Comparative of different modifiers on the crystallization properties of glass–ceramics derived from silicon manganese slag
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摘要: 以硅錳渣為主要原料，分別添加高硅、高鐵和含鉻的改質劑硅石、鐵鱗和鉻鐵渣，采用Petrurgic一步法制備了微晶玻璃，對微晶玻璃樣品進行X射線衍射(XRD) 、差示掃描量熱分析（DSC）、掃描電子顯微鏡（SEM-EDS）等測試和分析，討論了添加不同改質劑對硅錳渣微晶玻璃礦相和性能的影響規律. 研究表明: 將改質熔渣冷卻至析晶溫度保溫和700 ℃退火后，獲得滿足天然花崗巖石材對性能要求的微晶玻璃. 相對于原硅錳渣，改質熔渣的析晶性能都獲得了顯著提升，其中鐵鱗和鉻鐵渣更有利于促進粒度為0.2～0.5 μm粒狀或短棒狀輝石晶體形成，這些晶體為固溶了Fe、Mn離子的普通輝石（Ca(Mg,Fe,Al)(Si,Al)2O6）和鈣錳輝石（CaMnSi2O6）等. 添加改質劑均改變了硅錳渣中Mn離子的賦存形態，原渣中Mn離子主要以玻璃相和硫化錳形式存在，改質后樣品中的錳離子主要賦存于鈣錳輝石中.Abstract: Direct casting of smelting slag into glass–ceramic is considered as an efficient way to simultaneously utilize “slag” and “heat” to prepare high value-added materials, owing to which has become a research hot spot. In this paper, silico–manganese slag was used as the main raw material, and silica, iron scale, and ferrochromium slag respectively as high-silicon, high-iron and chromium-containing modifiers. Furthermore, glass–ceramics were prepared using the Petrurgic one-step method. The Petrurgic one-step method is a heat treatment method for preparing glass–ceramic using controlled crystallization during slag cooling process. Using X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM-EDS) and other tests, the effect of adding different modifiers on the mineral phase and properties of silicon–manganese slag glass–ceramics were discussed. Furthermore, the feasibility of preparing glass–ceramics by online modification of silicon–manganese slag was discussed based on thermal balance calculation and analysis. The research revealed that by cooling the modified slag to the crystallization temperature and annealing at 700 ℃, glass–ceramics that meet the performance requirements of natural granite can be obtained. Herein, the optimal sample of glass–ceramic had a flexural resistance of 74.67 MPa, bulk density of 2.95 g cm?3, and water absorption rate of 0.08%. The crystallization performance of the modified slag was considerably improved compared with that of the original silico–manganese slag, and the iron scale and ferrochromium slag were more conducive to promoting the formation of granular or short rod-shaped pyroxene crystals with a particle size of 0.2–0.5 μm. The obtained products have pyroxene group crystals, such as augite (Ca(Mg,Fe,Al)(Si,Al)2O6) and johannsenite (CaMnSi2O6) with a solid solution of Fe and Mn ions. The addition of modifiers altered the occurrence form of Mn ions in the silico–manganese slag. Mn ions in the original slag were mostly found in the form of glass phase and manganese sulfide, whereas Mn ions in the modified samples were mostly found in johannsenite. Microcracks appeared especially in the samples modified with silica after heat treatment, and the crystal density of pyroxene was greater than that of the glass matrix, and volume shrinkage caused by its precipitation was one of the causes of crack formation. During the modification process, it was observed that when 10% silica and iron scale were added as modifiers, the sensible heat of slag was greater than the melting endothermic heat of the modifier, and no additional heat was required in the modification process. Furthermore, when ferrochromium slag was used as a modifier, the glass–ceramic was prepared by the hot-state mixing method between silico–manganese slag and ferrochromium slag.
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Key words:
- silicon manganese slag /
- glass–ceramic /
- modification /
- crystallization /
- manganese ions consolidation
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圖 1 原料的XRD圖譜. (a) 硅錳渣; (b) 硅石; (c) 鐵鱗; (d) 鉻鐵渣
Figure 1. XRD patterns of raw materials: (a) silicon-manganese slag; (b) silica; (c) iron scale; (d) ferrochrome slag
圖 2 硅錳渣制備微晶玻璃的熱制度
Figure 2. Thermal regime for preparing glass–ceramics from silicon–manganese slag
圖 5 不同Al2O3質量分數的CaO–SiO2–MgO–Al2O3系相圖. (a) 13%; (b) 15%
Figure 5. Phase diagram of CaO–SiO2–MgO–Al2O3 with different Al2O3: (a) 13% mass fraction; (b) 15% mass fraction
圖 6 微晶玻璃樣品的SEM圖. (a) S1; (b) S2; (c) S3; (d) S4
Figure 6. SEM images of glass–ceramic samples: (a) S1; (b) S2; (c) S3; (d) S4
圖 7 S2～S4微晶玻璃樣品的能譜EDS圖. (a) Pt.1; (b) Pt.2; (c) Pt.3; (d) Pt.4
Figure 7. EDS analysis of S2～S4 glass-ceramic samples: (a) Pt.1; (b) Pt.2; (c) Pt.3; (d) Pt.4
圖 8 S1～S4樣品的力學性能. (a) 抗折強度; (b) 體積密度; (c) 吸水率
Figure 8. Mechanical properties of S1～S4 samples: (a) flexural strength; (b) bulk density; (c) water absorption
表 1 原料的化學組成（質量分數）
Table 1. Chemical composition of the raw material
% Raw material composition CaO SiO2 Al2O3 MgO MnO Fe2O3* K2O P2O5 TiO2 Cr2O3 SO3* BaO Other Silicon manganese slag 27.27 38.40 13.24 3.60 7.92 2.27 1.60 0.41 0.25 0.26 1.45 2.49 0.84 Silica 3.50 85.40 2.58 1.05 2.92 2.14 1.02 0.42 0.11 0.20 — — 0.66 Iron scale 0.40 3.46 1.04 — 0.54 87.62 — 0.48 — 5.08 0.79 — 0.59 Ferrochrome slag 3.30 28.78 24.16 27.08 0.42 4.21 0.17 0.38 0.80 8.00 2.25 — 0.45 Notes：“*” For only the elements contents were detected by XRF, the results of all Fe and S elements were presented here in the form of Fe2O3 and SO3. 
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表 2 配合料的主要化學組成（質量分數）
Table 2. Chemical composition of the formula
% Sample CaO SiO2 Al2O3 MgO MnO Fe2O3 K2O P2O5 TiO2 Cr2O3 SO3 BaO Other S1 27.27 38.40 13.24 3.60 7.92 2.27 1.60 0.41 0.25 0.26 1.45 2.49 0.84 S2 24.89 43.10 12.17 3.35 7.42 2.26 1.54 0.41 0.24 0.25 1.31 2.24 0.82 S3 24.58 34.91 12.02 3.24 7.18 10.81 1.44 0.42 0.22 0.74 1.39 2.24 0.81 S4 24.87 37.44 14.33 5.95 7.17 2.46 1.46 0.41 0.31 1.03 1.53 2.24 0.80
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表 3 熔渣改質具有的顯熱和改質劑熔解需要的熱量對比
Table 3. Comparison of sensible heat of slag modification and required heat of melting modifier
Sample Slag appreciable heat, Qs /J Modifier absorbs heat, Qen/J Silicon–manganese slag (90%, mass fraction)+silica (10%, mass fraction)（S2） 31356 15203 Silicon–manganese slag (90%, mass fraction)+iron scale (10%, mass fraction)（S3） 31356 12495
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