基于水合硅酸镁结构记忆特性制备低硅镁质浇注料

水合硅酸镁是炼钢连铸过程中间包用镁质浇注料的重要结合相，其含量多少决定着浇注料的强度大小。本工作以Na₂SiO₃·9H₂O和MgCl₂·6H₂O为原料，采用水热法合成水合硅酸镁(MgO–SiO₂–H₂O,M–S–H)，研究了焙烧温度和焙烧次数对水合硅酸镁的“结构记忆”特性；随后将预合成M–S–H复合硅微粉制备镁质浇注料，研究其对镁质浇注料性能的影响。结果表明：当焙烧温度低于400℃时，水合硅酸镁具有“结构记忆”特性，焙烧次数增加有利于M–S–H凝胶中层间羟基的插入，促进其层状结构晶粒的长大和结构稳定性的提高；在镁质浇注料制备过程中引入一定量的预合成水合硅酸镁和少量的硅微粉，使浇注料具有很好的施工性能和足够的早期结合强度；同时减少了高温热处理后浇注料缺陷形成，提高了材料力学性能，为开发低硅微粉镁质浇注料提供支撑。     

亚微米SiO2粉体对无水泥铁沟浇注料性能的影响

以致密刚玉、碳化硅等为主要原料，以w（SiO₂）=99.9%的亚微米SiO₂粉体(d₅₀=0.242μm)为结合剂，制备了一种新型无水泥铁沟浇注料。研究了亚微米SiO₂粉体加入量（质量分数分别为3%、4%、5%、6%、7%、8%、9%）对其性能的影响，并从亚微米SiO₂粉体的粒度分布、红外光谱等角度，分析探讨了亚微米SiO₂粉体的作用机制。结果表明：1)亚微米SiO₂粉体可以单独作为铁沟浇注料的结合剂制备出无水泥铁沟浇注料；2)相比传统铁沟浇注料，无水泥铁沟浇注料在加水量、高温抗折强度等方面取得突破性进展，亚微米SiO₂粉体的最佳加入量为4%～6%（w）。     

MgO源对纳米η-Al2O3制备镁铝尖晶石的影响

分别以轻烧氧化镁粉、碳酸镁、分析纯氢氧化镁为MgO源,纳米η-Al₂O₃为原料(其摩尔比为1∶1),采用固相反应法制备镁铝尖晶石。研究不同MgO源对纳米η-Al₂O₃制备镁铝尖晶石的显气孔率、体积密度、物相组成、晶胞参数以及微观结构的影响。结果表明,随着烧结温度升高,三种MgO源与纳米η-Al₂O₃制得镁铝尖晶石试样的致密性逐渐升高。在1 600 ℃下,以氢氧化镁为MgO源与纳米η-Al₂O₃制得尖晶石试样的体积密度最大为3.296 g/cm³,显气孔率最低为1.9%,晶粒发育最好,晶粒尺寸约为3~5 μm。1 300 ℃时,三种MgO源与纳米η-Al₂O₃全部生成镁铝尖晶石,与以α-Al₂O₃为Al₂O₃源制备镁铝尖晶石的传统固相法相比,镁铝尖晶石的合成温度降低了100 ℃,可以降低镁铝尖晶石的成本,对镁铝尖晶石的应用具有实际意义。     

添加Y2O3对CaO-MgO-SiO2体系中CMS的影响

为了提高镁质耐火材料的高温性能,以分析纯化学试剂MgO、CaO、SiO₂、Y₂O₃等为主要原料,研究了添加Y₂O₃对CaO-MgO-SiO₂体系中钙镁橄榄石(CMS)的生成和转化的影响,以及转化生成物Ca₄Y₆O(SiO₄)₆的耐火度。结果表明：1)Y₂O₃的添加不仅能够显著减少CaO-MgO-SiO₂体系中低熔点相CMS的生成量,而且能够从CMS中捕获CaO和SiO₂使CMS转化为高熔点相Ca₄Y₆O(SiO₄)₆、MgO和Y₂Si₂O₇,有利于提高镁质材料的高温性能。2)Ca₄Y₆O(...     

镁负载CaO基吸附剂捕集CO2性能及抗烧结机理

复合钙基吸附剂制备成本过高是限制其工业化应用的主要瓶颈问题。本文以不可溶的CaCO₃和Ca(OH)₂作为钙源,通过燃烧合成法制备钙镁复合吸附剂,在双固定床反应器上研究了其循环捕集CO₂性能。结果显示：制备得到的钙镁复合吸附剂具有更发达的孔隙结构,吸附剂表面Ca和Mg分散均匀,MgO均匀分布于CaO晶粒之间,有效提高了钙镁复合吸附剂的抗烧结特性,因此钙镁复合吸附剂循环反应过程中具有高捕集CO₂活性。以Ca(OH)₂作为钙源时,燃烧合成过程中Ca和Mg均匀同时析出,分散更加均匀,有效避免了CaCO₃作为钙源时Mg的团聚问题,因此得到的钙镁复合吸附剂循环捕集CO₂性能最优。最佳的Ca/Mg摩尔比为(8∶2)~(7.5∶2.5)。本研究以不可溶钙源制备得到高活性钙镁复合吸附剂,有效控制了吸附剂成本,具有更好的工程应用前景。     

熔盐种类对熔盐法合成镁橄榄石的影响

以分析纯MgO和SiO₂为原料,分别以分析纯NaCl、Na₂CO₃、NaCl-Na₂CO₃和Na₂SO₄为熔盐介质,采用熔盐法在1 100℃保温3 h合成镁橄榄石,并对合成镁橄榄石进行了XRD、SEM、EDS、Jade分析。结果表明：以Na₂CO₃或NaCl-Na₂CO₃为熔盐介质合成的镁橄榄石纯度很低,因为Na₂CO₃与MgO和SiO₂反应生成了大量的Na₂MgSiO₄。以NaCl为熔盐介质合成的镁橄榄石纯度非常高。以Na₂SO₄为熔盐介质合成的镁橄榄石纯度较高,有少量MgSiO₃生成。分析认为,在NaCl熔盐中合成镁橄榄石的机制为“模板生长”,在Na₂     

MgO-SiO2-H2O凝胶结合MgO浇注料的水化行为

虽然高性能耐火浇注料在先进炼钢中扮演着重要角色,然而镁质浇注料却没有被广泛使用. 其中一个首要的问题是MgO水化过程中水镁石的生成会导致体积膨胀和随之而来的开裂,通常被称为"熟化". 为了克服这些问题,开发了一种基于MgO-SiO2-H2 O结合的无水泥MgO浇注料的新特色产品( SioxX-Mag). 本文进行了系统的工作以弄清MgO水化和制备出无裂纹MgO浇注. 将SioxX-Mag和硅微粉配合,可以抑制水镁石生成产生的裂纹,也可以研制出干燥后无裂纹的大型预制块. 用XRD技术对干燥过程中水化后取自大型预制块内部的试样进行了研究. 结果表明,对于MgO浇注料,硅微粉是一种有效的抗水化添加剂. 当硅微粉为8%时,MgO的水化被抑制,也观察不到水镁石相,而且能制备出无裂纹的大型MgO浇注料预制块. 当硅微粉较少时(如6%) ,干燥过程中会生成水镁石,而且预制块中可以观察到裂纹.     

生物模板法制备SAPO-34分子筛及其对CO2/CH4吸附分离性能的研究

采用生物质模板（茶花粉）掺杂制备SAPO-34分子筛,研究了SAPO-34分子筛对CO₂和CH₄的静态吸附性能,同时考察了水热晶化时间、硅铝摩尔比（SiO₂/Al₂O₃摩尔比）和有机模板剂对茶花粉掺杂合成SAPO-34分子筛的影响。结果表明,茶花粉的加入可以制备性能良好的SAPO-34分子筛并降低其尺寸在1～2μm之间;晶化时间（24～36 h）的延长有利于分子筛结晶;当硅铝比为0.6、有机模板剂摩尔比为2时,SAPO-34分子筛的晶化效果最佳。茶花粉清液合成的SAPO-34分子筛在静态吸附实验压力为100 kPa时,CO₂和CH₄的总吸附量分别为2.92 mmol/g和0.58 mmol/g, CO₂/CH₄的理想分离系数为5.05。     

氯代碳酸乙烯酯的合成工艺

以碳酸乙烯酯(EC)为原料，加入偶氮二异丁腈的四氯化碳溶液，并在磺酰氯的条件下通入氮气反应合成氯代碳酸乙烯酯(CEC)。考察反应温度、EC与SO₂Cl₂摩尔比、AIBN与EC摩尔比、反应时间等对氯代碳酸乙烯酯收率的影响，得到最佳反应条件为：EC与SO₂Cl₂摩尔比为1∶1.3、AIBN与EC摩尔比为1∶600，反应温度为60℃。在最佳反应条件下，产品产率高达84.21%，减少了二氯代、三氯代副产物的生成，保证了产品的纯度。     

溶剂热浸渍法制备高稳定性Zn(OAc)2/SiO2催化剂及其催化合成苯氨基甲酸甲酯

Zn(OAc)₂对由碳酸二甲酯（DMC）和苯胺合成苯氨基甲酸甲酯（MPC）的反应具有优异的催化性能,但存在易失活、不能重复使用的缺点。为此,以DMC为溶剂,利用溶剂热浸渍法制备Zn(OAc)₂/SiO₂催化剂,并对其催化性能进行了研究。利用XRD、FTIR和TG-DTA等方法对其进行了表征,结果表明,Zn(OAc)₂/SiO₂催化剂表面存在Zn(OAc)₂和ZnO,且其在SiO₂表面分散较好;优化了Zn(OAc)₂/SiO₂催化剂的反应条件,当反应温度为190℃、反应时间为5h、苯胺与DMC的摩尔比为1∶20、催化剂与苯胺质量比为0.2时,苯胺的转化率为97.2%,MPC的选择性为89.4%。和等体积浸渍法制备的催化剂相比,溶剂热浸渍法制备的Zn(OAc)₂/SiO₂催化剂具有较好的稳定性,重复使用7次,苯胺的转化率下降至79.1%,MPC的选择性下降至79.2%。Zn(OAc)₂/SiO₂活性下降的原因是由于ZnO的生成,并对其进行了再生,再生后的催化剂活性与新鲜催化剂接近。     

M- S-H formation in MgO-SiO2slurries via wet milling for magnesia based castables

It is believed that the formation of hydration phase, MgO-SiO₂-H₂O (M-S-H), contributes to good workability and reliable comprehensive properties for magnesia based castables. In order to stimulate the formation of M-S-H in magnesia based castables and understand the minimum introduction of microslica amount, wet milling process was used to promote the dissolution of MgO and SiO₂ in this work. The slurry containing different content of microsilica with wet milling technology and the castables with/without wet milling slurry were prepared. The effects of microsilica content on the formation of hydration phases were analyzed by XRD, FT-IR and TG/DSC and the properties of magnesia based castables were evaluated by explosion resistance, CMOR, HMOR and so on. The results showed that the formation of M-S-H was accelerated because of the dissolution of Mg²⁺ and HSiO₃^? in wet milling process. Higher amount of M-S-H led to a tight bonding in the early stage, and a denser structure after firing at high temperature due to the limited formation of brucite and in-situ formation of evenly distributed forsterite phase. In addition, much higher HMOR were obtained when less microsilica was added, attributing to the suppressed formation of low-melting-point liquid. Therefore, 2–3 wt% microsilica addition was recommended in this process.     

MgO活性对新型水化硅酸镁水泥性能的影响

通过对原料轻烧氧化镁粉在不同温度下进行二次恒温煅烧1.5 h制备不同活性MgO,研究了不同活性MgO与硅灰(SF)和磷酸氢二钾(K₂HPO₄)所制备的新型水化硅酸镁水泥胶凝材料(又称水化磷硅酸镁水泥,MSPHC)的凝结时间、流动度、抗压强度、反应溶液pH值。结合X射线衍射(XRD)、热重分析(TG-DTG)和扫描电子显微镜(SEM)测试手段,分析其影响机理。结果表明:随着煅烧温度的升高,MgO衍射峰强度增大,MgO活性降低;活性越高的MgO制备的MSPHC净浆凝结时间越短且流动性越差,而活性适中MgO制备的MSPHC具有较好的力学性能。MSPHC最主要的水化产物是水化硅酸镁(M-S-H)凝胶,另外还有Mg(OH)₂和MgKPO₄·6H₂O(MKP)生成,原料轻烧氧化镁粉中的MgCO₃成分不参与体系反应。活性适中的MgO制备的MSPHC在28 d龄期内的水化产物M-S-H凝胶生成量最多,因此硬化体抗压强度最高。活性越高的MgO在MSPHC反应体系中溶解的速度越快,体系水化反应进程速度也越快。     

Effect of spinel content on slag attack resistance of high alumina refractory castables

High alumina refractory castables based on the Al₂O₃-MgO-CaO diagram ternary system were prepared using tabular alumina, white electrofused corundum, calcined alumina, synthetic spinel, dead-burned magnesia, dolomite, and calcium aluminate cement as starting raw materials. Two kinds of slags with 9.02 and 4.14 CaO/SiO₂ ratios were studied for slag resistance by means of crucible tests. The corrosion thickness increases with increase in magnesia content in all the designed compositions. The slag penetration decreases with increases in spinel content. Taking into account these results a refractory castable composition for its positioning into a steelmaking ladle was chosen.

Microstructural studies by SEM of samples taken from the slag line and wall in a steelmaking ladle were carried out. The correct amount of spinel required for practical applications was determined by the Al₂O₃-MgO-CaO-SiO₂ diagram quaternary system. A detailed model of the attack mechanisms is proposed.     

高岭土原位合成高硅铝比小晶粒NaY分子筛

以不同温度焙烧的苏州高岭土为原料,采用原位晶化法合成高硅铝比小晶粒NaY分子筛,考察晶种胶添加量、陈化温度、晶化温度和m(高土)∶m(偏土)对晶化过程和产物性质的影响。结果表明,m(高土)∶m(偏土)=1时,在晶种胶添加质量分数15%、陈化温度90℃和晶化温度100℃条件下,以普通高岭土为原料原位合成NaY样品的相对结晶度约为80%,骨架硅铝比(SiO2与Al2O3物质的量比)为6.4,平均粒径约500nm。调整原料中m(高土)∶m(偏土)可以控制原位晶化样品中的分子筛含量。以细化高岭土为原料合成的NaY分子筛(平均约445nm)粒径小于普通高岭土合成的样品。骨架硅铝比高于6.0的原位晶化样品的骨架坍塌温度高于950℃,具有很高的结构稳定性。     

小晶粒ZSM-5分子筛的合成

采用水热合成法,选择合理的原料和配料比合成ZSM-5分子筛,对影响分子筛合成的主要因素如n(SiO_2)∶n(Al_2O_3)、n(H_2O)∶n(SiO_2)、晶化时间和晶化温度进行考察优化。XRD和SEM表征结果表明,合成的分子筛为典型的ZSM-5结构分子筛,晶粒均匀且呈单分散。通过不同因素的调控,可以合成一系列粒度(350~650)nm的ZSM-5分子筛。     

Effects of additives on sintering of CVD-MgO powders

The effects of a large number of sintering aids for the densification of magnesia were examined. Al₂O₃, BaO, Fe₂O₃, P₂O₅, SiO₂, TiO₂, Y₂O₃ and ZrO₂ are effective for the sintering of CVD-MgO powders at low doping levels. The effects of TiO₂ and ZrO₂ are significant. Heavy doping is harmful for densification. The eight oxides above are also effective for the sintering of seawater MgO, but the degree of effectiveness is smaller than for CVD-MgO. In the doping of BaO, P₂O₅, SiO₂ and TiO₂, which form eutectic liquids with MgO below 1600°C, there is an optimum firing temperature for densification.

Vickers hardness of doped MgO is proportional to the relative density and is unaffected by doping. Corrosion resistance of MgO ceramics for liquid PbO is also unaffected by dopants, except for P₂O₅.     

Plasma-Sprayed Aluminum and Titanium Adherends: I. Characterization of Coatings

The morphological and surface chemical properties of plasma-sprayed coatings on metals have been investigated using surface characterization techniques. Organic polymeric and inorganic powders were plasma-sprayed on aluminum and titanium. Organic-polymeric coatings were prepared using epoxy, polyester, polyimide, and cyanate ester components. Inorganic coatings were obtained by plasma-spraying Al₂O₃, AlPO₄, MgO, and SiO₂ on aluminum adherends, and TiO₂, TiSi₂, MgO, and SiO₂ on titanium adherends. The organic-polymeric coatings were prepared at one thickness while the inorganic coatings were sprayed to obtain two different thicknesses. SEM photographs reveal various morphological differences in the sprayed specimens. The surface morphology ranged from smooth to nodular among the plasma-sprayed specimens. Surface chemical analysis of the plasma-sprayed coatings indicated that little or no chemical degradation of the components occurred as a result of plasma-spraying. However, plasma-sprayed TiSi₂ appeared to be a mixture of silica and a titanium silicate.     

Effect of compositional variation and fineness on the densification of MgO–Al2O3 compacts

Single stage densification of magnesia—alumina compacts were studied with MgO to Al₂O₃ molar ratios 1:1 (stoichiometric spinel), 2:1 (magnesia rich spinel) and 1:2 (alumina rich spinel). Attritor milling has been adopted to produce variation in fineness. Milling greatly improved the densification. Densification was found to be easier for the magnesia rich composition and difficult for the alumina rich one. X-ray diffraction patterns showed the expected phases in stoichiometric and magnesia rich spinel. Alumina rich composition showed no free corundum phase on sintering at 1650°C and only spinel phase marks the complete solid solution of excess alumina in spinel at this composition. EDAX analysis also supports the event and also reflects that the impurities are mainly present at the grain boundaries.