TENSILE STRENGTH AND CREEP RESISTANCE OF Mg-9Al-1Zn BASED ALLOYS WITH CALCIUM ADDITION

Small amount of calcium addition to the Mg-9Al-0.8Zn-0.2Mn (AZ91) alloy resulted in obvious influence on mechanical properties. The yield strength of the alloys increased with the increase of Ca addition and the maximum strength was obtained from the alloy containing 0.15% of Ca. The creep resistance at the temperatures between 150-220°C was also significantly increased with Ca addition. The creep rate (at 200°C, 50 MPa) of the alloy with 0.15% Ca addition was one order of magnitude lower than that of the base alloy (AZ91). Microstructural observations revealed that the addition of calcium refined the microstructure and enhanced the thermal stability of the β precipitates, which accounted for the improvement of creep resistance at high temperatures.

Surface characterization and corrosion behavior of calcium phosphate(Ca-P)base composite layer on Mg and its alloys using plasma electrolytic oxidation(PEO):A review

Magnesium has been known as an appropriate biological material on account of its good biocompatibility and biodegradability properties in addition to advantageous mechanical properties.Mg and its alloys are of poor corrosion resistance.Its high corrosion rate leads to its quick decomposition in the corrosive ambiance and as a result weakening its mechanical properties and before it is repaired,it will vanish.The corrosion and degradation rate must be controlled in the body to advance the usage of Mg and its alloys as implants.Different techniques have been utilized to boost biological properties.Plasma electrolytic oxidation(PEO)can provide porous and biocompatible coatings for implants among various techniques.Biodegradable implants are generally supposed to show enough corrosion resistance and mechanical integrity in the body environment.Much research has been carried out in order to produce PEO coatings containing calcium phosphate compounds.Calcium phosphates are really similar to bone mineral composition and present great biocompatibility.The present study deals with the usage of calcium phosphates as biocompatible coatings applied on Mg and its alloys to study the properties and control the corrosion rate.

Surface Coating of NiTi Shape Memory Alloys with Calcium Phosphates by Dip-coating or Plasma-spraying-biological Characterization Examined by in vitro Testing Methods

The influence of different surface coatings of NiTi shape memory allays was examined using in vitro testing methods. Plates of superelastic nickel-titanium shape memory allay （ NiTi ） were coated with calcium phosphates （ hydroxyapatite ） by high-temperature plasma-spraying or by dip-coating. The biocompatibility was tested in vitro by cultivation of isolated human granulocytes and whole blood cells. As substrates, pure NiTi, plasma-spray-coated NiTi and dip-coated NiTi were used. Isolated granulocytes showed an increased adhesion to both calcium phosphate-coated NiTi samples. Compared to non-coated NiTi or dip-coated NiTi, the number of dead granulocytes adherent to plasma-sprayed surfaces was significantly increased （ p 〈 0.01 ）. Whether the d/f- ferences in apoptosis of granulocytes on dip-coated vs plasma-sprayed coatings observed are due to differences in material surface morphologies has to be analyzed in further studies. Because of the cellular interactions with the coating layers, h is likely that the results obtained are not caused by the underlying NiTi but due to the coating itself.

Calcium phosphate conversion technique:A versatile route to develop corrosion resistant hydroxyapatite coating over Mg/Mg alloys based implants

Globally,vast research interest is emerging towards the development of biodegradable orthopedic implants as it overcomes the toxicity exerted by non-degradable implants when fixed in the human body for a longer period.In this context,magnesium(Mg)plays a major role in the production of biodegradable implants owing to their characteristic degradation nature under the influence of body fluids.Also,Mg is one of the essential nutrients required to perform various metabolic activities by the human cells,and therefore,the degraded Mg products will be readily absorbed by the nearby tissues.Nevertheless,the higher corrosion rate in the biological environment is the primary downside of using Mg implants that liberate H2gas resulting in the formation of cavities.Further,in certain cases,Mg undergoes complete degradation before the healing of damaged bone tissue and cannot serve the purpose of providing mechanical support.So,many studies have been focused on the development of different strategies to improve the corrosion-resistant behavior of Mg according to the requirement.In this regard,the present review focused on the limitations of using pure Mg and Mg alloys for the fabrication of medical implants and how the calcium phosphate conversion coating alters the corrosive tendency through the formation of hydroxyapatite protective films for enhanced performance in medical implant applications.

Microstructure and mechanical properties of ZA62 based magnesium alloys with calcium addition

As-cast microstructure and mechanical properties of Mg-6Zn-2Al-0.3Mn (ZA62) alloys with calcium addition were investigated.The as-cast microstructure of the base alloy ZA62 consists of the α-Mg matrix and eutectic phase Mg51Zn20.The Mg51Zn20 eutectic was gradually replaced by MgZn phase and Mg32(Al,Zn)49 phase when calcium is added into the base alloy.Further addition of calcium leads to the increase of grain boundary phases and formation of a new quaternary Mg-Zn-Al-Ca eutectic compound.In comparison with the base alloy,the increase of calcium addition to the base alloy results in the reduction of both strength and ductility at ambient temperature,but increase at elevated temperatures due to the thermal stability of Ca-containing phases.At elevated temperatures,the creep resistance of ZA62 based alloys containing calcium is significantly higher than that of AZ91 which is the most commonly used magnesium alloy.

Calcium phosphate deposition on surface of porous and dense TiNi alloys in simulated body fluid

Porous and dense TiNi alloys were successfully fabricated by powder metallurgy(P/M) method, and to further improve their surface biocompatibility, surface modification techniques including grind using silicon-carbide(SiC) paper, acid etching and alkali treatment were employed to produce either irregularly rough surface or micro-porous surface roughness. X-ray diffractometry(XRD), scanning electron microscopy(SEM) and energy dispersive X-ray spectroscopy(EDX) attached to SEM were used to characterize surface structure and the Ca-P coatings. Effects of the above surface treatments on the surface morphology, apatite forming ability were systematically investigated. Results indicate that all the above surface treatments increase the apatite forming ability of TiNi alloys in varying degrees when soaked in simulated body fluid(SBF). More apatite coatings formed on TiNi samples sintered at 1050℃ and 1100℃ due to their high porosity and pure TiNi phase that is beneficial to heterogeneous nucleation. Furthermore, more uniform apatite was fabricated on the sample sintered from the mixture of Ni and Ti powders.

甘油磷酸钙浓度对钛合金MAO涂层性能的影响

目的提高医用钛合金的生物活性。方法在含葡萄糖酸钙(CaGlu_(2))、葡萄糖酸镁(MgGlu_(2))、植酸钠(Na12Phy)和磷酸(H3PO_(4))的基本溶液中,分别添加8、10、12 g/L甘油磷酸钙(Ca-GP),采用MAO方法在Ti-6Al-4V表面制备3种涂层。使用SEM、EDS、XRD、XPS和AFM检测涂层表面形貌、化学成分、物相结构、元素存在状态和表面粗糙度,并测试涂层的接触角、结合强度以及体外生物活性。结果经过MAO处理后,钛合金表面可成功生长出多孔陶瓷涂层,Ca-GP参与了MAO涂层形成。当Ca-GP的质量浓度为8g/L时,涂层非常粗糙,Ca和Mg的原子数分数分别为7.56%和1.74%。随着Ca-GP浓度的增加,微孔均匀性变好,表面微裂纹减少,且钙磷原子比(Ca/P)显著提高。在含8、10g/L的Ca-GP溶液中,制备的涂层以Ti、锐钛矿和金红石型TiO_(2)组成为主;在12 g/L的Ca-GP溶液中生成的涂层,Ca/P原子比可达1.77,含有TiP_(2)O_(7)、Mg_(3)(PO_(4))_(2)和少量HA。Ca-GP能显著增加涂层的粗糙度,且稍微增加涂层与基体之间的结合强度。接触角测试结果表明,Ca-GP能明显改善涂层的亲水性。结论随着Ca-GP浓度增加,涂层中钙含量增加,表明钙离子通过扩散进入MAO涂层中。在含12 g/L Ca-GP溶液中制备的涂层,含TiP_(2)O_(7)、Mg_(3)(PO_(4))_(2)和HA,且Ca/P原子比与HA中的Ca/P原子比接近。模拟体液中浸泡试验结果表明,添加12g/L Ca-GP制备的MAO样品,表面形成了大量颗粒状HA,表现出优异的体外生物活性。

Ti-6Al-4V钛合金环保型阳极氧化及封闭处理研究

选用Ti-6Al-4V钛合金作为基体在环保型电解液中制备阳极氧化膜,然后分别浸没在沸水、氟锆酸铵溶液、乙酸钙溶液中对阳极氧化膜进行封闭处理。采用扫描电镜、能谱仪和X射线衍射仪表征和分析未封闭及封闭处理后阳极氧化膜的微观形貌、化学成分与物相结构,并配制酸性氯化钠溶液作为腐蚀介质,研究未封闭及封闭处理后阳极氧化膜的耐腐蚀性能。结果表明:与未封闭阳极氧化膜相比,在沸水、氟锆酸铵溶液、乙酸钙溶液中封闭处理后阳极氧化膜中微孔数量减少,化学成分发生变化,耐腐蚀性能进一步提高,但封闭处理未影响阳极氧化膜的物相结构。在乙酸钙溶液中封闭过程中发生化学反应,生成水合二氧化钛、氢氧化钛、氢氧化钙和钛酸钙等多种产物,达到协同封闭效果,赋予封闭处理后阳极氧化膜良好的表面致密性,其耐腐蚀性能好于在沸水、氟锆酸铵溶液中封闭处理后阳极氧化膜,对钛合金的防护作用更强。

In Situ Laser Coating of Calcium Phosphate on TC4 Surface for Enhancing Bioactivity

Titanium alloy has been a successful implant material owing to its excellent ratio of strength to weight, toughness, and bio-inert oxide surface. Significant progress has been made in improving the bioactivity of titanium alloy by coating its oxide surface with calcium phosphates. In the present study, in situ coating was reported on Ti6Al4V（TC4） surface with calcium phosphate （Ca-P） bioceramics synthesized and synchronously cladded by laser beam. This coating was grown by first preplacing directly the raw powders, which contain 80% of CaHPO4 · 2H2O, 20% of CaCO3, and dram of rare earth （RE）, on the TC4 surfaces, and then exposing the surfaces to the laser beam with a power density of 12. 73-15.27 MW · m^-2 and a scanning velocity of 10.5 m/s. The resultant coating was characterized using scanning electron microscopy （SEM）, X-ray diffraction （XRD）, thermogravimetric analysis and Different-thermal Scanning （TG-DSC）, and Energy Dispersive X-ray Detection （EDX）. The results show that these laser ceramics include hydroxyapatite （HA）, tricalcium phosphate （TCP）, Ca2 P2 O7, and other Ca-P phases, and the interface between the coating and the TC4 substrate has tighter fixation, in which the chemical bonding is approved. These laser hybrid coatings are useful in enhancing the bioactivity of titanium alloy surfaces.

Refinement Role of Electromagnetic Stirring and Calcium in AZ91 Magnesium Alloy

Effects of calcium addition and electromagnetic stirring on the microstructure of AZ91 magnesium alloy and refinement mechanism were investigated. The results show that calcium addition ranging from 0.1wt% to 0.3 wt% does not lead to formation of any new phases but cause the refinement of ascast microstructure.However, combined calcium alloying and electromagnetic stirring significantly decrease the grain size, change the morphologies of the β-Mg17Al12 phases,and reduce their volume percentage. The minimum grain size of AZ91 alloy is obtained in the case of the addition of 0.2 wt%Ca with exciting voltage of 100 V. The microstructural refinement is attributed to the increase of the degree of undercooling and nucleation temperature of primary α-Mg phases on the basis of DTA analysis results.

Recent advances in hydrothermal modification of calcium phosphorus coating on magnesium alloy

Magnesium(Mg) and its alloys have emerged as a favored candidate for bio-regenerative medical implants due to their superior biocompatibility, biodegradability and the elastic modulus close to that of human bone. Unfortunately, the rapid and uncontrollable degradation rate of Mg alloys in chloride-rich body microenvironments limits their clinical orthopedic applications. Recently, Calcium Phosphate(Ca-P)biomaterials, especially Hydroxyapatite(HA), have been broadly applied in the surface functional modification of metal-based biomaterials attributed to their excellent bioactivity and biocompatibility. Hydrothermal modification of Ca-P coatings on Mg alloys has been extensively exploited by researchers for its significant superiorities in controlling coating structure and improving interfacial bonding strength for better osseointegration and corrosion resistance. This work focuses on the up-to-the-minute advances in Ca-P coatings on the surface of Mg and its alloys via hydrothermal methods, including the strategies and mechanisms of hydrothermal modification. Herein, we are inclined to share some feasible and attractive hydrothermal surface modification strategies. From the perspectives of hydrothermal manufacturing technique innovation and coating structure optimization, we evaluate how to foster the corrosion resistance, coating bonding strength, osseointegration and antibacterial properties of Mg alloys with Ca-P coatings synthesized by hydrothermal method. The challenges and future perspectives on the follow-up exploration of Mg alloys for orthopedic applications are also elaborately proposed.

The Role of Calcium in Microstructural Refinement of AZ91 Magnesium Alloy

The effect of calcium addition on the microstructures of AZ91 magnesium alloy was investigated. It was found that a small amount of calcium in AZ91 allay produced a large decrease in the α- Mg grain size and the dispersed fine β-Mgt7 Alt2 phases. In addition, some Al4Ca particles were found to exist in the AZ91 alloy containing 0.5wt% Ca. EDS analysis and water-quenched technique revealed that the grain-refining mechanism of calcium for the AZ91 alloys was mainly attributed to the role of restricting growth of calcium in the primary α-Mg crystals.

Effects of Copper-Zinc Alloy Doped with Rare Earth Elements on Crystal of Calcium Carbonate

A copper-zinc alloy doped with rare earth elements was prepared and the mechanism was demonstrated in a simulating boiler and circulating cooling water with rigidity 1 mmol·L-1. The polar curve and scale inhibiting ability of the alloy was tested by a corrosion measurement system and a scale inhibition evaluation system, respectively. Scale samples were characterized with SEM and XRD. It is found that the transfer of cations could be promoted by doping with proper rare earth elements, and the corrosion potentials descend by 25～126 mV. The results indicated that the copper-zinc alloy doped with rare earth elements has higher scale inhibiting ability of CaCO3. The growth of calcite was affected by zinc ions dissolved because of primary battery reaction, and the transition of calcium carbonate from aragonite to calcite was hampered resulting in the proportion of aragonite to calcite is changed from 1.7∶1 to 2.7∶1.

Review on the phosphate-based conversion coatings of magnesium and its alloys

Magnesium(Mg)and its alloys are lightweight as well as biocompatible and possess a high strength-to-weight ratio,making them suitable for many industries,including aerospace,automobile,and medical.The major challenge is their high susceptibility to corrosion,thereby limiting their usability.The considerably lower reduction potential of Mg compared to other metals makes it vulnerable to galvanic coupling.The oxide layer on Mg offers little corrosion resistance because of its high porosity,inhomogeneity,and fragility.Chemical conversion coatings(CCs)belong to a distinct class because of underlying chemical reactions,which are fundamentally different from other types of coating.Typically,a CC acts as an intermediate sandwich layer between the base metal and an aesthetic paint.Although chromate CCs offer superior performance compared to phosphate CCs,yet still they release carcinogenic hexavalent chromium ions(Cr^(6+));therefore,their use is prohibited in most European nations under the Registration,Evaluation,Authorization and Restriction of Chemicals legislation framework.Phosphate-based CCs are a cost-effective and environment-friendly alternative.Accordingly,this review primarily focuses on different types of phosphate-based CCs,such as zinc,calcium,Mg,vanadium,manganese,and permanganate.It discusses their mechanisms,current status,pretreatment practices,and the influence of various parameters-such as pH,temperature,immersion time,and bath composition-on the coating performance.Some challenges associated with phosphate CCs and future research directions are also elaborated.

Influence of Electrolyte Composition on the Calcium-Phosphorus compound Coating on Titanium Substrate by Micro-arc Oxidation

The compound bioceramic coating containing calcium (Ca) and phosphorus (P) on titanium alloy substrate was prepared by means of micro-arc oxidation (MAO) treatment. The results show that under the different electrolyte the coating with the color of gray or black and surface morphology of cauliflower or honeycomb, where Ca content and P contain can attain 30% and 20% respectively, can be obtained. Meanwhile, the influences of electrolyte temperature, current density and discharge time on morphology and thickness of coating are also discussed here.

Crystal structures and hydrogenation behavior of (Ca_(0.9)Sr_(0.1))_8(Al_(1-x)Zn_x)_3 alloys

The crystal structures and hydrogenation behavior of the （Ca0.9Sr0.1）8（Al1-xZnx）3 （x = 0, 0.1, 0.2, 0.3 and 0.4） alloys were investigated. The new phase （Ca,Sr）E（Al,Zn） was found whenx 〉 0.1. （Ca, Sr）E（Al,Zn） crystallizes in space group 14/mmm （A-139）. The lattice parameters were calculated to be a = b = 1.1616（2） nm, c = 1.6422（4） nm. Zn atoms occupy the 8h and 16n sites together with Al atoms. The （Ca0.9Sr0.1）8Al3 alloy only contains a single Ca8Al3 phase. The （Ca0.9Sr0.1）8（Al1-xZnx）3 alloys consist of Ca8Al3, CasZn3, Ca and （Ca,Sr）2（Al,Zn） phases when x is from 0.1 to 0.3. As x increasing to 0.4, the alloy consists of （Ca,Sr）E（Al,Zn）, Ca8Zn3 and Ca. The hydrogenated （Ca0.9Sr0.1）8Al3 and （Ca0.9Sr0.1）8（Al0.9Zn0.1）3 samples consist of CartE and Al. The （Ca0.9Sr0.1）8（Al1-xZnx）3 （x = 0.2, 0.3 and 0.4） samples can be hydrogenated into CaH2, Al and CaZnl3 under a hydrogen pressure of 5 MPa at 473 K.

钢液Ca含量控制对Ds夹杂物的影响研究

分析研究了某公司生产的GCr15钢、45钢钢液Ca含量对Ds夹杂物的影响。研究了GCr15钢、45钢在LF精炼过程加入含Ca硅铁合金,钢液增Ca质量分数约(4~5)×10^(-6)。控制硅铁合金在BOF出钢时加入,同时取消Ca处理,可控制中包钢液w(Ca)≤3×10^(-6)。GCr15钢、45钢控制硅铁合金全部在BOF出钢过程加入,LF结束时夹杂物均主要为MgO·Al_(2)O_(3);控制硅铁合金全部在LF精炼过程加入,LF结束时夹杂物主要为CaO-Al_(2)O_(3)和MgO·Al_(2)O_(3)。随钢液Ca含量增加,轧材Ds夹杂物数量密度正比例增加;钢液Ca含量增加,Ds夹杂物极值尺寸并未明显增加。分析了多组不同钢种钢液Ca含量同轧材Ds夹杂物的关系,随钢液Ca含量增加,Ds夹杂物数量密度及极值尺寸均呈增加的趋势,但Ca含量降低Ds夹杂物极值尺寸并非必然降低。控制钢液Ca含量只能减少Ds类夹杂物的数量,但Ds夹杂物尺寸仍不能得到有效控制。

制备时的pH对AZ31镁合金表面铁离子掺杂磷酸氢钙转化膜性能的影响

为改善镁合金的耐蚀性,提高医用镁合金的使用寿命,采用液相沉积法,以硝酸钙、硝酸铁及磷酸二氢钠组成的转化液在AZ31镁合金表面制备了一层转化膜,研究了pH对成膜效果和膜层性能的影响。使用扫描电镜、能谱仪和X射线衍射仪探究了膜层的成分和形貌,采用电化学方法考察了试样在Hank’s溶液中的腐蚀行为。结果表明,转化液的pH为6时制备出的铁掺杂磷酸氢钙膜层能有效保护基体。最后探讨了成膜的过程。

50 kVA直流电弧炉处理卡尔多炉渣试验研究

卡尔多炉渣含有大量高熔点难熔物料,直接返回转炉处理对现有系统扰动大,返回量受限,堆存量逐年增加。本文采用理论与试验相结合方法探索卡尔多炉渣高效、低成本处理工艺。首先采用热力学计算得到熔炼卡尔多炉渣时主要反应的吉布斯自由能与时间的关系,表明温度在750~1500℃、以粒煤为还原剂、石灰石为熔剂的条件下,各主要反应均能发生,最终得到铜镍合金和硅酸钙渣。在此基础上,结合卡尔多炉渣中不同元素还原性的差异,利用粒煤作还原剂,在直流电弧炉中选择性还原熔炼卡尔多炉渣,获得合格的铜镍合金和弃渣。试验结果表明:在熔炼温度1420℃、还原剂用量10%、熔剂率15%、沉降时间60 min条件下,获得高品位铜镍合金,合金品位均大于90.00%;铜、镍回收率均大于98.50%,炉渣中镍、铜含量分别降至0.15%、0.32%,实现了一步从炉渣中提取有色金属。本研究有利于提高有色金属二次资源回收率,为直流电弧炉熔炼卡尔多炉渣奠定了理论及实践基础。

硅钙合金中硅的快速分析法

传统手工法用高氯酸脱水重量法对硅钙合金中硅元素的含量进行测定:通过两次灼烧后重量的差值,计算出二氧化硅的质量,进一步得到硅的含量。然而,该方法不仅步骤较为复杂,对操作人员要求较高,同时也需要较长的检测周期,不利于日常检测的时效性要求。对比其他铁合金样品中硅元素含量的测定,对硅钙合金中的硅元素含量可以使用容量法进行检测:对已符合要求的硅钙合金粉末,用硝酸和氢氟酸溶解,加入饱和硝酸钾溶液生成氟硅酸钾沉淀。过滤后,取滤纸和沉淀,先用氢氧化钠溶液中和剩余的硝酸和氢氟酸,再用沸水使氟硅酸钾水解,析出氢氟酸。再次用氢氧化钠溶液滴定,计算得出硅的质量分数。按此方法对两组硅钙合金标样中硅的成分进行了测定,检测结果与标准值相符,其相对标准偏差分别为0.177%和0.268%。该方法简便、迅速,数据结果准确性高,重复性好,符合日常检测工作的需要。