医用可降解Mg-3Zn-0.5Sr合金耐蚀性及细胞毒性

采用仿生法在Mg-3Zn-0.5Sr合金表面制备涂层,通过SEM,EDS和XRD分析表征涂层形貌和结构;采用电化学实验和浸泡腐蚀实验来研究涂层对合金降解速率的影响;采用生物毒性实验验证有无涂层Mg-3Zn-0.5Sr合金的毒性等级.实验结果表明:在Mg-3Zn-0.5Sr合金表面可以沉积致密的羟基磷灰石(HA)涂层,厚度约为30~40μm,HA涂层可以有效地降低Mg合金的降解速率;在体积分数为25%的有无涂层合金浸提液中培养细胞4d,细胞相对增值率均超过100%,有无涂层合金的细胞毒性均为0级.     

Mg-Zn-Ca合金的性能及降解速率控制

以经过铸造和热挤压的Mg-Zn-Ca合金为研究对象，利用光学显微镜、万能试验机对合金的微观组织以及机械性能进行了分析测试.采用仿生法在该合金表面形成了羟基磷灰石(HA)涂层.利用X射线衍射仪和扫描电子显微镜对涂层结构和形貌进行分析与观察，并对有、无涂层试样进行腐蚀实验研究.结果表明:采用铸造和热挤压技术制备的Mg-Zn-Ca合金抗拉强度和抗压强度与人骨接近，分别为365MPa和338MPa；屈服强度为360MPa，延伸率为1025%，弹性模量为4169GPa.HA涂层能一定程度上降低合金试样的降解速率.     

High thermal conductivity and high strength magnesium alloy for high pressure die casting ultrathin-walled components

With the rapid development of 3C industries,the demand for high-thermal-conductivity magnesium alloys with high mechanical performance is increasing quickly.However,the thermal conductivities of most common Mg foundry alloys(such as Mg-9wt%-1wt%Zn)are still relatively low.In this study,we developed a high-thermal-conductivity Mg-4Al-4Zn-4RE-1Ca(wt%,AZEX4441)alloy with good mechanical properties for ultrathin-walled cellphone components via high-pressure die casting(HPDC).The HPDC AZEX4441 alloy exhibited a fine homogeneous microstructure(average grain size of 2.8μm)with granular Al₁₁RE₃,fibrous Al₂REZn₂,and networked Ca₆Mg₂Zn₃ phases distributed at the grain boundaries.The room-temperature thermal conductivity of the HPDC AZEX4441 alloy was 94.4 W·m^-1·K^-1,which was much higher than 53.7 W·m^-1·K^-1 of the HPDC AZ91D alloy.Al and Zn in the AZEX4441 alloy were largely consumed by the formation of Al₁₁RE₃,Al₂REZn₂,and Ca₂Mg₆Zn₃ phases because of the addition of RE and Ca.Therefore,the lattice distortion induced by solute atoms of the AZEX4441 alloy(0.171%)was much lower than that of the AZ91D alloy(0.441%),which was responsible for the high thermal conductivity of the AZEX4441 alloy.The AZEX4441 alloy exhibited a high yield strength of~185 MPa,an ultimate tensile strength of~233 MPa,and an elongation of~4.2%.This result indicated that the tensile properties were comparable with those of the AZ91D alloy.Therefore,this study contributed to the development of high-performance Mg alloys with a combination of high thermal conductivity,high strength,and good castability.     

仿生涂层控制Mg-Zn-Sr合金的降解速率

镁合金作为生物医用材料面临最大的问题是降解速率过快,不能与骨愈合的速率配合.通过仿生法在Mg-Zn-Sr合金表面形成涂层,利用X射线衍射和扫描电子显微镜对涂层结构和形貌进行分析与观察;采用电化学和浸泡腐蚀实验,研究涂层对Mg-Zn-Sr合金在人体模拟液中降解速率的影响.实验结果表明:仿生法在合金表面形成的涂层为羟基磷灰石涂层;羟基磷灰石涂层提高了Mg-Zn-Sr合金在人体模拟溶液中的耐腐蚀性能.     

铸铝合金在潮湿大气中的腐蚀及其微观机制

用模拟湿热腐蚀试验方法在工业纯铝、ＺＬ１０２和ＺＬ１０９合金表面诱发腐蚀,用ＳＥＭ、ＥＤＳ和ＸＲＤ等实验手段观察和分析了铸铝合金中第二相和腐蚀产物的微观形貌及化学成分,研究了第二相与表面缺陷对铸铝合金大气腐蚀发生机制的影响．结果表明,在吸附了水分和侵蚀性Ｃｌ－的微观孔隙周围,由Ａｌ６Ｃｕ３Ｓｉ相粒子和铝基体构成的腐蚀微电池发生电化学反应,电位较负的Ａｌ首先发生溶解,导致了局部点状腐蚀;腐蚀产物中除了存在少量共晶硅、氧化铝外,主要由铝的不溶性氢氧化物构成．在０．５ｍｏｌ／ＬＮａＣｌ水溶液中的电化学测试结果表明,由于富铜Ａｌ６Ｃｕ３Ｓｉ第二相粒子的存在,在含侵蚀性Ｃｌ－的介质中,ＺＬ１０２、ＺＬ１０９合金比纯铝具有更强的腐蚀倾向．     

Electrodeposition of aluminium and aluminium-copper alloys from a room temperature ionic liquid electrolyte containing aluminium chloride and triethylamine hydrochloride

The electrodeposition of Al and Al-Cu binary alloys on to gold substrates from a room temperature ionic liquid electrolyte containing AlCl₃-Et₃NHCl was studied. The electrochemical behavior of the electrolyte and the mechanism of deposition were investigated through cyclic voltammetry (CV), and the properties of deposits obtained were assessed by scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Al of 70 μm in thickness and an Al-Cu alloy of 30 μm in thickness with 8at% copper were deposited from the electrolyte. SEM images of the deposits indicate that the Al deposit was smooth and uniform, whereas the Al-Cu deposit was nodular. The average crystalline size, as determined by XRD patterns, was found to be (30 ± 5) and (29 ± 5) nm, respectively, for Al and Al-Cu alloys. Potentiodynamic polarization (Tafel plots) and electrochemical impedance spectroscopic (EIS) measurements showed that Al-Cu alloys are more corrosion resistant than Al.     

快速凝固工艺对AZ91HP镁合金腐蚀性能的影响

通过铜模铸造制备快速凝固的AZ91HP镁合金.利用失重法及动电位极化曲线研究了常规铸造AZ91HP和快速凝固AZ91HP镁合金样品在NaCl腐蚀介质中的耐腐蚀性能;通过金相显微镜（OM）、扫描电镜（SEM）及X射线衍射（XRD）分析了腐蚀后合金微观组织及相结构.结果表明,快速凝固的AZ91HP镁合金具有更好的耐腐蚀性能.其主要原因是经快速凝固工艺后：①β-Mg17Al12相近似连续地分布于细小的α-Mg晶界上;②合金的元素分布更加均匀;③合金显微缩松减少.     

生物医用ZTM630镁合金微弧氧化表面改性研究

为了进一步优化生物医用镁合金的耐蚀性能，满足临床使用要求，对新型生物医用高强韧ZTM630镁合金进行了微弧氧化表面改性处理。分别制备了氧化时间为2、5、8和15 min的微弧氧化试样，并对其组织结构和耐腐蚀性能进行了表征和分析。结果发现：随着氧化时间的延长，涂层厚度与表面粗糙度均呈现增高的趋势；当氧化时间为5 min时，试样表现出最强的耐蚀性。研究表明，微弧氧化时间的合理调控对于生物医用镁合金耐蚀性的提高具有重要的意义。     

生物医用ZTM630镁合金微弧氧化表面改性研究

为了进一步优化生物医用镁合金的耐蚀性能，满足临床使用要求，对新型生物医用高强韧ZTM630镁合金进行了微弧氧化表面改性处理。分别制备了氧化时间为2、5、8和15 min的微弧氧化试样，并对其组织结构和耐腐蚀性能进行了表征和分析。结果发现：随着氧化时间的延长，涂层厚度与表面粗糙度均呈现增高的趋势；当氧化时间为5 min时，试样表现出最强的耐蚀性。研究表明，微弧氧化时间的合理调控对于生物医用镁合金耐蚀性的提高具有重要的意义。     

快速凝固AA8009耐热铝合金及其焊缝的耐腐蚀性能

通过剥落腐蚀实验、极化曲线测定和腐蚀形貌观察，研究了AA8009合金（Al-8．5Fe-1．3V-1．7Si）及其氩孤焊和电子束焊件的耐腐蚀性能，并与LF6和2024合金的耐腐蚀性能做了比较。实验结果表明：快速凝固AA8009耐热铝合金的耐腐蚀性能是最好的，这是由于该合金具有弥散分布、高含量的Al12（Fe，V）。Si增强相，该相的存在大大减少了合金形成腐蚀原电池的可能性。而LF6和2024合金由于在晶界处有析出相形成而降低了它们的耐蚀性。同时，AA8009合金电子束焊缝的抗蚀性要明显优于氩孤焊的抗蚀性。     

消失模镁合金铸件的腐蚀行为

对消失模镁合金铸件的表面成分与耐腐蚀能力进行了研究，发现消失模镁合金铸件比其他铸造方法获得的铸件的耐腐蚀性更好．在50g／L的NaCl盐浴中腐蚀，聚苯乙烯(EPS)消失模镁合金试样的耐腐蚀性能比普通铸造得到的镁合金试样耐腐蚀性提高了约3倍．其主要原因是以EPS为模样的镁合金消失模铸造得到的铸件表面有一层MgO-Al2O3-SiO2-无定型C粒子等组成的薄膜，该薄膜对镁合金起到了保护作用．因此，消失模铸造非常适用于镁合金的成形。     

FeV50合金浇铸沉降理论的应用及其影响因素

采用近似无限大流体重力沉降原理分析了多期法FeV50合金浇铸过程渣金分离及浇铸渣层钒的分布规律,考察了熔渣黏度、沉降粒度、浇铸温度、渣层厚度以及保温制度对渣中钒含量的影响.结果表明,浇铸渣中钒的赋存形式除了未还原完全的钒氧化物之外,还存在部分未完全沉降的初级合金;合金沉降速度随合金粒度的增加而增大,随熔渣黏度的增加而减小.1850℃条件下,当渣层厚度为50 mm,熔渣组分质量分数为65.2%Al2 O3、15.5%CaO、14.6%MgO、1.9%Fe2 O3、0.9%SiO2时,粒径为100μm的合金沉降时间及熔渣上浮时间分别为24.9和1.2 min.基于此,进行浇铸工艺优化试验,在渣层厚度35 mm,浇铸温度1900℃、熔渣主要成分质量分数Al2 O360%~65%、CaO 15%~20%、MgO 9%~15%、浇铸锭模保温层厚度9 cm的条件下,浇铸渣中平均TV质量分数由1.39%降低至0.58%.     

SO2/CO2气体对纯镁及AZ91D合金的保护行为

为探究气体保护纯镁及镁合金免于氧化及燃烧的机制,研究了体积分数为3%SO2和97%CO2混合气体在非封闭熔化炉中对熔融纯镁及AZ91D合金的保护行为。借助具有能谱测定(EDS)的扫描电镜(SEM)、X射线衍射仪(XRD)分别分析了熔融纯镁及AZ91D合金表面膜的显微组织、化学成分及相组成。结果表明:在680℃AZ91D合金表面膜密集连续,其厚度约为2μm,而纯镁表面膜厚度约为1μm,混合气体对AZ91D合金的保护效果优于纯镁。两种熔体表面膜由MgO、MgS及少量单质C相组成。除AZ91D表面膜含有少量Al外,两种表面膜均含有S、C、O及Mg元素。     

放电等离子烧结Al20Cr20Fe25Ni25Mn10高熵合金的硬度和腐蚀性能研究

采用放电等离子烧结(SPS)技术在不同温度（800、900和200°C）下保温不同时间（4、8和12 min）合成了Al₂₀Cr₂₀Fe₂₅Ni₂₅Mn₁₀高熵合金（HEA）。通过扫描电子显微镜、能谱仪（EDS）、维氏显微硬度计、极化曲线等对合金的微观结构、显微硬度和腐蚀进行了实验研究。X-射线衍射（XRD）表征了所制备合金的成分。EDS结果显示不论烧结参数如何变化,合金均由原始合金元素组成。XRD、EDS和扫描电子显微镜的结果说明所制备的合金具有球形微观结构,呈现出面心立方结构相,这是基于固溶机制形成的。这表明SPS合金具有HEAs的特征。在1000°C保温 12 min生产的合金显微硬度最高,为HV 447.97,热处理后其硬度降至HV 329.47。同一合金表现出优异的耐腐蚀性能。烧结温度升高,Al₂₀Cr₂₀Fe₂₅Ni₂₅Mn₁₀合金可具有更高的密度、显微硬度和耐腐蚀性。     

电磁铸造对金基合金微观组织和溶质分布的影响

为了更好地提高金基合金镀膜产品的性能,分别采用电磁铸造和传统模铸工艺制备了真空溅射靶材用Au-Cu系多元金基合金,研究了电磁场对该金基合金显微组织和各溶质元素分布的影响.结果表明:和传统模铸相比,采用电磁铸造技术制备的金基合金其凝固组织的枝晶化程度明显降低,各溶质元素的偏析程度也在很大程度上得到了抑制,并对在电磁场作用下金基合金凝固组织的细化机理和溶质元素的分布规律进行了探讨.     

机场道面除冰液对3D打印的Ti-6Al-4V腐蚀研究

本文研究了电子束熔融(EBM)和激光选区熔化3D打印(SLM)技术制备的Ti-6Al-4V合金在机场道面除冰液—醋酸钾溶液中的电化学腐蚀行为,并与传统锻造Ti-6Al-4V合合金进行对比,通过电化学阻抗谱和极化曲线分析三种合金的抗腐蚀性能.研究结果表明,传统锻造Ti-6Al-4V合金的表面阻抗值更大,极化电阻更高,致钝电流密度更低,更易形成钝化膜,耐蚀性更强.而SLM-和EBM-Ti-6Al-4V合金阻抗值、极化电阻、致钝电流密度非常接近,抗腐蚀性能相似.     

Corrosion mechanism of micro-arc oxidation treated biocompatible AZ31 magnesium alloy in simulated body fluid

The rapid degradation of magnesium(Mg) based alloys has prevented their further use in orthopedic trauma fixation and vascular intervention,and therefore it is essential to investigate the corrosion mechanism for improving the corrosion resistance of these alloys. In this work, the effect of applied voltage on the surface morphology and the corrosion behavior of micro-arc oxidation(MAO) with different voltages were carried out to obtain biocompatible ceramic coatings on AZ31 Mg alloy. The effects of applied voltage on the surface morphology and the corrosion behavior of MAO samples in the simulated body fluid(SBF) were studied systematically. Scanning electron microscope(SEM) and X-ray diffractometer(XRD)were employed to characterize the morphologies and phase compositions of coating before and after corrosion. The results showed that corrosion resistance of the MAO coating obtained at 250 V was better than the others in SBF. The dense layer of MAO coating and the corrosion precipitation were the key factors for corrosion behavior. The corrosion of precipitation Mg(OH)2and the calcium phosphate(Ca–P) minerals on the surface of MAO coatings could enhance their corrosion resistance effectively. In addition, the mechanism of MAO coated Mg alloys was proposed.     

离子注入TiNi SMA及Co合金耐蚀性与血液相容性研究

采用离子注入法对生物医用TiNi形状记忆合金及二种Co合金进行表面改性，利用电化学测试技术，动态凝血时间及溶血率的测量，研究了改性前后合金的耐蚀性及血液相容性，结果表明，离子注入后合金的电化学稳定性显著提高，阳极极化性能变优，对TiNi、CoCrNiW和CoCrNiMo合金分别进行Mo C和Ti C双离子注入后，表面改性合金的腐蚀电位升高200mV以上，维钝电流密度减小，钝化区拓宽；合金的凝血时间延长，溶血率下降，说明离子注入提高了合金的耐蚀性及血液相容性，其中双离子注入较单离子注入效果更为显著，对双离子注入合金进行X射线衍射分析发现，在TiNi合金表面主要形成了TiC相及少量TiO、Mo2C、Mo9Ti4及Mo，在Co合金表面主要为CoCx和Co3Ti及少量TiC、TiO相，这些相弥散分布在合金表面，形成无序膜层，阻止了合金元素溶解，改善了合金的耐蚀性及血液相容性。     

Surface characteristics and corrosion resistance of biodegradable magnesium alloy ZK60 modifi ed by Fe ion implantati on and deposition

The ZK60 magnesium alloy has been modified by Fe ion implantation and deposition with a metal vapor vacuum arc plasma source. The surface morphology, phase constituent and elemental distribution are determined by scanning electron microscopy, transmission electron microscopy, X-ray diffractometer and Auger electron spectroscopy. The results show that Fe thin film is deposited on ZK60 alloy and the corresponding thickness increases from 2.73 μm to 6.36 μm with increasing deposition time. A transition layer mainly composed of Mg, Fe and O elements is formed between Fe thin film and ZK60 substrate. The potentiodynamic polarization tests reveal that a high corrosion potential and a low corrosion current density are detected for the Fe deposited ZK60 alloy, indicating the improvement of corrosion resistance. The tensile deformation test indicates that the Fe deposited film on the ZK60 substrate can sustain 1% tensile strain without any cracks.     

化学镀CuNiP-碳纳米管复合材料的制备与表征

用化学镀的方法在多壁碳纳米管表面沉积Cu—Ni—P合金,制备碳纳米管复合材料．并对制备出来的复合材料进行透射电子显微镜（TEM）和X-射线衍射（XRD）表征．通过XRD对已制备的化学镀合金分析．得出沉积铜为立方面心结构而镍是非晶态．TEM观察复合碳纳米管,发现在其表面沉积有分散均匀纳米级的金属颗粒,Cu-Ni-P合金呈球形．