TW201036935A - Ceramic product - Google Patents
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- TW201036935A TW201036935A TW099102115A TW99102115A TW201036935A TW 201036935 A TW201036935 A TW 201036935A TW 099102115 A TW099102115 A TW 099102115A TW 99102115 A TW99102115 A TW 99102115A TW 201036935 A TW201036935 A TW 201036935A
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Description
201036935 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種用天然及/或合成無機非金屬原料、 至少一黏合劑及可能之其他添加劑所構成的混合物製成的 陶瓷製品。 【先前技術】 陶瓷製品軟化溫度超過1 〇〇〇°c,故應用廣泛,舉例而 ❹ 5,陶瓷製品可作為耐火材料應用於冶金容器裏襯,抑或 用作連續鑄造領域的關鍵零組件,例如:浸入式注口、滑 板、基棒或流槽。耐火製品(軟化溫度超過丨500。〔〕)此外亦 在咼爐領域、冶金運輸容器、廢物焚化工業、水泥工業及 化學工業中用作襯料。 耐火製品視處理技術分為成形材料(成形件)及未成形材 料(即,於使用過程中成形)。 未成开> 耐火材料領域在過去3 0年中歷經了重大發展。其 〇 在财火建築材料總產量中所佔份額接近45%,係一類重要 耐火材料。其中,耐火混凝土係為最重要之未成形耐火材 料。未成形耐火材料如今在很大程度上屬於品質上不遜於 '任何成形耐火製品的高級確定成分材料。 * 耐火材料係由粒狀耐火礦物氧化物及/或非氧化物原料 (氧化物,例如:A1203、MgO、MgAl2〇4、CaO、ΖιΌ2、 心2〇3、Ce〇2、Y2〇3、Ti〇2或含有此等物質的原料,如紹 礬土、紅柱石、白雲石、耐火黏土;及非氡化物,例如: SiC、Si#4、BN、Ββ)的混合物構成,該混合物通常具有 145848.doc 201036935 明確且與相關處理方法匹配之粒度分布。由於此混合物係 :'、、I的顆粒•合物,故須在其中添加適當的黏合劑或黏 合劑組合物來確保材料在所有技術處理步驟(如,製造、 力熱及使用)中均具有足夠強度。所用之黏合劑係為反應 f生物處,可與水、空氣及/或熱協同作用而自行變硬。未 成形耐火材料此外亦含有稀釋劑或助劑形式之添加劑。 最㊉用之黏合劑為基於鋁酸鈣的水泥,即氧化鋁水泥, 等夂泥可因水化過程(水化結合)而使财火製品得到強 化。但若該耐火材料含有氧化鈣(此為常見情況),則會形 成非期望的相’從而使材料特性受到不利影響,最終破壞 及降低該耐火材料之特性及使用溫度。鑒於存在上述之不 孝J因素,業界迄今已開展大量旨在減少或激底消除氧化紹 水泥的研製工作。 早先的傳統耐火混凝土含有15%_20%之氧化鋁水泥。其 最高使用溫度限於1500t左右之範圍,因為黏合劑成分與 顆粒間之反應會產生低熔點化合物。此現象促使業界開始 研製低水泥耐火混凝土。此項技術係藉由微細填充劑(例 如,矽灰)之使用並結合稀釋劑來降低水泥含量。此類低 水泥耐火混凝土之特點在於因顆粒充填經最佳化、強度最 小值大幅減小及密度尚而強度有所增大,此外其孔隙率亦 相對較小較細。但此類低水泥耐火混凝土因其孔隙率較小 而更容易變乾變熱。作為氧化鋁水泥水化結合之替代方 案,近年來可水合過渡氧化鋁的應用獲得了部分成效。此 種點合劑消除了氧化#5的不良影響。 145848.doc 201036935 另一類黏合劑包括化學無機物。此類黏合劑可應用於塑 性材料及捣打料、鑄塑料及噴敷料。基於鹼性矽酸鹽溶液 之水玻璃(使用範圍為1〇〇。(:_1〇〇〇。〔:)及適用溫度範圍高達 1600 C之磷酸化合物(通常為磷酸鋁)較為常用。此種化學 黏合之特點在於黏著效果極佳且不存在強度最小值。但此 處所用之黏合劑體系的化學機制亦會非期望地導致最高使 用咖度叉到不利影響。此外亦無法避免經化學黏合的系統 ❹ ❹ 因(例如)磷酸鹽蒸發而與周圍物質發生相互作用。 亞硫酸鹽廢液、甲基纖維素、海藻酸鹽、石夕酸乙醋、四 乙氧,石夕燒及其他大分子物質形式之耐火材料有機黏合劑 $許夕It况下亦可提供可接受的強度值。但此類體系亦經 常因所施加化合物引起非期望的反應而無法避免使用受限 之情f。所施加之化合物部分情況下會限制應用範圍或限 制可此之黏合劑用量。許多有機黏合劑“列如,亞硫酸鹽 廢液及纖維素)相當於暫時點合劑,因為此類點合劑在加 熱時會自某—溫度範圍起幾乎無殘留地燃盡,從而僅能暫 時起到黏合劑之你_田 J之作用。但某些黏合劑(例如,矽酸乙酯 月邑保留部分點A南丨鍊* ••口 d體系(右以矽酸乙酯為例,則為二 矽),故能繼續發揮黏合劑之作用。 對於未成形製品特別是經水化結合之材料而言 加熱等處理步驟萡ώ 知及 而難度頗大 自較㈣之結構移除較多之殘餘水分 m €已製成構件之整體裏襯設計及規格而定, :常,極長之乾燥時間方能 時亦存在Μ乾化〜 此處理步驟同 Μ之危險,從而使裏襯或預製 145848.doc 201036935 損。此外在初步加熱整體製品時須注意,整體製品通常在 300°C至900°C之範圍内具有強度最小值。此最小值處於材 料之水合物相脫水與陶瓷結合之間的溫度範圍内。其中, 黏合劑相脫水時會引起黏合強度的損失。僅當約1〇〇(rc以 上之燒結過程促成陶瓷結合過程開始時,方會出現強度上 升的現象。 對未成形耐火材料的處理(確切而言為成形處理)及熱處 理通常在其使用場所或在使用條件下進行。直接在送貨狀 恶下或在添加必要液體量後進行處理。藉由振動、無振動 澆注(自流材料)、撥捅、捣打或喷敷等方式來將此等材料 石切入。此等材料通常無需加熱便可實現黏合及硬化。填塞 耐火材料後即產生相對於砌體而言具整體(即,無縫)外觀 的裏襯。 成形耐火材料之製造方法如下:將原料裝入(例如)用於 製造耐火管或耐火磚的成形結構,將耐火管或耐火磚脫模 並藉由持續數天且溫度約為200°c至7〇〇t之乾燥過程為其 脫水。此法耗時極長且需要大量水來實現充分的流動性, 而此亦會引起一個需耗用相應時間的乾燥過程。但若加快 加熱過程’則會導致成品乾裂及爆裂。 EP 0 577 733 B1揭示一種藉由5 wt%至7 wt%之專用液態 西曰硬化甲階g分搭樹脂以酯為硬化劑用氧化鎂、氧化飼、氧 化鋁、矽酸鋁、鎂鋁尖晶石及其混合物製造耐火材料的方 法。但此種材料會在製造過程中因黏度高而產生不均勻 性。此外視具體用途亦會在該而才火材料中殘留大量殘碳。 145848.doc 201036935 此殘碳(亦如在含石墨混合物中般)會在該耐火材料使用過 程中自該耐火材料排出,致使該耐火製品之孔隙率增大。 當與(例如)液態鐵接觸時,液態鐵會自此等孔隙滲入,最 使該耐火製品之使用壽命縮短。此外,㈣燒被排出 — 的碳會被液態鐵吸收,從而導致待製鋼材特別是不鏽鋼出 現品質損失。 此外,EP 0 530 943⑴亦揭示一種製造耐火材料的方 0 法,該方法藉由使用至少3 wt%之熱固性酚醛樹脂及使用 可提供天冬胺酸陰離子、氟化物陰離子、二氟化物陰離 子、蘋果酸鹽陰離子、酒石酸鹽陰離子、擰檬酸鹽陰離 子、膦酸鹽陰離子且含有專用四烷氧矽烷的化合物來延遲 含燒硬氧化鎂或過燒氧化鎂之材料的硬化。 然而結果表明,上述成分會使製造過程中出現高黏度。 就處理技術而言,此種高黏度之不利之處在於會使成形環 境無法被完全填滿。 O JP 〇733〇451_A、JP 05070246-A 及 JP 2008-0249 所提及之 耐火材料含有礦考勿質成A、用4乍黏合劑之合成樹脂及其他 有機添加劑。藉此可以不同方式對該等耐火材料之特性施 •加影響。 【發明内容】 有鑒於此,本發明之目的在於提供一種至少可在腐蝕及 乜蝕方面肩除先前技術之上述習知缺點的陶瓷製品。 根據本發明,此目的之解決方案如下:用天然及/或合 成無機非金屬原料、至少—黏合劑及可能之其他添加劑所 145848.doc 201036935 構成的混合物製造該陶瓷製品,其中,該混合物含有 a) 至少1〇 wt%(以該混合物之全部固體物質的重量為參 照)之氧化物成分, b) 〇.〇5 wt%至2.7 wt%(以該混合物之全部固體物質的 重量為參照)的至少一有機系黏合劑,該黏合劑對該 混合物具有稀釋作用,及 c) 3 wt%至10 wt%(以該混合物之全部固體物質的重量 為參照)之含水分散劑, 該陶瓷製品在600°C以上之溫度下使用後含碳量低於〇1 wt%(以該陶瓷製品之總重為參照)。 因為本發明出人思料地發現,在製造本發明之陶竟製品 過程中該混合物具有就處理技術而言極為有利的低黏度, 故而無需以額外成本提供並使用會對其他特性產生影^之 附加稀釋劑。該混合物因黏度低而具良好之流動性,故而 得以有效填滿成形環境,進而製造出高品質的陶瓷製品。 此外,該陶瓷製品之製造過程所需水量亦相對較少,藉此 可鈿知乾燥時間,避免該陶瓷製品内部或表面發生乾裂及 爆裂。 ^ 本發明之陶瓷製品含碳量低於〇 1 wt%(以該陶竞製品之 總重為參照)’較佳為〇 wt%,與一般情況下含有耐火混凝 土之傳統耐火材料相比,其另一特點在於,本發明之陶瓷 製品乾燥後至少具有較高之常溫抗碎強度及較大之密度, 燒成後具有較小之孔隙率。此外,本發明之陶瓷製品亦可 用傳統製造工藝製造,故不會產生附加工作量。因此,成 145848.doc 201036935 品構件脫模及整體裏襯拆模所需時間與先前技術相同。隨 後之乾燥過程難度相對較小,因為本發明不產生會在特殊 :度範圍内加劇脫水程度的水合物相。作為乾燥輔助手 ,|’可如以水化結合為黏合手段之傳統耐火材料般添加纖 • 維(例如,天然纖維、塑性纖維),此等纖維可形成供物理 結合水逸出的通道。此夕卜亦可添加金屬纖維及/或非金屬 纖維以求在乾燥、加熱及使用過程中取得強化結構之效 ❹* &外,本發明之混合物因含碳量極低(或較佳不含碳) 而不會對鋼材品質產生影響。 較佳將 Al2〇3、Mg0、Si〇2、Ca〇、Zr〇2、心2〇3、 Ce〇2、Y2〇3、Ti〇2用作天然及/或合成無機非金屬原料, 以及/抑或將(例如)MgAl2〇4、尖晶石、鎂橄欖石、鋁礬 土、紅柱石、白雲石及/或耐火黏土用作含氧化物成分的 原料。此外亦可將非氧化物用作天然及/或合成無機非金 屬原料,其中的較佳之選為BN、Sic、叫队、¥或窗 ◎ 及/或加。但亦可使用先前技術中之其他習知的天然及/或 合成無機非金屬原料。 根據本發明,該陶曼製品如上所述含有至少ig心(以 該$合物之全部固體物質的重量為參照)之氧化物成分。 ’右所用氧化物成分少於10 wt%,則材料中會出現固體顆 粒與分散劑部分分離的現象。 較佳使用至少1 〇 wt%之氧化物成分來製造該陶瓷製品, 因為在10 wt%以上,耐火顆粒將不再出現分離及沈積現 145848.doc 201036935 氧化物成分與非氧化物成分之比尤佳為80:20至5〇 5〇, 此點既有利於可加工性,亦有利於高溫性能(例如,抗蠕 變性)。 依據所需使用之處理方法(例如,振動夯實、無振動淹 注(自流材料)、撥捅、捣打或噴敷)調整由上述原料構成之 充填料的粒度分布。根據常規理論(例如,關於粒度分布 之Andreassen顆粒堆積理論)實施此種粒度分布調整。其 中,藉由一有利於各種處理技術之粒度因子對材料進行最 佳化處理,以求獲得理想分布。粒度因子係粒度累積分布 上升的一種對數表示。故通常用有利於自流材料(無外力 作用夯實)之介於〇·25與0_30間的粒度因子來設計自流材 料。對振動料則一般採用比之更大的$,亦即〇 30-0.35。 該等材料在細粒、中粒及粗粒範圍内分別由相應的耐火氧 化物、由此等耐火氧化物之化合物構成的天然或合成原料 及/或上述物質之混合物構成。其教度範圍包括自奈米範 圍直至粗粒範圍之顆粒’其中,粗粒範圍之最大粒徑可達 =最後可以說’可在所有直至目前之先前技術所用 :火減物或氧化物中以含主成分之材料的形式用作替 代物。 較佳將以合成法製成的黏合劑(如,㈣樹脂、環氧杉 曰广樹脂、胺基樹脂、醇酸樹脂、間苯二龄樹脂及 清漆、甲階㈣樹脂及/或環氧樹脂構成的水七 刀政體、丙埽酸酯分散體及/岑平 媸及飞承胺酯分散體)及/或用天教 …、成的黏合劑(如,食糖、葡萄糖 '多糖、單寧及/資 145848.doc 201036935 木質素)用作该有機系黏合劑。天然原料因具再生長性而 為有利之選。酚醛樹脂、呋喃樹脂、環氧樹脂及胺基樹脂 可在室溫下硬化,作黏合劑用極為有利。如此便無需使用 附加硬化劑。若使用分散體,則低單體含量及低黏度的水 性分散體為有利的分散體。 使用水性酚醛樹脂為尤佳之選,因為水性酚醛樹脂可於 室溫下在添加硬化劑之情況下發生硬化,硬化時間便於控 制’且通常不含有機溶劑。 製造本發明之陶究製品時’以〇 〇5 wt%至I? (以該
〇 達到最大,該陶瓷製品煅燒後的孔隙率達到最低。
此外’該混合物㈣地含有硬化_式之其他添加劑。 ‘物之全部固體物質的重 因為在此範圍内,硬化 較佳以0.1 wt%至0.6 wt%(以該混合物 量為參照)之濃度添加該硬化劑, 145848.doc 201036935 速度及所產生之強度均能符合要求。先前技術中所有適用 於相應樹脂的習知硬化劑均可使用。選自酯(低分子内 酯,例如:丁内酯、己内酯、丙内酯、泛解酸内醋 (Pentyllacton)、碳酸丙烯醋、碳酸乙浠醋等)、酸(例如, 對經基苯績酸)或胺(例如,聚胺(脂族、環脂族或芳族)、 聚醯胺、曼尼希鹼、聚胺基咪唑啉、聚醚胺)等領域的硬 化劑尤佳,該硬化劑可與該樹脂的專門應用相匹配。 特別是酯類硬化劑之硬化時間可與處理過程精確匹配。 然而,一般情況下亦可放棄使用硬化劑,此時透過溫度 0 影響實現硬化。由此產生之優點在於可減少—種成分,從 而達到降低成本之目的,而該混合物之其他特性不會受到 任何影響。 可以但並非必須使用對該混合物具有稀釋及/或黏合作 用之其他有機及/或無機添加劑,如此便可免去此等添加 劏的製備工作及相應費用。由於成分少,其可能會對該混 合物或該陶瓷製品之特性產生的非期望影響亦得以避免。 本發明之陶瓷製品在6〇(Tc以上之溫度下使用後含碳量 ◎ 低於0.1 wt%(以該陶瓷製品之總重為參照),其中,若本發 明之陶竟製品明確不含碳,則為尤佳之選。據此,應以使 付4製硬化後含碳量低於〇. i wt%為原則來選擇該混合 物之各成分及使用參數。 本冬明之陶瓷製品可藉由一種包括下列步驟的方法製 成: a)製造該均勻混合物; J45848.doc 12 201036935 b) 對該混合物進行成形處理並在^它以上之溫度下進 行乾燥及/或硬化處理;及 c) 視情況進行脫模並在5〇它以上之溫度下進行進一步 之乾燥及/或硬化處理。 製造成形及未成形製品時,在(例如)EiHch公司的混合 器内將具有相應顆粒結構之陶瓷原料與相應量的黏合劑均 勻混合。 〇 t造未成形材料日寺,將±述混合物包裝並運送至使用場 所。就地在混合器内添加適量的硬化劑及水,隨後將澆注 材料送入(例如,用泵打入)待加襯之設備内。製造成形材 料時,視情況在混合器内將原料及黏合劑所構成之混合物 直接與相應量的硬化劑及水混合。用模具對該混合物進行 乾燥及硬化處理,直至其具有足以實施脫模的硬度。隨後 直接對該成形件進行使用,或在12(rc_i8〇<t之溫度下進 一步對該成形件進行持續數小時的回火處理。 〇 本發明之陶兗製品可應用於(例如)冶金工業的機組設 備。 【實施方式】 下文將藉由實施例對本發明進行詳細說明。 t中所列之組成可用於製造成形耐火製品(例如,多孔 隔)及/或未成形耐火製品(例如,運鋼桶裏概)。此處涉 及兩種包含有本發明之混合物的充填料(充填料2及3)、-種基於可水合氧化紹㈧phab〇nd 3〇〇,Μ— 體系(充填料一較充填料4。此四種充填料均= 145848.doc -13· 201036935 氧化銘(Almatis公司的板狀氧化銘T60/T64)及富含氧化銘 之錢銘尖晶石(Almatis公司的AR78)構成的一致混合物。 表1所列者係為此四種實施例之組成。該等充填料彼此間 之區別在於,傳統充填料(充填料1)除所添加之黏合劑 Alphabond 300(可水合氧化鋁)外亦含有添加劑ADW1及 ADS 1 (分散氧化鋁)。但自該表中可看出,另外兩份充填料 (充填料2及充填料3)既未添加Alphabond 300’亦未添加添 加劑ADW及ADS。充填料2及充填料3分別含2°/。及1%之本 發明之混合物的有機系黏合劑。 表1 :充填料1至4 充填料 1 充填料2 (發明) 充填料3 (發明) 充填料4 [ma.-%l [ma.-%l [ma.-%l [ma,%l 製造商: Almatis 板狀氧化Is T60/T64 2-5 mm 25 25 25 25 1-3 mm 15 15 15 15— 0.5-1 mm 11 11 11 11 0-0.02 mm 11 11 11 11 AR78 0-0.5 mm 7 7 7 _ 7 0-0.09 mm 9 9 9 9 0-0.02 mm 8 8 8 8 _ 活性氧化鋁 CTC50 10 13 13 13 CT3000SG 1 1 1 1 _ 黏合劑 Alphabond300 3 - • ——— 100 ma% 添加劑 ADW1 0.5 - — ADS1 0.5 水 5.5 5.0 5.0 6.5 樹脂’ - 2.0 1.0 3 0 硬化劑" - 0.3 0.15 0.45 145848.doc • 14- 201036935 *游離酚含量低於1%、20°C下黏度為200-400 mPas及樹脂 含量為52-55%的紛系甲階紛搭樹脂(PhenoIres〇1) "配比為30:70之丁内酯與乙二醇二乙酸酯的混合物 , 用ToniTechnik公司的實驗室用混合器按傳統混凝土技 術將上述充填料混合,隨後澆鑄規格為40x40x160 mm的 試樣。3小時後將該等試樣脫模,並於12(TC下乾燥至恆 重。表2列舉了製成試樣的部分材料常數。充填料4不具有 可澆注性。 ®表2 :材料常數 處理溫度 材料常數 充填料1 充填料2 (發明) 充填料3 (發明) 120°C 乾燥 容積密度[g/cm3] 2.90 2.97 2.95 常溫抗碎強度[MPa] 3.20 5.53 4.63 煅燒 容積密度[g/cm3] 3.05 2.91 3.04 1650〇C 常溫抗碎強度[MPa] 39.80 33.96 37.07 動態彈性模數[GPa] 69 63 85 開口孔隙率[%] 17.1 15.4 15.4 含碳量[%] 0 0 0 本發明之材料不易乾裂,故亦具有相對較高之濕強度, 煅燒後之較低孔隙率可使腐蝕及侵蝕性能得到改善。 145848.doc •15-
Claims (1)
- 201036935 七、申請專利範圍: 1’ -種用天然、及/或合成無機非金屬原料、至少—黏合劑及 可能之其他添加劑所構成的混合物製成的陶瓷製品,其 中,該混合物含有 I , a)至)1 〇 wt%(以該混合物之全部固體物質為參照) 之氧化物成分, b) 〇.〇5wt/Q至2.7wt%(以該混合物之全部固體物質為 參知、)的至少一有機系黏合劑,該黏合劑在該混合 物中起稀釋作用,及 c) 3 wt%至1〇 wt%(以該混合物之全部固體物質為參 照)之含水分散劑, 该陶瓷製品在600°C以上之溫度下使用後含碳量低於〇」 Wt%(以該陶瓷製品之總重為參照)。 2.如申請專利範圍第1項之陶瓷製品,其特徵在於,氧化 物成分與非氧化物成分之比為80:20至50:50。 Q 3.如别述申請專利範圍中至少一項之陶瓷製品,其特徵在 於’該等氡化物成分選自Al2〇3、MgO、MgAl2〇4、 CaO、Zr〇2 ' Cr2〇3、Ce〇2、γ2〇2及/或丁你及/或含有此 1 等物質的天然及/或合成原料。 ,4.如剛述申請專利範圍中至少一項之陶瓷製品,其特徵在 於’该等非氧化物成分選自SiC、Si3N4、BN及/或64(:。 5_如刖述申請專利範圍中至少一項之陶瓷製品,其特徵在 ^亥有機糸黏合劑選自以合成法製成的黏合劑(如,紛 醛枒脂、環氧樹脂、呋喃樹脂、胺基樹脂、醇酸樹脂、 145848.doc 201036935 間苯二酚樹脂及/或由酚醛清漆、甲階酚醛樹脂及/或環 氧樹脂構成的水性分散體、丙烯酸酯分散體及/或聚胺= 分散體)及/或用天然原料製成的黏合劑(如,食糖、葡萄0 糖、多糖、木質素及/或單寧)。 6. 如申請專利範圍第5項之陶瓷製品,其特徵在於,該有 機系黏合劑為水性酌駿樹脂。 7. 如别述申請專利範圍中至少一項之陶瓷製品其特徵在 於,該混合物含有硬化劑形式之其他添加劑。 8. 如申請專利範圍第7項之陶瓷製品,其特徵在於,該硬 化劑選自酯、酸及/或胺之群組。 9. 如蝻述申請專利範圍中至少一項之陶瓷製品,其特徵在 於,该製品為一耐火成形件。 I 〇·如岫述申請專利範圍中至少一項之陶瓷製品,其特徵在 於,該製品於使用過程中成形。 II · 一種如前述申請專利範圍中至少一項之陶瓷製品的應 用’應用於冶金工業的機組設備。 12. 一種製造如申請專利範圍第9或10項之陶瓷製品的方 法’包括下列步驟: a) 製造該均勻混合物; b) 對該混合物進行成形處理並在^艽以上之溫度下 進行乾燥及/或硬化處理;及 c) 視情況進行脫模並在5〇乞以上之溫度下進行進一 步之乾燥及/或硬化處理。 145848.doc 201036935 四、指定代表圖: (一) 本案指定代表圖為:(無) (二) 本代表圖之元件符號簡單說明: 五、本案若有化學式時,請揭示最能顯示發明特徵的化學式: (無) 145848.doc
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JP5633489B2 (ja) * | 2011-08-31 | 2014-12-03 | 新日鐵住金株式会社 | Ni基合金およびNi基合金の製造方法 |
EP2803652B1 (en) | 2013-05-13 | 2018-08-15 | Calderys France | Spinel forming refractory compositions, their method of production and use thereof |
DE102014010441B4 (de) | 2013-07-18 | 2019-03-14 | Technische Universität Bergakademie Freiberg | Verfahren zur Herstellung Kohlenstoff enthaltender feuerfester Bauteile |
CN107207353A (zh) * | 2014-11-10 | 2017-09-26 | 圣戈本陶瓷及塑料股份有限公司 | 烧结陶瓷部件及其形成方法 |
CN104926277A (zh) * | 2015-06-02 | 2015-09-23 | 安徽省含山瓷业股份有限公司 | 一种铁矾土陶瓷碗及其制备方法 |
DE102016100083B4 (de) * | 2016-01-04 | 2019-02-14 | Refractory Intellectual Property Gmbh & Co. Kg | Feuerfeste Formkörper und Massen sowie Bindemittel und Verfahren zu deren Herstellung |
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US4939188A (en) * | 1988-12-22 | 1990-07-03 | Borden, Inc. | Lithium-containing resole composition for making a shaped refractory article and other hardened articles |
US5036116A (en) * | 1989-04-27 | 1991-07-30 | Acme Resin Corporation | Ester hardeners for phenolic resin binder systems |
US5179177A (en) | 1990-08-02 | 1993-01-12 | Borden, Inc. | Method for retarding ambient temperature hardening of a phenolic resin composition |
AU663870B2 (en) * | 1991-03-27 | 1995-10-26 | Minteq International Inc. | Vibratable resin-bonded refractory composition |
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US5686506A (en) * | 1995-04-04 | 1997-11-11 | Borden Chemical, Inc. | Mixtures of phenolic novolaks for use with refractory aggregate and methods for making same |
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