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TW201609599A - 用於製造耐火性陶瓷產品的批料、用於將噴補塊體或鑄造塊體施加於表面上的方法、用於製造耐火性陶瓷產品的方法、耐火性陶瓷產品、及該批料之用途 - Google Patents

用於製造耐火性陶瓷產品的批料、用於將噴補塊體或鑄造塊體施加於表面上的方法、用於製造耐火性陶瓷產品的方法、耐火性陶瓷產品、及該批料之用途 Download PDF

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TW201609599A
TW201609599A TW104127925A TW104127925A TW201609599A TW 201609599 A TW201609599 A TW 201609599A TW 104127925 A TW104127925 A TW 104127925A TW 104127925 A TW104127925 A TW 104127925A TW 201609599 A TW201609599 A TW 201609599A
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Taiwan
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weight
batch
ceramic product
chromium oxide
refractory ceramic
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TW104127925A
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English (en)
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亞歷山大 西帕克
曼法特 卡帕爾
卡爾麥可 利托
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瑞法克托瑞智產股份有限公司
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Publication of TW201609599A publication Critical patent/TW201609599A/zh

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Abstract

本發明係有關於用於製造耐火性陶瓷產品的一批料、用於將噴補塊體或鑄造塊體施加於表面的一方法、用於製造耐火性陶瓷產品的一方法、一耐火性陶瓷產品，與批料之用途。

Description

用於製造耐火性陶瓷產品的批料、用於將噴補塊體或鑄造塊體施加於表面上的方法、用於製造耐火性陶瓷產品的方法、耐火性陶瓷產品、及該批料之用途
本發明係有關於用於製造一耐火性陶瓷產品的 一批料、用於將一噴補塊體或鑄造塊體施加至一表面的一方法、用於製造一耐火性陶瓷產品的一方法、一耐火性陶瓷產品，及一批料之用途。
於已知方式，一“批料”係描述自一或多重組份形 成之一組成物，一耐火性陶瓷產品可自此藉由陶瓷燒成而製造。
術語“耐火性陶瓷產品”於本發明之上下文中使 用時特別係描述具有多於600℃之伺服溫度的陶瓷產品，且較佳係依據DIN 51060之耐火性材料，即，具有>SK 17之測溫錐等值的材料。測溫錐等值可特別依據DIN EN 993-12判定。
耐火性陶瓷產品已知係呈未成型或成型的耐火 性產品之型式。
成型的耐火性陶瓷產品可為磚或功能性產品。
未成型的耐火性陶瓷產品亦稱為所謂的“耐火性 塊體”。特別地，未成型的耐火性陶瓷產品或耐火性塊體係作為鑄造塊體、抽送塊體，及搗打塊體。一耐火性材料的另一用途係作為一噴補塊體，其係用於修補一爐的高負載區。
耐火性陶瓷產品關於其等之耐火性質需遵守的 要求係嚴格的。因此，例如，其等需具有良好耐火性之熱性質，例如，儘可能高之強度。
噴補塊體及鑄造塊體係自習知技藝得知，特別係 呈基本噴補塊體之型式。此等基本之噴補塊體及鑄造塊體通常係由呈燒結氧化鎂之型式的一基本組份及，例如，呈一氧化鉻材料之型式的其它耐火性添加劑所組成。於將此型式之一噴補塊體或鑄造塊體施加至一表面後，當使用表面已施用此塊體的產品時，對其施用之溫度係使得此塊體繞結成一耐火性陶瓷產品。以經燒結的氧化鎂為主之一噴補塊體或鑄造塊體的燒結能力可藉由使用呈該氧化鉻原料之型式的一另外組份增加。有關於此，此氧化鉻原料可特別形成一結合劑基質，藉此，經燒結的氧化鎂之晶粒被熔融在一起。
原則上，以經燒結之氧化鎂為主且具有一添加的 氧化鉻原料之經適當構成的噴補塊體及鑄造塊體已經證實 其等於製造不成型耐火性陶瓷產品的價值。
但是，經改質的耐火性熱性質對於許多應用會係所欲的，特別是，例如，自此塊體製造的耐火性陶瓷產品的改良壓縮強度。
本發明之目的係提供用於製造一耐火性陶瓷產品，即，一成型的耐火性陶瓷產品或一耐火性塊體，的一批料，其中，與已知技藝已知之此型式的產品相比，具有改良耐火性熱性質的一耐火性陶瓷產品可被製造。
本發明之一另外目的係提供用於製造此種型式的一耐火性陶瓷產品的一方法。
本發明之一另外目的係提供具有此等改良耐火性質的一耐火性陶瓷產品。
第一提及之目的係依據本發明藉由提供用於製造一耐火性陶瓷產品的一批料而達成，個別有關於此產品之總重量，該批料包含以下列重量比例的下列組份：-50重量%至99.5重量%之經熔融的氧化鎂；-0至50重量%之經燒結的氧化鎂；-0.5重量%至5重量%之一氧化鉻組份，其係呈至少一以Cr2O3為主之原料的型式，其中，-相關於此氧化鉻組份的總重量，至少90重量%之此氧化鉻組份具有至多50μm之晶粒尺寸。
驚人地，於本發明之上下文，已顯示以此方式構成之一批料為基礎，一成型與未成型的耐火性陶瓷產品， 即，一耐火性塊體，可被獲得，其與此項技藝已知之產品相比，展現大量改良之熱性質。
本發明之批料係不同於此項技藝已知之相同型 式的批料，首先，特別地，其中，相對於通常用於此種型式之批料的技藝中之基本組份，其基本組份係排它地或主要地為經熔融的氧化鎂。其次，本發明之批料不同，其中，一高度特別的重量比例之經熔融及燒結的氧化鎂及一氧化鉻組份被使用。再者，本發明之批料亦不同，特別是其中，於其內，氧化鉻組份係以主要係至多50μm之極細微的特別晶粒尺寸存在。有關於此，本發明之批料的氧化鉻組份具有比相同型式之習知技藝批料的氧化鉻組份大量較小之晶粒尺寸。有關於此，相同型式之習知技藝批料中之氧化鉻組份的晶粒尺寸主要係多於100μm，特別是通常主要係範圍100μm至1000μm之晶粒尺寸。
驚人地，依據本發明，已顯示當本發明中之氧化 鉻組份具有一小晶粒尺寸時，自相同型式之一批料製造的一耐火性陶瓷產品之耐火性質可被大量改良。特別地，已顯示若塊體之氧化鉻組份係以依據本發明之小晶粒尺寸存在，一耐火性陶瓷產品之有關於其熱性質，特別是有關於其熱彎曲強度、長度線性改變，及冷壓縮強度的數字可被顯著改良。個別相關於氧化鉻組份之總重量，當本發明之 批料的至少90重量%之氧化鉻組份具有1至50μm，2至50μm，3至50μm，4至50μm或5 to 50μm之晶粒尺寸時，自本發明之批料製造的一耐火性陶瓷產品之此等耐火性質可進一步改良。
發明人假定氧化鉻組份之小晶粒尺寸的此有利 功效係由於此組份與呈經熔融的氧化鎂之型式的基本組份特別密集地反應，於經熔融之氧化鎂與氧化鉻組份間之接觸區域形成MgO-Cr2O3-尖晶石(鉻鎂尖晶石)，於是陶瓷產品之一特別固體燒微結構產生。
再者，依據本發明，已確認若基本組份係主要或 排它地呈經熔融之氧化鎂的型式且僅具有一小比例或零的經燒結之氧化鎂，自本發明之批料製造的一耐火性陶瓷產品的改良耐火性質係特別被調整。使用主要或排它地呈熔融的氧化鎂之型式的依據本發明之一基本組份意指自本發明之批料製造的一耐火性陶瓷產品展現特別良好之耐腐蝕性及耐沖蝕性。
依據本發明，已確認當本發明之批料陶瓷燒成時， 形成氧化鎂-鉻鐵礦-尖晶石，其對於自此批料製造之依據本發明的一產品之熱性質具有極正面的功效。耐火性產品之微結構係藉氧化鎂-鉻鐵礦-尖晶石強化，於是，氧化鎂晶粒以一特別強的方式結合至微結構內。
特別地，當經熔融的氧化鎂係以至少60重量%之 比例，包括，例如，以至少65重量%、70重量%、75重量%、80重量%、85重量%、90重量%、91重量%、92重量%、93 重量%、94重量%、95重量%、95.5重量%或96重量%之比例，存在於本發明之批料時，自本發明之批料製造的一耐火性陶瓷產品之耐腐蝕性及耐沖蝕性可進一步改良，其中，於被提及之最後二比例的情況之批料中之氧化鉻組份的最大比例係個別降至最多4.5重量%或4重量%。
再者，依據本發明已顯示，若批料中之氧化鉻組 份的比例增到至少0.8重量%或1.0重量%之比例，自本發明之批料製造的耐火性陶瓷產品之耐火性質，特別是關於其耐性，可被進一步增加，其中，批料中之經熔融的氧化鎂之最大比例係伴隨地限於最大值99.2重量%或99.0重量%。
基本組份中之經燒結的氧化鎂之比例可為0重量 %，但亦可為為最大值50重量%，包括，例如，最大值40重量%、35重量%、30重量%、25重量%、20重量%、15重量%、10重量%、9重量%、8重量%、7重量%、6重量%、5重量%、4重量%、3重量%、2重量%，或1重量%。
除非於個別情況以其它方式表示外，此處以重量 %提供之所有數據係相關於本發明之批料或本發明之產品的總重量。
本發明之批料中之經熔融的氧化鎂主要可呈任 何經熔融的氧化鎂之型式，較佳係以超純之經熔融的氧化鎂，特別較佳地，個別相關於經熔融之氧化鎂的總重量，係至少95重量%、96重量%、97重量%、98重量%或99重量%之MgO重量比例。
較佳地，具有儘可能小比例之CaO的一經熔融的 氧化鎂被使用，較佳地，個別相關於經熔融之氧化鎂的總重量，係少於3重量%、少於2.5重量%、少於2重量%、少於1.5重量%、少於1重量%，或少於0.5重量%之CaO比例。
較佳地，相關於經熔融之氧化鎂的總重量，此批 料之至少90重量%的經熔融之氧化鎂具有至多5.0mm之晶粒尺寸。
本發明之批料中的氧化鉻組份特別較佳係呈下 列氧化鉻原料之至少一者的型式：超純合成氧化鉻原料或具有至少90重量%之Cr2O3比例的氧化鉻原料材料，後者係相關於氧化鉻原料。
特別較佳地，本發明之批料的氧化鉻組份係排它 地選自此等氧化鉻原料。
超純合成氧化鉻原料可特別地係一超純技術氧 化鉻原料，例如，色料品質。特別地，超純合成氧化鉻原料可為一綠鉻礦材料。相關於氧化鉻原料，此型式之超純合成氧化鉻原料可具有多於90重量%之Cr2O3比例，包括，例如，多於92重量%、94重量%、96重量%、98重量%，或99重量%之Cr2O3。較佳地，個別相關於氧化鉻原料，具有至少90重量%之Cr2O3比例的氧化鉻原料亦可具有至少92重量%、94重量%、96重量%、98重量%或99重量%之Cr2O3的Cr2O3比例。
較佳地，相關於氧化鉻組份，氧化鉻組份包含少 於1.0重量%之CaO比例，包含，例如，少於0.5重量%或0.1重量%。
於本發明之上下文中，已確認若本發明之批料中 的總CaO含量係至少2重量%，自本發明之批料製造的一耐火性陶瓷產品的耐火性質會顯著受損。有關於此，依據本發明，本發明之批料中的CaO含量係設定為少於2.0重量%，較佳係包含，例如，少於1.5重量%、1.0重量%、0.7重量%、0.5重量%，或少於0.3重量%。
因為CaO之量係特別經由原料中之雜質引至批 料內，本發明較佳地提供超純氧化鎂原料與超純氧化鉻組份被使用。
再者，個別或組合使用之下列氧化物較佳係以少 於下列重量比例存在於批料中：-Al2O3：少於3重量%、少於2重量%，或少於1重量%；-SiO2：少於3重量%、少於2重量%，或少於1重量%；-Fe2O3：少於3重量%、少於2重量%，或少於1重量%；-TiO2：少於3重量%、少於2重量%，或少於1重量%。
如上所提及，本發明之批料較佳係包含純至超純 之組份。有關於此，批料中之MgO的比例可完全或其本上相對應於經熔融之氧化鎂的比例，且批料中之Cr2O3的比例可完全或基本上相對應於氧化鉻組份之比例。有關於此，例如，此批料可較佳地包含個別或呈組合的下列比例之MgO及Cr2O3：-MgO：95重量%至95.5重量%，包含，例如，至少95.5重量%或96重量%，及，例如，包含至多99.0重量%或98.5重量%；-Cr2O3：0.5重量%至5重量%，包含，例如，至少1.0重量% 或1.5重量%，及，例如，包含至多4.5重量%或4.0重量%。
批料亦可包含至少一塑化劑作為一另外組份。亦 稱為增塑劑之此型式的塑化劑係此項技藝已知，且用以增加經燒成之耐火性陶瓷產品的微結構之彈性。原則上，任何已知之習知技藝塑化劑可存在於本發明之批料中，例如，尖晶石、鐵尖晶石、錳尖晶石，或錳鐵礦。例如，塑化劑可以範圍0.1重量%至0.5重量%之比例存在於批料中。
本發明之批料可以已知習知技藝之技術作為一 塊體，例如，作為一抽送或搗打塊體。但是，依據本發明，顯示本發明之批料可以一特別有利之方式作為一鑄造塊體或噴補塊體，特別是當使用已知習知技藝之技術時。有關於此，本發明之批料可，例如，設有無機結合劑，例如，硫酸鹽或磷酸鹽結合劑，例如，下列結合劑之至少一者：六偏磷酸鈉或重硫酸鈉。例如，批料可包含範圍0.5重量%至5重量%之比例的結合劑，且無此結合劑的本發明批料之塊體表示100重量%。
於作為一耐火性塊體之情況下，若適當設有結合 劑，批料則可使用此項技藝已知之技術施加至一所欲位置或一所欲表面。有關於此，若批料被作為一噴補塊體，此批料可，例如，與水摻合，且，例如，施加至一鋼生產轉爐之流出口。
本發明進一步提供用於將一塊體施加於一表面 之方法，其具有下列特徵：-提供依據本發明之批料； -將此批料施加於一表面。
再者，此方法可包含此處所述之方法的步驟。
本發明亦提供用於製造一耐火性陶瓷產品的一方法，其中，於將其施加於表面後，此批料進行陶瓷燒成且經燒成形成一耐火性陶瓷產品。
一般，一噴補塊體或鑄造塊體之陶瓷燒成係於將此產品用於已施加噴補塊體之表面上時，藉由將施加至一表面的噴補塊體或鑄造塊體加熱而實行。以此方式，噴補塊體或鑄造塊體被燒結形成一耐火性陶瓷，即，經燒結的產品。
替代作為一耐火性塊體，本發明之批料可用於製造一成型耐火性陶瓷產品；於此情況，已知習知技藝之技術可被使用。有關於此，本發明之批料可，例如，設有無機或有機結合劑，例如，無機硫酸鹽或磷酸鹽結合劑，或呈木素磺酸鹽型式之有機結合劑，例如，範圍0.5重量%至5重量%之比例，且無結合劑之本發明批料的重量構成100重量%。其次，與一結合劑摻合之批料可被混合且最後成型為一成型物件，稱為一生壓胚。若適合，於居先乾燥後，此生壓胚最後可進行陶瓷燒成，且因此被燒成而形成一成型耐火性陶瓷產品，特別是於一爐內。
本發明進一步提供用於製造一成型耐火性陶瓷產品的一方法，其可包含此處所述之方法的步驟。
批料之陶瓷燒成可特別地於1300℃至1750℃之溫度範圍之溫度實行，特別佳係至少1350℃或1380℃且至 多1700℃、1650℃、1600℃、1550℃、1500℃、1450℃或1420℃，因為依據本發明，已顯示於此等溫度，已於此等溫度範圍燒成之依據本發明的產品展現特別良好之熱性質，例如，特別良好之熱彎曲強度、彎曲強度、冷壓縮強度，及長度性質之線性改變。
本發明亦有關於一耐火性陶瓷產品，其係藉由依 據本發明之一方法製造。以如上提及之本發明的批料為主，依據本發明之方法製造的一耐火性陶瓷產品特徵在於突出耐火性質。特別地，此型式之一產品展現突出之熱彎曲強度、突出之長度性質的線性改變，與突出之冷壓縮強度。
因此，本發明之產品的熱彎曲強度可，例如，至 少0.5N/mm2，包括，例如，至少0.6N/mm2、0.7N/mm2或0.8N/mm2。熱彎曲強度係依據DIN EN 993-7：1998於1400℃於一氧化氛圍中判定。
本發明之產品的彎曲強度可為，例如，至少5或6 N/mm2。彎曲強度係依據DIN EN 993-11：2007判定。
本發明之產品的冷壓縮強度可為，例如，至少15 N/mm2，包括，例如，至少16、18、20或22N/mm2。冷壓縮強度係依據DIN EN 993-5：1998判定。
本發明之產品的長度線性改變可，例如，至多 -0.15線性%，包括，例如，至多-0.14線性%。長度線性改變係依據DIN 51045-5：2007-01判定。
如此處所述，本發明之批料作為一耐火性噴補塊 體或鑄造塊體之用途亦構成本發明之一目的。
本發明可依據其揭露特徵使用。
本發明之進一步特徵係包含於申請專利範圍及 以下之本發明一例示實施例的說明。
此處揭露的本發明之所有特徵可個別地或組合地以任何方式組合在一起。
本發明之一例示實施例現將更詳細地說明。例示實施例係有關於依據本發明之一批料，其係依據本發明之方法處理，且作為一噴補塊體。
首先，一批料被製造，其包含97.08重量%之經熔融的氧化鎂及2.92重量%之一氧化鉻組份，其係呈一超純合成氧化鉻原料之型式，其係呈氧化鉻胚料之型式。
經熔融的氧化鎂係以相關於經熔融的氧化鎂之總重量係具有約97.63重量%之MgO比例的一超純型式使用。 最後，個別相關於經熔融的氧化鎂之總重量，經熔融的氧化鎂包含下列氧化物比例：0.08重量%之Al2O3；0.26重量%之SiO2；0.19重量%之Fe2O3；1.8重量%之CaO；0.04重量%之B2O3。
使用之氧化鉻胚料亦呈相關於氧化鉻胚料之總重量具有約99重量%之Cr2O3比例的超純型式。此外，氧化鉻胚料含有下列其它氧化物，於每一情況係相關於氧化鉻胚料之總重量：0.05重量%之Al2O3；0.05重量%之SiO2；0.05重量%之Fe2O3；0.2重量%之CaO；0.05重量%之MgO；0.1重量%之ZrO2；0.4重量%之TiO2。
然後，個別相關於無結合劑之批料的總重量，批 料係與呈1.92重量%之六偏磷酸鈉與0.38重量%之重硫酸鈉的型式之結合劑混合，與水摻合，及以一噴補塊體噴灑於一轉爐之一流出口的表面上。
當轉爐被使用時，噴補塊體加熱至1600℃之溫度，於是，噴補塊體進行陶瓷燒成，且噴補塊體燒結形成一耐火性陶瓷產品。
獲得之耐火性陶瓷產品具有個別係依據上述標準判定之下列物理性質：熱彎曲強度：0.9N/mm2；彎曲強度：7.0N/mm2；冷壓縮強度：24.0N/mm2；長度之線性改變：-0.13線性%。

Claims (8)

  1. 一種用於製造一耐火性陶瓷產品之批料，個別相關於該產品之總重量，該批料包含以下列重量比例之下列組份：1.1 50重量%至99.5重量%之經熔融的氧化鎂；1.2 0至50重量%之經燒結的氧化鎂；1.3 0.5重量%至5重量%之一氧化鉻組份，其係呈至少一以Cr2O3為主之原料的型式，其中，1.4 相關於該氧化鉻組份之總重量，至少90重量%之該氧化鉻組份具有至多50μm之晶粒尺寸。
  2. 如請求項1之批料，其中，相關於該經熔融的氧化鎂之總重量，至少90重量%之該經熔融的氧化鎂具有5.0mm之最大晶粒尺寸。
  3. 如請求項1至2中任一項之批料，具有呈下列氧化鉻原料之至少一者的型式之一氧化鉻組份：超純合成氧化鉻原料，或相關於氧化鉻原料係具有至少90重量%之Cr2O3比例的氧化鉻原料。
  4. 一種用於將一塊體施加至一表面之方法，其具有下列特徵：4.1 提供如請求項1至3中至少一項之一批料；4.2 將該批料施加至一表面。
  5. 一種用於製造一耐火性陶瓷產品之方法，其具有下列特徵： 5.1 提供如請求項1至3中任一項之一批料；5.2 將該批料成型；5.3 將該經成型的批料燒成而形成一經成型的耐火性陶瓷產品。
  6. 一種用於製造一耐火性陶瓷產品之方法，其中，如請求項4之施加至一表面的該批料於被施用至該表面後進行陶瓷燒成，且經燒成而形成一耐火性陶瓷產品。
  7. 一種耐火性陶瓷產品，其係藉由如請求項5或6之方法製造。
  8. 一種如請求項1至3中至少一項的批料之用途，其係作為一耐火性噴補塊體或鑄造塊體。
TW104127925A 2014-09-11 2015-08-26 用於製造耐火性陶瓷產品的批料、用於將噴補塊體或鑄造塊體施加於表面上的方法、用於製造耐火性陶瓷產品的方法、耐火性陶瓷產品、及該批料之用途 TW201609599A (zh)

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