TW201943674A

TW201943674A - Purified aluminosilicate refractory compositions

Info

Publication number: TW201943674A
Application number: TW108111950A
Authority: TW
Inventors: 丹娜克瑞格布可白德; 理察麥可費牙哥; 珍妮佛雷妮馬德斯利; 保羅美納德史雀瑪弘; 那森麥克辛克
Original assignee: 美商康寧公司
Priority date: 2018-04-06
Filing date: 2019-04-03
Publication date: 2019-11-16
Also published as: WO2019195635A1

Abstract

Disclosed herein are refractory materials comprising a reduced alkali metal content and a reduced creep rate, as well as ceramic bodies comprising such materials. Refractory bricks and tiles for constructing glass manufacturing vessels are also disclosed.

Description

純化的鋁矽酸鹽耐火成分Purified aluminosilicate refractory

本申請案根據專利法主張2018年4月6日申請的美國臨時申請案序列號第62/653866號之優先權權益，該申請案之內容為本案之基礎且以全文引用方式併入本文中。This application claims the priority right of US Provisional Application Serial No. 62/653866 filed on April 6, 2018 according to the Patent Law. The content of this application is the basis of this application and is incorporated herein by reference in its entirety.

本揭示內容大體上係關於耐火材料及用於製造耐火材料之方法，且更特定而言係關於純化的鋁矽酸鹽耐火材料。This disclosure relates generally to refractory materials and methods for making refractory materials, and more specifically to purified aluminosilicate refractory materials.

用於玻璃製造製程的諸如熔爐、熔化器、及精煉爐的容器可由耐火材料建構或可包含諸如窯頂、超結構、磚、或覆蓋瓷磚的耐火材料部件。此等容器之生命週期可取決於建構其的耐火材料之耐久性。例如容器壁可歸因於與熔融玻璃分批材料之接觸而逐漸磨損。容器之窯頂亦可歸因於材料潛變而隨時間下垂，此典型地係藉由將窯頂置於壓縮中以產生拱頂來抵消。用於建構用於玻璃製造之容器的耐火材料應因此展現高的耐腐蝕性及/或高機械強度以在經歷苛刻溫度及與處理熔融材料相關聯的其他條件後留存。Containers such as furnaces, melters, and refining furnaces used in glass manufacturing processes may be constructed from refractory materials or may contain refractory components such as kiln roofs, superstructures, bricks, or ceramic tiles. The life cycle of these containers may depend on the durability of the refractory materials from which they are constructed. For example, the container wall can gradually wear down due to contact with molten glass batch material. The kiln top of the container can also sag over time due to material creep, which is typically offset by placing the kiln top in compression to create a vault. Refractory materials used to construct containers for glass manufacturing should therefore exhibit high corrosion resistance and / or high mechanical strength to survive after harsh temperatures and other conditions associated with handling molten materials.

在玻璃製造製程期間耐火材料之磨損不僅在產生可折衷儀器之操作安全性的滲漏路徑方面帶來安全風險，而且會污染分批材料。例如，若一塊耐火材料脫落至熔融體中，可在最終產物中導致不可接受的雜質或夾雜物缺陷。替代地，若耐火材料不合需要地與熔融玻璃反應，則氣泡、夾雜物、或其他缺陷可形成在所得玻璃產品中，從而使其不適於使用。因此利用可耐受處理苛刻性達延長時期的耐火材料可為重要的。改良耐火材料之潛變性質亦可允許容器設計改變及/或提供較寬的操作窗。The abrasion of refractory materials during the glass manufacturing process not only poses a safety risk in creating a leaky path that compromises the operational safety of the instrument, but also contaminates batch materials. For example, if a piece of refractory material falls into the melt, it can cause unacceptable impurities or inclusion defects in the final product. Alternatively, if the refractory material reacts undesirably with the molten glass, bubbles, inclusions, or other defects may form in the resulting glass product, making it unsuitable for use. It may therefore be important to utilize refractory materials that can withstand harshness for extended periods of time. Improving the creep properties of refractory materials may also allow container design changes and / or provide wider operating windows.

因此，提供可耐受高溫及/或腐蝕條件達延長時期而不折衷安全性及/或產品品質的耐火材料將為有利的。提供用於製造玻璃處理容器及其部件的具有減小的潛變速率的耐火材料將亦為有利的，該等耐火材料具有適於建構大型儀器並隨時間推移下垂減少的尺寸。Therefore, it would be advantageous to provide refractory materials that can withstand high temperature and / or corrosion conditions for extended periods without compromising safety and / or product quality. It would also be advantageous to provide refractory materials with reduced creep rates for use in the manufacture of glass processing vessels and components thereof, such refractory materials having dimensions suitable for the construction of large instruments and reduced sag over time.

本揭示內容係關於一種氧化鋁-富鋁紅柱石耐火材料，其包含氧化鋁陶瓷相及富鋁紅柱石陶瓷相，其中該氧化鋁陶瓷相構成該耐火材料之至少約2重量%；以重量計小於或等於約1000 ppm之總鹼金屬含量；及小於約2.5 x 10^-5 h^-1 之潛變速率，如在1350℃下在250 psi之外加負載下所量測。本揭示內容亦係關於鋁矽酸鹽耐火材料，其包含陶瓷相、小於約3重量%之玻璃相、及以重量計小於或等於約1000 ppm之總鹼金屬含量。在一些實施例中，該些耐火材料亦可包括以下特徵之至少一者：
(1) 以重量計小於或等於約750 ppm之總鹼金屬含量；
(2) 以重量計小於或等於約500 ppm之總鹼金屬含量；
(3) 以重量計小於或等於約750 ppm之鈉；
(4) 以重量計小於或等於約10 ppm之鋰；
(5) 以重量計小於或等於約50 ppm之鉀；
(6) 以重量計小於或等於約200 ppm之鐵；
(7) 小於或等於約100 ppm之總鹼土金屬含量；
(8) 小於或等於約50 ppm之總鹼土金屬含量；
(9) 小於或等於約50 ppm鈣；
(10) 小於或等於約50 ppm鎂；及
(11) 至少一個陶瓷相，其包含氧化鋁、富鋁紅柱石、熔融富鋁紅柱石、紅柱石、矽線石、藍晶石、及其組合。The present disclosure relates to an alumina-mullite refractory material comprising an alumina ceramic phase and a mullite ceramic phase, wherein the alumina ceramic phase constitutes at least about 2% by weight of the refractory material; by weight A total alkali metal content of less than or equal to about 1000 ppm; and a creep rate of less than about 2.5 x 10 ^-5 h ^-1 , as measured at 1350 ° C with a load outside 250 psi. The present disclosure also relates to an aluminosilicate refractory material comprising a ceramic phase, a glass phase of less than about 3% by weight, and a total alkali metal content of less than or equal to about 1000 ppm by weight. In some embodiments, the refractory materials may also include at least one of the following features:
(1) a total alkali metal content of less than or equal to about 750 ppm by weight;
(2) a total alkali metal content of less than or equal to about 500 ppm by weight;
(3) less than or equal to about 750 ppm sodium by weight;
(4) less than or equal to about 10 ppm lithium by weight;
(5) potassium less than or equal to about 50 ppm by weight;
(6) less than or equal to about 200 ppm iron by weight;
(7) a total alkaline earth metal content of less than or equal to about 100 ppm;
(8) a total alkaline earth metal content of less than or equal to about 50 ppm;
(9) less than or equal to about 50 ppm calcium;
(10) less than or equal to about 50 ppm magnesium; and
(11) At least one ceramic phase comprising alumina, mullite, fused mullite, andalusite, sillimanite, kyanite, and combinations thereof.

本揭示內容之另外的特徵及優點將在隨後的詳細說明中闡述，且部分地來說，根據彼描述該等特徵及優點將對熟習此項技術者顯而易見或將藉由實踐如本文(包括隨後的實施方式、申請專利範圍、以及隨附圖式)描述的方法來識別。Additional features and advantages of this disclosure will be described in the detailed description that follows, and in part, describing those features and advantages based on them will be apparent to those skilled in the art or will be practiced as described herein (including subsequent The method described in the embodiment, the scope of patent application, and the method described in the accompanying drawings).

應理解前述一般描述及後文的詳細描述提出本揭示內容之各種實施例，且意欲提供用於理解申請專利範圍之性質及特性的概述或框架。隨附圖式係包括來提供對本揭示內容之進一步理解，且併入本說明書中並構成本說明書之一部分。圖式說明本揭示內容之各種實施例，且連同說明書一起用以解釋本揭示內容之原理及操作。It should be understood that the foregoing general description and the detailed description that follows present various embodiments of the disclosure and are intended to provide an overview or framework for understanding the nature and characteristics of the scope of a patent application. The accompanying drawings are included to provide a further understanding of this disclosure, and are incorporated in and constitute a part of this specification. The drawings illustrate various embodiments of the disclosure, and together with the description serve to explain the principles and operations of the disclosure.

本揭示內容之實施例將參考第 1 圖來論述，其描繪示範性玻璃製造系統。以下一般描述意欲僅提供所主張方法及設備之概述。各種態樣將在本揭示內容中參考非限制實施例來更特別地論述，該些實施例可在本揭示內容之上下文內彼此互換。Example embodiments of the present disclosure will be discussed with reference to FIG 1, which depicts an exemplary glass manufacturing system. The following general description is intended to provide only an overview of the claimed methods and equipment. Various aspects will be discussed more particularly in this disclosure with reference to non-limiting examples, which are interchangeable with each other within the context of this disclosure.

第 1 圖描繪用於生產玻璃帶275 之示範性玻璃製造系統100 。玻璃製造系統100 可包括熔融容器110 、熔融至澄清管116 、澄清容器120 、澄清至混合連接管122 (具有自其延伸的位準探針豎管118 )、混合容器124 、混合至遞送連接管126 、遞送容器128 、降流管132 、及熔融拉製機(fusion draw machine; FDM)200 ，其可包括入口管205 、成形主體(例如，溢流管)215 、及牽引輥總成265 。 FIG . 1 depicts an exemplary glass manufacturing system 100 for producing a glass ribbon 275 . The glass manufacturing system 100 may include a melting container 110 , a melting to clarification tube 116 , a clarification container 120 , a clarification to mixing connection tube 122 (with a level probe standpipe 118 extending therefrom), a mixing container 124 , and a mixing to delivery connection tube. 126 , delivery container 128 , downcomer 132 , and fusion draw machine (FDM) 200 , which may include an inlet pipe 205 , a forming body (e.g., an overflow pipe) 215 , and a traction roller assembly 265 .

如藉由箭頭112 所示可將玻璃批料引入熔融容器110 中以形成熔融玻璃114 。在一些實施例中，熔融容器110 可包含由耐火材料陶瓷磚、例如、熔融氧化鋯磚建構的一或多個壁。澄清容器120 係藉由熔融至澄清管116 連接至熔融容器110 。澄清容器120 可具有高溫處理區域，其接收來自熔融容器110 之熔融玻璃且可自熔融玻璃移除氣泡。澄清容器120 係藉由澄清至混合連接管122 連接至混合容器124 。混合容器124 係藉由混合至遞送連接管126 連接至遞送容器128 。遞送容器128 可經由降流管132 遞送熔融玻璃至FDM200 中。The glass batch can be introduced into the melting vessel 110 as shown by arrow 112 to form molten glass 114 . In some embodiments, the melting vessel 110 may include one or more walls constructed from a refractory ceramic tile, such as a fused zirconia tile. The clarification vessel 120 is connected to the melting vessel 110 by a melting-to-clarification pipe 116 . The clarification container 120 may have a high temperature processing area that receives molten glass from the melting container 110 and may remove bubbles from the molten glass. The clarification container 120 is connected to the mixing container 124 by a clarification to mixing connection pipe 122 . The mixing container 124 is connected to the delivery container 128 by a mixing-to-delivery connection tube 126 . The delivery container 128 may deliver molten glass into the FDM 200 via the downcomer 132 .

FDM200 可包括入口管205 、成形主體215 、及牽引輥總成265 。入口管205 可自降流管132 接收熔融玻璃，該熔融玻璃可自入口管流動至成形主體215 。成形主體215 可包括進口225 ，其接收熔融玻璃，該熔融玻璃可流動至流槽235 中，溢出流槽235 之側面，且沿兩個相反成形表面245 向下流動，之後在根部255 處熔合在一起以形成玻璃帶275 。在某些實施例中，成形主體215 可包含耐火陶瓷，例如，鋯石或氧化鋁陶瓷。牽引輥總成265 可遞送經拉製之玻璃帶275 以用於藉由另外的可選設備進一步處理。The FDM 200 may include an inlet pipe 205 , a forming body 215 , and a traction roller assembly 265 . The inlet tube 205 may receive molten glass from the downcomer tube 132 , and the molten glass may flow from the inlet tube to the forming body 215 . The shaped body 215 may include an inlet 225 that receives molten glass that can flow into the flow channel 235 , overflow the sides of the flow channel 235 , and flow down two opposite shaped surfaces 245 , and then fused at the root 255 at Together to form a glass ribbon 275 . In some embodiments, the shaped body 215 may include a refractory ceramic, such as a zircon or alumina ceramic. The pull roller assembly 265 may deliver a drawn glass ribbon 275 for further processing by additional optional equipment.

例如，可包括用於對玻璃帶劃線之機械劃線裝置的行進砧機(traveling anvil machine; TAM)可用以將帶275 分離成個別片材，該等片材可使用此項技術中所知的各種方法及裝置來機器加工、拋光、化學強化、及/或另外表面處理，例如，蝕刻。當然，雖然本文揭示的設備及方法係參考熔融拉製製程及系統來論述，但應理解此種設備及方法亦可結合其他的玻璃成形製程使用，諸如狹槽拉製及浮製製程，僅舉幾例。For example, a traveling anvil machine (TAM), which can include a mechanical scribing device for scribing glass ribbons, can be used to separate the strips 275 into individual sheets that can be used as known in the art Various methods and apparatus for machining, polishing, chemical strengthening, and / or other surface treatments, such as etching. Of course, although the equipment and methods disclosed in this article are discussed with reference to the melt-drawing process and system, it should be understood that this equipment and method can also be used in conjunction with other glass forming processes, such as slot-drawing and floating processes, just to mention A few cases.

熔融容器110 、澄清容器120 、混合容器124 、遞送容器128 、及/或成形主體215 可包含適用於玻璃製造製程之任何材料，例如，耐火材料，諸如鋯石、氧化鋯、氧化鋁、氧化鎂、碳化矽、氮化矽、氮氧化矽、磷釔礦、獨居石、富鋁紅柱石、沸石、其合金、及其組合。示範性鋁矽酸鹽耐火材料可包括氧化鋁、富鋁紅柱石、熔融富鋁紅柱石、紅柱石、矽線石、藍晶石、其合金、及其組合，諸如氧化鋁-富鋁紅柱石。在某些實施例中，氧化鋁-富鋁紅柱石可包含至少約2重量%之氧化鋁陶瓷相，諸如約2重量%至約10重量%之氧化鋁陶瓷相，例如，在約3重量%至約8重量%、約4重量%至約7重量%、或約5重量%至約6重量%範圍內之氧化鋁陶瓷相，包括其之間的所有範圍及子範圍。氧化鋁-富鋁紅柱石可包含例如至少約85重量%之富鋁紅柱石陶瓷相，諸如至少約90重量%、至少約95重量%、或至少約98重量%，諸如在約85重量%至約98重量%範圍內之富鋁紅柱石相，包括其之間的所有範圍及子範圍。氧化鋁-富鋁紅柱石亦可含有小量之二氧化矽，諸如約0.5重量%至約3重量%，例如，約1重量%至約2重量%，或約1.5重量%至約2.5重量%之二氧化矽。在某些實施例中，熔融容器110 及/或澄清容器120 可包括磚或磚片，其包含鋁矽酸鹽耐火材料，諸如氧化鋁-富鋁紅柱石，例如，在熔融容器之上層建築及/或窯頂中或澄清容器之覆蓋磚片中。The melting vessel 110 , the clarification vessel 120 , the mixing vessel 124 , the delivery vessel 128 , and / or the shaped body 215 may contain any material suitable for use in glass manufacturing processes, for example, refractory materials such as zircon, zirconia, alumina, magnesia , Silicon carbide, silicon nitride, silicon oxynitride, xenotime, monazite, mullite, zeolite, its alloys, and combinations thereof. Exemplary aluminosilicate refractories may include alumina, mullite, fused mullite, andalusite, sillimanite, kyanite, alloys thereof, and combinations thereof, such as alumina-mullite . In certain embodiments, the alumina-mullite may include at least about 2% by weight of an alumina ceramic phase, such as about 2% to about 10% by weight of an alumina ceramic phase, for example, at about 3% by weight The alumina ceramic phase in the range of about 8 wt%, about 4 wt% to about 7 wt%, or about 5 wt% to about 6 wt%, including all ranges and subranges therebetween. The alumina-mullite may include, for example, at least about 85% by weight mullite ceramic phase, such as at least about 90% by weight, at least about 95% by weight, or at least about 98% by weight, such as between about 85% by weight to The mullite phase in the range of about 98% by weight includes all ranges and subranges therebetween. Alumina-mullite may also contain small amounts of silicon dioxide, such as about 0.5% to about 3% by weight, for example, about 1% to about 2% by weight, or about 1.5% to about 2.5% by weight Of silicon dioxide. In certain embodiments, the melting vessel 110 and / or the clarification vessel 120 may include bricks or tiles that include an aluminosilicate refractory material, such as alumina-mullite, for example, on top of a melting vessel and / Or in the top of the kiln or in the covered tiles of the clarification container.

本文揭示的耐火材料可包括至少一個陶瓷相及晶粒間玻璃相。陶瓷相可包括一或多個結晶相及/或晶粒。陶瓷相可進一步包括藉由一或多個離子及電子以週期性佈置佔據的結晶基體或晶格。晶粒間玻璃相可圍繞陶瓷相中之一或多個晶粒且可為非晶形，例如，玻璃相中之離子及電子可不以週期性結構佈置。玻璃相可表示陶瓷相之相鄰晶粒之間的晶界區。在某些實施例中，耐火材料可包含小於約3重量%之晶粒間玻璃相，諸如小於約2.5重量%、小於約2重量%、小於約1重量%、小於約0.5重量%、小於約0.3重量%、或小於約0.1重量%之晶粒間玻璃相，例如，在0重量%至約2重量%範圍內之玻璃相。The refractory materials disclosed herein may include at least one ceramic phase and an intergranular glass phase. The ceramic phase may include one or more crystalline phases and / or grains. The ceramic phase may further include a crystalline matrix or crystal lattice occupied by one or more ions and electrons in a periodic arrangement. The intergranular glass phase may surround one or more crystal grains in the ceramic phase and may be amorphous. For example, the ions and electrons in the glass phase may not be arranged in a periodic structure. The glass phase may represent a grain boundary region between adjacent crystal grains of the ceramic phase. In certain embodiments, the refractory material may include less than about 3% by weight intergranular glass phase, such as less than about 2.5% by weight, less than about 2% by weight, less than about 1% by weight, less than about 0.5% by weight, and less than about An intergranular glass phase of 0.3% by weight, or less than about 0.1% by weight, for example, a glass phase in the range of 0% to about 2% by weight.

耐火材料之化學組成可包括各種雜質。此等雜質可以相對小的量(例如，「混入」或「痕量」之量)存在且可在陶瓷體之製造期間有意或無意地引入。例如，少量雜質可有意地添加至批料以在製造製程期間控制特定條件及/或雜質可無意地存在於起始分批材料中。替代地，雜質可在陶瓷體之製造期間，例如，藉由與諸如成型模具之一或多個部件接觸而無意地引入。雜質可包括例如鹼金屬(例如，Li、Na、K)、鹼土金屬(例如，Mg、Ca)、過渡金屬(例如，Fe、Cr、Ti、Mn、Sn)、及重金屬(例如，Ta、W、Mo、V、Nb)。The chemical composition of the refractory material may include various impurities. Such impurities may be present in relatively small amounts (eg, "incorporation" or "trace" amounts) and may be intentionally or unintentionally introduced during the manufacture of the ceramic body. For example, small amounts of impurities may be intentionally added to the batch to control certain conditions during the manufacturing process and / or impurities may be inadvertently present in the starting batch material. Alternatively, impurities may be introduced unintentionally during the manufacture of the ceramic body, for example, by contact with one or more parts such as a forming mold. Impurities may include, for example, alkali metals (e.g., Li, Na, K), alkaline earth metals (e.g., Mg, Ca), transition metals (e.g., Fe, Cr, Ti, Mn, Sn), and heavy metals (e.g., Ta, W , Mo, V, Nb).

耐火材料內之雜質離子可在不同的電位或梯度、諸如電及化學電位，或濃度、溫度及應力梯度下遷移。可活化不同的遷移機制，諸如但不限於與有序結晶固體中之諸如空位或空隙的點缺陷互換或密度波動或擾動，其允許更多鬆散黏接的原子在玻璃態結構中之遷移。如本文所使用，術語「活動離子」用於指在電位或梯度下活動的陽離子及陰離子。示範性活動離子包括但不限於鋰(Li⁺ )、鈉(Na⁺ )、鉀(K⁺ )、鈣(Ca²⁺ )、鎂(Mg²⁺ )、鐵(Fe³⁺ )、稀土金屬、及過渡金屬。當然，耐火材料可包含其他活動離子及/或所列活動離子可以不同於所列之彼等氧化態的氧化態存在。Impurity ions in the refractory can migrate at different potentials or gradients, such as electrical and chemical potentials, or concentration, temperature, and stress gradients. Different migration mechanisms can be activated, such as, but not limited to, interchange with point defects, such as vacancies or voids, or density fluctuations or perturbations in ordered crystalline solids, which allow more loosely bonded atoms to migrate in glassy structures. As used herein, the term "mobile ion" is used to refer to cations and anions that are active at a potential or gradient. Exemplary active ions include, but are not limited to, lithium (Li ⁺ ), sodium (Na ⁺ ), potassium (K ⁺ ), calcium (Ca ²⁺ ), magnesium (Mg ²⁺ ), iron (Fe ³⁺ ), rare earth metals, And transition metals. Of course, the refractory material may contain other mobile ions and / or the listed mobile ions may exist in oxidation states other than those listed.

化學電位或濃度梯度可使用許多技術來產生。例如，包含包括活動陽離子之耐火材料的陶瓷體可在其表面(或在內表面針對開孔孔隙度)藉由例如Na⁺ 、Fe³⁺ 等等的活動陽離子與至少一種含鹵素化合物之反應耗盡。陽離子可歸因於陶瓷體之內部(或主體)區與表面之間的化學電位或濃度差而遷移，例如，陽離子可經拉動至陶瓷體之表面，此處，其與至少一種含鹵素化合物反應。陶瓷體之表面(或內表面區域)可因此相較於主體陶瓷變得活動陽離子耗盡的，從而可用作活動離子自主體至表面之進一步擴散的驅動力。在活動離子自主體擴散至表面且與含鹵素化合物反應時，耐火材料將隨著處理進程變得進一步耗盡活動離子。活動離子之遷移可歸因於個別粒子物質之不同遷移率及/或偶合而以不同遷移率發生。Chemical potentials or concentration gradients can be generated using a number of techniques. For example, a ceramic body comprising a refractory material including mobile cations can be consumed on its surface (or on the inner surface for open-pore porosity) by the reaction of mobile cations such as Na ⁺ , Fe ^3+, etc. with at least one halogen-containing compound. Exhausted. The cations can be migrated due to a chemical potential or concentration difference between the inner (or body) region of the ceramic body and the surface. For example, the cations can be pulled to the surface of the ceramic body where they react with at least one halogen-containing compound . The surface (or inner surface area) of the ceramic body can thus become depleted of mobile cations compared to the host ceramic, and thus can be used as a driving force for the further diffusion of mobile ions from the body to the surface. As the mobile ions diffuse from the body to the surface and react with the halogen-containing compound, the refractory will further deplete the mobile ions as the process progresses. Migration of mobile ions can be attributed to different mobility and / or coupling of individual particulate matter with different mobility.

當陽離子到達陶瓷體之表面時，其可與至少一種含鹵素化合物反應以形成反應產物。例如，在金屬陽離子M⁺ 及鹵化物陰離子X^- 的情況下，示範性反應複合物可包括M_x O_y X_z 或M_x X_z ，其中x、y及z為化學計量數量。該些反應產物可為揮發性陽離子-陰離子複合物，其能夠自陶瓷體之表面擴散至周圍氣氛(例如，熔爐)中。陽離子亦可藉由首先使含鹵素化合物擴散至陶瓷體中(例如，經由開孔孔隙度)來遷移，在此點，含鹵素化合物與一或多個活動陽離子反應以形成揮發性反應複合物。揮發性複合物可隨後擴散至陶瓷體之表面且進入周圍氣氛中。隨著處理進程且陽離子遷移至表面並反應，陶瓷體之內部區可相較於表面相對地耗盡陽離子。可例如藉由空氣流動或真空來移除氣態反應產物，以自熔爐沖洗反應產物。在陶瓷體之表面處的任何固體反應產物可例如藉由拋光或研磨機械地移除，或藉由用水或其他溶劑洗滌來移除。所處理陶瓷體之剩餘部分可因此相較於初始、未處理陶瓷體包含顯著較低的活動陽離子濃度。When the cations reach the surface of the ceramic body, they can react with at least one halogen-containing compound to form a reaction product. For example, the metal halide anion and cation M ⁺ X ^- in the case of the exemplary reaction complex may include M _x O _y _X _z or M _{x X} _z, wherein x, y and z are stoichiometric amount. The reaction products can be volatile cation-anion complexes, which can diffuse from the surface of the ceramic body into the surrounding atmosphere (eg, a furnace). The cations can also be migrated by first diffusing the halogen-containing compound into the ceramic body (eg, via open-pore porosity), at which point the halogen-containing compound reacts with one or more active cations to form a volatile reaction complex. The volatile composite can then diffuse to the surface of the ceramic body and enter the surrounding atmosphere. As the treatment progresses and the cations migrate to the surface and react, the internal region of the ceramic body can be relatively depleted of cations compared to the surface. The gaseous reaction products can be removed, for example, by air flow or vacuum, to flush the reaction products from the furnace. Any solid reaction products at the surface of the ceramic body can be removed mechanically, for example, by polishing or grinding, or by washing with water or other solvents. The remainder of the treated ceramic body may therefore contain a significantly lower active cation concentration than the original, untreated ceramic body.

晶粒間相中的擴散可在增加的溫度下加速且因此可在較高溫度下賦能擴散。在非限制實施例中，陶瓷體可例如在熔爐或其他設備中加熱以促進耐火材料中陽離子之遷移率及/或陽離子經由開孔孔隙度之揮發性。較高溫度亦可促進含鹵素化合物擴散至陶瓷體中及/或揮發性反應產物擴散出陶瓷體。根據非限制實施例，陶瓷體可加熱至大於或等於約1000℃之溫度。在一些實施例中，處理溫度可在以下範圍：約1000℃至約1500℃，諸如約1100℃至約1400℃，或約1200℃至約1300℃，包括其之間的所有範圍及子範圍。處理之持續時間可例如取決於鹵素濃度及溫度而變化，但在各種非限制實施例中可在以下範圍：約1小時至約1000小時或更大，諸如約10小時至約500小時、約20小時至約360小時、約30小時至約240小時、約40小時至約120小時、約50小時至約80小時、或約60小時至約70小時，包括其之間的所有範圍及子範圍。Diffusion in the intergranular phase can be accelerated at increased temperatures and therefore can enable diffusion at higher temperatures. In a non-limiting embodiment, the ceramic body may be heated, for example, in a furnace or other equipment to promote the mobility of cations in the refractory material and / or the volatility of cations through open-cell porosity. Higher temperatures can also promote the diffusion of halogen-containing compounds into the ceramic body and / or the diffusion of volatile reaction products out of the ceramic body. According to a non-limiting embodiment, the ceramic body may be heated to a temperature greater than or equal to about 1000 ° C. In some embodiments, the processing temperature may be in the range of about 1000 ° C to about 1500 ° C, such as about 1100 ° C to about 1400 ° C, or about 1200 ° C to about 1300 ° C, including all ranges and subranges therebetween. The duration of the treatment can vary, for example, depending on the halogen concentration and temperature, but in various non-limiting embodiments can range from about 1 hour to about 1000 hours or more, such as about 10 hours to about 500 hours, about 20 Hours to about 360 hours, about 30 hours to about 240 hours, about 40 hours to about 120 hours, about 50 hours to about 80 hours, or about 60 hours to about 70 hours, including all ranges and subranges therebetween.

在一些實施例中，陶瓷體可在空氣或惰性氣氛中加熱至處理溫度，之後與含鹵素化合物接觸。在其他實施例中，陶瓷體可在與含鹵素化合物接觸期間加熱至處理溫度。根據各種實施例，含鹵素化合物可與一或多種載液或載氣混合以調整鹵化物濃度。示範性載氣可包括惰性氣體，例如，N₂ 、Ar、He、Kr、Ne、Xe、及類似物。在一些實施例中，含鹵素化合物可與例如O₂ 或CO之非惰性氣體混合，以修改含鹵素氣氛之氧化還原態。例如，O₂ 之添加可抑制矽及鈦自陶瓷的移除，而CO之添加可在化學上將某些活動陽離子還原至較低氧化態。例如，Fe³⁺ 可還原成Fe²⁺ ，其可促進鐵與含鹵素化合物之間的反應複合物形成。In some embodiments, the ceramic body may be heated to the processing temperature in air or an inert atmosphere, and then contacted with the halogen-containing compound. In other embodiments, the ceramic body may be heated to a processing temperature during contact with the halogen-containing compound. According to various embodiments, the halogen-containing compound may be mixed with one or more carrier liquids or carrier gases to adjust the halide concentration. Exemplary carrier gas may comprise an inert gas, _{e.g., N 2, Ar, He,} Kr, Ne, Xe, and the like. In some embodiments, the halogen-containing compound may be mixed with a non-inert gas such as O ₂ or CO to modify the redox state of the halogen-containing atmosphere. For example, the addition of O ₂ can inhibit the removal of silicon and titanium from the ceramic, while the addition of CO can chemically reduce certain active cations to a lower oxidation state. For example, Fe ³⁺ can be reduced to Fe ²⁺ , which can promote the formation of a reaction complex between iron and a halogen-containing compound.

含鹵素化合物可與載氣以任何適合的比率組合，例如，以體積計約9:1至約200:1之載劑對含鹵素化合物，諸如約20:1至約150:1、約30:1至約100:1、約40:1至約90:1、約50:1至約80:1、或約60:1至約70:1，包括其之間的所有範圍及子範圍。在一些實施例中，含鹵素化合物之濃度可在相對於總氣體體積，例如，熔爐中之氣體體積的約0.5體積%至約10體積%的範圍內。例如，含鹵素化合物可相對於氣體總體積具有在以下範圍內的濃度：約0.5體積%至約9體積%、約1體積%至約8體積%、約2體積%至約7體積%、約3體積%至約6體積%、或約4體積%至約5體積%，包括其之間的所有範圍及子範圍。在另外的實施例中，含鹵素化合物中之鹵素對陶瓷之總鹼金屬含量之莫耳比率大於或等於約5:1，諸如約10:1至約200:1、約20:1至約150:1、約30:1至約100:1、約40:1至約90:1、約50:1至約80:1、或約60:1至約70:1，包括其之間的所有範圍及子範圍。The halogen-containing compound may be combined with the carrier gas in any suitable ratio, for example, from about 9: 1 to about 200: 1 by volume of the carrier to the halogen-containing compound, such as about 20: 1 to about 150: 1, about 30: 1 to about 100: 1, about 40: 1 to about 90: 1, about 50: 1 to about 80: 1, or about 60: 1 to about 70: 1, including all ranges and subranges therebetween. In some embodiments, the concentration of the halogen-containing compound may be in a range from about 0.5% to about 10% by volume relative to the total gas volume, for example, the gas volume in the furnace. For example, the halogen-containing compound may have a concentration in the following range relative to the total volume of the gas: about 0.5 vol.% To about 9 vol.%, About 1 vol.% To about 8 vol.%, About 2 vol.% To about 7 vol.%, About 3 vol% to about 6 vol%, or about 4 vol% to about 5 vol%, including all ranges and subranges therebetween. In other embodiments, the molar ratio of the halogen to the total alkali metal content of the ceramic in the halogen-containing compound is greater than or equal to about 5: 1, such as about 10: 1 to about 200: 1, about 20: 1 to about 150 : 1, about 30: 1 to about 100: 1, about 40: 1 to about 90: 1, about 50: 1 to about 80: 1, or about 60: 1 to about 70: 1, including all in between Scope and subrange.

適合的含鹵素化合物可包括任何化合物，可自其產生至少一個鹵化物離子。示範性鹵化物離子可包括Br^- 、Cl^- 、及F^- 、或其組合。含鹵素化合物可在室溫下及/或在處理溫度下為氣體或液體。在各種實施例中，含鹵素化合物在處理溫度下為氣體。含鹵素化合物之非限制性實例可包括Br₂ 、Cl₂ 、及F₂ ，包含Br、Cl、或F之酸，包含Br、Cl、或F之有機化合物，及其組合，僅舉幾例。此種含鹵素化合物之非限制性實例包括例如Br₂ 、CHBr₃ 、CH₂ Br₂ 、CHBr₃ 、CBr₄ 、SiBr₄ 、SOBr₂ 、COBr₂ 、HBr、Cl₂ 、CHCl₃ 、CH₂ Cl₂ 、CHCl₃ 、CCl₄ 、SiCl₄ 、SOCl₂ 、COCl₂ 、HCl、F₂ CHF₃ 、CH₂ F₂ 、CHF₃ 、CF₄ 、SiF₄ 、SOF₂ 、COF₂ 、及HF。根據某些實施例，含鹵素化合物可不包括相應於耐火材料中之活動陽離子的元素。例如，含鹵素化合物可不包含Na、K、Li、Ca、Mg、Ti、Al、Fe、或P之一或多者，僅舉幾例。替代地，含鹵素化合物可含有此種元素，但可不具有與待清潔陶瓷體相同數量級的用於相應活動離子之化學電位。Suitable halogen-containing compounds can include any compound from which at least one halide ion can be generated. Exemplary halide ions may include Br ⁻ , Cl ⁻ , and F ⁻ , or a combination thereof. The halogen-containing compound may be a gas or a liquid at room temperature and / or at the processing temperature. In various embodiments, the halogen-containing compound is a gas at the processing temperature. Non-limiting examples of halogen-containing compounds may include Br ₂ , Cl ₂ , and F ₂ , acids including Br, Cl, or F, organic compounds including Br, Cl, or F, and combinations thereof, to name a few. Non-limiting examples of such halogen-containing compounds include, for example, Br ₂ , CHBr ₃ , CH ₂ Br ₂ , CHBr ₃ , CBr ₄ , SiBr ₄ , SOBr ₂ , COBr ₂ , HBr, Cl ₂ , CHCl ₃ , CH ₂ Cl ₂ , CHCl ₃ , CCl ₄ , SiCl ₄ , SOCl ₂ , COCl ₂ , HCl, F ₂ CHF ₃ , CH ₂ F ₂ , CHF ₃ , CF ₄ , SiF ₄ , SOF ₂ , COF ₂ , and HF. According to some embodiments, the halogen-containing compound may not include an element corresponding to a mobile cation in the refractory material. For example, the halogen-containing compound may not include one or more of Na, K, Li, Ca, Mg, Ti, Al, Fe, or P, to name a few. Alternatively, the halogen-containing compound may contain such an element, but may not have a chemical potential for the corresponding mobile ion of the same order of magnitude as the ceramic body to be cleaned.

用於藉由含鹵素化合物移除諸如鋰之鹼金屬的非限制機制展示在下文方程式1-5中。
2 Li₂ O + SiCl₄ --> 4 LiCl + SiO₂ 式1
Li₂ O + Cl₂ --> 2 LiCl + 1/2O₂ 式2
2 Li₂ O + CCl₄ --> 4 LiCl + CO₂ 式3
Li₂ O + SOCl₂ --> 2 LiCl + SO₂ 式4
Li₂ O + 2HCl--> 2 LiCl + H₂ O 式5A non-limiting mechanism for removing alkali metals such as lithium by halogen-containing compounds is shown in Equations 1-5 below.
2 Li ₂ O + SiCl _4- > 4 LiCl + SiO ₂ Formula 1
Li ₂ O + Cl _2- > 2 LiCl + 1 / 2O ₂ Formula 2
2 Li ₂ O + CCl _4- > 4 LiCl + CO ₂ Formula 3
Li ₂ O + SOCl _2- > 2 LiCl + SO ₂ Formula 4
Li ₂ O + 2HCl-> 2 LiCl + H ₂ O Formula 5

用於藉由含鹵素化合物移除諸如鐵之過渡金屬的非限制機制展示在下文方程式6-10中。
2 Fe₂ O₃ + 3 SiCl₄ --> 4 FeCl₃ + 3 SiO₂ 式6
Fe₂ O₃ + 6 Cl₂ --> 2 FeCl₃ + 3/2 O₂ 式7
2 Fe₂ O₃ + 3 CCl₄ --> 4 FeCl₃ + 3 CO₂ 式8
Fe₂ O₃ + 3 SOCl₂ --> 2 FeCl₃ + 3 SO₂ 式9
Fe₂ O₃ + 6 HCl--> 2 FeCl₃ + 3 H₂ O 式10A non-limiting mechanism for removing transition metals such as iron by halogen-containing compounds is shown in Equations 6-10 below.
2 Fe ₂ O ₃ + 3 SiCl _4- > 4 FeCl ₃ + 3 SiO ₂ Formula 6
Fe ₂ O ₃ + 6 Cl _2- > 2 FeCl ₃ + 3/2 O ₂ Formula 7
2 Fe ₂ O ₃ + 3 CCl _4- > 4 FeCl ₃ + 3 CO ₂ Formula 8
Fe ₂ O ₃ + 3 SOCl _2- > 2 FeCl ₃ + 3 SO ₂ Formula 9
Fe ₂ O ₃ + 6 HCl-> 2 FeCl ₃ + 3 H ₂ O Formula 10

本文揭示方法可用於處理耐火材料以減少諸如鹼金屬、鹼土金屬、鐵、或其他過渡金屬離子的至少一種活動離子之濃度。在某些實施例中，經處理耐火材料之鹼金屬含量可相較於未處理耐火材料之鹼金屬含量減少至少約75%，諸如至少約80%、85%、90%、95%、96%、97%、98%、99%、99.5%、或99.9%之鹼金屬含量減少。同樣地，經處理耐火材料之鐵及/或鹼土金屬含量可類似地減少達至少約10%，諸如減少至少約15%、20%、25%、30%、35%、40%、45%、50%、或更大。The methods disclosed herein can be used to treat refractory materials to reduce the concentration of at least one mobile ion, such as an alkali metal, alkaline earth metal, iron, or other transition metal ions. In certain embodiments, the alkali metal content of the treated refractory material may be reduced by at least about 75% compared to the alkali metal content of the untreated refractory material, such as at least about 80%, 85%, 90%, 95%, 96% , 97%, 98%, 99%, 99.5%, or 99.9% reduction in alkali metal content. Similarly, the iron and / or alkaline earth metal content of treated refractories can similarly be reduced by at least about 10%, such as by at least about 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or more.

如本文所使用，術語「經處理」、「經清潔」、「經純化」及其變化形式意欲指代已經受本文揭示的一或多種處理方法來減少耐火材料內之至少一種活動離子之濃度的耐火材料。類似地，「未處理」、「剛處理」及類似術語意欲指代處理之前的耐火材料，例如，如由分批材料產生或如自供應商所接收的。處理可在製造製程中之任一點，例如，在耐火材料之形成之後，在將耐火材料成型為具有所要形狀之陶瓷體之後，或在任何其他所要的處理步驟之後，在剛處理的耐火材料上進行。在一些實施例中，可使用處理方法之組合。As used herein, the terms "treated", "cleaned", "purified" and variations thereof are intended to refer to those that have been subjected to one or more processing methods disclosed herein to reduce the concentration of at least one mobile ion in the refractory material. Refractory. Similarly, "untreated", "as-processed" and similar terms are intended to refer to refractory materials prior to processing, for example, as produced from batch materials or as received from a supplier. The treatment can be at any point in the manufacturing process, for example, after the refractory is formed, after the refractory is formed into a ceramic body having a desired shape, or after any other desired processing step, on the refractory just treated get on. In some embodiments, a combination of processing methods may be used.

本文揭示的耐火材料可具有以前經由先前技術方法不可得到的低雜質位準。由於低雜質位準，諸如低鹼金屬位準，耐火材料可展現比當前可獲得的商業材料低的潛變速率。在非限制實施例中，可例如藉由在樣本暴露於給定溫度及壓力的同時進行三點彎曲測試來量測材料樣本之潛變速率。The refractory materials disclosed herein may have low impurity levels that were not previously available via prior art methods. Due to low impurity levels, such as low alkali metal levels, refractory materials can exhibit lower creep rates than currently available commercial materials. In a non-limiting embodiment, the creep rate of a material sample can be measured, for example, by performing a three-point bending test while the sample is exposed to a given temperature and pressure.

單相陶瓷之潛變機制可為科布潛變(晶界擴散)或納貝-西林潛變(晶格擴散)。當耐火材料包含多個相時，例如，陶瓷相及玻璃相，材料可具有針對玻璃相中之離子，例如，在晶界處的增強擴散係數。多相陶瓷可因此遵循經修改的科布潛變方程式，其中晶界厚度係藉由晶界處的玻璃相之厚度替代，晶界擴散係數係藉由玻璃相中離子之擴散係數替代。The latent mechanism of single-phase ceramics can be Cobb's latent (grain boundary diffusion) or Nabe-Cillin latent (lattice diffusion). When a refractory material includes multiple phases, such as a ceramic phase and a glass phase, the material may have an enhanced diffusion coefficient for ions in the glass phase, for example, at grain boundaries. Multiphase ceramics can therefore follow the modified Cobb latent equation, where the grain boundary thickness is replaced by the thickness of the glass phase at the grain boundary, and the grain boundary diffusion coefficient is replaced by the diffusion coefficient of the ions in the glass phase.

在一些情形中，歸因於耐火材料之微結構內的玻璃相之黏性流，潛變可發生，例如，玻璃可自壓縮晶界流動至拉伸晶界。取決於材料之孔隙率，陶瓷相及/或玻璃相可自壓縮晶界移動至具孔隙率之區，或玻璃相可自具孔隙率之區移動至拉伸晶界。在任何該些情況下，自玻璃相移除活動陽離子(而非Si)可增加玻璃相之黏度，從而引起玻璃更緩慢地流動，從而可因此減少玻璃之應變鬆馳速率。另外，來自玻璃相移除活動陽離子可減少玻璃在晶界處之總擴散率，包括陶瓷相成分(例如，在鋯石情況下為Zr、Si、O)之擴散。減少晶粒成分之擴散係數可在給定溫度下減慢質量運輸，從而可因此減少潛變速率。In some cases, due to the viscous flow of the glass phase within the microstructure of the refractory material, creep can occur, for example, the glass can flow from a compressed grain boundary to a stretched grain boundary. Depending on the porosity of the material, the ceramic phase and / or the glass phase can move from the compressed grain boundary to a region with porosity, or the glass phase can move from the porosity region to a stretched grain boundary. In any of these cases, removal of mobile cations (other than Si) from the glass phase can increase the viscosity of the glass phase, causing the glass to flow more slowly, which can therefore reduce the strain relaxation rate of the glass. In addition, removal of active cations from the glass phase can reduce the total diffusivity of the glass at the grain boundaries, including the diffusion of ceramic phase components (eg, Zr, Si, O in the case of zircon). Decreasing the diffusion coefficient of the grain components can slow down mass transport at a given temperature, thereby reducing the creep rate.

第 2 圖為說明藉由三點彎曲測試量測的耐火材料之潛變速率隨鋯石陶瓷樣本之鹼金屬(圓)及鈉(菱形)濃度之變化的圖(任意值)。如第 2 圖所示，耐火材料之潛變速率大體上隨鹼金屬(例如，鈉)濃度降低而降低。因而，藉由減少如本文揭示的耐火材料中之鹼金屬雜質位準，可能生產具有令人驚訝的低潛變速率之經處理耐火材料。減少耐火材料中之鹼金屬雜質位準亦可提供隨時間降低耐火材料之腐蝕速率的附加益處。例如，未處理耐火材料之腐蝕速率可高達未處理耐火材料之彼腐蝕速率的至少兩倍，諸如高3倍、4倍、或5倍。 FIG 2 is an explanatory view (arbitrary value) by three-point bending test creep rate measured with the alkali metal of the refractory material of zircon ceramic samples (circle) and the variation of sodium (diamonds) concentrations. As shown in FIG. 2, the creep rate of the refractory material with the substantially alkali metal (e.g. sodium) concentration decreases. Thus, by reducing the level of alkali metal impurities in refractories as disclosed herein, it is possible to produce treated refractories with surprisingly low creep rates. Reducing the level of alkali metal impurities in the refractory material may also provide the added benefit of reducing the corrosion rate of the refractory material over time. For example, the corrosion rate of the untreated refractory material can be at least twice as high as the corrosion rate of the untreated refractory material, such as 3 times, 4 times, or 5 times higher.

本文揭示的經處理耐火材料可包含以重量計小於或等於約1000 ppm之總鹼含量。本文揭示的經處理耐火材料可具有減小的潛變速率，例如，在1350℃及250 psi下，小於約2.5 x 10^-5 h^-1 ，諸如小於約2 x 10^-5 h^-1 、小於約1.5 x 10^-5 h^-1 、小於約1 x 10^-5 h^-1 、小於約5 x 10^-6 h^-1 、或小於約1 x 10^-6 h^-1 如在1350℃下，在250 psi負載下藉由三點彎曲測試所量測的。經處理耐火材料亦可包含小於約3重量%之玻璃相，諸如小於約2重量%或小於約1重量%之玻璃相。The treated refractories disclosed herein may include a total alkali content of less than or equal to about 1000 ppm by weight. The treated refractories disclosed herein may have reduced creep rates, for example, less than about 2.5 x 10 ^-5 h ^-1 at 1350 ° C and 250 psi, such as less than about 2 x 10 ^-5 h ^-1 , less than About 1.5 x 10 ^-5 h ^-1 , less than about 1 x 10 ^-5 h ^-1 , less than about 5 x 10 ^-6 h ^-1 , or less than about 1 x 10 ^-6 h ^-1 as at 1350 ° C, at Measured at 250 psi with a three-point bend test. The treated refractory material may also include a glass phase of less than about 3% by weight, such as a glass phase of less than about 2% by weight or less than about 1% by weight.

本文揭示的濃度係針對總耐火材料，例如，基於耐火材料之總重量來提供，除非另外明確地陳述。晶粒間玻璃相中之局部化濃度可藉由將總濃度除以存在的玻璃相之重量百分比來計算。藉助於非限制性實例，包含60 ppm鹼金屬含量及1 wt%玻璃相之總耐火材料可在玻璃相中具有多至約0.6 wt%的局部化鹼金屬濃度。其他部件之局部化濃度、其相對量、及玻璃相之相對量可類似地在下文針對總濃度中每一者來計算，且意欲落入本揭示內容之範疇內。The concentrations disclosed herein are for total refractory materials, for example, provided based on the total weight of the refractory material, unless explicitly stated otherwise. The localized concentration in the intergranular glass phase can be calculated by dividing the total concentration by the weight percentage of the glass phase present. By way of non-limiting example, a total refractory comprising 60 ppm alkali metal content and 1 wt% glass phase may have a localized alkali metal concentration in the glass phase of up to about 0.6 wt%. The localized concentrations of other components, their relative amounts, and the relative amounts of the glassy phase may be similarly calculated for each of the total concentrations below, and are intended to fall within the scope of this disclosure.

在某些實施例中，總鹼金屬含量以重量計可小於或等於約1000 ppm，諸如小於或等於約750 ppm、小於或等於約500 ppm、小於或等於約200 ppm、小於或等於約100 ppm、或小於或等於約10 ppm，例如，在以下範圍：約1 ppm至約1000 ppm，或約100 ppm至約1000 ppm，包括其之間的所有範圍及子範圍。類似地，鐵含量以重量計可小於或等於約300 ppm，諸如小於或等於約200 ppm、小於或等於約150 ppm、小於或等於約100 ppm、小於或等於約50 ppm、小於或等於約25 ppm、小於或等於約10 ppm，或以重量計小於或等於約5 ppm，例如，在以下範圍：約1 ppm至約300 ppm，包括其之間的所有範圍及子範圍。In certain embodiments, the total alkali metal content may be less than or equal to about 1000 ppm by weight, such as less than or equal to about 750 ppm, less than or equal to about 500 ppm, less than or equal to about 200 ppm, and less than or equal to about 100 ppm , Or less than or equal to about 10 ppm, for example, in the following range: about 1 ppm to about 1000 ppm, or about 100 ppm to about 1000 ppm, including all ranges and subranges therebetween. Similarly, the iron content may be less than or equal to about 300 ppm by weight, such as less than or equal to about 200 ppm, less than or equal to about 150 ppm, less than or equal to about 100 ppm, less than or equal to about 50 ppm, and less than or equal to about 25 ppm, less than or equal to about 10 ppm, or less than or equal to about 5 ppm by weight, for example, in the following range: about 1 ppm to about 300 ppm, including all ranges and subranges therebetween.

耐火材料中之示範性活動陽離子包括鹼金屬(例如，Li、Na、K)。在各種實施例中，該些金屬之濃度可使用本文揭示的處理方法來減少。例如，經處理耐火材料可包含以重量計小於約1000 ppm之鈉，諸如小於或等於約750 ppm、小於或等於約500 ppm、小於或等於約250 ppm、小於或等於約100 ppm、小於或等於約50 ppm、或小於或等於約10 ppm，例如，在以下範圍：約1 ppm至約1000 ppm，包括其之間的所有範圍及子範圍。同樣地，經處理耐火材料可包含以重量計小於約100 ppm之鋰或鉀，諸如小於或等於約50 ppm、小於或等於約40 ppm、小於或等於約30 ppm、小於或等於約20 ppm、小於或等於約10 ppm、小於或等於約5 ppm、或小於或等於約1 ppm，例如，在以下範圍：約1 ppm至約100 ppm，包括其之間的所有範圍及子範圍。Exemplary active cations in refractories include alkali metals (e.g., Li, Na, K). In various embodiments, the concentrations of these metals can be reduced using the processing methods disclosed herein. For example, the treated refractory material may contain less than about 1000 ppm sodium by weight, such as less than or equal to about 750 ppm, less than or equal to about 500 ppm, less than or equal to about 250 ppm, less than or equal to about 100 ppm, less than or equal to About 50 ppm, or less than or equal to about 10 ppm, for example, in the following range: about 1 ppm to about 1000 ppm, including all ranges and subranges therebetween. Likewise, the treated refractory material may contain less than about 100 ppm lithium or potassium by weight, such as less than or equal to about 50 ppm, less than or equal to about 40 ppm, less than or equal to about 30 ppm, less than or equal to about 20 ppm, Less than or equal to about 10 ppm, less than or equal to about 5 ppm, or less than or equal to about 1 ppm, for example, in the following range: about 1 ppm to about 100 ppm, including all ranges and subranges therebetween.

在另外的實施例中，鹼土金屬(例如，Mg、Ca)之濃度可使用本文揭示的處理方法減少。例如，經處理耐火材料可具有以重量計小於或等於約100 ppm之總鹼土金屬含量，諸如以重量計小於或等於約50 ppm、小於或等於約40 ppm、小於或等於約30 ppm，以重量計小於或等於20 ppm、或以重量計小於或等於10 ppm，例如，在以下範圍：約10 ppm至約100 ppm，包括其之間的所有範圍及子範圍。在某些實施例中，經處理耐火材料可包含以重量計小於或等於約100 ppm之鈣，諸如以重量計小於或等於約50 ppm、小於或等於約40 ppm、小於或等於約30 ppm，以重量計小於或等於20 ppm，或以重量計小於或等於10 ppm，例如，在以下範圍：約10 ppm至約100 ppm，包括其之間的所有範圍及子範圍。類似地，經處理耐火材料可包含以重量計小於或等於約100 ppm之鎂，諸如以重量計小於或等於約50 ppm、小於或等於約40 ppm、小於或等於約30 ppm，以重量計小於或等於20 ppm，或以重量計小於或等於10 ppm，例如，在以下範圍：約10 ppm至約100 ppm，包括其之間的所有範圍及子範圍。In other embodiments, the concentration of alkaline earth metals (eg, Mg, Ca) can be reduced using the treatment methods disclosed herein. For example, the treated refractory material may have a total alkaline earth metal content of less than or equal to about 100 ppm by weight, such as less than or equal to about 50 ppm, less than or equal to about 40 ppm, and less than or equal to about 30 ppm by weight. It is less than or equal to 20 ppm, or less than or equal to 10 ppm by weight, for example, in the following range: about 10 ppm to about 100 ppm, including all ranges and subranges therebetween. In some embodiments, the treated refractory material may include less than or equal to about 100 ppm calcium by weight, such as less than or equal to about 50 ppm, less than or equal to about 40 ppm, and less than or equal to about 30 ppm, Less than or equal to 20 ppm by weight, or less than or equal to 10 ppm by weight, for example, in the following range: about 10 ppm to about 100 ppm, including all ranges and subranges therebetween. Similarly, the treated refractory material may include magnesium less than or equal to about 100 ppm by weight, such as less than or equal to about 50 ppm by weight, less than or equal to about 40 ppm, less than or equal to about 30 ppm, and less than 20 ppm or less, or 10 ppm or less by weight, for example, in the following range: about 10 ppm to about 100 ppm, including all ranges and subranges therebetween.

本文揭示的耐火材料可為相對緻密的，例如，具有小於約20%之孔隙率，諸如小於約10%、小於約9%、小於約8%、小於約7%、小於約6%、小於約5%、小於約4%、小於約3%、小於約2%、或小於約1%，例如，在以下範圍：約0.1%至約20%、或約1%至約10%，包括其之間的所有範圍及子範圍。在某些實施例中，耐火材料可具有互連(「開孔」)孔隙率。示範性耐火材料包括但不限於鋁矽酸鹽耐火材料，其包含至少一個陶瓷相，諸如氧化鋁、富鋁紅柱石、熔融富鋁紅柱石、紅柱石、矽線石、藍晶石、及其組合，例如，氧化鋁-富鋁紅柱石。在一些實施例中，氧化鋁-富鋁紅柱石可包含至少約2重量%之氧化鋁陶瓷相。The refractory materials disclosed herein may be relatively dense, for example, having a porosity of less than about 20%, such as less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6%, less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1%, for example, in the following range: about 0.1% to about 20%, or about 1% to about 10%, inclusive All ranges and subranges. In some embodiments, the refractory material may have interconnect ("open cell") porosity. Exemplary refractory materials include, but are not limited to, aluminosilicate refractory materials including at least one ceramic phase, such as alumina, mullite, fused mullite, andalusite, sillimanite, kyanite, and A combination, for example, alumina-mullite. In some embodiments, the alumina-mullite may include at least about 2% by weight of an alumina ceramic phase.

將瞭解各種所揭開實施例可涉及結合彼特定實施例描述的特定特徵、要素或步驟。亦將瞭解，雖然關於特定實施例描述了特定特徵、要素或步驟，但該特定特徵、要素或步驟可以各種未說明組合或排列中與替代實施例互換或組合。It will be understood that various disclosed embodiments may involve specific features, elements or steps described in connection with that particular embodiment. It will also be understood that, although a particular feature, element, or step has been described with respect to a particular embodiment, the particular feature, element, or step may be interchanged or combined with alternative embodiments in various unexplained combinations or permutations.

亦應理解，如本文所使用，術語「該」、「一(a)」或「一(an)」意味著「至少一個」，且不應受限於「僅一個」，除非明確地指示為相反。因此，例如，提及「一組分」包括具有兩個或兩個以上此種組分之實例，除非上下文另外清楚地指示。It should also be understood that as used herein, the terms "the", "an", or "an" mean "at least one" and should not be limited to "only one" unless explicitly indicated as in contrast. Thus, for example, reference to "a component" includes examples having two or more such components, unless the context clearly indicates otherwise.

範圍可在本文表達為自「約」一個特定值，及/或至「約」另一特定值。在表達此種範圍時，實例包括自該一個特定值及/或至該另一特定值。類似地，在值係表達為近似值時，藉由使用前述詞「約」，應理解特定值形成另一態樣。將進一步理解，每一範圍之端點與另一端點顯著相關，且獨立於另一端點。Ranges may be expressed herein as "about" one particular value, and / or to "about" another particular value. In expressing such a range, examples include from the one particular value and / or to the other particular value. Similarly, when the value system is expressed as an approximate value, by using the aforementioned word "about", it should be understood that the specific value forms another aspect. It will be further understood that the endpoint of each range is significantly related to and independent of the other endpoint.

如本文所使用的術語「實質」、「實質上」、及其變化形式意欲指出所描述特徵係等於或近似等於一值或描述內容。此外，「實質上類似的」意欲表示兩個值相等或近似相等。在一些實施例中，「實質上類似的」可表示值彼此相差約10%以內，諸如彼此相差約5%以內，或彼此相差約2%以內。The terms "essential", "essential", and variations thereof as used herein are intended to indicate that the described feature is equal to or approximately equal to a value or description. Furthermore, "substantially similar" is intended to mean that two values are equal or approximately equal. In some embodiments, "substantially similar" may mean that values differ from each other within about 10%, such as within about 5% of each other, or within about 2% of each other.

除非另外明確地陳述，否則本文闡述的任何方法決不意欲解釋為需要以特定順序執行其步驟。因此，在其中方法請求項實際上並未敘述其步驟所遵循之順序或在申請專利範圍或說明書中並未另外明確地陳述步驟將限於特定順序的情況下，決不意欲推斷任何特定順序。Unless explicitly stated otherwise, any method set forth herein is in no way intended to be construed as requiring its steps to be performed in a particular order. Therefore, in the case where a method claim does not actually describe the order in which its steps are followed or in the scope of the patent application or the specification does not expressly state otherwise that the steps will be limited to a particular order, no particular order is intended to be inferred.

雖然特定實施例之各種特徵、要素或步驟可使用過渡片語「包含」來揭示，但應理解暗示了替代實施例，包括可使用過渡片語「由...組成」或「主要由...組成」描述的彼等實施例。因此，例如，對包含A+B+C之產品的所暗示替代實施例包括其中產品由A+B+C組成之實施例及其中產品主要由A+B+C組成之實施例。Although various features, elements, or steps of a particular embodiment may be revealed using the transitional phrase "comprising", it should be understood that alternative embodiments are implied, including that the transitional phrase "consisting of" or "mainly consisting of ... "Composition" describes their embodiments. Thus, for example, an implied alternative embodiment for a product containing A + B + C includes an embodiment where the product consists of A + B + C and an embodiment where the product consists primarily of A + B + C.

將對熟習此項技術者明顯的是，在不脫離本揭示內容之精神及範疇的情況下，可對本揭示內容做出各種修改及變化。因為納入本揭示內容之精神及實質的所揭示實施例之修改組合、子組合及變化可由熟習此項技術者思及，所以本揭示內容應解釋為包括隨附申請專利範圍及其等效物之範疇內的所有事物。It will be apparent to those skilled in the art that various modifications and changes can be made to the present disclosure without departing from the spirit and scope of the disclosure. Since the modified combinations, sub-combinations, and changes of the disclosed embodiments incorporating the spirit and substance of this disclosure can be considered by those skilled in the art, this disclosure should be construed to include the scope of the accompanying patent application and its equivalents Everything in the category.

以下實例意欲僅為非限制性及說明性的，其中本發明之範疇係藉由申請專利範圍來界定。
實例
實例 1 ：元素分析 The following examples are intended to be non-limiting and illustrative, in which the scope of the invention is defined by the scope of patent applications.
Examples
Example 1 : Elemental analysis

在密封Thermaltek管式爐中，在流動氯氣(75 sccm)與氮(1.4 slpm)下，將具有0.2 cm x 1 cm x 1 cm之樣本大小的兩個高氧化鋁富鋁紅柱石耐火材料樣本(來自HarbisonWalker International之GEM®)加熱至1200℃且在此溫度下保持6小時。在處理之後，關閉氯氣且將氧引入管式爐中。將樣本在流動氧氣(1.5 slpm)下，在1200℃下保持一小時，且隨後以300℃/hr之速率在流動氧氣下冷卻至室溫。In a sealed Thermaltek tube furnace, two samples of high alumina mullite refractory material with a sample size of 0.2 cm x 1 cm x 1 cm were sampled under flowing chlorine (75 sccm) and nitrogen (1.4 slpm) ( GEM® from Harbison Walker International) was heated to 1200 ° C and held at this temperature for 6 hours. After the treatment, the chlorine gas was turned off and oxygen was introduced into the tube furnace. The sample was held under flowing oxygen (1.5 slpm) at 1200 ° C for one hour, and then cooled to room temperature under flowing oxygen at a rate of 300 ° C / hr.

Thermaltek管式爐含有二氧化矽高溫爐 (4吋x4吋)，其中陽極化鋁端蓋係以空氣冷卻的Viton®O型環密封。熔爐包括12吋熱均勻熱區。熔爐之進口端為連接至氯氣槽及氮氣管線之不銹鋼(416 SS)管件。單獨的儲氧箱係栓系至進口端蓋中。襯於端蓋上之Teflon™允許氣體流出熔爐進入氫氧化鉀(KOH)污染減少洗滌器中以在將出口氣體排氣之前自其移除氯及鹽酸。The Thermaltek tube furnace contains a silicon dioxide high temperature furnace (4 "x 4") with anodized aluminum end caps sealed with an air-cooled Viton® O-ring. The furnace includes a 12-inch hot uniform hot zone. The inlet end of the furnace is stainless steel (416 SS) fittings connected to the chlorine tank and nitrogen pipeline. A separate oxygen storage tank is tethered into the inlet end cap. Teflon ™ lined with an end cap allows the gas to flow out of the furnace into a potassium hydroxide (KOH) pollution reduction scrubber to remove chlorine and hydrochloric acid from the outlet gas before venting it.

感應耦合電漿質譜測定儀(inductively coupled plasma mass spectrometer; ICP-MS)元素分析係在經處理樣本以及未處理樣本上執行。下文表1中提供實驗結果，其表明經處理樣本的鹼金屬(Na、Li、K)含量(78.7%)之顯著減少。
實例 2 ：潛變測試 Inductively coupled plasma mass spectrometer (ICP-MS) elemental analysis is performed on processed and unprocessed samples. The experimental results are provided in Table 1 below, which indicate a significant reduction in the alkali metal (Na, Li, K) content (78.7%) of the treated samples.
Example 2 : Creep Test

在密封Thermaltek管式爐中，在流動氯氣及氮氣下，將具有7.5 mm x 7 mm x 165 mm之樣本大小的三個高氧化鋁富鋁紅柱石耐火材料條(來自HarbisonWalker International之凝膠鑄製GEM®)加熱至1361℃且在此溫度下保持8小時。在處理之後，關閉氯氣且將氧引入管式爐中。將樣本在流動氧氣下，在1350℃下保持一小時，且隨後以125℃/hr之速率在流動氧氣下冷卻至室溫。所有氣體之流率與上文實例1中揭示的彼等流率相同。處理後的三個耐火材料GEM®條之累計重量比預處理累計重量小2.8%。In a sealed Thermaltek tube furnace, three strips of high alumina mullite refractory material (gel cast from HarbisonWalker International) with a sample size of 7.5 mm x 7 mm x 165 mm were cast under flowing chlorine and nitrogen. GEM®) was heated to 1361 ° C and held at this temperature for 8 hours. After the treatment, the chlorine gas was turned off and oxygen was introduced into the tube furnace. The sample was kept under flowing oxygen at 1350 ° C for one hour, and then cooled to room temperature under flowing oxygen at a rate of 125 ° C / hr. The flow rates of all gases are the same as those disclosed in Example 1 above. The cumulative weight of the three refractory GEM® bars after treatment was 2.8% less than the cumulative weight of the pretreatment.

使用高溫三點彎曲實驗對經處理及未處理耐火材料條執行潛變量測。將條之每一端部藉由樣本固持器支撐，且自每一條之中間懸掛砝碼以施加所要應力位準。在1350℃及250 psi外加負載下對經處理及未處理GEM®條執行潛變測試達100小時之時間段。潛變應變率係由每一條之撓度計算以針對樣本固持器中的任何移動之校正來計算。Latent variable measurements were performed on treated and untreated strips of refractory material using high temperature three-point bending experiments. Each end of the bar is supported by a sample holder, and a weight is suspended from the middle of each bar to apply a desired stress level. Perform creep tests on treated and untreated GEM® bars at 1350 ° C and 250 psi for a period of 100 hours. The creep strain rate is calculated from the deflection of each bar to correct for any movement in the sample holder.

第 3 圖中提供實驗結果，其中圖A 表示未處理樣本且圖B 表示經處理樣本。未處理樣本A在到達溫度之後極快速進入第三期潛變(例如，其中發生破壞的最終階段潛變)，且在100小時測試中破壞29小時。對比而言，經處理樣本B 在測試中保存，無破壞或不進入第三期潛變且替代地保持在第二期潛變(例如，不發生破壞的穩態條件)。在1350℃及250 psi下經處理樣本之潛變速率係計算為2.35 x 10^-5 h^-1 。歸因於條之破壞，未計算未處理樣本之潛變速率。在不希望受理論約束的情況下，咸信經處理樣本之潛變效能歸因於實例1中所用的氯處理而隨鹼金屬含量的減少而改良。 The experimental results are provided in Figure 3 , where Figure A represents unprocessed samples and Figure B represents processed samples. Untreated sample A entered the third phase of creep very quickly after reaching the temperature (eg, the final phase of creep in which damage occurred), and broke for 29 hours in a 100 hour test. In contrast, the processed sample B was stored during the test without damage or entering the third phase of creep and instead remained in the second phase of creep (eg, steady state conditions where no damage occurred). The latent rate of the treated sample at 1350 ° C and 250 psi was calculated as 2.35 x 10 ^-5 h ^-1 . Due to the destruction of the bars, the creep rate of untreated samples was not calculated. Without wishing to be bound by theory, the latent performance of the Xianxin treated samples is attributed to the chlorine treatment used in Example 1 and improved with decreasing alkali metal content.

100‧‧‧玻璃製造系統100‧‧‧ Glass Manufacturing System

110‧‧‧熔融容器 110‧‧‧melt container

112‧‧‧箭頭 112‧‧‧arrow

114‧‧‧熔融玻璃 114‧‧‧ molten glass

116‧‧‧熔融至澄清管 116‧‧‧ fused to clarified tube

118‧‧‧位準探針豎管 118‧‧‧ quasi-probe standpipe

120‧‧‧澄清容器 120‧‧‧ clarification container

122‧‧‧澄清至混合連接管 122‧‧‧ Clarified to mixed connection

124‧‧‧混合容器 124‧‧‧mixing container

126‧‧‧混合至遞送連接管 126‧‧‧ mixed to delivery connection

128‧‧‧遞送容器 128‧‧‧ delivery container

132‧‧‧降流管 132‧‧‧ Downcomer

200‧‧‧熔融拉製機 200‧‧‧melt drawing machine

205‧‧‧入口管 205‧‧‧Inlet tube

215‧‧‧成形主體 215‧‧‧formed body

225‧‧‧進口 225‧‧‧import

235‧‧‧流槽 235‧‧‧ flume

245‧‧‧成形表面 245‧‧‧Formed surface

255‧‧‧根部 255‧‧‧root

265‧‧‧牽引輥總成 265‧‧‧traction roller assembly

275‧‧‧玻璃帶 275‧‧‧glass ribbon

以下詳細描述可在結合以下圖式閱讀時得以最好的理解，其中在可能的情況下相同結構利用相同參考數字指示，且其中：The following detailed description may be best understood when read in conjunction with the following drawings, where the same structure is indicated with the same reference numerals when possible, and where:

第 1 圖說明示範性玻璃製造系統； FIG 1 illustrates an exemplary glass manufacturing system;

第 2 圖為描繪示範性耐火材料之潛變速率隨鹼金屬濃度變化的圖；及 FIG 2 is a graph depicting an exemplary creep rate of the refractory metal with the alkali concentration of Figure 1; and

第 3 圖為描繪經處理及未處理耐火材料之潛變撓度曲線的圖。 FIG 3 is a graph depicting the treated and untreated refractories creep deflection curve of FIG.

國內寄存資訊 (請依寄存機構、日期、號碼順序註記)
無Domestic storage information (please note in order of storage organization, date, and number)
no

國外寄存資訊 (請依寄存國家、機構、日期、號碼順序註記)
無Information on foreign deposits (please note according to the order of the country, institution, date, and number)
no

Claims

一種氧化鋁-富鋁紅柱石耐火材料，其包含：一氧化鋁陶瓷相及一富鋁紅柱石陶瓷相，其中該氧化鋁陶瓷相構成該耐火材料之至少約2重量%；以重量計小於或等於約1000 ppm之一總鹼金屬含量；及在1350℃下在250 psi下小於約2.5 x 10^-5 h^-1 之一潛變速率。An alumina-mullite refractory material comprising: an alumina ceramic phase and a mullite ceramic phase, wherein the alumina ceramic phase constitutes at least about 2% by weight of the refractory material; less than or Equal to one of the total alkali metal content of about 1000 ppm; and a creep rate of less than about 2.5 x 10 ^-5 h ^-1 at 250 psi at 1350 ° C.

一種鋁矽酸鹽耐火材料，其包含：至少一個陶瓷相；小於約3重量%之一玻璃相；及以重量計小於或等於約1000 ppm之一總鹼金屬含量。An aluminosilicate refractory material comprising: At least one ceramic phase; a glass phase of less than about 3% by weight; and a total alkali metal content of less than or equal to about 1000 ppm by weight.

如請求項1或2所述之耐火材料，其中該總鹼金屬含量為以重量計小於或等於約750 ppm。The refractory material according to claim 1 or 2, wherein the total alkali metal content is less than or equal to about 750 ppm by weight.

如請求項1或2所述之耐火材料，其中該總鹼金屬含量為以重量計小於或等於約500 ppm。The refractory material according to claim 1 or 2, wherein the total alkali metal content is less than or equal to about 500 ppm by weight.

如請求項1或2所述之耐火材料，其包含以下各項中之至少一者：以重量計小於或等於約750 ppm之鈉；以重量計小於或等於約10 ppm之鋰；或以重量計小於或等於約50 ppm之鉀。The refractory material according to claim 1 or 2, comprising at least one of the following: Sodium is less than or equal to about 750 ppm by weight; lithium is less than or equal to about 10 ppm by weight; or potassium is less than or equal to about 50 ppm by weight.

如請求項1或2所述之耐火材料，其包含以重量計小於或等於約200 ppm之一鐵含量。The refractory material according to claim 1 or 2, comprising an iron content of less than or equal to about 200 ppm by weight.

如請求項1或2所述之耐火材料，其包含小於或等於約100 ppm之總鹼土金屬含量。The refractory material according to claim 1 or 2, comprising a total alkaline earth metal content of less than or equal to about 100 ppm.

如請求項1或2所述之耐火材料，其包含小於或等於約50 ppm之一總鹼土金屬。The refractory material according to claim 1 or 2, comprising less than or equal to about 50 ppm of a total alkaline earth metal.

如請求項1或2所述之耐火材料，其包含以下各項中之至少一者：小於或等於約50 ppm鈣；或小於或等於約50 ppm鎂。The refractory material according to claim 1 or 2, comprising at least one of the following: Less than or equal to about 50 ppm calcium; or less than or equal to about 50 ppm magnesium.

如請求項1所述之耐火材料，其中在1350℃及250 psi下的該潛變速率小於或等於約1 x 10^-5 h^-1 。The refractory material according to claim 1, wherein the creep rate at 1350 ° C and 250 psi is less than or equal to about 1 x 10 ^-5 h ^-1 .

如請求項2所述之耐火材料，其中該玻璃相構成該耐火材料之小於約1重量%。The refractory material according to claim 2, wherein the glass phase constitutes less than about 1% by weight of the refractory material.

如請求項2所述之耐火材料，其中該至少一個陶瓷相係選自氧化鋁、富鋁紅柱石、熔融富鋁紅柱石、紅柱石、矽線石、藍晶石、及其組合。The refractory material according to claim 2, wherein the at least one ceramic phase is selected from the group consisting of alumina, mullite, fused mullite, andalusite, sillimanite, kyanite, and combinations thereof.

如請求項12所述之耐火材料，其包含一氧化鋁陶瓷相及一富鋁紅柱石陶瓷相。The refractory material according to claim 12, comprising an alumina ceramic phase and a mullite ceramic phase.

一種耐火磚或磚片，其包含一如請求項1或2所述之耐火材料。A refractory brick or tile comprising a refractory material according to claim 1 or 2.

一種熔融容器，其包含一如請求項14所述之耐火磚。A melting vessel comprising a refractory brick as described in claim 14.

一種澄清容器，其包含一如請求項14所述之耐火磚。A clarification container comprising a refractory brick as described in claim 14.