1269783 玖、發明_ (發明說明應敘明：發明所屬之技術領域、先前技術、內容、實施方式及圖式簡單說明） 技術領域 本發明涉及一種浮法玻璃製造設備用之浮動室（float chamber)，其底部外殻中容納多個互相平放之底唇，底唇 之上方形成一種池區以容納流體錫，該池區在池輸入端及 池輸出端之間延伸。 建築-及汽車用之平面玻璃目前依據浮法製程來製成。 特殊之平面玻璃，例如，防火玻璃、薄層光電池用之基 板、生物晶片及顯示器用之薄玻璃，這些玻璃之製造目前 是使用一種浮法製程。 玻璃在熔液盒中熔化且在一種精煉組件中以無泡方式’’ 精煉π。流體玻璃藉由攪拌器在連接於熔液盆之後之通道 中均勻化且藉由明確地調整玻璃溫度而具有該造形所需之 黏度（空調）。 已空調之玻璃熔液經由溢流唇（Spout Lip)而流至浮動池 中之流體錫上。玻璃在浮動池中造形成一種連續之玻璃帶 。此玻璃帶在浮動池輸出端上連續地拉出，在滾筒冷卻爐 中鬆開且在切割部中裁切，流體錫因此不會氧化成氧化錫 ，此種浮法製程以形成氣（5〜1 0 Vo 1 · %之Η 2，9 0〜9 5 Vo 1 · % 之N2)在還原用之大氣中進行。浮動池本身由一種鋼盆所 構成，其舖設該防火用之底唇。各底唇之尺寸通常是300mm X 6 0 0 m m X 1 0 0 0 m m。由於各底唇之比重小於流體錫，則各 底唇以鋼螺栓固定在鋼盆之底部上。 流體錫可侵入各底唇之間之裂縫中且到達底部外殼之鋼 1269783 底。 爲了使流體錫與鋼底不會直接相接觸或底唇之下（under) 水槽不會與流體錫直接相接觸，則底唇之下側須保持在小於 2 3 1 . 9 °C (錫之熔化溫度）之溫度。 通常須測定該鋼容器之外部溫度且藉由冷卻空氣而保持 在小於1 5 0 °C之溫度。底唇上側之溫度在硼形7酸鹽玻璃之 情況下是介於1 2 5 0 °C及6 5 0 °C之間。 相位邊界Snfest-Snfliissig存在於底唇之各裂縫之間。 由於不可能使錫溫度保持定値’則相位邊界Snfest_ Snniissig在底唇之各裂縫內部亦不固定。 先前技術 以下之各專利文件描述各浮動底部之底部結構： 0 S DE 1 8 0 7 7 3 2 S chmelzbbehalter OS DE 1 8 0 7 7 3 1 Wanne fii r die H er s tellung von gegossenen F 1 a c h g 1 a s J P 74010132 Continuous Sheet Glass Production1269783 玖 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 ( ( ( ( ( ( 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术 技术The bottom housing houses a plurality of bottom lips that are placed one above the other, and a pool region is formed above the bottom lip to accommodate fluid tin, the pool region extending between the pool input and the pool output. Plane glass for construction and automotive is currently produced in accordance with a float process. Special flat glass, such as fire-resistant glass, substrates for thin-film photovoltaic cells, bio-wafers, and thin glass for displays, are currently manufactured using a float process. The glass melts in the melt box and refines π in a non-foaming manner in a refining assembly. The fluid glass is homogenized by a stirrer in a passage connected to the melt basin and has a viscosity (air conditioner) required for the shape by specifically adjusting the glass temperature. The air-conditioned glass melt flows through the overflow lip (Spout Lip) onto the fluid tin in the floating cell. The glass is formed into a continuous glass ribbon in the floating pool. The glass ribbon is continuously pulled out at the output end of the floating pool, loosened in the drum cooling furnace and cut in the cutting portion, so that the fluid tin is not oxidized to tin oxide, and the float process is used to form gas (5~) 1 0 Vo 1 · % of Η 2,9 0~9 5 Vo 1 · % of N2) is carried out in the atmosphere for reduction. The floating pool itself consists of a steel basin on which the bottom lip for fire protection is laid. The size of each bottom lip is typically 300 mm X 6 0 0 m X 1 0 0 m m. Since the bottom lip has a smaller specific gravity than the fluid tin, the bottom lip is fixed to the bottom of the steel basin by steel bolts. Fluid tin can penetrate the crack between the bottom lips and reach the bottom of the steel 1269783. In order for the fluid tin to not directly contact the steel sole or the underside of the bottom lip does not directly contact the fluid tin, the underside of the bottom lip must be maintained at less than 2 3 1 . 9 ° C (tin Melting temperature). The external temperature of the steel vessel is usually determined and maintained at a temperature of less than 150 °C by cooling air. The temperature of the upper side of the bottom lip is between 1 250 ° C and 65 ° ° C in the case of boron-shaped 7-sodium phosphate glass. The phase boundary Snfest-Snfliissig exists between the cracks of the bottom lip. Since it is impossible to keep the tin temperature constant, the phase boundary Snfest_ Snniissig is not fixed inside the cracks of the bottom lip. Prior Art The following patent documents describe the bottom structure of each floating bottom: 0 S DE 1 8 0 7 7 3 2 S chmelzbbehalter OS DE 1 8 0 7 7 3 1 Wanne fii r die H er s tellung von gegossenen F 1 achg 1 As JP 74010132 Continuous Sheet Glass Production
Using Molten Metal Bath··· US 500 7 950 Bottom Structure of Float Glass Tank F R 2 6 7 3 1 7 5 Bolcks of Refractory Materials··· 須注意：在硼矽酸鹽-特殊玻璃之情況中，交變之錫溫 度且特別是相位邊界Snfest-Snniissig之偏移會使氣體由錫 中分離而出。 氣體以小氣泡之形式在流體錫中上升而在浮法Ϊ皮璃巾造成 玻璃缺陷。這些玻璃缺陷是開口向下之氣泡且位於玻璃帶 之下側上。這些氣泡通常形成在浮動液輸入端之區域中該 1269783 浮動池之最熱之區域中。 依據浮法過程製造硼矽酸鹽平面玻璃時，錫溫度可達 1 2 5 0 〇C。 發明內容 本發明之目的是提供本文開頭所述之浮動室，其中可使 浮法玻璃中形成向下敞開之浮動液氣泡之危險性大大地下 降。 上述目的以下述方式達成：底唇之至少一部份在其面向 液區之此側上至少以區域方式由鎢或鎢合金所形成之覆層 來覆蓋，且覆層區由液區輸入端在輸送方向中延伸。 利用該覆層可防止：在液區輸入端之臨界（critical)區中 所形成之玻璃氣泡到達液區中。氣泡在覆層下側上被捕獲 。本發明中使用以下之認知：非貴重之金屬鎢在目前之使 用區中在流體錫中不具有明顯之溶解度。鎢材料因此亦不 會在錫液中形成對玻璃品質有影響之污染物。 依據本發明可能之形式，該覆層區至少在液區輸入端及 5公尺之間之部份區域中在玻璃輸送方向中延伸。在該區 域中通常會形成玻璃氣泡。覆層區之延伸可依據浮法玻璃 形式來改變。在多種應用中在第一液灣（B a d - B a y )之區域（ 由液區輸入端直至玻璃之輸送方向中3公尺處爲止之區域） 中覆蓋該底唇即已足夠。 較佳是至少該臨界之液區（其中錫溫度大約1 2 5 (TC )應設 有該覆層。若該覆層配置在液區（其中錫溫度是在1 1 5 (TC 及1 2 5 0 °C之間）中，則可達成特別好之結果。 本發明中該覆層可直接與底唇之上側相接觸。但亦可使 1269783 覆層在承載層之中間層下方覆蓋該底唇。 本發明較佳形式之特徵是：在底唇上設有一或多個金屬 片，其至少在其面向液區之此側上具有一由鎢或鎢合金所 構成之外層，或該金屬片由鎢或鎢合金所構成。金屬片在 0.5 m m及3 m m之間之區域中可較厚。表面積在1 . 5 m 2及 2.5m2之範圍中之各金屬片可良好地構成格式區段。這些 金屬片可有利地在所有側面上設有襯墊。 特別是在底唇之接縫區中由於在流體錫中可發生劇烈之 溫度變動，則本發明之較佳之設計方式是：覆層區內部中 之覆層覆蓋各相鄰之底唇之間所形成之接縫。 若該覆層之鎢材料之最大氧含量 2 Oppm或該覆層之鎢 由燒結材料（其藉由氧化鎢之還原而製成）所形成，則鎢材 料特別適用於目前之應用中。該燒結材料亦可含有H2。 本 發 明 亦 涉及 .以 浮 法製程 來 製 造 玻 璃 所 用 之 方法，其中 依 據 串 請 專 利範 :圍 第 1項至 1 1項來使月 § — -種浮動液容納 盆 〇 這 樣 可 對硼 丨矽 酸 鹽玻璃 造 成 特 別 好 之 品 質 ，其 b203 含 量 5 w t .%中。 玻 璃 成份特 別 由 以 下 之 成 份 所 組成： 5 5 至 6 5 W t · % Si〇2 15 至 2 0 W t · % ai2o3 5 至 1 2 w t · % B 2〇3 0 至 5 w t. % B aO 3 至 9 w t _ ,% CaO 1 至 5 w t, .% Mg〇 0 至 5 w t .% Sr〇 1269783 實施方式 本發明以下將依據圖式中之實施例來描述。 第1圖中顯示平面玻璃製造設備之浮動室，其通常用來 製造由硼矽酸鹽玻璃所構成之玻璃帶1 4。浮動室具有由 鋼片所構成之底部外殼1 〇，其在液區輸入端1 5及液區輸 出端1 6之間形成一種液區。底部外殼1 0中設定許多底唇 1 1。各底唇1 1在形成多個接縫1 1 . 1下緊密地相鄰，如第 3圖所示。第3圖中又可看出：在底唇11上以區段方式 在其上側上設置金屬片1 2，其由鎢材料製成。金屬片1 2 較佳是具有正方形之格式，面積例如是2 m2。在液區邊緣 之區域中金屬片1 2相對較大。各金屬片1 2施加在底唇1 1 上，使其覆蓋各底唇1 1之間之接縫1 1 . 1。金屬片1 2之接 口 1 2 . 1配置在底唇1 1之面向液區之上側區中。 如第1圖所示，金屬片1 2只配置在液區之一部份中， 該部份中錫1 3之溫度主要是介於1 2 5 0 °C及1 1 5 0 °C (臨界溫 度範圍）之間。其餘之液區同樣至少一部份是以金屬片1 2 覆蓋，以便防止所謂鹼性刷所造成之底唇1 1之損耗。 如第1圖所示，臨界溫度區配置在第1及第2灣（Bay) 之區域中。灣1經由長形區在玻璃之輸送方向中大約延伸 3公尺。這種臨界溫度區就錫液中氣泡之形成而言會在浮 動液中形成熱區。錫溫度因此會變動。氣泡形成因此發生 在接縫1 1 . 1之區域中，該處會在Snfest及Snfliissig之間發 生相位邊界之偏移。本實施例中在底唇1 1之上側上設置 金屬片12。但亦可使用多個金屬片12，其互相緊靠。錫 中所形成之氣泡在金屬片1 2之下側上被捕獲而不會到達 -10- 1269783 玻璃區中。 金屬片1 2由耐火金屬鎢所構成。此種材料在錫中溶解 度不大，使液區污染物由於所導入之金屬片1 2而只形成 在特別小之範圍中或根本不會形成。 由於鎢之密度（19.1§/〇^3)較錫者（6.5§/_3)大很多，因 此不必將金屬片1 2固定在液區底部上。 特別適當的是使用一種〇2含量最大是 20ppm之鎢材料。 圖式簡單說明 第1圖 浮動室之圖解及俯視圖。 第2圖係第1圖之垂直切面圖。 第3圖 係第2圖之區域之放大圖。 要部分 之代表 符 號 說 明 10 底 部 外 殻 11 底 唇 11.1 接 縫 12 金 屬 片 13 錫 14 玻 璃 帶 15 液 區 輸 入 端 16 液 區 輸 出 端Using Molten Metal Bath··· US 500 7 950 Bottom Structure of Float Glass Tank FR 2 6 7 3 1 7 5 Bolcks of Refractory Materials··· Note: In the case of borosilicate-special glass, alternating The shift in tin temperature and especially the phase boundary Snfest-Snniissig causes the gas to separate from the tin. The gas rises in the fluid tin in the form of small bubbles and causes glass defects in the float glass towel. These glass defects are bubbles that open downward and are located on the underside of the glass ribbon. These bubbles are typically formed in the hottest zone of the 1269783 floating cell in the region of the input end of the floating fluid. When the borosilicate flat glass is produced according to the float process, the tin temperature can reach 1 250 〇C. SUMMARY OF THE INVENTION It is an object of the present invention to provide a floating chamber as described herein at the outset wherein the risk of forming a downwardly open floating liquid bubble in the float glass is greatly reduced. The above object is achieved in that at least a portion of the bottom lip is covered at least on a side of the liquid-facing region by a coating formed of tungsten or a tungsten alloy in a regional manner, and the coating region is at the liquid region input end. Extending in the conveying direction. The use of the coating prevents the glass bubbles formed in the critical zone at the input end of the liquid zone from reaching the liquid zone. The bubbles are trapped on the underside of the coating. The following recognition is used in the present invention: non-precious metal tungsten does not have significant solubility in fluid tin in the current use zone. Tungsten materials therefore do not form contaminants in the tin bath that have an effect on the quality of the glass. According to a possible form of the invention, the coating zone extends in the direction of glass transport at least in the region of the liquid zone input and between 5 meters. Glass bubbles are usually formed in this area. The extension of the cladding zone can vary depending on the form of the float glass. It is sufficient to cover the bottom lip in the region of the first liquid bay (B a d - B a y ) (the region from the liquid region input end to the point of 3 meters in the direction in which the glass is transported) in various applications. Preferably, at least the critical liquid region (wherein the tin temperature is about 1 25 (TC) should be provided with the coating. If the coating is disposed in the liquid region (wherein the tin temperature is at 1 1 5 (TC and 1 2 5) Particularly good results can be achieved in the case of 0 ° C. In the present invention, the coating can be directly in contact with the upper side of the bottom lip, but the 1269783 coating can also be placed under the intermediate layer of the carrier layer. A preferred embodiment of the invention is characterized in that one or more metal sheets are provided on the bottom lip, at least on the side facing the liquid region, having an outer layer made of tungsten or a tungsten alloy, or the metal sheet is composed of Tungsten or tungsten alloy. The metal sheet can be thicker in the region between 0.5 mm and 3 mm. The metal sheets in the range of 1.5 m 2 and 2.5 m 2 can form well in the format section. The metal sheet may advantageously be provided with a liner on all sides. In particular, in the seam region of the bottom lip, a sharp temperature change in the fluid tin may occur, the preferred design of the invention is: the interior of the cladding region The coating in the middle covers the seam formed between the adjacent bottom lips. If the coating is tungsten The maximum oxygen content of the material is 2 Oppm or the tungsten of the coating is formed from a sintered material which is produced by reduction of tungsten oxide. The tungsten material is particularly suitable for use in current applications. The sintered material may also contain H2. The invention also relates to a method for manufacturing glass by a float process, wherein according to the series of patents: the first to the eleventh item, the § ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ ─ Salt glass gives a particularly good quality with a b203 content of 5 wt.%. The glass composition consists in particular of the following components: 5 5 to 6 5 W t · % Si〇2 15 to 2 0 W t · % ai2o3 5 to 1 2 wt · % B 2〇3 0 to 5 w t. % B aO 3 to 9 wt _ , % CaO 1 to 5 wt, .% Mg〇0 to 5 wt .% Sr〇1269783 Embodiments The present invention will The description is based on the embodiment in the drawings. Fig. 1 shows a floating chamber of a flat glass manufacturing apparatus, which is generally used to manufacture a glass ribbon 1 composed of borosilicate glass. 4. The floating chamber has a bottom casing 1 由 formed of a steel sheet which forms a liquid zone between the liquid zone input end 15 and the liquid zone output end 16. A plurality of bottom lips 11 are provided in the bottom casing 10. Each of the bottom lips 11 is closely adjacent under the formation of a plurality of seams 11.1, as shown in Fig. 3. It can be seen in Fig. 3 that a metal sheet 12 is provided on the bottom lip 11 in a section on its upper side, which is made of a tungsten material. The metal piece 12 is preferably in the form of a square having an area of, for example, 2 m2. The metal sheet 12 is relatively large in the region of the edge of the liquid region. Each of the metal sheets 12 is applied to the bottom lip 1 1 so as to cover the seam 1 1 . 1 between the bottom lips 1 1 . The interface of the metal piece 12 is set in the upper side of the liquid lip of the bottom lip 11. As shown in Fig. 1, the metal piece 12 is only disposed in one of the liquid regions, and the temperature of the tin 13 in the portion is mainly between 1 2 50 ° C and 1 150 ° C (critical Temperature range). The remaining liquid zone is also at least partially covered with a metal sheet 12 in order to prevent the loss of the bottom lip 11 caused by the so-called alkaline brush. As shown in Fig. 1, the critical temperature zone is arranged in the area of the first and second bays. Bay 1 extends approximately 3 meters in the direction of glass transport via the elongated section. This critical temperature zone forms a hot zone in the float liquid in terms of the formation of bubbles in the tin bath. The tin temperature will therefore change. The bubble formation thus occurs in the region of the seam 11.1 where a phase boundary shift occurs between Snfest and Snfliissig. In the present embodiment, the metal piece 12 is provided on the upper side of the bottom lip 11. However, it is also possible to use a plurality of metal sheets 12 which are in close proximity to each other. The bubbles formed in the tin are trapped on the underside of the metal sheet 12 without reaching the -10- 1269783 glass zone. The metal piece 12 is composed of refractory metal tungsten. This material has a low solubility in tin, so that the liquid area contaminants are only formed in a particularly small range or not formed at all due to the introduced metal piece 12 . Since the density of tungsten (19.1§/〇^3) is much larger than that of tin (6.5§/_3), it is not necessary to fix the metal piece 12 on the bottom of the liquid zone. It is particularly appropriate to use a tungsten material having a cerium 2 content of at most 20 ppm. Brief description of the diagram Figure 1 Diagram and top view of the floating chamber. Figure 2 is a vertical cutaway view of Figure 1. Fig. 3 is an enlarged view of the area of Fig. 2. Part of the representative symbol description 10 bottom shell 11 bottom lip 11.1 seam 12 metal sheet 13 tin 14 glass belt 15 liquid area input end 16 liquid area output end