真空硅浴熔融还原白云石炼镁的实验研究

通过往煅烧白云石中添加适量的Al2O3和SiO2,使其在1500～1600℃之间形成熔融炉渣,并在真空下采用硅铁还原液态渣中的MgO。研究了造渣剂对MgO还原率的影响,结果表明,在能够获得熔融炉渣的情况下,增大Al2O3/SiO2比能够极大地提高渣中MgO的还原率,理想的炉渣成分为32.0%CaO-23.0%MgO-35.0%Al2O3-10%SiO2。同时,对该炉渣进行了正交实验,通过分析得出影响MgO还原率因素的顺序依次是:反应温度、还原剂硅铁添加量、反应时间、催化剂CaF2添加量。在熔融还原工艺参数为:反应温度1600℃,还原剂硅铁添加量n(Si)/n(2MgO)=1.2,反应2h,催化剂CaF2添加量3%条件下,渣中的MgO还原率高达97.3%。     

硼镁石真空铝热还原提镁实验研究

热力学分析了铝还原剂从MgO、2MgO·B2O3和3MgO·B2O3中提取金属镁的化学反应。实验研究了制团压力、CaF2添加、还原温度、还原剂用量等对氧化镁还原率的影响。结果表明,适当地提高反应物料的制团压力有利于改善氧化镁还原率,但较大的制团压力会导致球团孔隙率降低,从而阻碍了产物Mg蒸气的释放以及氧化镁还原过程。对还原渣的X射线衍射分析表明,铝热还原生成的Al2O3会先与CaO结合。添加少量的Ca F2有利于氧化镁的还原,CaF2与还原渣结合成11CaO·7Al2O3·Ca F2。添加3%的CaF2,制团压力为90 MPa,在1200℃下还原120 min,氧化镁的还原率为85%,铝利用率为74%。     

氧化镁真空碳热还原法炼镁的工艺研究

采用物料失重率、金属Mg还原率、X射线衍射(XRD)与扫描电子显微镜(SEM)等手段与方法,研究了真空条件下氧化镁碳热还原温度、物料造球成型压力、物料配比、碳热还原保温时间以及催化剂对氧化镁碳热还原法炼镁工艺的影响。研究结果表明,在30~100 Pa时,碳热还原温度高于1553 K,控制物料压块压力为8 MPa,此时物料失重率最大,最有利于氧化镁的还原。随着焦煤还原剂与氧化镁摩尔比以及碳热还原时间的增加,碳热还原反应速率加大,还原率提高,但是变化效果不明显,加入氟盐CaF2后,物料失重率明显提高,添加CaF2的质量超过物料总质量的3%时,物料失重率超过95%,还原率也相应大幅提高。因此,选择适当的焦煤还原剂与氧化镁摩尔比值以及碳热还原时间,添加超过3%CaF2,将有利于该法炼镁过程的顺利进行与金属Mg还原率的提高。此研究为真空碳热法从氧化镁中提取金属Mg工艺提供了很好的实验依据。     

真空热还原氧化镁的理论分析与实验研究

通过对C、Si和Al热还原MgO的热力学计算,分析了不同条件下热还原吉布斯自由能和反应初始温度的变化.计算结果表明:在常压下C、Si和Al还原MgO时,反应初始温度分别高达1900,2200和1600℃;通过添加CaO造渣和使用真空,不但能提高MgO的还原率,而且使标准自由能降低;在系统压力为10 Pa时,碳热还原所需的初始温度为1100℃,加入CaO造渣的硅热还原、铝热还原所需的初始温度分别为800和690℃.在采用焦炭真空热还原MgO的验证试验中,发现在1500℃下还原120min,MgO的还原率高达84.59％.     

Al-Si-Fe合金真空热还原法制镁工艺研究

以Al-Si-Fe合金为还原剂,采用真空热还原白云石煅白制取金属镁。通过对还原温度、还原时间、还原剂过量系数、制团压力以及氟盐的添加对还原过程的影响分析,确定本工艺最佳工艺条件为:还原温度1413 K、还原时间120 min、真空度4 Pa、还原剂过量10%、制团压力150 MPa、CaF2添加量为3%。在该条件下金属镁还原率为91.3%,产品纯度达到99.1%。     

钒钛铁精矿碳热还原制备Fe-Ti(C,N)复合材料

以钒钛铁精矿和煤粉为原料,通过碳热还原法制备Fe-Ti(C,N)复合材料。采用正交实验研究了还原温度、碳氧比、还原时间和MgO添加量对还原产物的物相组成和碳氮化钛中C/N比的影响。对还原产物进行了X射线衍射分析,结果表明,还原温度对还原产物中碳氮化钛的C/N比的影响程度较大,而MgO的添加不利于碳氮化钛的形成。还原温度为1450℃、还原时间为40min、碳氧比为1.4时,还原产物的C/N比达到较大值。     

新法真空铝热还原炼镁的研究

对以煅后白云石和煅后菱镁石为原料,以铝粉为还原剂的新法炼镁技术的热力学进行了分析,并进行了真空热还原实验。通过X射线衍射和扫描电子显微镜对还原渣的主要物相与物质形态进行了分析。实验结果表明:以煅后白云石和煅后菱镁石为原料,以铝粉为还原剂的新法真空热还原炼镁技术是可行的,在还原温度1200℃,还原时间2 h,铝粉过量5%和无氟盐添加剂的条件下,氧化镁的还原率可达90%,CaF2或MgF2的添加可大幅度地提高还原过程中氧化镁的还原率,降低还原温度。还原后还原渣主要物相为CaO.2Al2O3,还原渣中氧化铝的含量在65%以上,氧化硅含量低于2%,是一种非常适合生产氢氧化铝的原料。     

氟磷酸钙真空碳热还原反应机理

在真空条件下,本文采用热力学分析、XRD及化学分析等方法与手段,对SiO2在氟磷酸钙碳热还原制磷的过程进行了研究,考察了SiO2的添加量对磷矿还原率的影响.通过热力学研究,在压力100Pa温度低于1075℃ 时,Ca5(PO4)3F与C、SiO2的反应满足反应发生的热力学条件.实验研究表明:在真空度10Pa～80Pa,温度达到实验最高温度1550℃时,二氧化硅不能使氟磷酸钙发生脱氟反应,与热力学计算结果一致.还原率随着温度升高而增大,在低于1450℃时,添加SiO2有利于提高还原率;随m增加,还原率也增加,在1350℃时,还原率增大速度较快.由此作者提出了SiO2对氟磷酸钙真空碳热还原的反应机理.     

SiO2对氟磷酸钙真空碳热还原反应的影响

采用热力学分析、X射线衍射及化学分析等手段,对真空下SiO2在氟磷酸钙碳热还原过程的行为以及siO2添加量对还原率的影响进行了研究.热力学结果表明,当压力为100 Pa和温度高于1075℃时,Ca5(PO4)3F与C、SiO2的反应满足反应发生的热力学条件.实验研究表明:在系统压力10～ 80 Pa,温度达到实验最高温度1550℃,siO2不能使氟磷酸钙发生脱氟反应,与热力学计算结果吻合.还原率随着温度升高而增大,低温下,添加SiO2有利于氟磷酸钙碳热还原反应;当硅钙摩尔比SiO2／CaO从0.3增至1,还原率随之增加.     

MgO含量及其赋存形态对Al2O3-MgO系浇注料热膨胀性能的影响

研究了MgO的含量及其赋存形态(游离MgO,富铝尖晶石,理论组成尖晶石,富镁尖晶石)对经不同温度(110℃×24h、1100℃×3h、1500℃×3h和1600℃×3h)热处理后浇注料试样的热膨胀性能的影响.结果表明:(1)随着MgO含量的增加,试样的平均热膨胀系数呈增大的变化趋势,随着热处理温度的提高,MgO含量对试样的平均热膨胀系数影响逐渐变小.(2)对于经110℃×24h和1100℃×3h热处理后的试样,MgO以理论组成尖晶石的赋存形态引入时,其平均热膨胀系数最小.     

CaF2在真空铝热还原炼镁过程中的行为研究

对CaF2在以白云石和菱镁石为原料的铝热还原过程中的行为进行了研究,通过X射线衍射对还原渣和结晶产物的物相进行了分析,对CaF2在铝热还原过程的反应过程以及加速还原反应的机理进行了探讨。实验研究结果表明,在还原过程中加入CaF2可降低还原反应的活化能,加快还原反应速率,可使还原过程中的氧化镁还原率提高3%以上,但添加CaF2的效果随还原温度的升高而降低。加入CaF2后一部分CaF2参与还原反应生成了11CaO.7Al2O3.CaF2,另外一部分CaF2被铝还原在结晶器上生成了一种主要成分为MgF2和Al的结晶物。CaF2对铝热还原反应的促进作用是化学反应促进和提高煅白表面活性共同作用的结果。     

Effect of heating rate on the responses of CaF2:Cu,CaF2:Tm,CaF2:Dy and CaF2:Mn

Recent development of CaF2:Cu (the most sensitive material for radiation dosimetry) exhibiting a TL glow peak around 270 degrees C similar to that of CaF2:Mn has made it attractive to study the influence of heating rate on the response of CaF2 based TLDs. Influence of heating rate on CaF2:Mn (known to reduce the response with increasing heating rate) was confirmed in view of the reported controversy about other TLDs. Responses of TL glow peaks around 270 degrees C in CaF2:Cu, CaF2:Tm, CaF2:Dy and CaF2:Mn were studied. Except CaF2:Mn, no other CaF2 based TLD exhibited a reduction in response with increasing heating rate. On the contrary, in some cases a small increase (10-15%) was noted with increasing heating rate from 1 degrees Cs(-1) to 50 degrees Cs(-1). The shape and the position of the glow peak and the parameters derived from the shape of the glow curve appear to have no relation to reduction of TL efficiency at higher heating rates. Apart from the increased probability of non-radiative transitions at higher temperatures, the observed effects have been assigned to the effect of heating rate on the migration of charge carriers released during the TL readout.     

Sinterability of magnesium-oxide powder containing spherical agglomerates

The magnesium-oxide (MgO) powders were prepared by calcining basic magnesium carbonate (4MgCO₃·Mg(OH)₂·4H₂O; BMC) powder at a temperature between 600°C and 1200°C for 1 to 5 h. The resulting MgO powders contained spherical agglomerates with diameters of 10–50 m; the external shapes of these BMC agglomerates remained unchanged even after the calcination. With increasing compaction pressure, the densification of MgO powder compacts proceeded by (i) the rearrangement of agglomerates (50 MPa), (ii) the collapse of agglomerates (50–100 MPa), and (iii) the closer packing of primary particles (100 MPa). The MgO compact was fired at 1400 °C for 5 h. The relative density of the sintered MgO compact whose starting powder was prepared by calcining the BMC at 1000°C for 3 h attained 98.0%. The bending strength of this sintered MgO compact attained 214 MPa.     

铸态和T6热处理Al-Si-Cu-Ni-Ce-Cr铸造耐热铝合金的组织和力学性能

使用OM、SEM观察、XRD物相分析和拉伸性能测试等手段研究了铸态、固溶态和时效Al-Si-Cu-Ni-Ce-Cr铸造耐热铝合金的组织和力学性能。结果表明:对Al-Si-Cu-Ni-Ce-Cr合金进行490℃×2 h+520℃×2 h双步固溶处理,不仅使θ-Al2Cu相完全固溶进基体中,还使更多的γ-Al7Cu4Ni相和δ-Al3CuNi相充分固溶进基体中,实现了更好的固溶效果;经过490℃×2 h+520℃×2 h和185℃×6 h热处理后,Al-Si-Cu-Ni-Ce-Cr合金的室温抗拉强度为336.8 MPa、高温(300℃)抗拉强度为153.3 MPa,比铸态分别提高了74%和19.3%。     

Structural Stability and Magnetic Properties of the TbCu$_{7}$ -Type SmCo$_{x - 0.4}$Ti$_{0.4} (x = 5.0hbox{–}8.5)$ Alloys

We have studied the composition dependence, thermal stability, long-term stability at 500°C, and magnetic properties of the nanostructural TbCu₇-type (1:7) Sm-Co-Ti alloys. We prepared the SmCox-0.4Ti_0.4 alloys with a wide composition range from x = 5.0 to x = 8.5 by high-energy ball-milling, followed by annealing at 700-1100°C for 2 h. After annealing at 700°C, the powders with x = 7.0-8.5 showed a single 1:7 structure, while the powders with x = 5.0-6.5 presented the 1:7 plus CaCu₅-type (1:5) structure. At an annealing temperature higher than 800°C, a minor Th₂Zn₁₇-type (2:17) phase precipitated in the matrix of the 1:7 phase. Intrinsic coercivity iHc exhibits a maximum of 2.3 T at room temperature and 0.4 T at 500°C in the x = 7.0 samples annealed at 700°C. The temperature coefficient of iHc seems stable as the Sm/Co ratio changes from 1/6.5 to 1/7.5. The coercivity decreased with increasing annealing temperature Ta, from 2.3 T at Ta = 700°C to 1.3 T at Ta = 1100°C, which is mainly attributed to the grain growth from 35 nm for Ta = 700°C to 1 ?m for Ta = 1100°C. After holding at 500°C for up to 360 h, the microstructure and magnetic properties of the 1:7-type nanograin alloys remained almost unchanged, indicating a structurally and magnetically long-term stabilization at the potential high-temperature application environment.     

Dual-phase magnesia-zirconia ceramics with strength retention at elevated temperatures

Two-phase polycrystalline ceramics containing MgO and ZrO₂ were fabricated by pressureless sintering powder compacts in air to near theoretical density. MnO was added as a densification aid in most compositions. For samples fabricated with 20 vol% ZrO₂ and 80 vol% MgO (which actually contained 23 vol% ZrO₂(ss) after sintering because some of the MgO dissolved in zirconia), densities in excess of 98% theoretical were achieved at temperatures as low as about 1250° C. However, most of the samples were typically sintered at 1420±10° C. The grain sizes of the two phases, ZrO₂(ss) and MgO(ss), were of the order of 1.4m. Thermal etching of the specimens showed the presence of very uniform sized domains (approximately 240 nm in size) in zirconia grains. Some samples were also fabricated in which 8 mol% CaO was added in order to stabilize the high-temperature cubic polymorph of zirconia to room temperature. The grain sizes of the two phases in this composition were also of the order of 1.4m. No domains were observed in zirconia grains in CaO-doped samples. Fracture strength was measured as a function of volume fraction of zirconia. Strength values in excess of 500 MPa have been measured on samples fabricated with 40 vol% zirconia (the amount of zirconia (ss) is 43 vol%). Samples of similar composition but with CaO doping exhibited strength of the order of 300 MPa despite an essentially identical grain size and density. Fracture toughness of samples containing CaO was 3.0 MPa m^1/2 while that of the samples without CaO was 5.2 MPam^1/2. No monoclinic phase was observed on either the fracture or the ground surfaces of CaO-doped and undoped samples. Fracture strength and toughness, measured as a function of temperature up to 1000° C, were found to be nearly independent of temperature. The temperature independence of the strength suggests that strengthening and toughening in this material does not occur by transformation toughening.     

New preparation method of low-temperature sinterable Pb(Mg1/3Nb2/3)O3 powder and its dielectric properties

A relaxor ferroelectric material, Pb(Mg_1/3Nb_2/3)O₃(PMN) with perovskite phase was prepared by one-step calcination in the present study. The PMN powder with >99% perovskite phase was prepared successfully by adding an aqueous Mg(NO₃)₂ solution rather than MgO to the alcoholic slurry of PbO and Nb₂O₅, followed by calcination at 950°C for 2 h. The DSC and XRD analysis showed that the pathway in the one-step calcination was different from those of the known columbite or solution processes. The PMN powder sintered to 95.6% of the theoretical density at even 900°C for 2 h. Its room temperature dielectric constant showed 13800 at 1 kHz, the loss of dielectric constant of 0.05% and the specific resistivity of 2.4 × 10¹⁰ ·cm.