Influence of impurities on microstructure and mechanical properties of ZK60 magnesium alloy

The influence of impurity content on the microstructure and mechanical properties of ZK60 magnesium alloys was investigated by optical microscopy,scanning electron microscopy and tensile test.ZK60 alloys were prepared by changing holding time of alloy melt during semi-continuous casting in order to control the content of impurity elements.The alloy with lower purity content is found to have less second precipitates and larger grain size in the as-cast state.However,in the as-extruded state,reducing impurities brings about a decrease in grain size and an increase in yield strength from 244 MPa to 268 MPa,while the elongations in the as-extruded alloys with different contents of impurities are almost the same.After T5 treatment,impurity content is found to have more obvious effect on the yield strength of ZK60 alloy.The yield strength of ZK60-45 alloys with low impurity content is increased up to 295 MPa after T5 treatment.

Influence of impurities on damping properties of ZK60 magnesium alloy

The influence of impurities on damping capacities of ZK60 magnesium alloys in the as-cast,as-extruded and T4-treated states was investigated by dynamically mechanical analyzer at room temperature.Granato and Lucke dislocation pinning model was employed to explain damping properties of the alloys.It is found that reducing impurity content can decrease the amount of second-phase particles,increase grain size and improve damping capacity of the as-cast alloy slightly.The as-extruded alloy with lower impurity content is found to possess obviously higher damping capacity in the relatively high strain region than that with higher impurity concentration,which appears to originate mainly from different dislocation characteristics.The variation tendency of damping property with change of impurity content after solution-treatment is also similar to that in the as-extruded and as-cast states. Meanwhile,the purification of the alloy results in an evident improvement in tensile yield strength in the as-extruded state.

Improved Mechanical Properties in AZ31 Magnesium Alloys Induced by Impurity Reduction

Mechanical properties and microstructures of AZ31 magnesium alloys containing different impurity levels but having the same alloying element content, were investigated at ambient temperature. These AZ31 alloys were produced by semi-continuous casting, wherein the content of impurity was varied systematically. Microstructure observation shows that finer grains are existent in the alloy with lower impurity level. Tensile testing reveals that a reduction of impurity content results in a noticeable increase of the strength and elongation in the alloys in the cast, homogenized and extruded states. As the impurity content decreases from 0.0462wt% to 0.0163wt%, the ultimate tensile strength is evidently enhanced by 62 MPa and the elongation is nearly doubled in the homogenized specimen. The observed property improvement was discussed in terms of the microstructure variation with impurity reduction.

A novel approach to melt purification of magnesium alloys

A novel low-cost method for melt purification of magnesium alloys,the melt self-purifying technology(MSPT),has been developed successfully based on a low temperature melt treatment(LTMT)without adding any fluxes.The iron solubility in the molten liquid of magnesium and its alloys,and the settlement velocity of iron particles were calculated.It is shown that the low temperature melt treatment is an effective method to decrease the impurity Fe content in magnesium and its alloys.Without any additions,the Fe content in the AZ31 alloy was reduced to 15 ppm from the initial 65 ppm,and the Fe content in the AZ61 melt was decreased to 20 ppm from the initial 150 ppm after the low temperature melt treatment.The results also showed that the Fe content in AM60 and AM50 dropped to 15 and 18 ppm,respectively,from the initial 150 ppm after the low temperature melt treatment.For ZK 60,the Fe content in the melt down to less than 5 ppm was achieved.After the low temperature melt treatment,the Si content in the above alloys was also decreased obviously.

Mechanism of Mn on inhibiting Fe-caused magnesium corrosion

In the present study,to understand the mechanism of Mn on inhibiting Fe-caused Mg corrosion,the corrosion behaviour of commercial pure Mg and Mg-6 Mn alloy in 0.6 M NaCl solution is investigated.It is found that in Mg-6 Mn alloy,Fe impurity is incorporated into Mn to form Mn(Fe)phase with Fe as solid solute.The initial galvanic corrosion cannot be reduced through converting Fe-rich phase to Mn(Fe)phase,since Mn(Fe)phase also has relatively strong cathodic activity and has much larger volume fraction than Fe-rich phase.However,the cathodic activation behaviour of pure Mg is inhibited.The cathodic activity even decreases for Mg-Mn alloy with increased exposure time,due to the reduced cathodic HER at the Mn(Fe)particles.Mn can be oxidized at the OCP of Mg-6 Mn alloy,resulting in relatively dense Mn-rich corrosion film on particle surface,which separates the particle from the electrolyte and,consequently,inhibits HER.

Characterizations on the instantaneously formed Ni-containing intermetallics in magnesium alloys

Instantaneous reactions of Al,Mn,Zn,Zr and Y with Ni by mixing the prepared Mg-8Al-0.4Mn,Mg-6Zn-2Y-0.5Zr and Mg-0.6Ni melts were investigated in this work to reveal the underlying mechanisms of their effects on the removal of Ni impurity.The results indicate three Ni-containing intermetallics,namely Al_(4)NiY,Al_(4)Ni(Y,Zr)and Al_(31)Ni_(2)Mn_(6).The former two phases present lath-like and have a relatively larger size(>20μm in length)than the latest one which is granular with the diameter of∼120 nm.This illustrates that Al and Y(/Zr)can efficiently remove Ni by forming Al_(4)NiY or Al_(4)Ni(Y,Zr)which would precipitate to the bottom of the melt.Furthermore,adding Y into Mg-Al based alloys can simultaneously remove Fe and Ni,which contributes their excellent corrosion resistance.Finally,this paper proposes two methods helped to efficiently remove Ni for both Mg-Al based alloys and Al-free Mg alloys,and both of them are also benefit to improve alloys’strength.

Minimizing pest aluminum in magnesium for the production of high-purity titanium

It is practically difficult to find titanium sponges with low and stable aluminum impurities on the market even though it is the precondition to prepare high-purity titanium. Analysis indicates that almost all the aluminum impurities in the titanium sponge are inherited from the magnesium used to reduce titanium tetrachloride. However, it remains elusive for decades why magnesium produced through the silicothermic reduction method contains a high content of aluminum impurities with large fluctuations. By recourse to thermodynamic calculations and comparative experiments, we demonstrate that fluorite, a material used as a catalyst in the silicothermic reduction method to produce magnesium, is the chief culprit for the pest aluminum and propose a mechanism to rationalize the observed phenomena. Our findings indicate that one practical way to produce qualified magnesium for the production of high-purity titanium is to abandon fluorite during the production of magnesium with the silicothermic reduction method.

高钙高锂型卤水制碳酸锂钙镁离子脱除工艺研究

对高钙、高锂、低镁锂比(Mg/Li=0.02)国外阿根廷某盐湖卤水进行钙、镁、锂深度分离的工艺研究。采用两步法去除溶液中的Ca^(2+)、Mg^(2+):首先加入硫酸钠生成硫酸钙沉淀除去大量的Ca^(2+),后加入氢氧化钠形成氢氧化镁和氢氧化钙除去少量的Ca^(2+)、Mg^(2+);分别考察了物料比、反应温度、加料时间、加料速率、pH值对卤水除杂效果的影响因素。结果表明:在反应温度60℃、硫酸钠用量为1.3、加料速率6 mL/min、反应时间70 min条件下,溶液中Ca^(2+)的脱除率为96.22%,Li+的损失率为1.44%;在pH值为14、10 mol/L NaOH、反应时间50 min、反应温度50℃、加料速率为8 mL/min条件下,最终溶液中Ca^(2+)脱除率为99.75%,Mg^(2+)去除率为100%,Li+的损失率为0.04%;实现了钙镁离子的深度去除,为后续工序制备碳酸锂创造了有利的条件。

污泥4种热处理产物中磷的化学提取-沉淀回收性能

污水处理厂污泥中磷含量较高,对磷进行回收能有效实现磷资源的二次利用。采用磷酸铵镁(MAP)回收法分别对污泥4种热处理产物阴燃灰、掺烧灰、焚烧灰和热解焦的酸浸出液进行磷回收试验,重点分析了各热处理产物在酸浸出-MAP路线下的磷回收性能,包括磷沉淀率、产物中磷和杂质含量,并进一步探究了沉淀产物的环境安全性。结果表明,通过酸浸出-MAP回收法,单位质量沉淀产物磷质量分数达19.82~31.71 mg/g,原污泥中磷回收率达49.25%~65.81%。磷回收性能由高到低依次为焚烧灰、热解焦、阴燃灰、掺烧灰。酸浸出-MAP回收产物中含有大量Ca、Fe、Al和Si杂质,且含有一定量Zn、Pb、Cr、Cu、Cd、As和Ni,其中Zn含量远高于其他重金属含量。产物纯度和环境安全性由高到低依次为焚烧灰、掺烧灰、热解焦、阴燃灰。在沉淀产物的环境安全性方面,阴燃灰、焚烧灰和热解焦的酸浸出-MAP回收产物中重金属含量均符合GB/T 23349—2009《肥料中砷、镉、铅、汞生态指标》和GB 4284—2018《农用污泥污染物控制标准》。掺烧灰的酸浸出-MAP回收产物中Cd质量分数为3.20 mg/kg,超过农用污泥污染物控制标准限值3.00 mg/kg。

从离子型稀土镁盐富集物中提取稀土工艺初探

以MgO为沉淀剂沉淀MgSO_(4)稀土浸出母液时,得到的稀土镁盐富集物REO总量较低,需要进一步除去杂质以沉淀富集稀土。以离子型稀土镁盐富集物为原料,进行碳化—酸溶—中和除杂—沉淀等工艺初步探索研究。结果表明:REO在碳化过程中的损失很少甚至可以忽略不计,有24.33%~30.9%MgO由稀土镁盐富集物转化进入碳化后液,在中和除杂过程中Fe去除率约99.5%,Al去除率约98.6%。以碳化后液为沉淀剂沉淀中和除杂后液得到碳酸稀土,经过灼烧,获得了符合《GB/T 20169—2015离子型稀土矿混合稀土氧化物》标准质量要求的稀土氧化物,该工艺总渣率为19.81%~23.22%,REO总收率平均89.43%。为了从离子型稀土镁盐富集物中提取稀土的工艺形成成套工艺技术,获取最优的工艺技术参数,有待于后续深入研究和优化。

铁配合型镁合金缓蚀剂的阴极阻蚀机制

研究阴极缓蚀剂(3-甲基水杨酸盐,3-MeSA)对含铁纯镁腐蚀性能的影响。高铁杂质颗粒成分、腐蚀表面形貌以及3-MeSA分子结构特征为揭示含铁镁合金的腐蚀行为及3-MeSA的阴极型阻蚀机理提供了实验与理论依据。研究结果表明:含铁杂质颗粒中含有固溶态硅,而Fe/Si比可能是导致不同局部腐蚀形态差异的主要原因。虽然3-MeSA能在镁基体上形成吸附层,但其阻蚀机制主要归因于其螯合从富铁颗粒中自腐蚀释放Fe^(2+)/Fe^(3+)的能力,阻止被还原的铁物质再次沉积至腐蚀金属表面。

含钴萃余液中和除杂及钴回收试验研究

试验以某铜钴矿回收过程的萃铜余液为原料,采用中和除杂-沉钴工艺回收氢氧化钴产品。结果表明,从中和除杂的最佳条件来看,反应温度为80℃,终点pH为5.0~5.5,空气流量为400 L/min,搅拌速度为2200 r/min,反应时间为4 h。最佳条件下,Al、Fe、Mn沉淀率分别为98.66%、98.81%、8.53%,Co沉淀率仅为0.21%。后续对除杂后液进行MgO沉钴,Co沉淀率超过99%,在沉钴过程中,维持惰性气氛对Mn沉淀具有明显抑制效果。

菱镁矿除杂提纯及应用研究进展

菱镁矿是制备镁系阻燃材料的关键原料,利用酸化和碳化改性工艺手段能极大地增强其化学性能。碳化法具备仅与菱镁矿中镁反应且碳化热解产品碱式盐酸镁形貌易控的特点,可以制备出不同形貌的高纯氧化镁煅烧前驱物碱式碳酸镁,得到高纯度、高活性、形貌好的氧化镁,实现我国菱镁矿资源的高附加值利用。综述了近年来菱镁矿除杂应用技术研究进展,并叙述了各方法的优势与特点。

杂质元素对镁合金组织与性能的影响及其对应措施

镁及镁合金中杂质元素的含量及作用已受到广泛关注。介绍了镁合金中Fe、Cu、Ni、Si等杂质的存在形式,综述了杂质元素对镁合金显微组织、腐蚀性能、力学性能的影响规律及机制,并叙述了几种提高镁合金纯度常见的方法,包括选用高纯原料、优化熔炼工艺、镁合金熔体纯净化,指出有效降低杂质含量将是未来高性能镁合金材料研究的重要方向。

高纯微细氢氧化镁的水热法制备

以国内丰富的镁资源为应用背景,借助SEM、X荧光光谱仪等现代测试手段,研究水热枝术在制备高纯微细氢氧化镁中的应用,测试结果表明水热技术使氢氧化镁平均粒径明显增大,晶型发育完善,纯度提高,有助于改善氢氧化镁作为高效阻燃剂在合成材料中的分散和阻燃性能,为海水镁资源的有效利用提供了适宜的处理途径.

电磁场对镁合金熔体的净化作用

对无磁场与静磁场作用下AZ61镁合金的凝固组织进行了研究。结果发现,静磁场作用下的镁合金凝固组织中夹杂物明显减少或呈球状分布,说明静磁场对AZ61镁合金熔体具有净化的作用,因此,静磁场可以改善镁合金的性能。

工业硫酸锰中钙、镁深度除杂的工艺研究

研究了工业硫酸锰中钙、镁杂质的深度除杂工艺。采用硫酸锰溶液预处理、加入晶种、控制工艺条件相结合的方法,以氟化锰为钙镁除杂剂,改善体系的过滤性能,提高钙、镁的去除率,使产品中钙、镁含量之和降低至小于0.05‰。所得产品可以达到电池级高纯硫酸锰对钙、镁含量的要求。

离子色谱法测定磷酸锂中微量的杂质元素

对离子色谱法测定磷酸锂中钾、钙、镁杂质离子的方法进行研究.采用DX-80型离子色谱仪,分离柱为Ion Pac CS12A-5μm阳离子分离柱,用2×10^-2.mol·L^-1甲基磺酸溶液为淋洗液,流速为2 mL·min^-1,测定了磷酸锂中各钾、钙、镁杂质离子的含量,相关系数分别为0.999 6,0.999 3,0.999 4,相对标准偏差小于3%,样品回收率为98.1%～100.3%.

轻烧粉蒸氨液中杂离子对氢氧化镁晶体的影响

以轻烧粉精制液和氨气为原料,研究了蒸氨精制液中杂质离子对氢氧化镁形貌的影响。选取阳离子NH_4^+、Ca^(2+)和阴离子SO_4^(2-)作为研究对象,考察了其对氢氧化镁的形貌和颗粒大小的影响。采用扫描电镜(SEM)、X射线衍射仪(XRD)和激光粒度仪对产品进行表征。结果表明,NH_4^+、Ca^(2+)对氢氧化镁产品的性能影响较小,而SO_4^(2-)对氢氧化镁产品的形貌和粒径影响较显著。并利用氯化钡除去溶液中的SO_4^(2-),比较未除硫、除硫后与用纯氯化镁制备的产品的差别。

电感耦合等离子体质谱法测定镧镁合金中稀土杂质

采用硝酸溶解样品,建立了电感耦合等离子体质谱法（ICP-MS）测定镧镁合金中稀土杂质的含量.选择合适的测定同位素以及选用干扰元素校正方程克服了质谱干扰.对仪器工作条件进行了优化,确定功率为1 100 W,载气流量为0.80 L/min.讨论了测定条件对结果的影响,确定测定介质为1％硝酸,内标元素为Cs,基体浓度小于0.3 mg/mL.方法测定下限为0.006 9～0.046 ng/mL.采用方法对实际样品进行测定,回收率为98％～102％.与电感耦合等离子体发射光谱法（ICP AES）进行方法对照,两种方法测定结果基本一致,相对标准偏差（RSD,n=6）在1.7％～4.5％之间.