利用高炉矿渣等工业废弃物制备耐碱玻璃纤维的研究

发布时间：2018-01-17 18:08

本文关键词：利用高炉矿渣等工业废弃物制备耐碱玻璃纤维的研究　出处：《济南大学》2016年硕士论文　论文类型：学位论文

【摘要】：本文以主要化学成分为SiO_2、CaO、MgO、Al_2O_3、Fe_2O_3等氧化物的高炉矿渣、粉煤灰、赤泥三种工业固废物为主要研究对象,通过调整配比和添加其它玻璃纤维用工业原料制备了一系列的硅酸盐玻璃试样。以耐腐蚀性能和玻璃纤维成型性能为主要依据,分析了固废物玻璃结构与性能的变化情况,探索了利用这几种工业固废物制备耐碱玻璃纤维的可行性。初步设计出了以高炉矿渣和赤泥作为原材料的耐碱玻璃纤维组合物。本文的研究过程和得出结论如下;首先使用高炉矿渣和粉煤灰配合工业原料制备了一系列的铝硅酸盐玻璃,通过结构、性能以及纤维成型性的研究,优选出了耐碱性能高于普通E纤维玻璃且符合纤维成型要求的固废物玻璃试样。研究发现:随着网络形成体(SiO_2)逐步替代作为网络修饰体的碱土金属氧化物,固废物玻璃的网络结构聚合度因[SiO4]四面体中的桥氧数增多而逐渐升高,玻璃化转变温度Tg逐渐升高,密度逐渐变小。随着网络中间体(Al_2O_3)逐渐的取代部分碱土金属氧化物,固废物玻璃的结构聚合度逐渐提高,Tg和低温析晶峰温度Tc均逐渐升高,密度逐渐下降。在耐碱腐蚀性能方面,随着SiO_2取代量的增大,固废物玻璃的耐碱性能先提高后降低,SiO_2含量在56.85wt%的A3试样具有最优耐碱性能,其碱侵蚀失重率比E纤维玻璃降低57.3%左右。当Al_2O_3的取代量增加时,玻璃的耐碱性能逐渐变差。在此基础上,本文通过引入赤泥研究了铁氧化物与Al_2O_3比例的变化对固废物玻璃结构与性能的影响,同时探索了赤泥作为耐碱玻璃纤维原料的可行性。以高炉矿渣和赤泥作为部分原料试制了含铁铝硅酸盐纤维玻璃,其优选试样的耐碱性能也高于普通E纤维玻璃且符合纤维成型要求。在研究中发现:Fe_2O_3/Al_2O_3比值的变化对本体系玻璃的网络结构聚合度影响不大,随着这一比值的增大玻璃结构聚合度仅有轻微的先提高后下降的趋势,随着Fe_2O_3/Al_2O_3的比值的逐渐变大玻璃的密度先增大后减小,当Fe_2O_3/Al_2O_3摩尔比值为1时,玻璃试样具有最优的耐酸碱腐蚀性能。最后,本文在优选的玻璃试样组分中添加ZrO_2进一步改善它们的耐酸碱性能,并研究了Zr O_2添加量对固废物玻璃结构性能的影响,进而探索其最优添加量。发现ZrO_2的添加对玻璃网络结构聚合度的影响不大,但结构致密度和试样密度因ZrO_2添加量的增加而增大,当ZrO_2添加量大于10wt%之后密度的增长也开始变缓。在本文中的固废物玻璃体系中,ZrO_2的最大添加量应在15wt%以下,耐碱最优添加量在10wt%左右,此时试样的耐酸碱侵蚀性能可达到市场上的AR耐碱纤维玻璃水平。另外,通过玻璃纤维成型参数测试,发现随着ZrO_2添加量的增加,固废物玻璃的纤维成型温度T_(lg3)和析晶上限温度T_(uc)均变大,且拉丝区间ΔT(ΔT=T_(lg3)-T_(uc))变小,玻璃纤维成型性能下降,但ZrO_2含量为10wt%的耐腐蚀性能较优的试样仍满足纤维成型要求。单丝拉制实验证明它们能够连续拉制纤维直径小于20μm的单丝,达到制备连续耐碱玻璃纤维的性能和工艺要求。
[Abstract]:In this paper, the main chemical components of SiO_2, CaO, MgO, Al_2O_3, Fe_2O_3 and other oxides of blast furnace slag, fly ash, red mud three kinds of industrial solid waste as the main research object, by adjusting the ratio and adding other glass fiber material for industrial preparation of silicate glass samples. With a series of corrosion resistance and glass fiber the forming performance is mainly based on the analysis of the changes of the structure and properties of solid waste glass, to explore the feasibility of preparation of alkali resistant glass fiber by using solid waste for this industry. Some preliminary design of a blast furnace slag and red mud as raw materials of alkali resistant glass fiber composition. The research process and conclusions are as follows; first use of blast furnace fly ash and slag with aluminum silicate glass, has prepared a series of industrial raw materials through the structure, performance and research of fiber forming, optimized the alkali resistance is higher than that of PU E glass fiber and glass fiber forming solid waste samples meet the requirements. The study found that: with the network forming (SiO_2) gradually replaced as the alkaline earth metal oxide modified body network, network structure of solid waste glass because the degree of polymerization of bridge oxygen numbers in [SiO4] tetrahedron increased gradually increased, the glass transition temperature of Tg increased gradually and the density decreases gradually. With the network intermediate (Al_2O_3) to replace part of the alkaline earth metal oxide solid waste glass structure gradually, the degree of polymerization increases, Tg and low temperature crystallization peak temperature of Tc gradually increased, the density decreased gradually. The alkali corrosion resistance, with SiO_2 content increasing, the alkali resistance of solid waste glass the first increased and then decreased, SiO_2 content has the best performance in the A3 sample 56.85wt% alkali, alkali erosion loss rate of about 57.3% lower than E fiber glass. When the substitution amount of Al_2O_3 is increased , the alkali resistance glass becomes worse. On this basis, the influence of iron oxides and the ratio of Al_2O_3 was studied by introducing the red mud on glass structure and properties of solid waste, while exploring the red mud as raw materials. The feasibility of alkali resistant glass fiber with blast furnace slag and red mud produced as part of the iron aluminum silicate fiber the alkali resistance of glass, the selected sample is higher than that of common E fiber glass fiber forming and meet the requirements. In the study found: ratio of Fe_2O_3/Al_2O_3 network structure of this glass system has little effect on the degree of polymerization, with the increase of the degree of polymerization of glass structure only a slight downward trend after the first increase this ratio, with the gradual change the big glass Fe_2O_3/Al_2O_3 ratio of the density increased first and then decreased when the Fe_2O_3/Al_2O_3 molar ratio is 1, acid and alkali corrosion of glass samples has the best Inhibition performance. Finally, this paper in the glass sample group preferred in adding ZrO_2 to further improve their performance of acid and alkali resistance, and studied the Zr effect of O_2 addition on the structure and properties of solid waste glass, and then explore the optimal dosage. Found that the addition of ZrO_2 has little effect on the degree of polymerization of the glass network structure, but the structure caused by the density and density of the sample due to the increase of the amount of ZrO_2 increases, when the amount of ZrO_2 is greater than the density of 10wt% growth also slowed. Solid waste glass system in this paper, the maximum amount of ZrO_2 should be below 15wt%, the optimal dosage of alkali in about 10wt%, the samples of acid and alkali corrosion resistance can reach AR level on the market of alkali resistant fiber glass. In addition, the forming parameters of glass fiber testing, found that with the increase of ZrO_2, fiber forming temperature of T_ solid waste glass (Lg3) and crystallization temperature limit T_ (UC) are larger, and the drawing interval Delta T (T=T_ (Lg3) -T_ (UC)) decreased, decreased glass fiber forming properties, but the content of ZrO_2 is resistant to corrosion better performance 10wt% can still meet the requirements. The molding of the fiber monofilament drawing experiment showed that they can be continuously drawn monofilament fiber diameter less than 20 m, meet the requirements of continuous preparation of alkali resistant glass fiber performance and process.

【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2016
【分类号】：TQ171.774

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