TW201843127A - 多孔耐火澆鑄材料、其用途及製造 - Google Patents

多孔耐火澆鑄材料、其用途及製造 Download PDF

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TW201843127A
TW201843127A TW107110732A TW107110732A TW201843127A TW 201843127 A TW201843127 A TW 201843127A TW 107110732 A TW107110732 A TW 107110732A TW 107110732 A TW107110732 A TW 107110732A TW 201843127 A TW201843127 A TW 201843127A
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particle size
refractory
aggregate
porous refractory
weight
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TW107110732A
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TWI841524B (zh
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杜安Ｌ 迪巴思提安尼
翔新 周
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美商維蘇威美國公司
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    • B01D39/2068—Other inorganic materials, e.g. ceramics
    • B01D39/2072—Other inorganic materials, e.g. ceramics the material being particulate or granular
    • B01D39/2075—Other inorganic materials, e.g. ceramics the material being particulate or granular sintered or bonded by inorganic agents
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    • B22D41/02—Linings
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Abstract

一種多孔耐火澆鑄材料含有封閉耐火骨材部分14，其具有最小粒度及最大粒度；最大粒度對最小粒度的比例為10：1或以下。此封閉耐火骨材部分全為粒徑大於0.1毫米之多孔耐火澆鑄材料。該多孔耐火澆鑄材料亦含有黏合劑相16，其含有選自鋁酸鈣水泥、磷酸鋁、可水合氧化鋁、膠態氧化矽、及其組合之耐火材。本發明亦揭示一種冶金容器，其具有帶有該多孔耐火澆鑄材料之內襯。

Description

多孔耐火澆鑄材料、其用途及製造
本發明大致關於一種用於冶金方法及容器(如漏斗)之耐火澆鑄材料、其用途、及其製造方法。
在金屬成形方法中，金屬熔化物被從一個冶金容器轉移到另一個冶金容器、模具、或器具。例如藉澆斗將大容量漏斗規律地以金屬熔化物進料，而將金屬熔化物從熔爐轉移到漏斗。如此可將金屬從漏斗連續澆鑄至器具或模具。金屬熔化物被重力驅動通過位於容器底部之噴嘴系統，其通常具有控制(開或關)金屬熔化物通過該噴嘴系統之閘系統，而從冶金容器流出。為了抵抗金屬熔化物之高溫，容器壁被襯以耐火材料。
金屬熔化物，尤其是鋼，對氧化為高反應性，因此必須防護隔離任何氧化性物種來源。其經常添加少量鋁以移除氧。實務上，顯然其經常不足以防止在熔化物中形成氧化物內含物，其在由該熔化物製造的最終零件中產生缺陷。據稱10公斤之鋼鑄件可含有至多十億個非金屬內含物，其大部分為氧化物。現已嚐試從浮選或 過濾方法移除內含物。
內含物可能為與金屬熔化物反應的結果；已知這些內含物為內生內含物。外生內含物為其中材料不由金屬熔化物生成者，如砂、熔渣、及噴嘴之碎屑；外生內含物通常比內生內含物更大量。
內生內含物大部分包含鐵(FeO)、鋁(Al2O3)之氧化物，及存在於或接觸該熔化物之其他化合物，如MnO、Cr2O3、SiO2、TiO2。其他內含物可包含硫化物及最小程度的氮化物與磷化物。由於金屬熔化物之溫度非常高(對低碳鋼為1600℃之級數)，顯然鐵原子對氧化物之反應性非常高，且無法防止反應。
迄今，大部分減少鋼鑄件中內含物存在之手段為將其留置在其被形成之冶金容器中。現已設計由耐火材料構成的各種裝置，以選擇性留置其中內含物集中之金屬熔化物部分。這些裝置可由各種物理組態構成，且可具有用於此目的之開口、通路、通道、或孔。
現已製造許多種在冶金容器及方法中用於特殊目的之多孔陶瓷材料。
US 1,027,004(1912)號專利揭述SiC(金剛砂)多孔陶瓷之製造，其係精細研磨SiC粉末成為漿料或糊體，及將該漿料或糊體模塑且在非氧化大氣中燒製而製造。結果為具有用於製造薄膜的微孔之多孔陶瓷。大部分孔為封閉且過濾效率低。
US 2,021,520(1935)號專利揭述多孔陶瓷之製造，如氧化鋁陶瓷，其製造片狀物或碎塊，然後壓製 或壓實，最後在高於1600℃之溫度燒製材料。這些多孔陶瓷之指定應用包括古氏(Gooch)坩堝用於鹼性液體之濕式過濾器、淨水廠中可讓空氣通過之多孔板、及表面燃燒用之板。
US 2,463,979(1949)號專利教示孔隙度為20%至50%之Al2O3多孔陶瓷之製備，其係將40%至80%之未研磨(200篩目)及60%至20%之經研磨(325篩目)氧化鋁混合成泥狀糊體，將該糊體在150℃乾燥，及將乾燥材料在1300℃至1850℃之溫度範圍內燒製。
US 5,177,035(1993)號專利揭示熔融液體過濾用之基於Al2O3之陶瓷過濾器。過濾器形成組成物含有65體積百分比至75體積百分比之+4-6篩目CaCl2(或脲或蠟)粒作為孔形成劑，藉由將該孔形成材料瀝濾或熔化而製造孔度範圍為約500微米至約1300微米之孔。其使用樹脂作為黏合劑。
US 5,861,057(1999)號專利揭述孔隙度在10體積百分比至35體積百分比之範圍的水管理用排水混凝土。該混凝土由10重量百分比-35重量百分比之作為黏合劑的水硬水泥、及65重量百分比-85重量百分比之大小為2毫米-32毫米(較佳為5毫米-8毫米)的骨材(aggregate)、以及水硬水泥黏合劑之5重量百分比至40重量百分比的黏合劑添加劑組成。
GB 2,410,282(2005)號專利有關包括多孔混凝土層之水管理系統。該多孔混凝土包含15-21重量百分比之水泥、5重量百分比之細砂、及65重量百分比-75 重量百分比之單一大小為10毫米之粗骨材(如礫石、石灰石、花崗石等)。該混凝土混合物亦包含多孔混凝土中水泥之5-15重量百分比的程度之微矽石添加劑。該多孔混凝土之最小氣隙含量(孔隙度)大約為15%。
US 2015/0145186(2015)及WO 2015/191426(2015)號專利關於陶瓷發泡過濾器，其係將漿料塗覆於有孔聚合物發泡體(通常為聚胺基甲酸酯發泡體)，然後將型材乾燥及燒製以燒除發泡體並以具有多孔結構而製造。該漿料可為富鋁紅柱石、MgO、或其他的耐火材料。
US 6,508,852(2003)號專利顯示由封堵法形成的多孔蜂巢微粒過濾器。該過濾器用於柴油引擎或汽車引擎。孔通道為筆直不迂迴。
US 3,524,548(1970)號專利有關含有熔凝氧化鋁或管狀氧化鋁骨材且以玻料作為黏合劑的熔融鋁過濾用剛性過濾器。該骨材之平均粒度0.165毫米至約2.8毫米之範圍；該孔之平均直徑為0.25毫米至0.92毫米，且孔隙度低。因此，該過濾器的過濾效率低。其將含有低熔材料(如15%至80%之氧化硼)之玻料粉末用於黏合劑以黏結骨材。玻料必須在特定溫度燒製以使玻璃黏結，故以此技術製造的物品在生胚階段的黏結強度低。該專利並未教示封閉耐火骨材部分之用法。
US 4,528,099(1985)號專利有關2個具有大及小孔徑的過濾熔融材料用過濾器之結構。其使用中空金剛砂球體作為骨材，且以低熔玻料作為黏合劑混合上釉混合物。US 4,528,099號專利並未教示其中最大粒度 對最小粒度的比例為10：1或以下的封閉耐火骨材部分。
US 5,998,322(1999)號專利有關熔融金屬用之過濾介質，其具有5至12重量百分比之B2O3作為低溫無機黏合劑。其並未教示封閉耐火骨材部分之用法。
本發明關於具有安排孔隙度之耐火材料，及具有安排孔隙度之耐火材料在各種結構中減少冶金容器中內生內含物形成之用途，以及將內生內含物隔離且保留在一定體積的熔融金屬體外部。本發明之材料為含有骨材(aggregate)及黏合劑之耐火組成物，其可承受冶金方法之熱、物理、及化學環境。本發明之材料利用水泥，如鋁酸鈣水泥，或黏合劑，如Al2O3，而對調配物賦與生胚強度。本發明之材料可以生胚或預先燒製而使用。在本發明之材料中，孔隙性為開放(open)、連續、及迂迴，其係設計成可使熔融金屬進入且留置熔融金屬。
本發明之材料可用於過濾，容許滲入，提供隔熱，作為氣體擴散劑，及用於處理熱氣體或熔融金屬液體之其他功能。
現已發現，特定的組成物特徵單獨或以特定組合產生一種多孔耐火澆鑄材料，其具有設計的結構組態，可用於熔融材料之圍阻、引導、處理、及保留。這些特徵包括：
1)封閉耐火骨材部分、或最粗耐火粒部分，其組成乾燥組成物之70重量百分比或以上、75重量百分比或以上、80重量百分比或以上、85重量百分比或以 上、90重量百分比或以上、或95重量百分比或以上。
2)該封閉耐火骨材部分就粒度而言為封閉部分，其中封閉耐火骨材部分中的最大粒子之篩目值為封閉耐火骨材部分中的最小粒子之篩目值之1.5倍或以下，其中封閉耐火骨材部分中的最大粒子之篩目值為封閉耐火骨材部分中的最小粒子之篩目值之2.0倍或以下，其中封閉耐火骨材部分中的最大粒子之篩目值為封閉耐火骨材部分中的最小粒子之篩目值之2.5倍或以下，其中封閉耐火骨材部分中的最大粒子之篩目值為封閉耐火骨材部分中的最小粒子之篩目值之3.0倍或以下，其中封閉耐火骨材部分中的最大粒子之篩目值為封閉耐火骨材部分中的最小粒子之篩目值之4.0倍或以下，其中封閉耐火骨材部分中的最大粒子之篩目值為封閉耐火骨材部分中的最小粒子之篩目值之5.0倍或以下，其中封閉耐火骨材部分中的最大粒子之篩目值為封閉耐火骨材部分中的最小粒子之篩目值之8.0倍或以下，其中封閉耐火骨材部分中的最大粒子之篩目值為封閉耐火骨材部分中的最小粒子之篩目值之10.0倍或以下。
3)該封閉耐火骨材部分含有由直徑等於或大於100微米之粒子所構成的組成物部分之至少80重量百分比，由直徑等於或大於100微米之粒子所構成的組成物部分之至少85重量百分比，由直徑等於或大於100微米之粒子所構成的組成物部分之至少90重量百分比，由直徑等於或大於100微米之粒子所構成的組成物部分之 至少95重量百分比，或由直徑等於或大於100微米之粒子所構成的組成物部分之100重量百分比。
4)該封閉耐火骨材部分中的最小粒子之篩度或粒徑比組成物其餘部分中的最大粒子大2、或5、或10倍。或者該組成物可被揭述為具有粒度分布上的空缺間隙，間隙之最小粒徑或篩度限度與間隙之最大粒徑或篩度限度之間相差2、或5、或10倍，其中間隙之最小粒徑或篩度限度為45微米或以下之值。該空缺間隙內調配物之重量百分比(排除溶劑)等於或小於5重量百分比、等於或小於2重量百分比、等於或小於1重量百分比、或等於或小於0.5重量百分比。
5)該封閉耐火骨材部分完全由粒徑篩目值為12毫米(含)至6毫米(含)、6毫米(含)至3毫米(含)、3毫米(含)至1毫米(含)、1毫米(含)至0.5毫米(含)、20毫米(含)至6毫米(含)、及20毫米(含)至10毫米(含)之骨材或粒子所構成。
6)該封閉耐火骨材部分完全由高溫耐火材料所構成(compose)、所組成(consist)、或本質上所組成(consist essentially)。高溫耐火材料包括氧化鋁(包括管狀、熔凝、及棕熔凝形式)、鋁礬土、菱鎂石、氧化鋯、氧化鈣、氧化矽、尖晶石、鋁酸鈣、富鋁紅柱石、橄欖石、鎂橄欖石、鋯石、矽酸鈣、矽酸鋁鋯(alumina zirconia silicate)、及這些材料的組合，且排除玻料。
7)除了封閉耐火骨材部分，該組成物含有黏合劑系統，其含有可亞鐵質耐火黏合劑。可亞鐵質耐火 黏合劑為可製造在高於攝氏1400度仍可使用的調配物之黏合劑。可亞鐵質耐火黏合劑之實例為鋁酸鈣水泥、磷酸鋁、可水合氧化鋁、及膠態氧化矽。
8)該組成物具有20體積百分比(含)至60體積百分比(含)、20體積百分比至50體積百分比(含)、25體積百分比至45體積百分比(含)、20體積百分比至40體積百分比(含)、25體積百分比至40體積百分比(含)、30體積百分比至60體積百分比(含)、30體積百分比至50體積百分比(含)、或30體積百分比至40體積百分比(含)之開放孔隙度。
9)該組成物具有迂迴孔隙度。迂迴孔隙度為其中孔不為直線或弧形形式，或其中孔帶有複數個轉彎的孔隙度。
10)由(a)細粒、(b)黏合劑、及/或(c)漿料製造的黏合劑相。
11)二層結構，其含有彼此相連之二層。該二層之封閉耐火骨材部分篩目值或粒度分布不同。或多層結構，其含有彼此循序相連之複數層。各層之封閉耐火骨材部分篩目值或粒度分布各不相同。
本發明亦關於冶金容器用之襯墊結構，其包含具有前述特徵1-11中至少之一之多孔耐火材料。本發明亦關於此襯墊結構在冶金容器中之用途。
本發明亦關於一種具有內部及外部之冶金容器，其中冶金容器內部包含襯墊結構，其包含具有前述特徵1-11中至少之一之多孔耐火材料。
本發明亦關於一種將熔融金屬之氧化最小化之方法，其包含(a)將熔融金屬轉移到具有包含具有前述特徵1-11中至少之一之多孔耐火材料的襯墊結構之容器，及(b)將熔融金屬從該容器轉出。
本發明之特定具體實施例關於一種多孔耐火澆鑄材料，其包含封閉耐火骨材部分，其具有最小粒度及最大粒度，其中最大粒度對最小粒度的比例為10：1或以下、5：1或以下、或2：1或以下；及包含耐火黏合劑之黏合劑相，其中封閉耐火骨材部分包含100重量百分比的材料，其粒徑大於0.1毫米、大於0.2毫米、大於0.5毫米、大於1毫米、大於2毫米、或大於5毫米。骨材部分對骨材部分與黏合劑相的組合重量之重量百分比可在70重量百分比(含)至98重量百分比(含)、75重量百分比(含)至98重量百分比(含)、80重量百分比(含)至98重量百分比(含)、85重量百分比(含)至98重量百分比(含)、及90重量百分比(含)至98重量百分比(含)之範圍內。該耐火骨材之最小粒子與黏合劑相中最大粒子的大小之間的比例為至少2：1、至少5：1、至少10：1、或至少20：1。本發明之多孔耐火澆鑄材料可具有20體積百分比(含)至60體積百分比(含)、20體積百分比至50體積百分比(含)、25體積百分比至45體積百分比(含)、20體積百分比至40體積百分比(含)、25體積百分比至40體積百分比(含)、30體積百分比至60體積百分比(含)、30體積百分比至50體積百分比(含)、或30體積百分比至40體積百分比(含)之孔隙度。該孔可為迂迴。
在本發明之特定具體實施例中，100重量百分比之封閉耐火骨材部分之粒度為直徑大於1毫米、直徑大於2毫米、直徑大於5毫米、或直徑大於10毫米。該封閉耐火骨材部分可包含氧化鋁(包括管狀、熔凝、及棕熔凝形式)、鋁礬土、菱鎂石、氧化鋯、氧化鈣、氧化矽、尖晶石、鋁酸鈣、富鋁紅柱石、橄欖石、鎂橄欖石、鋯石、矽酸鈣、矽酸鋁鋯、及這些材料的組合。
在本發明之特定具體實施例中，該黏合劑相可包含反應性氧化鋁、煅燒氧化鋁、管狀氧化鋁、熔凝氧化鋁、富鋁紅柱石、碳、碳化矽、二氧化鋯、氧化鎂、矽酸鋁、膠態或奈米矽石形式的氧化矽、煙矽石(fume silica)、尖晶石、鋁礬土、氧化鉻、及其組合。100重量百分比之黏合劑相可由直徑為500微米或以下、200微米或以下、100微米或以下、或50微米或以下的粒子組成。
本發明亦關於一種含有如前所述彼此相連的至少二層之結構，其中第一層含有具有第一層最小骨材粒度之骨材，及第二層含有第二層最大骨材粒度，且第一層最小骨材粒度大於第二層最大骨材粒度。本發明進一步關於一種結構，其由含有前述第一組成物及前述第二組成物的結構所構成，其中第一組成物被形成可為實心或者可為相對圓柱軸為對稱空心之圓柱形結構，及其中第二組成物與第一組成物相連。在特定具體實施例中，第二組成物被配置在第一組成物的徑向外部。
本發明亦關於前述多孔耐火澆鑄材料作為高 溫冶金或鑄造容器(如澆斗、漏斗、及坩堝)中襯墊結構之用途。由這些材料形成的裝置可作為鋁或金屬合金之液體純化用深床過濾器。本發明之材料可被滲入金屬形成煞車墊。本發明之材料可作為氣體或液體擴散物。本發明進一步關於一種具有內部及外部之冶金容器，其中冶金容器內部包含襯墊結構，其包含前述的多孔耐火澆鑄材料。本發明進一步關於一種製造冶金容器中的襯墊結構之方法，其包含(a)在冶金容器內部提供具有內表面之耐火內襯，及(b)將前述的澆鑄多孔耐火材料固定在耐火內襯的內表面上。
本發明亦關於一種將熔融金屬之氧化最小化之方法，其包含(a)將熔融金屬轉移到具有包含前述多孔耐火澆鑄材料的襯墊結構之容器，及(b)將熔融金屬從該容器轉出。
10‧‧‧含有本發明多孔耐火澆鑄材料之結構
14‧‧‧耐火骨材部分
16‧‧‧黏合劑相
18‧‧‧迂迴通路
30‧‧‧含有本發明多孔耐火澆鑄材料之多層結構
32‧‧‧第一層
34‧‧‧耐火骨材部分
36‧‧‧黏合劑相
42‧‧‧第二層
44‧‧‧耐火骨材部分
46‧‧‧黏合劑相
52‧‧‧第一層之主面
54‧‧‧第一層之主面
56‧‧‧第二層之主面
58‧‧‧第二層之主面
在附圖中描述本發明之各種具體實施例：第1圖為含有本發明多孔耐火澆鑄材料之結構的切面示意圖；第2圖為含有本發明多孔耐火澆鑄材料之結構的切面示意圖；第3圖為含有本發明多孔耐火澆鑄材料之結構的切面圖；及第4圖為含有本發明多孔耐火澆鑄材料之結構的切面圖。
現已發現，特定組成特徵的組合之存在產生一種多孔澆鑄耐火材料，其可承受在冶金方法之容器中遭受的高溫及化學反應性。該材料呈現冶金應用(如耐火襯墊)所需的結構強度。該材料含有寬度足以接納熔融材料，及迂迴度足以限制熔融材料但接納雜質之孔。
耐火襯墊係由壁或板形式的抗高溫材料所構成，以包容熔爐及/或容器中的熱、熔融金屬及/或熔渣。耐火材料可包括氧化鋁、鋁礬土、耐火泥、MgO、或含石墨壓製磚或形狀之磚塊；整體耐火材(monolithic refractories)，如可振動澆鑄材料、可自我流動澆鑄材料、塑膠耐火材，及噴補混合物；以及乾燥振動混合物。耐火襯墊可用於漏斗、澆斗、鼓風爐溝槽、電弧爐(EAF)底部、及容器或約束裝置(如溝槽、流道、與通道)。本發明之多孔澆鑄耐火材料可用於吸引熔渣/雜質，將容器隔熱，抑制氧進入熔融金屬，及減少襯墊侵蝕或腐蝕。
可用於實行本發明之骨材為在高溫保留其強度之耐火材料。耐火材被視為具有使其適用於暴露於高於攝氏538度(華氏1000度)的環境之結構或作為系統組件的化學及物理性質之非金屬材料。耐火骨材與用於建築應用混凝土之由碎石(如石灰石、熔渣、或花崗石)組成的骨材有所差別。由於如Na2O與K2O之材料之存在、及骨材之碳酸鹽分解，混凝土強度及這些材料的彈性模數隨溫度提高而逐漸減小，及當溫度超過大約攝氏300度時，強度下降變得更快。當通過攝氏500度門檻時， 混凝土的壓縮強度通常下降50%至60%，且混凝土被視為完全損壞。藉由乾燥混凝土材料，則此現象的程度顯著降低或甚至在最高攝氏400度消除。高於此溫度，骨材(膨脹)與水泥糊體(收縮)之間的熱變形失配明顯，且造成裂痕發生。顯著的裂開持續，因此改變材料機械性質。耐火骨材亦與陶瓷玻料有所差別，其熔化溫度低於攝氏800度，且可能含有矽酸鈉與矽酸鉀。
可用於實行本發明之粗骨材包括氧化鋁(Al2O3)、菱鎂石(MgO)、氧化鋯(ZrO2)、氧化鈣(CaO)、氧化矽(SiO2)，或任何組合耐火材料，如尖晶石(Al2O3+MgO)、鋁酸鈣(CaO+Al2O3)、富鋁紅柱石(Al2O3+SiO2)、橄欖石與鎂橄欖石(MgO+SiO2)、鋯石(ZrO2+SiO2)、矽酸鈣(CaO+SiO2)、與AZS(Al2O+ZrO2+SiO2)。
可用於實行本發明之粗骨材可為塊狀、長方形、纖維狀、棒狀、角形、或球形或球晶形。陶瓷球晶可由耐火礦物質形成，如氧化鋁、MgO、氧化矽，或由組合材料形成，如富鋁紅柱石或尖晶石。可用的球晶為例如直徑在1毫米至25毫米之範圍。球晶可具有均勻的大小，或者具有一定範圍的大小。球晶可為稠密或輕量。藉輥-粒化法形成的球晶為多孔性，且具有類似甘藍菜內部之葉狀內結構。這些葉狀球晶具有可留置雜質及熔渣且提供一些隔熱效果之結構。
該多孔耐火材料的強度係由黏合劑成分經由膠結黏合、化學黏合、或陶瓷燒結黏合而提供。對應的三型黏合劑為耐火膠結漿料、化學溶液、及有機聚合物。 對應的三型處理後生成黏合劑相為耐火黏合劑、沉澱溶液、及有機聚合物。
該膠結黏合劑可由細微耐火粒子(直徑小於100微米(100微米，0.1毫米)、或小於88微米(88微米，0.088毫米)、或小於50微米(50微米，0.05毫米)、或小於25微米(25微米，0.025毫米)製成，其包括耐火黏合劑、耐火細粉、及一些添加劑(如減水劑)。將細微乾燥材料混合水而製造漿料(懸浮液)以塗覆及將耐火骨材黏結在一起。該水泥可為可亞鐵質高溫耐火黏合劑，因此可在高於攝氏1400度的溫度使用。該耐火黏合劑可為鋁酸鈣水泥、磷酸鋁、可水合氧化鋁、膠態氧化矽、及這些材料的組合。
該化學溶液可含有磷酸鹽，如磷酸單鋁鹽(為液體或為混合粉末與水而製造的溶液)、膠態氧化矽、可水合氧化鋁(為懸浮液或為混合粉末與水而製造的溶液)、或聚矽氧黏膠。
該有機聚合物黏合劑可含有聚合物黏膠或樹脂。
用於基質之黏合劑可含有鋁酸鈣水泥、鋁酸鈣鎂水泥、α-黏合水泥、波特蘭水泥、磷酸單鋁鹽(MALP)、黏土、反應性氧化鋁、可水合氧化鋁、膠態氧化矽、及其組合。在特定具體實施例中，本發明之基質材料不含水泥。
用於基質之其他原料可包括反應性氧化鋁、煅燒氧化鋁、管狀氧化鋁、熔凝氧化鋁、富鋁紅柱石、 碳(石墨或碳黑)、碳化矽、二氧化鋯、氧化鎂、矽酸鋁(如藍晶石、紅柱石、或矽線石)、煙矽石、鋁礬土、氧化鉻、及其組合。直徑在0.01至10微米、或0.01至50微米、或0.01至100微米之範圍的調配物部分，亦已知為細粒，可含有反應性氧化鋁及煙矽石。
該基質亦可含有分散劑、塑化劑、消泡或發泡劑、及去除空氣成分。這些試劑在所屬技術領域為眾所周知。
第1圖為含有本發明多孔耐火澆鑄材料之結構10的切面示意圖。耐火骨材部分14的粒子藉示為個別粒子之黏合劑相16而彼此黏結。迂迴通路18不用直線或弧形之形式而提供開放孔隙度。
第2圖為含有本發明多孔耐火澆鑄材料之多層結構30的切面示意圖。第一層32含有多孔耐火澆鑄材料，其含有藉示為個別粒子之黏合劑相36而彼此黏結之耐火骨材部分34之粒子。與第一層32相連之第二層42含有多孔耐火澆鑄材料，其含有藉黏合劑相46而彼此黏結之耐火骨材部分44之粒子。迂迴通路18不用直線或弧形之形式而提供開放孔隙度。
多層結構30之各層擁有2個主面。主面為一對配置於層之對立側上，且最大面積為全部層面之面。在第2圖中，第一層32具有主面52與54。第二層42具有主面56與58。第一層32之主面52與第二層42之主面56相連。
第3圖為含有本發明多孔耐火澆鑄材料之結 構10的切面圖。耐火骨材部分14之粒子藉黏合劑相16彼此黏結。迂迴通路18不用直線或弧形之形式而提供開放孔隙度。
第4圖為含有本發明多孔耐火澆鑄材料之多層結構30的切面圖。第一層32含有多孔耐火澆鑄材料，其含有藉黏合劑相36彼此黏結之耐火骨材部分34之粒子。與第一層32相連之第二層42含有多孔耐火澆鑄材料，其含有藉黏合劑相46彼此黏結之耐火骨材部分44之粒子。迂迴通路18不用直線或弧形之形式而提供開放孔隙度。
〔實施例I〕
本發明之組成物可由骨材及黏合劑製備。
可用於本發明之黏合劑包括粒狀懸浮液或漿料、液體溶液、或液態黏合劑，如基於樹脂或聚合物的黏膠。
在膠結性黏合劑中可使用直徑或通路篩度為100微米或以下，由如反應性氧化鋁、煙矽石、MgO、或鋁酸鈣水泥之材料所構成的耐火細粒。其可添加如分散劑之添加劑以改良流動力。然後可在懸浮液混合器中將固態成分混合在水中而製造流動力良好的均質漿料。對於某些調配物，建議在漿料製造1小時內將漿料組合骨材。
液態溶液黏合劑可藉合適化學化合物與水的混合物製造。可組合水而製造液態溶液黏合劑的化合物 包括磷酸氫鋁、磷酸二氫鋁、矽酸鈉、矽酸鉀、超細粉末形式之可水合氧化鋁、或奈米氧化鋁，或者可使用市售液態溶液，如膠態氧化矽或膠態氧化鋁。
其可使用液態黏合劑，如樹脂、聚合物黏膠、聚矽氧黏膠、或聚胺基甲酸酯黏膠，形成本發明之組成物。
為了形成本發明之耐火組成物，可將骨材與黏合劑的部分按所欲重量比例稱重。將黏合劑緩慢加入骨材，及在如水泥混合器之混合器中將骨材與黏合劑的組合混合。在將全部黏合劑加入骨材之後，混合可持續一段時間(如5分鐘)以確保全部骨材具有均勻的黏合劑塗層。
然後可使用黏合劑與骨材的組合形成耐火片材。然後將混合的骨材與黏合劑置於模具中，及藉搗實或振動將表面整平及沉降。後續層可以此方式加入模具。然後將模具以塑膠膜覆蓋，及將混合物硬化或定形。在沉降結束後將片材從模具脫模，及將膜移除。成形片材可在例如攝氏15-30度之範圍的溫度固化。然後可將片材在烤箱中於例如攝氏110度的溫度乾燥例如24小時的時間。生成的片材可直接使用，或者可在例如攝氏1400-1600度的溫度燒製例如3小時的時間，其依片材尺寸而定。
本發明亦關於含有前述耐火組成物之襯墊結構在冶金容器中之用途，以及一種具有內部及外部之冶金容器，其中冶金容器內部包含前述襯墊結構。
本發明亦關於一種將熔融金屬在轉移期間的氧化最小化之方法，其包含(a)將熔融金屬轉移到具有前述襯墊結構之容器，及(b)將熔融金屬從該容器轉出。
本發明亦關於一種形成冶金容器襯墊之方法，其步驟包含(a)將具有最小粒度及最大粒度之封閉耐火骨材部分，其中最大粒度對最小粒度的比例為10：1或以下，混合包含選自由鋁酸鈣水泥、磷酸鋁、可水合氧化鋁、膠態氧化矽、及其組合所組成的群組之耐火黏合劑之黏合劑相，其中封閉耐火骨材部分包含100重量百分比之粒徑大於0.1毫米之材料，而形成可澆鑄耐火混合物，及(b)澆鑄該可澆鑄耐火混合物而接觸冶金容器內部，以形成襯墊。在本發明之具體實施例中，該可澆鑄耐火混合物在模具與冶金容器內部之間所界定的體積中澆鑄。
本發明之其他特徵及優點由以下的詳細說明及實行例而變得更明白。
〔實施例II〕
各種骨材對黏合劑比例均可用於本發明之調配物。
在本發明之特定具體實施例中，使用的骨材為封閉粒度範圍在12毫米至6毫米之間的管狀氧化鋁T64粒(由Almatis,Inc.供應)。漿料黏合劑含有反應性氧化鋁、矽石煙、及結合水及添加劑(如分散劑)的鋁酸鈣水泥。對於70/30或以下的骨材對漿料重量比例，其發現過量的漿料黏合劑會阻塞孔(個別骨材粒之間的空 隙)，及在一些情形，在片材底部形成一堆漿料。如果重量比例為85/15或以上，則全部孔開放。但是如果重量比例為95/5或以上，則黏合劑強度不足以將骨材黏合在一起。其發現90/10的重量比例提供開放孔及合適的黏合劑強度。
〔實施例III〕
耐火材形成時骨材粒度範圍之比較
研究骨材化學組成物(管狀氧化鋁T64)相同但是具有各種封閉粒度分布範圍之調配物。使用的最大骨材粒子範圍為20毫米至6毫米部分；使用的最小骨材粒子範圍為1.0毫米至0.5毫米部分。其觀察到，如果粒子大於100微米，則在該骨材封閉粒度分布範圍可包含令人滿意的片材。在該封閉粒度分布範圍中最大對最小骨材粒子的比例可為10(含)至1(含)。在該封閉粒度分布範圍中，最大粒子與最小粒子之間的大小差異越小，則產生空隙及孔越多的片材。現已發現，5至1之間的比例、3至1之間的比例、2.5至1.5之間的比例、及2的比例產生令人滿意的耐火材。TAB-7a為總粒度分布範圍中最大粒度對最小粒度的比例為4：1之調配物的實例， 其中由2種粒度分布相鄰的耐火骨材組成物形成單一封閉耐火骨材組成物。
〔實施例IV〕
耐火材調配物中骨材化學組成物之比較
測試骨材對漿料黏合劑的比例相同但是骨材化學組成物不同的調配物。骨材包括尖晶石AR 90或AR 78、僵燒菱鎂石、熔凝菱鎂石、六鋁酸鈣(CA6，由Almatis Ltd.以商標名Bonite供應)、白熔凝氧化鋁、棕熔凝氧化鋁、與鋁礬土。其均發現可形成具有開放孔之片材。
〔實施例V〕
耐火材調配物中骨材形狀之研究
骨材可取為球形或角形粒之形式。如果使用合適的骨材對漿料黏合劑比例且骨材具有均勻的漿料黏合劑塗層，則生成耐火材中的孔係開放。
〔實施例VI〕
膠結性黏合劑漿料
黏合劑漿料可藉耐火黏合劑以水力黏合。該黏合劑漿料可包括鋁酸鈣水泥Secar-71(得自Kerneos Aluminate Technologies)、反應性氧化鋁A-3000FL(得自Almatis Ltd USA)、矽石煙955U(得自ELKEM AS Materials)、及/或例如添加劑Budit 8H(得自BASSTECH)形式的粉碎聚磷酸鈉玻璃。表5顯示在90%之大小為12毫米-6毫米之管狀氧化鋁T64存在下，可用以將骨材黏合在一起的不同黏合劑組合。
〔實施例VII〕
溶液或聚合物黏合劑
漿料黏合劑亦可為化學溶液/液體或聚合物樹脂之形式。表6顯示，在96%之大小為12毫米-6毫米之管狀氧化鋁T64存在下，可用以將骨材黏合在一起的不同液態化學黏合劑或聚合物樹脂。
〔實施例VIII〕
完整調配物
表7提供一些調配物。前3種調配物(TAB-32至TAB-34)使用相同的骨材及黏合劑，但是骨材/黏合劑比例不同。TAB-35至TAB-39之5種調配物使用不同的骨材但是漿料黏合劑相同。TAB-40至TAB-42之3種調配物使用相同的骨材但是漿料黏合劑不同。
表7之百分比為相對調配物之固態成分總重量之重量百分比。
本發明之調配物可以預鑄板之形式裝設在冶金容器內部，且藉水泥或機械支撐固定在定位。現場裝設本發明之調配物可藉由將模具置於冶金容器中，使得冶金容器內壁與模具外壁之間的餘隙界定被調配物佔據的體積而進行。然後將調配物置於此體積中及沉降。調配物可硬化或定形。其然後接受固化方法及乾燥方法。
由本發明材料所形成之裝置含有可控制的多孔結構且呈現抗高溫性。因此，可預期其之各種用途。 該材料可被形成預鑄板(預製)，或直接澆鑄至模具中形成指定形狀。由這些材料形成的裝置可作為過濾裝置，例如從熱金屬液體移除內含物，或從任何溶液或氣體移除雜質。該材料可被用以形成高溫冶金或鑄造容器(如澆斗、漏斗、及坩堝)用之襯墊。該材料可被用以形成耐火裝置中的溢流口、擋渣壩、及隔板而過濾熔融金屬。由這些材料形成的裝置可作為鋁或金屬合金之液體純化用深床過濾器。本發明之材料可被滲入金屬，以形成煞車墊。本發明之材料可作為氣體或液體擴散物。
本發明之許多修改及改變為可能的。因此應了解，在以下申請專利範圍之範圍內，本發明可如指定揭述之外而實行。

Claims (17)

  1. 一種多孔耐火澆鑄材料，其包含封閉耐火骨材(aggregate)部分 (14)，其具有最小粒度及最大粒度，其中最大粒度對最小粒度的比例為10：1以下；及黏合劑相 (16)，其包含選自由鋁酸鈣水泥、磷酸鋁(alumina phosphate)、可水合氧化鋁、膠態氧化矽、及其組合所組成的群組之耐火黏合劑，其中該封閉耐火骨材部分包含100重量百分比之粒徑大於0.1毫米之材料。
  2. 如請求項1之多孔耐火材料，其中最大粒度對最小粒度的比例為5：1以下。
  3. 如請求項1之多孔耐火材料，其中最大粒度對最小粒度的比例為2：1以下。
  4. 如請求項1之多孔耐火材料，其中該骨材部分對該骨材部分與該黏合劑相的組合重量之重量百分比為70重量百分比以上至98重量百分比以下。
  5. 如請求項4之多孔耐火材料，其中該骨材部分對該骨材部分與該黏合劑相的組合重量之重量百分比為75重量百分比以上至98重量百分比以下。
  6. 如請求項1之多孔耐火材料，其中100重量百分比之該封閉耐火骨材部分之粒度為直徑至少0.2毫米。
  7. 如請求項1之多孔耐火澆鑄材料，其中該封閉耐火骨材部分包含選自由氧化鋁、菱鎂石、氧化鋯、氧化鈣、氧化矽、尖晶石、鋁酸鈣、富鋁紅柱石、橄欖石、鎂 橄欖石、鋯石、矽酸鈣、AZS、及這些材料的組合所組成的群組之材料。
  8. 如請求項1之多孔耐火材料，其中該黏合劑相包含選自由反應性氧化鋁、煅燒氧化鋁、管狀氧化鋁、熔凝氧化鋁、富鋁紅柱石、碳、碳化矽、二氧化鋯、菱鎂石、矽酸鋁、煙矽石(fume silica)、鋁礬土、氧化鉻、及其組合所組成的群組之材料。
  9. 如請求項1之多孔耐火材料，其中該耐火骨材之最小粒子與該黏合劑相中最大粒子的大小之間的比例為至少10：1。
  10. 如請求項1之多孔耐火材料，其中該耐火骨材之最小粒子與該黏合劑相中最大粒子的大小之間的比例為至少2：1。
  11. 如請求項1之多孔耐火材料，其中100重量百分比之該黏合劑相由大小為100微米以下的粒子所組成。
  12. 如請求項1之多孔耐火材料，其中孔隙度為20體積百分比以上開放(open)孔隙度至60體積百分比以下開放孔隙度之範圍。
  13. 如請求項1之多孔耐火材料，其中該孔隙度為迂迴性。
  14. 一種多孔耐火澆鑄材料結構，其包含：第一層，其包含如請求項1且具有第一層最小骨材粒度之第一多孔耐火材料；及第二層，其包含如請求項1且具有第二層最大骨材粒度之第二多孔耐火材料， 其中該第一層最小骨材粒度大於該第二層最大骨材粒度。
  15. 一種如請求項1之多孔耐火澆鑄材料之用途，其係用於耐火容器中之襯墊結構中。
  16. 一種具有內部及外部之冶金容器，其中該冶金容器內部包含襯墊結構，該襯墊結構包含如請求項1之多孔耐火澆鑄材料。
  17. 一種將熔融金屬的氧化最小化之方法，其包含：a)將熔融金屬轉移到具有襯墊結構之容器，該襯墊結構包含如請求項1之多孔耐火澆鑄材料，及b)將該熔融金屬從該容器轉出。
TW107110732A 2017-04-17 2018-03-28 多孔耐火澆鑄材料、其用途及製造 TWI841524B (zh)

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