纳米晶Co-Ni-Fe合金镀层在3.5%NaCl溶液中的腐蚀特性

利用脉冲电沉积技术制备纳米晶Co-Ni-Fe合金镀层。用EDS、XRD、TEM和SEM等手段分析纳米晶镀层的成分、微观组织结构和表面形貌。用电化学极化方法研究镀层中Co含量和退火温度对纳米晶Co-Ni-Fe合金镀层在3.5%（质量分数,下同）NaCl溶液中腐蚀行为的影响。结果表明,纳米晶Co-Ni-Fe合金镀层的晶体结构为单一面心立方结构,其晶粒尺寸随镀层Co含量的增加而减小。镀层的晶粒尺寸随退火温度的升高而增大,并呈现强的（111）织构。纳米晶镀层的腐蚀速率随Co含量的增加先下降而后上升。退火可明显降低纳米晶镀层的腐蚀速率。纳米晶与粗晶Co-Ni-Fe合金镀层经电化学腐蚀后呈现出完全不同的腐蚀形貌。     

电沉积纳米晶Ni-Co-Fe合金镀层的热稳定性

用脉冲电沉积方法制备表面平整光亮的纳米晶Ni-Co-Fe合金镀层.采用XRD、TEM、EDS、DSC和显微硬度计分别研究纳米晶Ni-Co-Fe合金镀层的微观结构、化学成分、热稳定性及其硬度.结果表明:纳米晶Ni-Co-Fe合金镀层的晶体结构为单相的面心立方结构,其晶粒尺寸随镀层Co含量的增加而减小;合金镀层的显微硬度随退火温度的升高而提高,在300～375℃时达最大值,存在明显的退火再强化,之后,随着退火温度的继续升高明显下降;当镀层在低于375℃退火时,晶粒长大速度较慢;而当镀层在高于450℃退火时,晶粒迅速长大,并呈现较强的(111)织构.升温速率为20℃/min时,纳米晶Ni-Co-Fe合金镀层的DSC结果显示,晶粒长大的峰值温度随镀层Co含量的增加而升高.由Kissinger方程求得纳米晶Ni-Co-Fe合金的晶粒长大激活能随镀层Co含量的增加而增大.     

脉冲电沉积纳米晶Ni-Co合金镀层腐蚀特性研究

采用X射线衍射(XRD)、扫描电镜(SEM)、能谱分析(EDS)等方法研究了脉冲电沉积法制各纳米晶Ni和纳米晶Ni-Co合金镀层的组织结构、表面形貌和成分.用浸泡法和电化学极化法研究了纳米晶Ni和不同Co含量的纳米晶Ni-C0合金镀层在3.5%NaCl(质量分数,下同)和5%HCl溶液中的腐蚀行为.结果表明:通过脉冲电沉积法制各的Ni和Ni-Co合金镀层具有典型的纳米晶结构; 随着含Co量的增加,镀层的晶粒尺寸减小,硬度增加;所制备的纳米晶Ni-Co合金镀层组织结构均匀致密,其在3.5%NaCl溶液和5%HCl溶液中的耐蚀性均优于纳米晶Ni镀层;纳米晶Ni-Co合金镀层在3.5%NaCl溶液的浸泡腐蚀中腐蚀极少,表现出优异的耐腐蚀性能,而在5%HCl溶液中的腐蚀形态则为均匀腐蚀.     

低温退火对电刷镀纳米晶Ni-Co合金镀层性能的影响

采用X射线衍射(XRD)、干滑动磨损、电化学分析等方法研究了低温退火(100～500℃)对电刷镀方法制备的纳米晶Ni-Co合金镀层的组织结构、耐磨性、耐蚀性的影响.结果表明:随着退火温度的升高,纳米晶Ni-44.16%Co合金镀层的晶粒尺寸逐渐增大,从原始晶粒尺寸12.7 nm长大到500℃时的微米晶尺寸.合金镀层的显微硬度随退火温度的升高而提高,300℃退火后达到最大值,以后随加热温度的升高而急剧降低.纳米晶Ni-44.16%Co合金镀层的耐磨性300℃退火后最好,500℃以后急剧下降,与镀层显微硬度的变化密切相关.浸泡试验与电化学分析均表明纳米晶Ni-44.16%Co合金镀层在300℃退火后的耐蚀性优于其他温度,300℃以上退火耐蚀性随温度升高而下降.     

脉冲电沉积纳米晶Ni-Co-Fe-P合金镀层的热稳定性

用脉冲电沉积方法制备了纳米晶Ni-Co-Fe-P合金镀层.采用X射线衍射(XRD)、透射电镜(TEM)、能谱分析(EDS)、差示扫描量热法(DSC)以及显微硬度计等测试方法研究合金镀层的微观结构、显微硬度和热稳定性.结果表明,纳米晶Ni-40.41%Co-6.16%Fe-1.63%P合金镀层的晶体结构为单一面心立方结构,其平均晶粒尺寸仅为8.8 nm,并具有(111)织构.该镀层的显微硬度随着退火温度的升高而上升,在300和450℃之间达到最大值,之后随退火温度的继续提高而逐步降低.在450℃退火后,晶粒长大到35.1 nm;600℃退火后,晶粒长大到160.8 nm,达亚微米级.在晶粒长大过程中伴有结构的转变,镀层由(111)织构向(200)织构转变.在升温速率为20 K/min的DSC曲线中,该镀层在474.4℃开始放热,并出现明显的放热峰,峰值温度为499.1℃,放热焓为9.086 J/g;通过Kissinger方程式求出该镀层晶粒长大的激活能为369.3 kJ/mol,具有很好的热稳定性.     

退火对化学镀Ni-W-P合金晶化及耐蚀性的影响

在不同温度下对制备的Ni-W-P合金镀层进行退火处理,利用X射线衍射技术定量分析了镀层的晶化、晶粒尺寸和晶格应变,采用扫描电镜(SEM)和光学显微镜观察了镀层腐蚀前后的表面形貌,并通过在0.5mol/L H2SO4溶液中的浸泡腐蚀速率和阳极极化曲线对退火前后镀层的耐蚀性进行了分析.结果表明:Ni-W-P镀层在镀态为非晶...     

非晶态Ni-W-P镀层退火晶化和激光晶化组织结构的演变

用XRD定量分析法并结合扫描电镜形貌观察,研究化学沉积高磷(13.3%)含量的Ni-W-P镀层在不同热处理条件下的晶化程度、晶粒尺寸及晶格应变等组织结构的演变规律。结果表明:高磷非晶态镀层在退火晶化过程中,Ni3P相的体积分数始终高于Ni相的,700℃时,两相的体积分数之差显著增大,镀层仍有残存的非晶相;在400~500℃之间形成的Ni3P的晶粒尺寸大于Ni的;温度为500~700℃时,Ni相的尺寸大于Ni3P的,但均未超过纳米级。镀层晶格应变表现为随退火温度的升高而降低,镀态时晶格应变最大。激光晶化处理的非晶态Ni-W-P镀层的显微结构特征介于400~500℃之间退火的镀层晶化特征。随扫描速度增加,不仅Ni3P晶粒尺寸增大,而且两相的尺寸差变大。     

脉冲电沉积WC-Co-Ni镀层的制备及性能研究

目的提高WC-Co-Ni纳米晶复合镀层的综合性能。方法利用脉冲电沉积法制备WC-Co-Ni纳米晶复合镀层,分析镀层的结构、表面形貌及元素成分,测试镀层的显微硬度。对WC-Co-Ni纳米晶复合镀层和304不锈钢进行5%(质量分数)H2SO4溶液浸泡实验,计算腐蚀速率,对比其耐蚀性。结果当脉冲参数为阴极电流密度5 A/dm2、脉冲占空比50%、脉冲频率2000 Hz时,施镀2 h制备的WC-Co-Ni复合镀层为纳米晶结构。镀层表面平整、光亮,无裂纹,由立方晶型的Ni、六方结构的WC和立方晶型的Co组成,WC-Co颗粒均匀弥散在纳米晶Ni镀层内,且m(Ni)∶m(W)∶m(C)∶m(Co)=6∶2∶1∶1。WCCo纳米颗粒起到了促进形核的作用,晶粒尺寸大多分布在20 nm左右。WC-Co纳米颗粒对镀层起到了弥散强化作用,使复合镀层的显微硬度达到600HV。在浸泡腐蚀实验中,随着温度从20℃升高至80℃,复合镀层的腐蚀速率增加缓慢,20℃下的腐蚀速率仅为0.4192 mm/a,80℃下的腐蚀速率也低于20mm/a。结论脉冲电沉积法制备的WC-Co-Ni纳米晶复合镀层硬度高于传统的不锈钢材料,耐蚀性也优于304不锈钢,综合性能较好。     

电刷镀纳米晶镍铁合金镀层腐蚀特性的研究

采用可溶性阳极电刷镀的方法制备纳米晶Ni-Fe合金和纳米晶Ni镀层,用浸泡法和电化学极化法研究了纳米晶Ni、Ni-5.84%Fe和Ni-13.49%Fe镀层在3.5%NaCl和10%HCl溶液中的腐蚀行为.结果表明:通过此法制备的Ni和Ni-Fe合金镀层具有典型的纳米晶结构;随着含Fe量的增加,镀层的晶粒尺寸减小,硬度增加;所制备的纳米晶Ni-13.49%Fe合金镀层组织结构均匀致密,晶界处没有明显的孔洞或缺陷,晶界及三叉晶界处的原子错配度小,过渡均匀,其在3.5%NaCl溶液中的耐蚀性优于纳米晶Ni镀层,而在10%HCl溶液中的耐蚀性与纳米晶Ni镀层相当;纳米晶Ni和纳米晶Ni-Fe合金刷镀层在3.5%NaCl溶液中的腐蚀形态均为点蚀,而在10%HCl溶液中的腐蚀形态则为均匀腐蚀.     

激光热处理对化学沉积Ni-W-P耐蚀性能的影响

通过分析激光退火前后Ni-W-P合金镀层腐蚀前后的表面形貌、晶化程度、晶粒尺寸及在0.5 mol/L的H_2SO_4溶液中的腐蚀速率,研究合金镀层的耐腐蚀性能。结果表明,镀态镀层的耐蚀性最差,随激光扫描速率的减小,镀层晶化程度增大,Ni和Ni_3P相的晶粒尺寸增大,微应变逐渐减小,镀层的耐蚀性增大。     

A combined composition and morphology study of electrodeposited Zn-Co and Zn-Co-Fe alloy coatings

The composition and morphology of electrodeposited Zn-Co and Zn-Co-Fe alloy coatings are studied by a variety of complementary analytical techniques. Morphology of the alloy deposits is shown to change significantly with Co content in the alloy coating. An increase in the Co content in the range of 0.7-9 wt.% Co in Zn-Co and Zn-Co-Fe alloys results in a change in grain shape from angular to nodular and a further increase up to 10 wt.% Co corresponds to a characteristic growth mode. In the range of 10-29 wt.% of Co, the deposit contains two types of grains, i.e. one with low Co content (5-7 wt.%) and another with higher Co content (i.e. 15-35 wt.%). Zn-Co and Zn-Co-Fe alloys with Co contents of or higher than 32 wt.% Co show a homogeneous structure, which can be considered to be nanocrystalline in nature. The presence of two or more phases is not desired in terms of enhanced local corrosion by (micro-)galvanic coupling of phases while the single phase or nanocrystalline coatings provide good corrosion protection properties.     

The effects of heat treatments on hardness and wear resistance in Ni-W alloy coatings

The relationship of processing parameters, microstructure, and mechanical responses of the electrodeposited nickel-tungsten alloys exposed to elevated temperatures in the range 700-1100 °C are investigated. Reverse pulse electrodeposition technique is employed to control the tungsten content and nanocrystalline grain size of the deposits. The application of heat treatment at 700 °C on the alloy with high tungsten content (22 at.%) and small grain size (3 nm) gives hardness enhancement and a small decrease in wear resistance. Prolonging annealing duration and increasing annealing temperature promote more grain growth and reductions of both hardness and wear resistance, despite the formations of secondary phases. For alloys with lower tungsten contents (6% and 13%) and larger grain sizes (13 and 56 nm), higher degrees of grain growth coupled with monotonic decline of hardness are observed. The study indicates that the electrodeposited nickel-tungsten alloys with a high tungsten content potentially serve as strong candidates for high temperature applications.     

钴含量对电沉积纳米晶镍钴合金组织与力学性能的影响

采用脉冲电沉积技术制备钴含量在2.4%～59.3%范围内的镍钴合金.利用XRD与TEM技术对纳米晶镍钴合金的组织结构进行表征.结果表明:所有成分的纳米晶镍钴合金均为面心立方结构的单相固溶体,平均晶粒尺寸为11～24 nm,且平均晶粒尺寸随钴含量的增加而减小,镍钴合金镀态下TEM组织中观察到的晶粒尺寸与XRD测量结果一致;纳米晶镍钴合金抗拉强度为1 300～1 650 MPa,断裂伸长率为10.5%～14.5%,镍钴合金的抗拉强度与断裂伸长率均随钴含量的增加而提高;随着钴含量的不断增加,镍钴合金在单向拉伸过程中的应力诱发晶粒长大被逐渐抑制,提高加工硬化率,塑性失稳被延迟,从而提高塑性.     

Process Recycling and Environmental Treatment

A useful coating technology for electroless Ni-1.5wt%P has been developed. The bath can work normally for more than 5 turnovers with a plating rate of 20 μm/h. In the as-deposited condition, Ni-1.5wt%P deposit is a supersaturated solid solution of P dissolved in a nanocrystalline Ni matrix with a grain size of several nanometers. The microstructure transformed into a larger grain size Ni matrix with dispersive Ni₃P precipitates with increasing the heat treatment temperature. Ni-1.5wt%P deposit possesses as-deposited hardness and wear resistance superior to Ni-10.5wt%P deposit. The microhardness and wear resistance can be further improved by proper heat treatment. The optimum wear resistance of Ni-1.5wt%P deposit corresponds to its peak hardness (annealing at 375°C for 1 h), whereas for Ni-10.5wt%P deposit the optimum wear resistance is obtained after annealing at 650°C for 1 h. Ni-1.5wt%Ppossesses a corrosion resistance in NaOH solution superior to conventional medium and high phosphorus deposits, which have much better corrosion resistance in NaCl and HCl solution. The rotating fatigue results indicate that electroless nickel deposits cause a decrease in the fatigue strength of 30CrMo steel, and increase the fatigue strength of LY12 alloy. Ni-1.5wt%P deposit demonstrates higher fatigue resistance than Ni-10.5wt%P deposit.     

等温退火对Ni-P、Ni-W-P镀层的晶粒尺寸和显微硬度的影响

研究了不同镀态结构的Ni-P、Ni-W-P镀层经等温退火后，其晶粒尺寸和硬度随退火时间的变化规律，镀层的热稳定性以及成分、结构和晶粒尺寸对镀层硬度的影响规律。结果表明，W元素可以促进Ni-P合金的非晶化，显著提高Ni-P镀层的硬度；Ni-（W）-P体系纳米晶镀层具有较好的热稳定性；等温退火获得的三元Ni-W-P单相纳米晶镀层在耐磨、耐蚀性能方面均优于同类非晶态镀层。     

退火热处理对Nd0.75Mg0.25(Ni0.8Co0.2)3.5储氢合金结构和性能的影响

采用中频感应熔炼制备Nd0.75Mg0.25(Ni0.8Co0.2)3.5储氢合金,在0.03 MPa氩气氛围进行退火,退火温度分别为850,900和950 ℃,保温时间均为7 h。分别对合金的电化学性能、气态储氢性能和合金的微观结构进行研究。结果表明,合金在退火热处理前后的相组成没有发生明显变化,主相均为Ce2Ni7型(Nd,Mg)2(Ni,Co)7相和CaCu5型NdNi5相。合金中晶粒尺寸随着退火温度的升高而增大,相界面则减少,退火消除晶格应力、增加成分均匀性、增加储氢容量;同时有部分Mg在热处理过程中损失导致储氢容量的下降。900 ℃热处理使得Nd0.75Mg0.25(Ni0.8Co0.2)3.5合金表现出较好的储氢性能,最大电化学放电容量为359 mAh/g,合金电极在100次循环后容量保持率为90.3%,气态储氢容量达到1.65%（质量分数,下同）。     

Study on corrosion behaviour of nanocrystalline and amorphous Co–P electrodeposits

Abstract

In this study, corrosion properties of nanocrystalline and amorphous Co–P coatings prepared using dc electrodeposition were investigated. The morphology of amorphous coatings was smoother and brighter than nanocrystalline coatings with 'cauliflower' morphology. Tafel polarisation tests of the coatings in 0·1M H₂SO₄ solution revealed that the amorphous coating had better corrosion resistance than the nanocrystalline one. Corrosion resistance of both coatings decreased after annealing. On the nanocrystalline coating, corrosion attacks were localised around the nodules on the surface while a more uniform type of attack was observed on amorphous coatings. Neither nanocrystalline nor amorphous coatings showed passivation in 0·1M H₂SO₄ solution, but both of them showed an active–passive behaviour in 10%NaOH solution due to the formation of Co(OH)₂ as fine hexagonal shape products which acted as a passive layer. The passive current density of the amorphous coating was higher than that of the nanocrystalline one, but it was decreased markedly by annealing. However, annealing had no significant effect on the passivation behaviour of the nanocrystalline coating.     

液相还原法制备的纳米晶Ag-50Ni合金在含Cl-介质中腐蚀电化学行为研究

用液相还原法制备纳米尺寸Ag-50Ni粉末而后热压制得其纳米块体合金,并与传统粉末冶金法制备的粗晶Ag-50Ni合金对比研究了它们在含Cl-介质中的腐蚀电化学行为.结果表明：合金粉末平均粒径约为45nm,真空热压后,晶粒有所长大,但仍为纳米尺度;随Cl-浓度增加,两种尺寸Ag-50Ni合金的腐蚀电流密度均增加,腐蚀速度加快;晶粒尺寸降低后,腐蚀电流密度略有增加,腐蚀速度变快;当极化电位增到某一程度后,两种尺寸Ag-50Ni合金均出现钝化;纳米尺寸Ag-50Ni合金在含0.02mol/L Cl- 介质中的交流阻抗谱由双容抗弧组成,其余均由单容抗弧组成,腐蚀受电化学反应控制.     

Crystallization process and soft magnetic properties of nanocrystalline (Fe0.5 Co0.5 ) 86 Hf7 B6 Cu1 alloy used in elevated temperature applications

Nanocrystalline (Fe0.5 Co0.5 )86 Hf7 B6 Cu1 HITPERM alloy was investigated as the candidate of soft magnetic material for high temperature applications, compared with Fe86 Hf7B6 Cu1 NANOPERM alloy. Amorphous alloy ribbons were prepared by single-roller melt-spinning technology. Crystallization process of as-quenched ribbon was investigated using differential scanning calorimeter at different heating rates. The coercivity was determined from quasi-static hysteresis loop measured at room temperature using a computerized hysteresis loop tracer. X-ray diffraction with Cu Kα radiation was used to determine the structure. The vibrating sample magnetometer was usedto measure the magnetization as a function of temperature of the nanocrystllized alloys. That Co substitution for Fein alloy enhances the Curie temperature of amorphous alloy and the magnetization of nanocrystalline alloy at hightemperature. After annealing amorphous precursor, the optimum nanocrystalline alloy obtained shows the local minimum coercivity. The coercivity increases with the increasing annealing temperature corresponding to the formation of ferromagnetic phase in the secondary crystallization.     

Microstructural characterisation and corrosion behaviour of electroless Ni–W–P deposits of mixed nanocrystalline/amorphous structures

Abstract

An investigation has been undertaken of the influence of the mixed nanocrystalline and amorphous microstructure on the corrosion behaviour of electroless Ni–5·5W–6·5P (wt-%) deposits on steel substrates. The effects of annealing temperature on microstructure evolution were investigated. The corrosion behaviour of the deposits was evaluated by potentiodynamic polarisation in 0·5M H₂SO₄ solution and EIS measurements in 3·5%NaCl solution. Relationships between the microstructure and corrosion mechanisms of the as plated and the annealed deposits were considered by reference to microstructural information, including degree of crystallisation, grain sizes of both nickel and Ni₃P phases, porosity development, microstrains and residual stresses.