高耐腐蚀Fe-(Cr,Ni)-Mo-P-C-B块体非晶合金

Fe-Mo-P-C-B铁基块体非晶合金具有高强度、高塑性和良好的软磁性,作为结构和功能材料具有较好的应用前景。本研究通过Cr、Ni合金化制备了耐腐蚀Fe-(Cr,Ni)-Mo-P-C-B块体非晶合金,其非晶形成临界直径达5mm。Cr、Ni合金化显著提高了Fe-Mo-P-C-B块体非晶合金在HCl、H2SO4、NaCl溶液中的耐腐蚀性能,使钝化电流密度降低、腐蚀速度降低、电化学反应电阻增大。     

Ti-Zr-Ni-Cu非晶系的等电子浓度特征

以准晶成分Ti40Zr40Ni20为基准，在Ti—Zr-Ni-Cu系中设计出电子浓度为1.200和原子尺寸为0．1474nm的系列合金，并用铜模吸铸法制备直径为3mm的合金棒试样．结果表明，Ti12Zr55Ni13Cu20成分附近可形成块体非晶合金，而Ti3Zr60Ni12Cu25和Zr60Ni10Cu30成分点上形成了单一的四方Zr2Cu型非晶相关相．准晶、块体非晶合金和Zr2Cu相是具有相同电子浓度的电子化合物，它们在成分图上表现出鲜明的等电子浓度特征，表明块体非晶合金的等电子浓度判据适用于Ti-Zr-Ni-Cu非晶系．二十面体与截角八面体间的结构关联可作为准晶或非晶合金多型性转变成Zr2Cu相的结构模型．     

添加微量Mo对铜基块体非晶合金耐蚀性的影响

采用动电位极化和交流阻抗谱技术(EIS)研究了(Cu47Zr11Ti34Ni8)100-x Mox(x=0,2)块体非晶合金在1mol/L H2SO4溶液中的室温电化学行为.结果表明,x=2的钝化膜破裂电位(Eb)显著上升,致钝化电位(E0)与维钝电流密度(ip)明显减小.这主要是由于在稳定的钝化区内,微量Mo的添加增加了基体合金中的"氧空位"和表面活性,抑制了阴离子空位在金属/表面膜(M/F)界面上的形成,促使元素Zr和Ti在M/F界面上快速形成相应的氧化物,并增加了钝化层中氧化层的厚度和稳定性.根据该体系在电解质中的电化学反应,基于点缺陷模型(PDM)建立了简单的动力学模型.利用该模型,结合EIS数据,分析了微合金化提高铜基块体非晶合金耐蚀性能的机理.     

Cu47Ti34Zr11Ni8块体非晶合金的制备

采用差压铸造法成功制备了圆棒状与板片状的Cu417Ti34Zr11Ni8块体非晶合金，研究了合金的热稳定性。在试验条件下，Cu47Ti34Zr11Ni8块体非晶合金棒状试样的最大直径可达3mm，板片状试样的最大厚度可达1mm。该成分块体非晶合金具有良好的热稳定性，其玻璃转变温度Tg=672K，晶化温度Txl=735K，过冷液相区△Tx=63K，约化玻璃温度Trg=0．575。     

Zr-Al-Co-Er-Cu系块体非晶合金的形成及其力学性能和腐蚀行为

制备了具有高非晶形成能力的Zr-Al-Co-Er-Cu系非晶块体合金,并研究了Cu元素对Zr-Al-Co-Er块体非晶合金的形成、力学性能和腐蚀行为的影响。研究表明以适量的Cu元素替代Zr-Al-Co-Er合金的Co元素有利于非晶形成能力的提高和力学性能的改善。其中,Zr49Al20Co23Er6Cu2非晶合金的临界直径达6mm,压缩断裂强度达到1950MPa,表现出1.4%的塑性变形。Zr49Al20Co25-xEr6Cux(x=0～8at%)非晶合金在1mol/LH2SO4、3%NaCl(质量分数,下同)溶液中的均发生自钝化,并且具有较低的钝化电流密度。Cu含量的变化对Zr-Al-Co-Er-Cu非晶合金的腐蚀行为没有明显影响。     

块状非晶合金CU-Zr-Ti-Sn在3.5%NaCl溶液中的腐蚀行为

利用电化学极化曲线方法和电化学阻抗谱(EIS)技术研究了Cu60Zr30Ti10和(Cu60Zr30Ti10)99Sn1块状非晶合金及其晶化后在3．5％NaCl溶液中的腐蚀行为．极化曲线测试结果表明，(Cu60Zr30Ti10)99Sn1非晶合金在3．5％NaCl溶液中的阳极极化衄线有一定的钝化倾向，且其阳极电流密度较Cu60Zr30Ti10非晶合金的阳极电流密度有所降低；同时EIS结果显示，其电化学反应电阻Rt较Cu60Zr30Ti10的Rt值有所增大，说明添加1％Sn使非晶合金Cu60Zr30Ti10的耐蚀性能有所改善．相应成分晶化后的合金与非晶合金的极化曲线相比较，阳极极化表现出较大的钝化倾向，且阳极电流密度略有降低．晶化后合金的EIS测试显示有两个时间常数，即由高频容抗弧和低频容抗弧构成．晶化后合金与其非晶合金相比较，电化学反应电阻见明显增大，表明晶化后合金的耐蚀性能有所提高。     

Nb对Zr基块体非晶合金热稳定性、非晶形成能力及机械性能的影响

利用水冷铜模铸造法成功制备了(Zr70Ni10Cu20)90-xNbxAl10(x=0，2，5，7)块体非晶合金，采用XRD，DSC和DTA研究了Nb对该合金体系热稳定性和非晶合金形成能力(GFA)的影响．结果表明，适量Nb的添加可有效提高该合金的GFA和热稳定性．当Nb含量为x=2时，合金具有最宽的过冷液态区(△Tx=119K)和最大的非晶形成能力(参数γ=Tx／(Tg T1)=0．435)，Nb的适量添加也有利于提高块体非晶合金的强度和塑性应变，其中x=2的块体非晶的抗压强度和断裂应变量分别达到1783MPa和11．1％。     

微量添加In对铜基块体非晶合金在3.5% NaCl溶液中耐蚀性的影响(英文)

研究了铜基块体非晶合金Cu55-x Zr37Ti8Inx(x=0～5,at%)及Cu61-x Zr34Ti5Inx(x=0～3,at%)在质量分数3.5%NaCl溶液中的耐蚀性。极化曲线结果表明,在铜基非晶合金中添加In元素能明显提高合金的腐蚀电位、降低腐蚀电流密度,即能明显提高耐蚀性。含In的铜基块体非晶合金的腐蚀电流密度(Icorr)值比不含In的铜基块体非晶合金低约1个数量级。而且,利用In适量取代Cu可进一步提高耐蚀性。但过量添加In不利于形成富Zr保护膜,从而降低合金的耐蚀性。     

Ni-Ti-Zr-Al-Cu-Si块体非晶合金的形成及压缩性能

利用DSC，DTA，XRD研究了NiTiZrAlCuSi块体非晶合金的形成。采用铜模铸造工艺使块体金属玻璃最大直径从Ni42Ti25Zr25Al8合金的小于0．5mm增加到Ni42Ti20Zr25Al8Cu5的1mm，然后增加到Ni42Ti20Zr21.5Al8Cu5Si3.5合金的4mm。在Ni42Ti20Zr21.5Al8Cu5Si3.5和Ni42Ti20Zr20.5Al8Cu5Si4.5合金中获得最大的约化玻璃转变温度Trg（=Tg／T1）及最大的过冷液相区△Tx（=Tx-Tg），分别为0．570和93K。Si显著增加玻璃形成能力主要是抑制引起异质形核的Ni（TiZr）相和（TiZr）（CuAl）2相的形成。室温压缩实验表明：Ni42Ti20Zr21.5Al8Cu5Si3.5合金抗压断裂强度为2724MPa。     

Influence of Minor Addition of In on Corrosion Resistance of Cu-Based Bulk Metallic Glasses in 3.5% NaCl Solution

研究了铜基块体非晶合金Cu55-x Zr37Ti8Inx(x=0～5,at%)及Cu61-x Zr34Ti5Inx(x=0～3,at%)在质量分数3.5%NaCl溶液中的耐蚀性。极化曲线结果表明,在铜基非晶合金中添加In元素能明显提高合金的腐蚀电位、降低腐蚀电流密度,即能明显提高耐蚀性。含In的铜基块体非晶合金的腐蚀电流密度(Icorr)值比不含In的铜基块体非晶合金低约1个数量级。而且,利用In适量取代Cu可进一步提高耐蚀性。但过量添加In不利于形成富Zr保护膜,从而降低合金的耐蚀性。     

Improvement of corrosion resistance of Cu-based bulk metallic glasses by the microalloying of Mo

(Cu₄₇Zr₁₁Ti₃₄Ni₈)_100−xMo_x bulk metallic glasses (BMGs) with x = 0, 1 and 2 at% were prepared by water-cooled copper mold casting. The effect of the addition of a small amount of Mo on the corrosion resistance of the Cu-based BMGs was examined by electrochemical polarization and weight loss measurement in 1 mol/L H₂SO₄ open to air. It is found that the corrosion resistance of Cu-based BMGs enhanced with increasing Mo content, as indicated by the decrease in passive current density and corrosion rate with the increase in Mo content. X-ray photoelectron spectroscopy (XPS) was employed to study the composition and the state of elements in the passive film, which revealed that the improvement of corrosion resistance of Cu-based BMGs microalloyed with Mo originated from the enrichment of ZrO₂ and TiO₂, but depletion in Cu- or Ni-oxide in the passive films formed during electrochemical polarization. In addition, the galvanostatic-step measurement was performed to investigate the formation kinetics of the passive films. It is demonstrated that the addition of an appropriate amount of Mo can promote the formation of the passive film on the surface.     

Improvement of corrosion resistance in NaOH solution and glass forming ability of as-cast Mg-based bulk metallic glasses by microalloying

The influences of the addition of Ag on the glass forming ability (GFA) and corrosion behavior were investigated in the Mg-Ni-based alloy system by X-ray diffraction (XRD) and electrochemical polarization in 0.1 mol/L NaOH solution.Results shows that the GFA of the Mg-Ni-based BMGs can be improved dramatically by the addition of an appropriate amount of Ag;and the addition element Ag can improve the corrosion resistance of Mg-Ni-based bulk metallic glass.The large difference in atomic size and large negative mixing enthalpy in alloy system can contribute to the high GFA.The addition element Ag improves the forming speed and the stability of the passive film,which is helpful to decrease the passivation current density and to improve the corrosion resistance of Mg-Ni-based bulk metallic glass.     

Towards improved integrated properties in FeCrPCB bulk metallic glasses by Cr addition

Fe-based soft-magnetic metallic glasses (MGs) of Fe_80−xCr_xP₉C₉B₂ (x = 0, 2, 5, 8 and 16 at.%) with high glass-forming ability (GFA), good soft-magnetic properties and high corrosion resistance are fabricated. With the addition of Cr to FePC-based alloys, the GFA and saturation magnetization (M_s) slightly decrease while the corrosion resistance effectively increases. The Fe–Cr–P–C–B BMGs exhibit good GFA and fully glassy rods can be produced up to 1.8 and 1.5 mm in diameter for the 2 and 5 at.% Cr added alloys, respectively. The alloys with 2 and 5 at.% Cr addition also show good soft-magnetic properties featured by high M_s of 1.16 and 1.04 T, low coercivity of 2.7 and 2.2 A/m, respectively. Besides, the corrosion behavior of the alloys was studied by immersion tests and potentiodynamic polarization measurements. It was found that the addition of Cr efficiently enhances the corrosion resistance of Fe–Cr–P–C–B alloys and the glassy alloy with 5 at.% Cr addition exhibits better corrosion resistance in comparison with the stainless steel SUS304 in 3 mass% NaCl solution. The combination of large GFA, good soft-magnetic properties, high corrosion resistance as well as low cost makes the Fe–Cr–P–C–B alloys as promising soft-magnetic and anti-corrosive materials for industrial applications.     

Enhancement on GFA and mechanical properties of Ni-based bulk metallic glasses through Fe addition

Bulk Ni_76-xFe_xP₁₄B₆Ta₄ (x = 10, 20, 30, all in at.%) glassy alloy rods with diameters of 1.5–3.0 mm are synthesized by combining fluxing treatment and J-quenching technique, and the effects of Fe substitution for Ni on the glass forming ability (GFA), thermal stability, mechanical properties, and corrosion resistance of the present Ni-based bulk metallic glasses (BMGs) have been studied systematically in this work. It is found that the appropriate substitution of Fe for Ni can greatly enhance the GFA of the present Ni-based alloys, and the critical diameter for fully glass formation gets to the maximum value of 3.0 mm when the substitution content of Fe for Ni is 20 at.%. The corrosion tests show that the substitution of Fe for Ni causes a certain reduction of the corrosion resistance of the present Ni-based BMGs, but the corrosion current densities in both 1 M NaCl and 1 M HCl solutions are below the order of magnitude of 10⁻⁵ A/cm² and the corrosion rate in1 M HCl solution is in the order of magnitude of 0.1 mm/year, still exhibiting a good corrosion resistance. The present Ni-based BMGs exhibit a compressive strength of more than 2.6 GPa and, more significantly, the substitution of Fe for Ni greatly enhances the compressive plasticity of the present Ni-based BMGs and the compressive plastic strain gets up to 6.6% when 20 at.% of Ni is substituted by Fe. This work indicates that the GFA and mechanical properties of Ni-based BMGs can be enhanced significantly through the Fe addition.     

闭合场非平衡磁控溅射镀Cr-C层的耐蚀性研究

    利用闭合场非平衡磁控溅射离子镀技术在高速钢表面制备Cr-C镀层。采用电化学腐蚀法研究了Cr-C镀层、电镀Cr层及高速钢基体的腐蚀行为.结果表明,在1 mol/L NaCl、1 mol/L HCl及7.5 mol/L NaOH溶液中,闭合场非平衡磁控溅射离子镀制备的Cr-C镀层的耐蚀性优于电镀Cr镀层,并且其Cr含量越高耐腐蚀性越好.     

一种新型Fe-Mn-Al-Cr奥氏体不锈钢的耐蚀性能

研究了一系列铬含量不同而锰含量都为15%的Fe-Mn-Al-Cr钢在几种典型酸、碱、盐水溶液中的耐腐蚀性能,并与锰含量为26%的Fe-Mn-Al-Cr钢和1Cr18Ni9Ti相比较,结果表明新型的Fe-Mn-Al-Cr钢在水溶液中的耐腐蚀性能比原来的Fe-Mn-Al-Cr钢的都要好,在有些溶液中的耐蚀性能比1Cr18Ni9Ti还要好。这种新型不锈钢的价格非常低,有较高的实用价值。研究还表明,对该钢种而言,铬含量升高并不意味着耐蚀性能提高,铬含量增至某一值时钢的耐蚀性能反而降低,此时组织中出现铁素体。用XPS对Fe-Mn-Al-Cr钢在0.5mol/L H2SO4中的钝化膜进行了研究.     

Fe-20Cr纳米涂层的电化学行为

利用磁控溅射技术在玻璃基体上制备了Fe-20Cr纳米晶涂层.分别测试了Fe-20Cr铸态和纳米晶涂层在含氯离子溶液(0.005 mol/L H2SO4 0.5 mol/L NaCl)与不含氯离子的溶液(0.005 mol/L H2SO4 0.25 mol/LNa2SO4)中的动电位极化曲线.结果表明,纳米化使材料的溶解速度增大,纳米晶涂层在两种溶液体系中均容易钝化;与铸态合金相比,纳米涂层的维钝电流增大两个数量级.在含氯离子溶液中,纳米晶涂层的维钝区间是铸态合金的两倍,耐局部腐蚀性能得到很大提高.利用电容测试技术和Mott-Schottky关系研究了Fe-20Cr铸态合金与纳米晶涂层分别在两种溶液中所形成钝化膜的半导体性能.结果表明铸态合金在不含氯离子的溶液中低电位下所形成的钝化膜为p型半导体,高电位下形成n型半导体,在含氯离子溶液中形成的钝化膜为p型半导体;而纳米晶涂层在两种溶液体系中形成的钝化膜均为n型半导体.钝化膜的结构类型的不同是导致Fe-20Cr纳米晶涂层与铸态合金具有不同电化学行为的主要原因.     

Ti-Zr-Cu-Fe-Sn-Si-Ag-Ta bulk metallic glasses with good corrosion resistance as potential biomaterials

Ti_(47)Cu_(38-x)Zr_(7.5)Fe_(2.5)Sn_2 Si_1 Ag_2 Ta_x(x=1-4;at%,the same below) bulk metallic glasses(BMGs) with good bio-corrosion resistance and mechanical properties were fabricated by copper mold casting.Critical diameter of the Ti-based BMGs with 1 at%-4 at% Ta was 3 mm.The Ta-incorporated Ti-based BMGs exhibit higher open current potential and parallel passive current density in comparison with those of Ti-6 Al-4 V alloy in 0.9 wt%NaCl and Hank's solution,implying their good corrosion resistance.The pitting corrosion potential of the Ti-based BMGs gradually increases up to about 1.25 V with Ta addition increasing up to 4 at% in 0.9 wt% NaCl solution.Among the present Ti-based BMGs,the alloy bearing2 at% Ta exhibits the optimal integration of mechanical properties,including the compressive fracture strength exceeding 2000 MPa,relative low Young's modulus of98 GPa,plastic strain of 3.4% and high hardness of HV599.The Ta-bearing Ti-based bulk metallic glasses with integration of relative high GFA,good mechanical properties and high bio-corrosion resistance are beneficial for biomedical applications.     

Fe41Co7Cr15Mo14C15B6Y2块体非晶合金在HCl溶液中的腐蚀行为

采用电化学极化曲线和电化学阻抗(EIS)测试方法研究Fe_(41)Co_7Cr_(15)Mo_(14)C_(15)B_6Y_2块体非晶合金在0.5,1,2以及4 mol/L HCl溶液中的腐蚀行为,并比较了1 mol/L HCl溶液中非晶合金和不锈钢的腐蚀行为.极化曲线测试结果表明,Fe_(41)Co_7Cr_(15)Mo_(14)C_(15)B_6Y_2块体非晶合金在各种浓度的HCl溶液中都具有很好的耐蚀性,阳极极化曲线表现出明显的钝化特征.随着HCl溶液浓度的增大,其耐蚀性能逐渐下降.在1 mol/L HCl溶液中,非晶合金的自腐蚀电位高于不锈钢,自腐蚀电流密度比不锈钢小1个数量级.EIS结果显示,在开路电位下,Fe_(41)Co_7Cr_(15)Mo_(14)C_(15)B_6Y_2非晶合金和不锈钢的Nyquist图均由单一的容抗弧构成,但非晶合金的电化学转移电阻Rt比不锈钢的大2个数量级,这一结果与极化曲线结果一致,说明非晶合金在HCl溶液中的耐蚀性能优于不锈钢.