts. The purpose of the refractory is to provide mechanical support and thermal insulation to the assembly. Pt material in contact with an oxygen atmosphere at south temperature will cause pt oxidation. The formation of the 疋5's platinum dioxide pt〇2 is volatile. Even at temperatures above 1,2 ', the loss of precious metals caused by Pt oxidation and oxide vaporization will cause considerable economics. Loss. As the temperature increases, the vaporization loss is so significant that the wall thickness is greatly reduced and the mechanical stability of the component is impaired. Interestingly, the steam observed in actual use. Loss far less than the standard rate experiment to experiment, the observed. For a review of scientific research on metals and vaporized pt loss of the been Jehn (Hermann Jehn, "High
Temperature Behaviour of Platinum Group Metals inTemperature Behaviour of Platinum Group Metals in
Oxuhzmg Atmospheres」，J0urnai of the Less c〇rnm〇nOxuhzmg Atmospheres", J0urnai of the Less c〇rnm〇n
Metals，100, 1984,第321至339頁）發表。基於由發表 之值’在氧氣氛圍（1巴）中在UOOt下壁厚度預期每年減 少8 mm至9 mm(對於一個表面而言_另_表面通常由炫融玻 璃保護）。儘管由jehn報導之於空氣氛圍中進行實驗所得之 值變化較大，但在暴露於空氣下壁厚度之損失仍預期達每 年若干毫米。4目比之下，在實際使用中觀察到之壁厚度損 失最大為每年十分之幾毫米。較低汽化率與在Pt組件之表 面上形成穩定擴散邊界有關。限速因素於是主要為h氧化 物物質穿過邊界層的擴散作用。在實驗室實驗中，採取確 保在Pt表面上直接存在足夠氣流用於氧化步驟而非待限制 159215.doc 201221491 速率之穿過邊界層擴散作用的措施。 通常觀察到組件與耐火材料接觸之區域的汽化率顯$車交 低且在1，60(TC下通常在每年0.1 mm範圍之内，但仍會相 當大地削弱厚度最初為0.8 mm之壁。 然而，汽化損失在凸緣附近嚴重得多。由於鉑材料與環 繞其之耐火材料相比溫度較高且熱膨脹係數較大，所以在 凸緣處出現凸緣與耐火材料之間的間隙且通常可為若干毫 米寬。在該間隙處沣意到有強對流導致Pt汽化率劇烈升 高。在1，600。(：下在此等區域内可觀察到高達每年〇 5 mm 之壁厚度損失。 先前技術 wo 2008052626A1描述在玻璃製造中對銀進行氧化保 護’其中亦導引熔融玻璃通過玻璃傳導部件之外側且形成 保護層。可另外施加保護性氣體氛圍（第12頁，第1段）。 【發明内容】 本發明之目標 本發明旨在顯著地降低在高溫下使用由pt材料製成之組 件時在其中，尤其在電力連接凸緣附近所觀察到之壁厚度 損失。 本發明 藉由部分地包裹由pt材料製成之尤其經電加熱之管道狀 、且件，尤其在特別易受影響之管道末端附近，減少揮發性 Pt氧化物汽化。 因此’本發明係關於如技術方案1之管道、如技術方案 159215.doc 201221491 13之方法及如技術方案14之用途。其他及較佳實施例在附 屬項中說明。 可主要經由穩定Pt材料表面上之邊界層以阻礙鉑氧化物 分子擴散穿過該層來減少汽化損失。以下可選方案可用於 此目的： 1 ·在欲保護之管道外側施加一或多個套頭且將其定位以 相對於管道大致同心。 套頭較佳經定位而與管道相距O.i mm至1〇〇 111111距 離。將套頭之一端固定至凸緣（較佳焊接）；另一端開 放。套頭寬度通常為10 mm至200 mm。套頭宜近距離 附接至由Pt材料製成之Pt組件之表面。隨著距離增加， 出於成本原因而較佳使用例如Ni基合金或高溫鋼。 2. 此外，施加由耐高溫陶瓷材料製成之多孔塗層或由汽或 Pt基材料製成之纖維網（fleece)及/或發泡體於欲保護之 管道上以減慢Pt氧化物分子之擴散。 3. 如前述項目2之多孔塗層或纖維網及/或發泡體之外表面 "T另外具備氣密層。 4. 如剛述項目2之多孔塗層或纖維網及/或發泡體可以使其 填充組件與套頭（如項目1)之間之間隙的方式附接。 雖然以上說明之可選方案之主要功能為減少Pt分子擴 散仁可以保濩性氣體（例如N2、Ar)沖洗組件與套頭之間 审、使付Pt氧化物最先較難形成。類似地，可例如經 由附接適合之有孔進料管道以保護性氣體沖洗多孔層。 在另一實施例中，在以惰性氣體沖洗情況下可將吸氣劑 159215.doc 201221491 安置於組件與套頭之間的間隙中以更大程度降低惰性氣體 氛圍中之氧氣分率。適合吸氣劑材料為熟習此項技術者已 知且基於例如鉛及釔。 優勢 p t之化受熱組件附近之空氣滿流大幅影響。滿流愈 強’接近表面之含pt氧化物擴散層之移除愈快速。本發明 之主要優勢為包裹引起擴散障壁產生，從而實質上降低汽 化率。包裹亦使得導引保護性氣體氛圍穿過Pt表面從而減 慢關鍵區域中揮發性Pt氧化物形成成為可能β根據本發 明，此使得在製造特用玻璃（例如用於平板螢幕）中在極高 溫度（南達約1，65 0 °C )下使用之Pt組件之使用壽命延長。 【實施方式】 例示性實施例 本發明在以下實例中得以更詳細地說明而不限於該等實 施例。如同在整個說明書中，術語（諸如「平行」、「垂 直」、「環形」、「同心」及「圓柱形」）應理解為導引 術語且包括其不改變其功能之變體。此外，對材料之說明 應包括經由具有相同功能之材料替換。除非另外規定否 則對份數及百分比之說明指重量。 實例1 -例示性實施例示意地展示於圖K。在右側頂部，對 進料管線至凸緣1之橫截面描繪顯而易見，其過渡至凸緣^ 中，繼而展示為垂直於環平面之部分橫截面圖。由耐火纖 維材料2製成之圓盤狀環將凸緣丨與耐火襯層3分離。中空 1592l5.docMetals, 100, 1984, pp. 321-339). Based on the published value 'in the oxygen atmosphere (1 bar), the UOOt lower wall thickness is expected to decrease by 8 mm to 9 mm per year (for one surface, the surface is usually protected by glare glass). Although the value obtained by the jehn report in the air atmosphere varies greatly, the loss of the thickness of the wall under exposure to air is still expected to be several millimeters per year. At 4 mesh, the wall thickness loss observed in actual use is a maximum of a few tenths of a year. The lower vaporization rate is related to the formation of a stable diffusion boundary on the surface of the Pt component. The rate limiting factor is then primarily the diffusion of the h-oxide species across the boundary layer. In laboratory experiments, measures are taken to ensure that there is sufficient airflow directly on the Pt surface for the oxidation step rather than to be limited by the diffusion of the boundary layer at the rate of 215215.doc 201221491. It is generally observed that the vaporization rate of the area where the component is in contact with the refractory material is low and the vehicle cross is low at 1,60 (TC is usually within 0.1 mm per year, but still considerably weakens the wall initially with a thickness of 0.8 mm. The vaporization loss is much more severe near the flange. Since the platinum material has a higher temperature and a higher coefficient of thermal expansion than the refractory material surrounding it, a gap between the flange and the refractory material occurs at the flange and is usually A few millimeters wide. At this gap, there is a strong convection that causes a sharp increase in the vaporization rate of Pt. At 1,600 ((): wall thickness loss of up to mm5 mm per year can be observed in these areas. WO 2008052626 A1 describes the oxidation protection of silver in the manufacture of glass. The molten glass is also guided through the outer side of the glass conducting member and forms a protective layer. A protective gas atmosphere can be additionally applied (page 12, paragraph 1). OBJECT OF THE INVENTION The present invention is directed to significantly reducing the wall thickness observed in the vicinity of a power connection flange when using an assembly made of a pt material at high temperatures. The present invention reduces the vaporization of volatile Pt oxides by partially wrapping a particularly electrically heated tube-like material made of pt material, and particularly near the end of a particularly susceptible pipeline. Regarding the piping of the first aspect, the method of the technical solution 159215.doc 201221491 13 and the use of the technical solution 14. Other and preferred embodiments are described in the dependent items. The boundary layer on the surface of the Pt material can be stabilized mainly by The diffusion of platinum oxide molecules is prevented from diffusing through the layer to reduce vaporization losses. The following alternatives can be used for this purpose: 1 - Apply one or more ferrules on the outside of the pipe to be protected and position it to be substantially concentric with respect to the pipe. Preferably, it is positioned at a distance of Oi mm to 1〇〇111111 from the pipe. One end of the ferrule is fixed to the flange (preferably welded); the other end is open. The width of the ferrule is usually 10 mm to 200 mm. It is connected to the surface of the Pt component made of Pt material. As the distance increases, for example, Ni-based alloy or high-temperature steel is preferably used for cost reasons. A porous coating made of a high temperature resistant ceramic material or a fleece and/or foam made of a vapor or Pt based material on the pipe to be protected to slow the diffusion of Pt oxide molecules. The porous coating or web of the above item 2 and/or the outer surface of the foam "T additionally has an inner liner. 4. The porous coating or web and/or foam as described in item 2 can be used. The gap between the filling assembly and the ferrule (such as item 1) is attached. Although the main function of the alternative described above is to reduce the diffusion of Pt molecules, the rinsing component and the ferrule can be protected by a gas (such as N2, Ar). It is difficult to form Pt oxides first. Similarly, the porous layer can be flushed with a protective gas, for example, by attaching a suitable apertured feed conduit. In another embodiment, the getter 159215.doc 201221491 can be placed in the gap between the assembly and the ferrule in an inert gas purge to reduce the oxygen fraction in the inert gas atmosphere to a greater extent. Suitable getter materials are known to those skilled in the art and are based, for example, on lead and antimony. Advantages p t is greatly affected by the full flow of air near the heating element. The stronger the full flow, the faster the removal of the pt-containing oxide diffusion layer close to the surface. The main advantage of the present invention is that the package causes diffusion barriers to be created, thereby substantially reducing the vaporization rate. The wrapping also makes it possible to guide the protective gas atmosphere through the Pt surface to slow the formation of volatile Pt oxides in critical areas. According to the invention, this makes it extremely high in the manufacture of special glass (for example for flat screens). The service life of the Pt components used at temperatures (about 1,65 0 °C in the south) is extended. [Embodiment] Illustrative Embodiments The present invention is explained in more detail in the following examples without being limited to the embodiments. As used throughout the specification, terms such as "parallel," "vertical," "circular," "concentric," and "cylindrical" are to be understood as guiding terms and including variations that do not alter their function. In addition, the description of the material should include replacement with materials that have the same function. Unless otherwise stated, the reference to the number of parts and percentages refers to the weight. Example 1 - An illustrative embodiment is shown schematically in Figure K. At the top right side, the cross-section of the feed line to the flange 1 is clearly depicted, transitioning into the flange, and then showing a partial cross-sectional view perpendicular to the plane of the ring. A disc-shaped ring made of refractory fiber material 2 separates the flange rim from the refractory lining 3. Hollow 1592l5.doc
S 201221491 間隙4以陶究粉末填充。玻璃傳導管道$由經由焊接連接件 連接至凸緣1之套頭6部分環繞。至少一個間隔件7確保套 頭不電接觸管道5 °較多耐火纖維材料2在套頭未達到之位 置上環繞玻璃傳導管道5。 實例2 圖2展示與實例1之實施例類似，例外為套頭為圍繞管道 轴同〜配置之雙套頭之-實施例。自-般描述及f請專利 範圍顯而易見的是，雙套頭之内部部分可較佳由鉑材料製 成且外部部分可由Ni基合金或高溫鋼製成。 實例3 圖3展示與貫例2之實施例類似，例外為雙套頭由另一套 頭環繞之一實施例。在此情況下該套頭由鎳製成。 實例4 圖4展示與實例丨之實施例類似，例外為氣體進料管線8 經導引穿過中空間隙4之陶瓷粉末之一實施例。 【圖式簡單說明】 圖1展示具有單套頭之一實施例。 圖2展示具有由同心配置之兩個套頭製成之雙套頭之一 貫施例。 圖3展示具有由同心配置之三個套頭製成之三套頭之一 實施例。 圖4展示有保護性氣體進料管線之一實施例。 橫截面圖為示意圖且未必實際按比例繪製。 【主要元件符號說明】 1592l5.doc .9· 201221491 1 凸緣 2 耐火纖維材料 3 财火襯層 4 中空間隙 5 玻璃傳導管道/管道 6 套頭 7 間隔件 8 氣體進料管線 159215.doc -10-S 201221491 Gap 4 is filled with ceramic powder. The glass conducting conduit $ is partially surrounded by a ferrule 6 that is connected to the flange 1 via a welded joint. At least one spacer 7 ensures that the sleeve does not electrically contact the pipe 5 °. The refractory fiber material 2 surrounds the glass conducting conduit 5 at a position not reached by the ferrule. Example 2 Figure 2 shows an embodiment similar to that of Example 1, with the exception that the ferrule is a double ferrule disposed around the axis of the pipe. It is obvious from the general description and the scope of the patent application that the inner portion of the double sleeve can be preferably made of platinum material and the outer portion can be made of Ni-based alloy or high temperature steel. Example 3 Figure 3 shows an example similar to the embodiment of Example 2, with the exception that one of the two sets of heads is surrounded by another set of heads. In this case the sleeve is made of nickel. Example 4 Figure 4 shows an example similar to the example of the example, with the exception of one embodiment of a ceramic powder that is directed through the hollow gap 4 by a gas feed line 8. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows an embodiment with a single set of heads. Figure 2 shows an embodiment of a double head made of two sets of heads arranged in a concentric arrangement. Figure 3 shows an embodiment with three sets of heads made from three sets of concentrically configured heads. Figure 4 shows an embodiment of a protective gas feed line. The cross-sectional views are schematic and are not necessarily drawn to scale. [Main component symbol description] 1592l5.doc .9· 201221491 1 Flange 2 Refractory fiber material 3 Fiery lining 4 Hollow gap 5 Glass conducting pipe/pipe 6 Nesting 7 Spacer 8 Gas feed line 159215.doc -10-