TW201014810A - Method for producing flat glass - Google Patents
Method for producing flat glass Download PDFInfo
- Publication number
- TW201014810A TW201014810A TW098128646A TW98128646A TW201014810A TW 201014810 A TW201014810 A TW 201014810A TW 098128646 A TW098128646 A TW 098128646A TW 98128646 A TW98128646 A TW 98128646A TW 201014810 A TW201014810 A TW 201014810A
- Authority
- TW
- Taiwan
- Prior art keywords
- protective atmosphere
- glass
- floating
- weight
- flat glass
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/20—Composition of the atmosphere above the float bath; Treating or purifying the atmosphere above the float bath
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B18/00—Shaping glass in contact with the surface of a liquid
- C03B18/02—Forming sheets
- C03B18/04—Changing or regulating the dimensions of the molten glass ribbon
- C03B18/08—Changing or regulating the dimensions of the molten glass ribbon using gas
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
Description
201014810 六、發明說明: 【發明所屬之技術領域】 本發明係有關於如申請專利範圍第丨項之平板玻璃之 製法。 【先前技術】 利用浮式法(float process)製得之平板玻璃稱為浮 式玻璃(float glass),此製程技術主要基於pukingt〇n 所發表之專利(US 3, 083, 551,DE 147 1 9 50),並且自上 個世紀起開始發展,目前已為眾所皆知的製法。 在浮式法製程中,係利用一通道將液態玻璃自工作槽 中注入一熔融金屬浴槽中,且該金屬通常使用錫。藉由一 活動式閘門的設置,不僅能夠控制液態破璃的流速,同時 亦可控制玻璃之厚度。 順著液態玻璃流動的方向觀察’上述活動式閘門之後 為一;主入口,液態玻璃係藉由此注入口連續地注入溶融金 屬浴槽中’並於此熔融金屬浴槽中塑形(shape)且固化,以 形成一尺寸固定之玻璃帶(glass ribbon)。隨後,為了自 溶融金屬浴槽中取出此固化之玻璃帶,於此浮動浴槽 (float bath)之後需設置一舉升裝置(Hf1;ing instrument) ° 以此法所製造之平板玻璃’ 一般而言其厚度小於 毫米(mm)’常被當作薄型玻璃基材,特別是用於製造平面 顯示器’例如電漿顯示面板(plasma display panels, 201014810 PDPs)、場發射顯示器(fieid-emission displays, FEDs)、 溥膜電晶趙(thin film transistor, TFT)液晶顯示螢幕、 超扭轉向列(super-twisted nematic, STN)液晶顯示螢 幕、電漿輔助液晶(plasma-assisted liquid-crystal, PALC)顯示器以及電致發光(eiect rolumine scent, EL)顯 示器等等,此外也可用於製造薄膜太陽能電池。 在平面顯示器的製程中,依照顯示器類型的不同,可 φ 能是將一液晶分子灌入兩片玻璃平板之間,也可能是將介 電層施加於後玻璃板(rear sheet)之前側以及前玻璃板 (front sheet)之後側,並利用這些介電層形成可容納螢光 體的格狀空腔(cell)。 為了避免干擾色彩缺陷(perturbing colour deieets) 或相似性偏差(similarity deviations)的發生,特別是對 於大尺寸的平面顯示器而言’準確地維持液晶材料層或介 電層的厚度非常重要。由於材料層的厚度(目前約為3〇微 ® 米)趨向薄型化,而顯示器的尺寸則曰漸大型化,上述條件 的精確控制也就顯得益發重要。 浮式玻璃的表面品質會因表面缺陷而降低,這些表面 缺陷被稱為板面斑污(top speck),主要是因為當使用溶融 錫浴時’含有錫的微粒(例如踢或氧化錫微粒)沉積於玻璃 帶的上表面而形成污潰所致。雖然製程中會以形成氣體 (forming gas)(典型組成為5 - 8%氫氣,其餘為氮氣)沖 洗内部’然而浮動浴槽上方之空氣仍殘留有氧氣,此殘留 的氧氣會進入熔融錫浴槽’並於其中形成氧化錫微粒。隨 201014810 著浴槽溫度的提升,氧化錫或錫會蒸發並接觸到空氣,導 致含有錫的微粒沉積於玻璃帶的上表面而形成污溃。 為避免上述表面缺陷的發生,必須利用各種方法阻止 玻璃帶與其上方受污染的空氣接觸。—方面要使氧氣無法 從外界進入浮動浴槽外罩(float bath h〇using)内部另 方面要使已經存在的氧氣無法進入溶融錫浴槽接觸其表 面。 除了表面缺陷之外’因玻璃帶上方或下方之保護氣氛 所造成的開口氣泡(open bubbles),可能發生於破璃帶底 側。 在塑形之初,玻璃熔融液的黏度很低,形成位於玻璃 下方的底端開口氣泡(open-bottomed bubble)因受到氣 體擠壓而被壓入玻璃之中。在固化步驟中,開口氣泡被保 留且形成玻璃的缺陷。此類氣泡也被稱為底端開口種核 (bottom open seed, B0S)。 目前的無鹼特種玻璃(Alkali-free speeial glass)(例如LCD顯示器用玻璃)也是採用浮式法製造。由 於會在玻璃表面上施以細微的電子結構,因此即使是很小 的表面缺陷也會引起問題。一般而言,底端開口氣泡的直 徑小於50微米,深度小於1 〇微米。可藉由研磨除去這些 開口氣泡。然而,此最後的研磨步驟亦需要大量的花費。 US 20 04/01 1 0625 A1揭露’位於玻璃底側之氣泡是因 從玻璃中逃脫的水分產生交互作用的結果,此水分之所以 無法溶解於熔融錫中’係因在熔融錫中的氫濃度過高所 201014810 致。水在玻璃中的擴散係受到玻璃中場強度(field strengths)的影響。藉由添加二氧化鈦(Ti〇〇、氧化鎮 (erbium oxide)或鈥(neodymium)增加場強度,能夠減少水 的擴散,進而降低缺陷的發生。 US 20 04/0107732 A1揭露一方法,將浮動浴槽的熱區 中氣氛的氳氣濃度調整至低於3%,即可避免us 2004/01 1 0625 A1揭露的氣泡發生。採取此方法可降低在 φ 溶融錫中的氫濃度,因此從玻璃中擴散的氫能夠溶解於熔 融錫中,從而避免氣泡的產生。 相較於此一先前技術,US 3, 337, 322揭露一保護氣氛 (protective gas atmosphere),其中含有超過 5〇%的惰性 風體’其餘部分則為還原性氣體(reducing gas),特別是 氫氣。此專利案揭露保護氣氛之較佳組成為85%氮氣與15% 氫氣;3-10%氫氣,其餘為氮氣;2-8%氫氣,其餘為氮氣; 以及0. 25-⑽氫氣,其餘為氮氣。特別是當保護氣氛中氫 ® 氣含量低時,可在浮動浴槽外罩内部建立不同氫濃度的環 境。 US 5, 364, 435揭露一包括88-95%氮氣與5_12%氫氣之 保護氣氛。 【發明内容】 本發明提供一種平板玻璃之製作方法,包括以下步驟: 將一玻璃置於一熔化槽(melting tank)中以獲得一玻璃熔 融液(glass melt);將該玻璃熔融液倒入一液態金屬浴槽 7 201014810 (liquid metal bath)中並塑造該玻璃熔融液以 〜取I —破璃 帶(glass ribbon),其中該液態金屬浴槽位於一浮動浴槽 外罩(float bath housing)中,且該浮動浴槽外罩具有一 自由内部體積(free internal volume);導入一含氯之保 護氣氛至浮動浴槽外罩之自由内部體積中,隨後將該含氫 之保護氣氛抽離至浮動浴槽外罩外,其中對每立方八 該浮動浴槽外罩之内部體積而言’導入該保護氣氛之流速 為至少0.2標準立方米/分鐘(^1)。 min 【實施方式】 本發明之目的係為了降低板面斑污與底端開口種核 (bottom 〇pen seed,B〇s)的數量與尺寸。 藉由申請專利範圍第i項可達到本發明之目的。 單位” N,’稱為保護氣氛的標準立方米㈣ 。標準立方求係指一立方米氣體在絕對麼力 UI325巴(bar)、渔度"(乾燥環境)與溫度饥(符合 ISO 2533)的條件下,所測得之數量。 /子動浴槽外罩之自由内部體積(free inf al V〇1滕 係指此*動浴槽外罩内部的體積,其可填充保護氣氛,^ :於玻璃帶表面或溶融錫浴槽表面上方與傳統用來固定加 熱器之懸吊頂蓋下方。 由内部體積,導入 )之保護氣氛,並且 對於每立方公尺之浮動浴槽外罩自 流速至少為0.2標準立方米/分鐘 min 201014810 以相同流速(氣體量/單位時間)將保護氣氛抽出 其抽離浮動浴槽外罩,以將保護氣氛快逮的置換。疋 在平均理論置換時間tav,the。小於等於12分鐘(純粹電 滕核擬計真)的時間内,與此浮動浴槽外軍之自由 相當的保護氣氛被置換。 ° 孩 為了計算平均理論置換時間t—(單位為分鐘),將 自由内部體積(單位為立方公尺)除以在操作狀態 • (〇Peratlng state)下所施加的氣氛流速(單位為立方 公尺/分鐘)。 依上慣例,在標準狀態下所測量3到的氣氛流速標記為 L.S,其早位為標準立方米/分鐘一 min 為了計算匕。與吖5的關係’標準狀態下所測量的氣氛 流速Ls必須乘以在浮動浴槽中氣氛的平均絕對溫度 τ〜ν(單位為飢氏溫度κ)’並除以在標準狀態下氣氛的絕 對溫度 Ti.s.(依據 IS〇 2533 規定,n 288 15Κ)。 • 因此可得到下列關係式: "tev, theo201014810 VI. Description of the Invention: [Technical Field to Be Invented by the Invention] The present invention relates to a method for producing flat glass according to the scope of the patent application. [Prior Art] The flat glass produced by the float process is called float glass, and the process technology is mainly based on the patent issued by pukingt〇n (US 3, 083, 551, DE 147 1 9 50), and has been developing since the last century, and is now known as a system of law. In the floating process, a liquid glass is injected into a molten metal bath from a working tank by a passage, and the metal is usually tin. With the setting of a movable gate, not only the flow rate of the liquid glass can be controlled, but also the thickness of the glass can be controlled. Observing the direction of the flow of the liquid glass, 'the above movable gate is one; the main inlet, the liquid glass is continuously injected into the molten metal bath through the injection port' and is shaped and solidified in the molten metal bath To form a fixed-size glass ribbon. Subsequently, in order to take out the solidified glass ribbon from the molten metal bath, a lifting device (Hf1; ing instrument) is required after the floating bath. The flat glass produced by this method is generally thick. Less than millimeters (mm) is often used as a thin glass substrate, especially for the manufacture of flat panel displays such as plasma display panels (201014810 PDPs), field emission displays (Fieds-emission displays, FEDs), 溥Thin film transistor (TFT) liquid crystal display screen, super-twisted nematic (STN) liquid crystal display screen, plasma-assisted liquid-crystal (PALC) display, and electroluminescence (eiect rolumine scent, EL) displays, etc., can also be used to manufacture thin film solar cells. In the process of a flat panel display, depending on the type of display, φ can be used to fill a liquid crystal molecule between two glass plates, or a dielectric layer can be applied to the front side and the front of the rear glass sheet. The back side of the front sheet and the dielectric layers are used to form lattice cells that can accommodate the phosphor. In order to avoid the occurrence of perturbing colour deieets or similarity deviations, it is important to accurately maintain the thickness of the liquid crystal material layer or dielectric layer, especially for large-sized flat panel displays. Since the thickness of the material layer (currently about 3 〇 micro ® meters) tends to be thinner, and the size of the display is gradually larger, the precise control of the above conditions becomes more important. The surface quality of floating glass is reduced by surface defects, which are called top specks, mainly because of the tin-containing particles (such as kick or tin oxide particles) when using a molten tin bath. Deposited on the upper surface of the glass ribbon to form a foul. Although the process will flush the interior with a forming gas (typically 5 - 8% hydrogen, the rest being nitrogen). However, the air above the floating bath still has oxygen, and the residual oxygen will enter the molten tin bath. Tin oxide particles are formed therein. With the increase in bath temperature in 201014810, tin oxide or tin will evaporate and come into contact with air, causing particles containing tin to deposit on the upper surface of the glass ribbon to form a foul. In order to avoid the above surface defects, various methods must be used to prevent the glass ribbon from coming into contact with the contaminated air above it. - In terms of oxygen, it is not possible to enter the inside of the float bath h〇using from the outside, and the existing oxygen cannot enter the molten tin bath to contact its surface. In addition to surface defects, open bubbles caused by a protective atmosphere above or below the glass ribbon may occur on the bottom side of the ribbon. At the beginning of the shaping, the viscosity of the glass melt is very low, and an open-bottomed bubble formed under the glass is pressed into the glass by being squeezed by the gas. In the curing step, the open cells are retained and form defects of the glass. Such bubbles are also known as bottom open seed (BOS). Current Alkali-free speeial glass (for example, glass for LCD displays) is also manufactured by a floating method. Since a fine electronic structure is applied to the surface of the glass, even a small surface defect causes a problem. In general, the open-ended bubble has a diameter of less than 50 microns and a depth of less than 1 〇 microns. These open cells can be removed by grinding. However, this final grinding step also requires a lot of expense. US 20 04/01 1 0625 A1 discloses that the bubbles located on the bottom side of the glass are the result of interactions between the water escaping from the glass. The reason why this moisture cannot be dissolved in the molten tin is due to the concentration of hydrogen in the molten tin. Too high by 201014810. The diffusion of water in the glass is affected by the field strengths of the glass. By adding titanium dioxide (Ti〇〇, erbium oxide or neodymium) to increase the field strength, water diffusion can be reduced, thereby reducing the occurrence of defects. US 20 04/0107732 A1 discloses a method for floating baths The concentration of helium in the atmosphere in the hot zone is adjusted to less than 3% to avoid the occurrence of bubbles disclosed in us 2004/01 1 0625 A1. This method can reduce the concentration of hydrogen in the molten tin of φ and thus diffuse from the glass. Hydrogen can be dissolved in molten tin to avoid the generation of bubbles. In contrast to this prior art, US 3, 337, 322 discloses a protective gas atmosphere containing more than 5% of inert gas body 'the rest Part of it is a reducing gas, especially hydrogen. This patent discloses that the preferred composition of the protective atmosphere is 85% nitrogen and 15% hydrogen; 3-10% hydrogen, the rest is nitrogen; 2-8% hydrogen, The remainder is nitrogen; and 0.25-(10) hydrogen, the remainder being nitrogen. Especially when the hydrogen® gas content in the protective atmosphere is low, an environment of different hydrogen concentrations can be established inside the floating bath enclosure. US 5, 364, 435 discloses a The present invention provides a method for producing flat glass, comprising the steps of: placing a glass in a melting tank to obtain a glass melting. (glass melt); pouring the glass melt into a liquid metal bath 7 201014810 (liquid metal bath) and shaping the glass melt to take a glass ribbon, wherein the liquid metal bath is located a floating bath housing having a free internal volume; introducing a chlorine-containing protective atmosphere into the free internal volume of the floating bath cover, followed by the hydrogen containing The protective atmosphere is evacuated to the outside of the floating bath cover, wherein the flow rate into the protective atmosphere is 'at least 0.2 standard cubic meters per minute (^1) for each cubic volume of the floating bath cover. min [Embodiment] The purpose of the invention is to reduce the number and size of the bottom surface seed and the bottom 种pen seed (B〇s). The i-th term can achieve the purpose of the invention. The unit "N," is called the standard cubic meter of the protective atmosphere (4). The standard cubic system refers to a cubic meter of gas at the absolute force UI325 bar, the degree of fishing " The amount measured under conditions of temperature and hunger (in accordance with ISO 2533). / Free moving inner volume of the bath housing (free inf al V〇1 滕 refers to the volume inside the housing of this * dynamic bath, which can be filled with a protective atmosphere, ^: used on the surface of the glass ribbon or above the surface of the molten tin bath Fix the heater under the suspended top cover. The internal atmosphere, introduce) the protective atmosphere, and for a floating bath cover per cubic meter, the self-flow rate is at least 0.2 standard cubic meters / minute min 201014810 at the same flow rate (gas volume / unit time The protective atmosphere is withdrawn from the floating bath cover to replace the protective atmosphere.疋 In the average theoretical replacement time tav, the. In the time of less than or equal to 12 minutes (purely calculated), the protective atmosphere equivalent to the freedom of the military outside the floating bath was replaced. ° In order to calculate the average theoretical replacement time t—(in minutes), divide the free internal volume (in cubic meters) by the atmospheric flow rate (in cubic meters) applied in the operating state • (〇Peratlng state) /minute). According to the convention, the atmospheric flow rate measured in the standard state is marked as L.S, and the early position is standard cubic meter/minute and one minute in order to calculate enthalpy. Relationship with 吖5 'The atmospheric flow rate Ls measured under standard conditions must be multiplied by the average absolute temperature τ~ν of the atmosphere in the floating bath (in hunger temperature κ)' and divided by the absolute temperature of the atmosphere under standard conditions. Ti.s. (in accordance with IS〇2533, n 288 15Κ). • The following relationship is therefore available: "tev, theo
VV
free,FB i.O. 分i.sTWav 本案已經證實如此快速地置換浴槽中的氣氛有助於降 低板面斑污與底端開口種核0—openseed,卜 min 士對於,立方公尺(m3)之浮動浴槽外罩自由内部體積而 保護氣氛之流速較佳為至少0.23標準立方米/分鐘 JVm3 .),最佳為 更佳為至少0.26標準立方米/分Free, FB iO sub-i.sTWav This case has proved that the rapid replacement of the atmosphere in the bath helps to reduce the surface stain and the bottom opening seed core 0-openseed, 卜min, floating, cubic meter (m3) The bath cover has a free internal volume and the flow rate of the protective atmosphere is preferably at least 0.23 standard cubic meters per minute JVm3.), preferably more preferably at least 0.26 standard cubic meters per minute.
Nm3 min 至少0.28標準立方米/分鐘 9 201014810 在本案中也已證實,以保護氣氛不斷地置換浮動浴槽 外罩自由内部體積至少8〇%的體積,即可達到功效。 隨著保護氣氛之流入口與流出口的設置與操作位置不 同,上述至少80%的浮動浴槽外由 於浮動浴槽外罩内側的一固定區•,也可能是一變 (例如可能在操作的期間中遷移位置)。 為了避免污染物微粒堆積在無效體積(dead v〇lumes) 中,洋動浴槽外罩中保護氣氛體積完全被置換的平均理論 置換時間tavthe。較佳控制在小於等於1.2分鐘($12 min)。此外,較佳為所有自由内部體積皆參與保護氣氛置 換的過程。 所有自由内部體積皆參與保護氣氛置換的過程並不表 示沒有任何内部體積的置換過程較為快速,也不表示沒有 任何内部體積的置換過程較為緩慢。保護氣氛置換的過程 較佳為至少80%的自由内部體積具有相同的置換速度。 在本案中也已證實,對於每立方公尺(m3)之浮動浴槽 外罩自由内部體積而言,當保護氣氛之流速為至少〇 2標 準立方米/分鐘(^),並且以相同流速抽離時,在不同區 域的保護氣氛置換過程具有不同的置換速度應無害於對於 製程。 保護氣氛之導入及/或抽離可以採取連續式實施或脈 衝式實施。 此外’在本案中也已證實,於浮動浴槽外罩前半部分 201014810 :母立方公尺(ffl)之浮動浴槽外罩自由内部體積 而吞,流速為至少〇·2標準立方米/分鐘(^)的保 & min ^ 氛’應有利於製程。 —,護氣t的流速可減要進行調*,例如於浮動浴槽 刖半。P (亦即熱區),可提高導入保護氣氛之流速,例如對 於每立方公尺(m3)之浮動浴槽外罩自由内部體積流速為 標準立方米/分鐘(=_);於其他區域則可降低導入保 護軋巩之流速,例如對於每立方公尺(ffl3)之浮動浴槽外罩 自由内部體積,流速為0.15標準立方米/分鐘(^)。只 min '、文 能確保對於每立方公尺(Π]3)之浮動浴槽外罩自由内部避 積^言,保護氣氛之平均流料至少G.2標準立方米/分鐘 (:)即可。 保護氣氛導入浮動浴槽外罩的過程較佳為在此空間中 皆以均一的速度導入。 一於本案中,將保護氣氛以均一的速度導入並通過整個 子動公槽’較佳為亦以均一的速度將保護氣氛經由浮動浴 槽槽壁上之抽氣設備(亦稱為排氣設備,veirting-out instruments)抽離。 可將浮動浴槽分割成多個浮動浴槽區(n〇at以讣 sections)’此浮動浴槽區也可稱為隔間(bays)。在每一個 浮動浴槽區中,較佳為以相同流速(流量/單位時間)導入並 抽離保護氣氛。 依照本案浮動浴槽之尺寸,為了使保護氣氛的置換時 201014810 間小於等於1. 2分鐘(S 1 · 2 in i η ),必須將流速較佳為高達 1 000標準立方米/小時之保護氣體導入浮動浴槽外罩。相 較於保護氣氛置換時間約等於h5分鐘,藉由控制保護氣 氛置換時間小於等於1.2分鐘1.2 min),將可降低缺陷 與氣泡數量達60%。較佳之保護氣氛置換時間為小於等於j 刀鐘min),最佳為(in particular)小於等於〇· 8分 鐘(SO.8min),且缺陷與氣泡之數量將可隨保護氣氛置換 時間的減少而降低。 依照習知技術,保護氣氛中氩氣的含量介於5-12%之⑩ 間。本案發現當保護氣氛中氫氣的含量增加至超過12%, 將可增強快速置換保護氣氛對製程所造成的正面影響。保 護氣氛中氫氣的含量較佳為大於12%至14%之間(> 12 _ 14/〇。對位於浮動浴槽前半部熱區之浮動浴槽區而言,保 護氣氛中氫氣的含量更佳為大於等於m至14%之間〇 Η 。因此,藉由此方法能夠大幅降低底端開口種核(B0S) 之密度。 如第1圖所示,對於每立方公尺之浮動浴槽外罩自由® 内部體積’導入流速為0.23標準立方米/分鐘(¾之保護 min 氣氛,且保護氣氛中氫氣的含量為5%時,判定其底端開口 核(B0S)數量之平均百分比為約。然而當保護氣氛 中氣氣的含量增加袁1 q # 為13· 5/°時,則底端開口種核(B0S)數量 之平均百分比降低至約30%。 第2圖係將每平方公尺之板面斑污數量百分比對時間 12 201014810 作圖。於起始5週内, 、、母立方公尺之浮動浴槽外罩自 内β體積,導入流速為〇 9標準立方米/分鐘(^)之保護 氣氛之平均理論置換時間“。二鐘; 積,伴雙Ρ料母立心料罩Η内部體 積保護氣氛導入流逮增加至。.28標準立方米/分鐘 :)’且經電腦模擬計算,將保護氣氛之平均理論置換時 Φ ❹ 量百八比2 3() η 1 ^ US圖可確認板面斑污數 罝百刀比明顯降低至少於80% 〇 上述百分比係為在各個指定時 平均值之相對比例。 -時間間隔内板面斑污數量 除氫氣之外,保護氣氛尚包括一 含氮氣、氲氣及/或氦氣。 ’較佳為包 本方法特別適合於製造财酸破璃,例如應用 其Γ包括(成分後方之數字代表該氧 化物之重量百分比):Si02 70 _ 8 …τ …。 85 β2〇3 7 - 13、Na2〇 + ⑷一-8、_ + Ca0 + Sr00、3、Ai2〇32_7。 又如無驗^⑷讀玻璃,其組成包括:sim H、Al2〇3l0-25、Mg〇〇_1〇、Ca"_i2、w 〇-12二〇〇一15,以及如 + _ + _ + _8_ 2 -1°、Zr〇2°-5'Ti〇2°~5、Sn〇2。— 2。 又如製錢不器用玻璃’包括下列組成:siQ2>55_65、 β2〇3 5 — U、Al2。3〉14 — 25、_ 0 〜8、Ca〇 〇 8 SrOO-8>BaO,l〇^^Mg〇 + Ca〇 + Sr〇 + Ba〇8 13 201014810 21、ZnO 〇 - 5、Zr〇2 〇 _ 2、Ti〇2 0 - 3、Sn〇2 0 - 2 ; 其中特別包括下列組成:Si〇2 > 58 — 65、B2〇s > 6 - l〇. 5、 A1z〇3 > 14 - 25、MgO 〇 - < 3、CaO 0 - 9、BaO > 3 - 8、 以及 MgO + CaO + BaO 8 - 18、ZnO 0 - < 2、無 As2〇3、 無Sb::〇3 ’其中較佳為不含氧化鋅(Zn 〇xide)、氧化鈽(ce 0Xlde)、氧化錄(Zr oxide)及氧化鈦(Ti oxide)。 本方法尚特別適合於製造玻璃-陶瓷用之各種生胚玻 璃(green glasses),其組成包括:Si〇2 55 _ 69、19 -25、Li2〇 3 - 5、Na2〇 〇 - 1. 5、K2〇 0 - 1, 5、工 + K2〇0.2-2'Mg00.1-2.2'CaOO-15'SrO〇- BaO 0 - 2. 5、Σ MgO + CaO + SrO + BaO < 6、ZnO 〇 一Nm3 min at least 0.28 standard cubic meters per minute 9 201014810 It has also been demonstrated in this case that the protective atmosphere is continuously replaced by a volume of at least 8〇% of the free internal volume of the floating bath cover. Depending on the setting and operating position of the inlet and outlet of the protective atmosphere, at least 80% of the floating bath outside may be a change due to a fixed area inside the floating bath cover (for example, may migrate during operation) position). In order to avoid the accumulation of contaminant particles in the dead v〇lumes, the average theoretical replacement time tavthe of the protective atmosphere volume in the outer casing of the oceanic moving bath is completely replaced. It is preferably controlled to be 1.2 minutes or less ($12 min). Furthermore, it is preferred that all free internal volumes participate in the process of protecting the atmosphere. The fact that all free internal volumes participate in the protective atmosphere replacement process does not indicate that the replacement process without any internal volume is relatively fast, nor does it mean that the replacement process without any internal volume is slow. The process of protective atmosphere replacement preferably has at least 80% of the free internal volume having the same displacement velocity. It has also been demonstrated in this case that for a free internal volume of a floating bath enclosure per cubic meter (m3), when the flow rate of the protective atmosphere is at least 标准2 standard cubic meters per minute (^) and is withdrawn at the same flow rate The protective atmosphere replacement process in different regions with different replacement speeds should be harmless for the process. The introduction and/or extraction of the protective atmosphere can be carried out in a continuous or pulsed manner. In addition, 'in this case, it has also been confirmed that in the first half of the floating bath cover 201014810: the floating cubicle cover of the female cubic meter (ffl) is free from the internal volume and the flow rate is at least 〇 2 standard cubic meters / minute (^) & min ^ atmosphere ' should be beneficial to the process. — The flow rate of the protective gas t can be reduced by, for example, half of the floating bath. P (ie hot zone) increases the flow rate into the protective atmosphere, for example, the free internal volume flow rate per cubic meter (m3) of the floating bath cover is standard cubic meters per minute (=_); in other areas it can be reduced The flow rate of the protective rolling mill is introduced, for example, for a free internal volume of the floating bath cover per cubic meter (ffl3), the flow rate is 0.15 standard cubic meters per minute (^). Only min ', text can ensure that the floating bath cover per cubic meter (Π) 3) free internal avoidance, the average flow of the protective atmosphere is at least G.2 standard cubic meters / minute (:). The process of introducing the protective atmosphere into the floating bath cover is preferably introduced at a uniform speed in this space. In the present case, the protective atmosphere is introduced at a uniform speed and through the entire sub-moving slot' preferably, at a uniform speed, the protective atmosphere is passed through the suction device on the floating bath wall (also known as the exhaust device, Veirting-out instruments). The floating bath can be divided into a plurality of floating bath zones (n〇at 讣 sections). This floating bath zone can also be referred to as bays. In each of the floating bath zones, it is preferred to introduce and evacuate the protective atmosphere at the same flow rate (flow rate/unit time). According to the size of the floating bath in this case, in order to make the protection atmosphere replacement time between 201014810 less than or equal to 1.2 minutes (S 1 · 2 in i η ), it is necessary to introduce a shielding gas with a flow rate of preferably up to 1 000 standard cubic meters per hour. Floating bath cover. Compared with the protective atmosphere replacement time of about h5 minutes, by controlling the protective gas replacement time of 1.2 minutes or less and 1.2 minutes, the number of defects and bubbles can be reduced by 60%. Preferably, the protective atmosphere replacement time is less than or equal to j knives min), and the optimum is less than or equal to 〇·8 minutes (SO. 8 min), and the number of defects and bubbles will be reduced with the protective atmosphere replacement time. reduce. According to the prior art, the content of argon in the protective atmosphere is between 10 and 12%. The case found that when the hydrogen content in the protective atmosphere is increased to more than 12%, it will enhance the positive impact of the rapid replacement of the protective atmosphere on the process. The content of hydrogen in the protective atmosphere is preferably greater than 12% to 14% (> 12 _ 14/〇. For the floating bath zone located in the hot zone of the first half of the floating bath, the content of hydrogen in the protective atmosphere is preferably Between m and 14% 〇Η. Therefore, the density of the bottom open seed core (B0S) can be greatly reduced by this method. As shown in Fig. 1, for the floating bath cover per m ^ 3 free ® When the volumetric introduction flow rate is 0.23 standard cubic meters per minute (3⁄4 of the protective min atmosphere, and the content of hydrogen in the protective atmosphere is 5%, the average percentage of the number of bottom open cores (B0S) is determined to be about. However, when the atmosphere is protected When the content of medium gas increases by Yuan 1 q # is 13·5/°, the average percentage of the number of open end seed nucleus (B0S) is reduced to about 30%. Fig. 2 shows the plate surface area per square meter. Percentage of contamination is plotted against time 12 201014810. During the first 5 weeks, the floating bath cover of the parent cube is measured from the internal beta volume, and the average flow rate of the protective atmosphere is 〇9 standard cubic meters per minute (^). Theoretical replacement time ". two clocks; product, with double eyes The internal core material Η Η 体积 体积 Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η The η 1 ^ US map can confirm that the board surface stain number is significantly reduced by at least 80%. The above percentage is the relative ratio of the average values at each specified time. - The number of board surface stains in addition to hydrogen in the time interval The protective atmosphere also includes a nitrogen, helium and/or xenon. 'It is preferred that the method of the present invention is particularly suitable for the production of acid and acid, such as the application of the crucible (the number behind the component represents the weight percentage of the oxide) ): Si02 70 _ 8 ... τ .... 85 β2 〇 3 7 - 13, Na2 〇 + (4) -8, _ + Ca0 + Sr00, 3, Ai2 〇 32_7. Another example is no inspection ^ (4) reading glass, its composition includes :sim H, Al2〇3l0-25, Mg〇〇_1〇, Ca"_i2, w 〇-12二〇〇一15, and such as + _ + _ + _8_ 2 -1°, Zr〇2°-5 'Ti〇2°~5, Sn〇2.-2. Another example is the use of glass for making money' including the following composition: siQ2>55_65, β2〇3 5 — U, Al2. 3>14 — 25, _ 0 -8, Ca 〇〇 8 SrOO-8 gt; BaO, l 〇 ^ ^ Mg 〇 + Ca 〇 + Sr 〇 + Ba 〇 8 13 201014810 21, ZnO 〇 - 5, Zr 〇 2 〇 _ 2, Ti 〇2 0 - 3, Sn 〇 2 0 - 2 ; particularly including the following composition: Si〇2 > 58 — 65, B2〇s > 6 - l〇. 5, A1z〇3 > 14 - 25, MgO 〇- < 3, CaO 0 - 9, BaO > 3 - 8, and MgO + CaO + BaO 8 - 18, ZnO 0 - < 2, no As2〇3, no Sb::〇3 ' It is free of zinc oxide (Zn 〇xide), cerium oxide (ce 0Xlde), Zr oxide, and titanium oxide (Ti oxide). The method is particularly suitable for the manufacture of various green glasses for glass-ceramic, and the composition thereof includes: Si〇2 55 _ 69, 19 -25, Li 2 〇 3 - 5, Na 2 〇〇 - 1.5. K2〇0 - 1, 5, work + K2〇0.2-2'Mg00.1-2.2'CaOO-15'SrO〇- BaO 0 - 2. 5, Σ MgO + CaO + SrO + BaO < 6, ZnO 〇 One
Na2〇 1.5、 1.5、Na2〇 1.5, 1.5,
Ti〇2 成:Ti〇2 into:
TiCh 1 - 5、Zr〇2 卜 2. 5、Sn〇2 0-< 1、ΣTiCh 1 - 5, Zr〇2 Bu 2. 5, Sn〇2 0-< 1, Σ
Sn〇2 2· 5 - 5、P2〇5 〇 - 3 ;或是具有下列組Sn〇2 2· 5 - 5, P2〇5 〇 - 3 ; or have the following groups
Si〇2 55 -69 A 1 2〇3 19 -25 Li2〇 3. 2 -5 Na2〇 0 _ -1.5 K2〇 0 - 1.5 MgO 0 - 2. 2 CaO 0 - 2. 0 SrO 0 - 2. 0 BaO 0 - 2. 5 ZnO 0 - < 1. Ti〇2 0 - 3 14 201014810Si〇2 55 -69 A 1 2〇3 19 -25 Li2〇3. 2 -5 Na2〇0 _ -1.5 K2〇0 - 1.5 MgO 0 - 2. 2 CaO 0 - 2. 0 SrO 0 - 2. 0 BaO 0 - 2. 5 ZnO 0 - < 1. Ti〇2 0 - 3 14 201014810
Zr〇2 1Zr〇2 1
Sn〇2 0. 1 - < i Σ Ti〇2 + Zr〇2 + Sn〇22. 5-5 P2O5 O-3 F 0-1 B2O3 0-2Sn〇2 0. 1 - < i Σ Ti〇2 + Zr〇2 + Sn〇22. 5-5 P2O5 O-3 F 0-1 B2O3 0-2
Nd2〇3 0. 01 - 〇. 6Nd2〇3 0. 01 - 〇. 6
或是一玻璃-陶瓷之前驅物玻璃,其組成包括:Si 〇2 55 -75、AI2O3 15 - 30、LhO 2. 5 - 6、Σ Na2〇 + K2O <6、 Σ MgO + CaO + SrO + BaO < 6 ' B2O3 0 - < 4 ' Σ Ti〇2 + Zr〇2 <2。又或是一玻璃-陶瓷之前驅物玻璃,其組成包括:Or a glass-ceramic precursor glass comprising: Si 〇 2 55 -75, AI2O3 15 - 30, LhO 2. 5 - 6, Σ Na2 〇 + K2O < 6, Σ MgO + CaO + SrO + BaO < 6 ' B2O3 0 - < 4 ' Σ Ti〇2 + Zr〇2 <2. Or a glass-ceramic precursor glass, the composition of which includes:
Si〇2 60 - 72、Al2〇3 18 - 28、U2O 3 一 6、Σ Na2〇 + K2O 0.2-2、 Σ MgO + CaO + SrO + BaO < 6 ' ZnO 0 - 1· 5、 B2〇3 0 -< 4、SnO 0. 1 - 1· 5、x Ti〇2 + Zr〇2 < 2、P2〇5 〇_3'F〇-2° 適合利用本發明所提供方法製造之其他較佳破璃包 括:為銘梦酸玻璃,其具有至少55重量%SiCh,較佳為至 少60重量%,且最佳為64重量%。其中Si(h之上限為7〇 重量%,較佳為低於68重量%,最佳為至多67重量%。 ㈣酸玻璃尚包…她上…,較佳為至;。。5 重量%,且最佳之最小含量4 0」。此㈣酸玻璃之 Βζ〇3最大含量為2重量%,且較佳為15重量%。 重量%以上之Α!2〇3,較 20重量% ;而αι2〇3最大 此鋁矽酸玻璃尚包括至少18 佳至少19重量%,且最佳為至少 15 201014810 含量為25重量%,較佳為24. 5重量%,且最佳為24重量 此鋁矽酸玻璃尚包括3 重量%到至多5重量%之 Li2〇,Li2〇最小含量為3.25重量%,且較佳為3.5重量°/〇; 而Li 2〇最大含量為至多5重量%,較佳為至多4. 8重量%, 至多之上限為4. 75重量%,且最佳為至多4. 6重量%。此 鋁石夕酸玻璃尚包括0重量%到至多3重量%之Na2〇及K2O, 其中Na2〇含量上限為至多1.5重量%,較佳為至多1重量 % ;而K2O最大含量為1.5重量%,較佳為1重量%。在此 IS石夕酸玻璃中,驗金屬氧化物Na2〇及K2O之總含量為0重 量%到至多3重量%,最小總含量為0.25重量%,較佳為 0. 5重量%;而最大總含量為3重量%,較佳為2. 75重量 %,且最佳為至多2. 5重量%。 此鋁矽酸玻璃尚包括CaO與SrO,其中CaO與SrO之 含量彼此獨立,分別為0重量%到至多2重量%。在此鋁 矽酸玻璃中,CaO與SrO之較佳最小含量分別為0. 1重量 % ;而CaO與SrO較佳之最大含量分別為2重量%,最佳為 1. 5重量%。此鋁矽酸玻璃尚包括0重量%到至多3重量% 之Ti〇2與1重量%到至多2.5重量%之21*〇2。其中Ti〇2之 最小含量為0.5重量%,較佳為0.8重量%;Ti〇2之最大含 量為2. 75重量%,最佳為2. 5重量%。而Zr〇2之最小含量 較佳為1.5重量%; Zr〇2之最大含量為2.25重量%,最佳 為2重量%。此鋁矽酸玻璃尚包括0. 1重量%到至多1重 量%之Sn〇2,其中Sn〇2之最小含量為0. 15重量%,較佳為 16 201014810 0.18重量%; SnOz之最大含量為〇· 9重量%’最佳為0.8重 量%。在此銘梦酸玻璃中’氧化物Ti〇2、Zr〇2及Sn〇2之總 含量為至少2. 5重量%到至多5重量% ’最小總含量為3 重量%,最佳為3.25重量%;而最大總含量為4.9重量%, 最佳為至多4. 8重量%。 此銘梦酸玻璃尚包括MgO及/或BaO,MgO與BaO之含 量彼此獨立並可視需要調整,其中MgO含量為0重量%到 2.2重量%,而BaO含量為0重量%到2. 5重量%。在此鋁 矽酸玻璃中,MgO與BaO之最小含量分別為〇. 〇5重量%, 較佳最小含量分別為0· 1重量% ;而MgO與BaO之較佳最 大含量分別為2重量%。此鋁矽酸玻璃尚包括ZnO及/或 P2〇s,ZnO及/或P2〇s之含量彼此獨立並可視需要調整,其 中ZnO含量為0重量%到小於5重量%,而p2〇5含量為〇 重量%到3重量其中ZnO之最小含量較佳為〇 〇5重量 %,最佳為0.1重量%; ZnO之最大含量較佳為【重量%, • 最佳為〇. 75重量%。而P❿之最小含量較佳為0.5重量 %,最佳為1重量% ; P2〇5之最大含量為2·5重量%,最佳 為2重量%。此鋁矽酸玻璃尚包括〇〇1重量%到〇6重量 %之Nd2〇3, Nd2〇3最小含量較佳為〇〇5重量%,最佳為 重量% ;而NchCh最大含量較佳* 〇 ςς去旦η/ π 双住马ϋ.55重量%,最佳為0.5 重量%。 露如上,然其並非 具有通常知識者, 作任意之更動與潤 雖然本發明已以數個較佳實施例揭 用以限定本發明,任何所屬技術領域中 在不脫離本發明之精神和範圍内,當可 17 201014810 飾’因此本發明之保護範㈣視後m★專利範圍所界 定者為準。 【圖式簡單說明】 第】圓為一底端開口種核(B0S)數量之平均百分比輿 時間之關係圖’用以說明本發明可達成之功效。 第2圏為一板面斑污數量百分比與時間之 以說明本發明可達成之功效。 ^Si〇2 60 - 72, Al2〇3 18 - 28, U2O 3 - 6, Σ Na2〇 + K2O 0.2-2, Σ MgO + CaO + SrO + BaO < 6 ' ZnO 0 - 1· 5, B2〇3 0 -< 4, SnO 0. 1 - 1· 5, x Ti〇2 + Zr〇2 < 2, P2〇5 〇_3'F〇-2° Other suitable for manufacturing by the method provided by the present invention The glaze comprises: glazing glass having at least 55 wt% SiCh, preferably at least 60 wt%, and most preferably 64 wt%. Wherein Si (the upper limit of h is 7〇% by weight, preferably less than 68% by weight, most preferably at most 67% by weight. (4) The acid glass is still packaged...she is ..., preferably up to 5 wt%, And the minimum content of 40%. The maximum content of Βζ〇3 of the (4) acid glass is 2% by weight, and preferably 15% by weight. 重量% by weight or more; 2〇3, more than 20% by weight; and αι2 〇3 max. The aluminosilicate glass further comprises at least 18% at least 19% by weight, and most preferably at least 15 201014810 content is 25% by weight, preferably 24.5% by weight, and most preferably 24% by weight of the aluminophthalic acid The glass further comprises from 3 wt% to up to 5% by weight of Li2〇, the minimum content of Li2〇 is 3.25 wt%, and preferably 3.5 wt/〇; and the maximum content of Li 2〇 is up to 5% by weight, preferably at most重量重量。 The upper limit is at most 4.75% by weight, and most preferably at most 4.6% by weight. The aluminite glass further comprises 0% by weight to up to 3% by weight of Na2 〇 and K2O, wherein The upper limit of the Na2 content is at most 1.5% by weight, preferably at most 1% by weight; and the maximum content of K2O is 1.5% by weight, preferably 1% by weight. The total content of the metal oxides, the total content of the metal oxides, from 0% by weight to at most 3% by weight, the minimum total content is 0.25% by weight, preferably 0.5% by weight, and the maximum total content. The content of 5% by weight, preferably 2.75% by weight, and most preferably at most 2.5% by weight. The aluminosilicate glass further comprises CaO and SrO, wherein the contents of CaO and SrO are independent of each other, respectively 0% by weight. 5%。 The maximum content of CaO and SrO is preferably 2% by weight, preferably 1.5%, respectively. % by weight. The aluminosilicate glass further comprises from 0% by weight to up to 3% by weight of Ti〇2 and from 1% by weight to at most 2.5% by weight of 21*〇2, wherein the minimum content of Ti〇2 is 0.5% by weight. Preferably, the content of Ti〇2 is 2.75% by weight, most preferably 2.5% by weight, and the minimum content of Zr〇2 is preferably 1.5% by weight; the maximum content of Zr〇2 is 2.25. % by weight, preferably 2% by weight. The aluminosilicate glass further comprises from 0.1% by weight to at most 1% by weight of Sn 〇 2, wherein the minimum content of Sn 〇 2 0. 15% by weight, preferably 16 201014810 0.18% by weight; The maximum content of SnOz is 〇·9% by weight 'optimally 0.8% by weight. In this name acid glass, 'oxide Ti〇2, Zr〇2 And the total content of Sn 〇 2 is at least 2. 5 wt% to at most 5% by weight 'minimum total content is 3% by weight, most preferably 3.25 wt%; and the maximum total content is 4.9 wt%, most preferably at most 4. 8 wt%. 5重量%。 The content of the BaO content is 0% by weight to 2.5% by weight, and the content of BaO is 0% by weight to 2.5% by weight. . In the aluminosilicate glass, the minimum content of MgO and BaO is 〇. 〇 5% by weight, preferably the minimum content is 0.1% by weight, respectively, and the preferred maximum content of MgO and BaO is 2% by weight, respectively. The aluminosilicate glass further comprises ZnO and/or P2〇s, and the contents of ZnO and/or P2〇s are independent of each other and can be adjusted as needed, wherein the ZnO content is from 0% by weight to less than 5% by weight, and the p2〇5 content is 〇% by weight to 3 parts by weight, wherein the minimum content of ZnO is preferably 〇〇5% by weight, most preferably 0.1% by weight; the maximum content of ZnO is preferably [% by weight, • optimally 〇.75% by weight. The minimum content of P❿ is preferably 0.5% by weight, most preferably 1% by weight; the maximum content of P2〇5 is 2.5% by weight, most preferably 2% by weight. The aluminosilicate glass further comprises d1% by weight to 〇6% by weight of Nd2〇3, and the minimum content of Nd2〇3 is preferably 〇〇5% by weight, most preferably % by weight; and the maximum content of NchCh is better* 〇 Σς 旦 η / π double live horse ϋ. 55% by weight, preferably 0.5% by weight. The present invention has been described as a preferred embodiment, and the present invention has been described in terms of several preferred embodiments, which are intended to be within the scope and spirit of the invention. , when can be 17 201014810 decorated 'so the protection of the invention (four) is defined by the scope of the patent after the m ★ patent. [Simple description of the figure] The first circle is the average percentage of the number of bottom open seed nucleus (B0S) 舆 time relationship diagram ' to illustrate the achievable effect of the present invention. The second step is the percentage and time of a board surface stain to illustrate the achievable effect of the present invention. ^
【主要元件符號說明】 無[Main component symbol description] None
1818
Claims (1)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102008041662 | 2008-08-28 | ||
DE102009000348A DE102009000348B4 (en) | 2008-08-28 | 2009-01-21 | Process for the production of flat glass |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201014810A true TW201014810A (en) | 2010-04-16 |
TWI422541B TWI422541B (en) | 2014-01-11 |
Family
ID=41606257
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW098128646A TWI422541B (en) | 2008-08-28 | 2009-08-26 | Method for producing flat glass |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP5254159B2 (en) |
KR (1) | KR101263543B1 (en) |
DE (1) | DE102009000348B4 (en) |
TW (1) | TWI422541B (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI498292B (en) * | 2011-07-01 | 2015-09-01 | Asahi Glass Co Ltd | Chemical reinforcement with floating glass |
CN114014539A (en) * | 2017-04-26 | 2022-02-08 | Agc株式会社 | Chemically strengthened glass |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6144622B2 (en) * | 2011-03-23 | 2017-06-07 | 旭硝子株式会社 | Float glass |
JP5327279B2 (en) * | 2011-06-13 | 2013-10-30 | 株式会社デンソー | Ultrasonic sensor device |
FR2978758B1 (en) * | 2011-08-02 | 2013-08-02 | Saint Gobain | GLASS FLOATING SPEAKER |
JP6003978B2 (en) * | 2012-03-14 | 2016-10-05 | 旭硝子株式会社 | Float glass plate and manufacturing method thereof |
JP2015171957A (en) | 2012-07-17 | 2015-10-01 | 旭硝子株式会社 | Production method of glass sheet, and glass sheet |
JP6128418B2 (en) * | 2013-01-10 | 2017-05-17 | 日本電気硝子株式会社 | Glass plate for thin film solar cell |
CN106458707B (en) | 2014-05-21 | 2019-12-06 | Agc株式会社 | Alkali-free float plate glass and method for producing alkali-free float plate glass |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL128086C (en) * | 1957-05-03 | 1900-01-01 | ||
US3337322A (en) | 1962-10-17 | 1967-08-22 | Pilkington Brothers Ltd | Method of manufacture of flat glass with reducing atmosphere |
BE639778A (en) * | 1962-11-09 | |||
US3337332A (en) * | 1964-07-23 | 1967-08-22 | Dow Chemical Co | Aluminum alloys and galvanic anodes made therefrom |
US5364435A (en) * | 1992-11-20 | 1994-11-15 | Libbey-Owens-Ford Co. | Method of introducing protective atmosphere gases into a glass forming chamber |
US6094942A (en) * | 1997-06-13 | 2000-08-01 | Ppg Industries Ohio, Inc. | Method and apparatus for reducing tin defects in float glass |
US7087307B2 (en) * | 2001-12-28 | 2006-08-08 | Nippon Sheet Glass Company, Limited | Glass sheet and glass sheet photoelectric converter device |
WO2004028990A1 (en) * | 2002-09-27 | 2004-04-08 | Ppg Industries Ohio, Inc. | Method for making float glass having reduced defect density |
JP5032744B2 (en) * | 2002-09-27 | 2012-09-26 | ピーピージー インダストリーズ オハイオ,インコーポレイテッド | Apparatus and method for producing float glass with reduced defect density |
JP4276021B2 (en) * | 2003-08-04 | 2009-06-10 | セントラル硝子株式会社 | Float glass plate for display substrate and manufacturing method thereof |
FR2866328B1 (en) * | 2004-02-16 | 2006-05-26 | Saint Gobain | LEAD FLAT GLASS BY FLOATING ON A METAL BATH |
JP5088603B2 (en) * | 2006-12-12 | 2012-12-05 | 日本電気硝子株式会社 | Manufacturing method of glass substrate |
CN102112404B (en) * | 2008-07-28 | 2013-08-21 | 旭硝子株式会社 | Apparatus and process for producing float glass |
-
2009
- 2009-01-21 DE DE102009000348A patent/DE102009000348B4/en not_active Expired - Fee Related
- 2009-08-26 TW TW098128646A patent/TWI422541B/en not_active IP Right Cessation
- 2009-08-28 KR KR1020090080511A patent/KR101263543B1/en not_active IP Right Cessation
- 2009-08-28 JP JP2009198667A patent/JP5254159B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI498292B (en) * | 2011-07-01 | 2015-09-01 | Asahi Glass Co Ltd | Chemical reinforcement with floating glass |
CN114014539A (en) * | 2017-04-26 | 2022-02-08 | Agc株式会社 | Chemically strengthened glass |
Also Published As
Publication number | Publication date |
---|---|
DE102009000348B4 (en) | 2011-09-01 |
KR20100027054A (en) | 2010-03-10 |
TWI422541B (en) | 2014-01-11 |
JP5254159B2 (en) | 2013-08-07 |
DE102009000348A1 (en) | 2010-03-04 |
KR101263543B1 (en) | 2013-05-13 |
JP2010053032A (en) | 2010-03-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TW201014810A (en) | Method for producing flat glass | |
US7582581B2 (en) | Alkali-free glass | |
EP2081875B1 (en) | Method for making alkali-free glass containing iron and tin as fining agents | |
US9932262B2 (en) | Dimensionally-stable, damage-resistant, glass sheets | |
TW201136847A (en) | Glass plate manufacturing method and glass plate manufacturing apparatus | |
JP7421171B2 (en) | glass | |
JP5070828B2 (en) | Alkali-free glass and method for producing the same | |
KR100750990B1 (en) | High Strain-point Glass composition for substrate | |
WO2008056527A1 (en) | Glass substrate for flat panel display, process for producing the same, and display panel employing the same | |
CN107935378A (en) | A kind of high strength glass for display device and preparation method thereof | |
JPWO2012137780A1 (en) | Non-alkali glass for substrate and method for producing non-alkali glass for substrate | |
JP5704500B2 (en) | Manufacturing method of glass plate | |
WO2014002932A1 (en) | Glass substrate for organic el device and manufacturing method therefor | |
JP5231358B2 (en) | Sheet glass manufacturing method, float bath apparatus, sheet glass and use of sheet glass | |
JP7410462B2 (en) | Li2O-Al2O3-SiO2 system crystallized glass | |
US20140356628A1 (en) | Glass ceramics having low rhodium levels | |
CN103420610A (en) | Glass substrate, glass plate and preparation method thereof | |
JP4370704B2 (en) | Glass coloring method | |
KR102080003B1 (en) | Method for producing glass plate, and glass plate | |
CN117602823A (en) | Composition for alkali-free aluminoborosilicate glass, and preparation method and application thereof | |
EP3932881A1 (en) | Glass composition, glass plate and method for producing same, and substrate for information recording medium | |
JP2001213663A (en) | Bricks for metal bath and its manufacturing method, and metal bath | |
WO2006064845A1 (en) | Process for producing glass |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |