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研究生： 吳文彬
Suprayugi, Erfan
論文名稱： 盛鋼桶燃燒合成熱間修補材料
Hot Repairing Material For Ladle Based on Self Propogating High Temperature Synthesis Reaction
指導教授： 鍾賢龍
Chung, Shyan-Lung
學位類別： 碩士
Master
系所名稱： 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年： 2010
畢業學年度： 98
語文別： 英文
論文頁數： 158
外文關鍵詞： hot repairing material, SHS, molten steel and molten slag corrosion, mechanical properties and degree of conversion, ladle
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    • 應用鋁尖晶石磚作為盛鋼桶精煉爐的防火內襯。在接觸熔融態的鋼與爐渣其遭受裂化時會引起腐蝕，導致性能受限。耐火修補材料必須減少鋁尖晶石的腐蝕效應並且增加熔融態的鋼與爐渣接觸的耐久性。近幾年使用射擊技術發展熱修補材料。本論文研究利用自我蔓延高溫合成技術(SHS)開發熱修補材料。自我蔓延高溫合成修補材料基於金屬材料的燒結過程與盛鋼桶有強的鍵結力並且適當的被使用在修補情況。SHS合成熱修補材料主要有四種組成:燃料(鋁、鎂)、氧化劑(金屬氧化物)、惰性物質及添加劑。為了評估機械性能及轉化程度各種SHS合成修補材料系統包含氧化物及非氧化物系統，進一步非氧化物系統，當Al含量為44 wt%、Mg含量為6 wt%以及50 wt%的惰性物，其中添加6 wt%二氧化鈦、3 wt%氧化鋯、4 wt%鋁化蓋水泥、1.5 wt%矽酸鈉時，其機械強度為 0.58 MPa、 rebound loss為11.52 wt%、孔隙率為24.04、molten steel的腐蝕速率為0.06 mm/hr而molten slag 的腐蝕速率為0.92 mm/hr。

    Rich alumina spinel bricks are used as refractory lining inside ladle. In contact with molten steel and molten slag, they suffer of degradation to molten steel and molten slag due to corrosion by penetration and reaction of molten steel and molten slag and limit their performance. Refractory repairing material is needed in order to reduce the corrosion effect of alumina spinel bricks and increasing their durability contact with molten steel and molten slag. Hot repairing material with gunning technique was developed in recent years. The purpose of this thesis is developing hot repairing materials based on the self propogating high temperature synthesis (SHS) reaction. Self propogating high temperature synthesis reparing material based on the sintering process of metallic material is believed have a high bonding strength with ladle brick refractory and suitable used in repairing condition of ladle furnace.
    SHS hot repairing materials were formulated four major constituents: aluminum and magnesium as a fuel, oxidizer (intentionally added metal oxides or naturally available O2 in air), inert as framework (china steel refractory material with various particle size distribution) and additives (for modifying combustion or product properties). To evaluate the mechanical properties and degree of conversion, various SHS repairing material system which consists of oxidizer system and non-oxide system has been developed. In advanced, non oxide system with 44 wt% of Al, 6 wt% of Mg and inert 50% added with 3 wt% of Titanium oxide, 3 wt % of zirconia oxide, 4 wt% of calcium aluminate cement and 1.5 wt% of sodium silicate has a result : MOR (0.58 MPa), Rebound loss (11.52 wt%), apparent porosity (24.04), metal corrosion rate (0.06 mm/hr) and molten slag corrosion rate (0.92 mm/hr).

    TABLE OF CONTENTS 摘要 i ABSTRACT ii ACKNOWLEDGMENT iii TABLE OF CONTENTS iv LIST OF TABLES vii LIST OF FIGURES xi CHAPTER I INTRODUCTION 1 CHAPTER II LITERATURE REVIEW 3 II.1 Ladle Application of Refractories. 3 II.2 Various Repairing Technique. 6 II.3 Self-Propagating High-Temperature Synthesis (SHS) 12 II.4 Magnesium Aluminate Spinel 16 II.4.1 Structure 16 II.4.2 Physical Properties 17 II.4.3 Alumina-Rich Spinel 18 II.5 Thermodynamic consideration 18 II.6 Reaction between molten aluminum and refractories 20 II.7 Reaction and sintering 21 II.8 Reactant list. 22 II.8.1 Fuel Based on Thermite Reaction. 22 II.8.2 TiO2-B2O3-Al System. 24 II.8.3 Non-Thermite system 26 II.9 Corrosion 38 II.10 Amount of water in gunning installation. 44 CHAPTER III EXPERIMENTAL SECTION 46 III.1 Properties and Characteristic of reactant. 46 III.2. Experimental System. 47 III.2.1 Combustion based on Thermite Reaction System 47 III.2.2 Combustion based on sintering process. 48 III.3 Experimental Procedure. 48 III.3.1 Surface Treatment. 48 III.3.2 Preliminary study of SHS reactant. 49 III.3.3 Ignition temperature and combustion temperature measurement. 51 III.3.4 Measurement method for apparent porosity, water absorption, and densities 51 III.3.5 Modulus of rupture (bonding strength) 52 III.3.6 Rebound Loss. 54 III.3.7 Molten Steel and Molten Slag Resistance. 55 III.4 Crystaline Phase and Phase Composition. 56 III.5 Microstructure 58 CHAPTER IV RESEARCH POLICY, METHODS AND STEPS. 59 IV.1 Basic informations for ladle. 59 IV.2 Requirements to the SHS hot repairing materials 59 IV.2.1 General requirement 59 IV.2.2 General requirement Specific requirements 60 CHAPTER V RESULT AND DISCUSSION 61 V.1 Basic Information of ladle. 61 V.1.1 China steel product analysis. 62 V.2 Preliminary Study of reactant 65 V.2.1 Aluminum Surface Treatment 65 V.2.2 Calcined aluminum. 69 V.2.3 Aluminum hydroxide preheating treatment. 69 V.3. Study of the SHS hot repairing material reactant for ladle. 71 V.3.1 Aluminum surface treatment effect. 72 V.3.2 Effect of aluminum hydroxide preheating treatment 74 V.3.3 Additives effect for increasing the formation of oxide and spinel 77 V.3.4 Effect of CaO additives in different preheating aluminum treatment 81 V.3.5 Effect of different heating time of SHS repairing material at 8000C 83 V.3.6 Effect of the different heating temperature. 85 V.3.7 Effect of the different composition of Inert. 88 V.3.8 Effect of aluminum surface treatment preheating time using calcium aluminate cement 90 V.3.9 Effect of additives in different percentage composition 92 V.4. Developing SHS repairing material receipt. 94 V.4.1 Thermite System. 94 V.4.2 Non-Thermite system 110 V.5 Proposed Reaction Mechanism of SHS combustion product. 125 V.6 Rebound loss measurement. 129 V.7 Molten Steel and Slag attack Corrosion test. 130 V.8 Microstructure Observation. 138 V.8.1 Interface between combustion product and china steel brick at 8000C 138 V.8.2 Corrosion reaction on SHS repairing material. 144 V.9 Origin of The Bonding strength. 151 CHAPTER VI CONCLUSION 153 References 155

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