采用Ag-Cu-Ti+Mo复合钎料钎焊Si3N4陶瓷

采用Ag-Cu-Ti+Mo复合钎料连接Si3N4陶瓷,利用SEM,TEM,Nanoindentation研究了钎料内钼颗粒含量对接头组织和力学性能的影响.结果表明,在Si3N4/钎料界面处形成了一层致密的反应层,该反应层由TiN和Ti5Si3组成.接头的中间部分由银基固溶体、铜基固溶体、钼颗粒和Ti-Cu金属间化合物组成.借助于纳米压痕技术测定了接头内Ti-Cu化合物以及钎料金属的弹性模量和硬度值.随着钎料内钼颗粒含量的提高,母材/钎料界面反应层厚度逐渐降低;钎料金属中Ti-Cu化合物数量增多;此外,银和铜基固溶体组织逐渐变得细小.当添加5%Mo时,得到最高的接头强度429.4 MPa,该强度相比合金钎料提高了114.7%.     

Deposition and characterization of CrN/Si3N4 and CrAlN/Si3N4 nanocomposite coatings prepared using reactive DC unbalanced magnetron sputtering

Nanocomposite coatings of CrN/Si₃N₄ and CrAlN/Si₃N₄ with varying silicon contents were synthesized using a reactive direct current (DC) unbalanced magnetron sputtering system. The Cr and CrAl targets were sputtered using a DC power supply and the Si target was sputtered using an asymmetric bipolar-pulsed DC power supply, in Ar + N₂ plasma. The coatings were approximately 1.5 μm thick and were characterized using X-ray diffraction (XRD), nanoindentation, X-ray photoelectron spectroscopy and atomic force microscopy. Both the CrN/Si₃N₄ and CrAlN/Si₃N₄ nanocomposite coatings exhibited cubic B1 NaCl structure in the XRD data, at low silicon contents (< 9 at.%). A maximum hardness and elastic modulus of 29 and 305 GPa, respectively were obtained from the nanoindentation data for CrN/Si₃N₄ nanocomposite coatings, at a silicon content of 7.5 at.%. (cf., 24 and 285 GPa, respectively for CrN). The hardness and elastic modulus decreased significantly with further increase in silicon content. CrAlN/Si₃N₄ nanocomposite coatings exhibited a hardness and elastic modulus of 32 and 305 GPa, respectively at a silicon content of 7.5 at.% (cf., 31 and 298 GPa, respectively for CrAlN). The thermal stability of the coatings was studied by heating the coatings in air for 30 min in the temperature range of 400-900 °C. The microstructural changes as a result of heating were studied using micro-Raman spectroscopy. The Raman data of the heat-treated coatings in air indicated that CrN/Si₃N₄ and CrAlN/Si₃N₄ nanocomposite coatings, with a silicon content of approximately 7.5 at.% were thermally stable up to 700 and 900 °C, respectively.     

Structure and mechanical properties of TiAlSiN/Si3N4 multilayer coatings

TiAlSiN/Si₃N₄ multilayer coatings which have different separate layer thicknesses of TiAlSiN or Si₃N₄ were deposited onto glass sheets, single-crystal silicon wafers and polished WC-Co substrates by reactive magnetron co-sputtering. The morphology, crystalline structure and thickness of the as-prepared multilayer coatings were characterized by TEM, SEM, XRD and film thickness measuring instrument. The mechanical properties of the coatings were evaluated by a nanoindenter. The effects of monolayer thickness on the microstructure and properties of TiAlSiN/Si₃N₄ multilayer coatings were explored. The coatings showed the highest hardness when the thickness of Si₃N₄ and TiAlSiN monolayers was 0.33 nm and 5.8 nm, respectively. The oxidation characteristics of the coatings were studied at temperatures ranging from 700 °C to 900 °C for oxidation time up to 20 h in air. It was found that the coatings displayed good oxidation resistance.     

Strengthening of transparent spinel/Si3N4 nanocomposites

In response to a need for improving the mechanical properties of optically transparent ceramics, the nanocomposites approach is used to strengthen transparent magnesium-aluminate spinel with Si₃N₄ nanodispersoids. The as-processed nanocomposites are found to be >70% transparent in the critical infrared wavelength range of 3-4.5 μm. Mie scattering combined with absorption by the Si₃N₄ nanodispersoids explains quantitatively the IR transmission behavior of these nanocomposites. The nanocomposites are also found to be transparent in the visible region. Upon heat treatment (1000 °C for 4 h in air), the optical properties of the nanocomposites remain unchanged. However, the heat treatment results in a 29% increase in the average strength, accompanied by almost doubling of the Weibull modulus, and an 85% increase in the indentation toughness. The improvements in mechanical properties after the heat treatment in these nanocomposites are explained qualitatively, based on generally accepted arguments involving surface-oxidation-induced surface compression and flaw-healing. While further work is needed to fully understand and exploit these effects, this first report on transparent nanocomposites could have broad implications for the creation of mechanically robust, transparent ceramics of the future.     

Effects of pelletization of reactants and diluents on the combustion synthesis of Si3N4 powder

Reactants were pelletized, and then combustion synthesis of Si₃N₄ powder was achieved under the N₂ pressure of 3.0 MPa. Effects of the pelletization of reactants and Si₃N₄ diluents on the combustion process parameters and the characteristics of products were studied. The combustion mode of single reactant pellet was preliminarily discussed. The results indicated that the combustion reaction of single pellet was layer-by-layer from the surface to the core, which led to two peaks on the combustion temperature variation waves. With increasing the diluents content, the morphologies of Si₃N₄ particles changed from short rods into equiaxed grains, and residual Si in the final products obviously decreased. Single phase β-Si₃N₄ powder mainly contained equiaxed grains was prepared when 58 wt.% diluents was added.     

Infrared brazing of Ti50Ni50 shape memory alloy using gold-based braze alloys

Infrared brazing Ti₅₀Ni₅₀ shape memory alloy using pure Au and Au-20Cu as the fillers has been investigated. The Au-rich and Au₄Ti phases, and Au₂TiNi, AuCu and Ni₃Ti phases are formed in the brazed joints using Au filler and Au-20Cu filler, respectively. The bending test shows the shape memory effect of brazed joint using Au filler is superior to that using Au-20Cu filler because the detrimental AuCu and Ni₃Ti phases exist in the latter case.     

Abrasive wear behavior of Ni-P coated Si3N4 reinforced Al6061 composites

Ni-P coated Si₃N₄ reinforced Al6061 composites were fabricated by vortex method. Percentage of reinforcement was varied from 6 wt.% to 10 wt.% in steps of 2. Cast matrix alloy and developed composites were hot forged at a temperature of 500 °C using a 300T hydraulic hammer. Both as cast and hot forged matrix alloy and its composites were subjected to microstructure studies, grain size analysis, microhardness and abrasive wear tests. Microstructure studies reveal uniform distribution of silicon nitride particles with good bond between matrix and reinforcement in both as cast and hot forged condition. It is observed that, increased content of reinforcement in both as cast and hot forged composites do result in significant grain refinement. However, when compared with as cast matrix alloy and its composites hot forged alloy and its composites exhibits higher extent of grain refinement. Both as cast and hot forged composites exhibit improved microhardness and abrasive wear resistance when compared with the unreinforced alloys under identical test conditions. Abraded worn surfaces were examined using scanning electron microscopy (SEM) for possible wear mechanisms. Increased abrasive particle size and load has resulted in larger extent of grooving leading to increased abrasive wear loss for both the matrix alloy and developed composites.     

The formation and role of interfaces in superhard nc-MenN/a-Si3N4 nanocomposites

The early finding of Veprek and Reiprich that the maximum hardness in the nc-TiN/Si₃N₄ nanocomposites is achieved at about one monolayer of the interfacial Si₃N₄ has been confirmed for a number of different nc-Me_nN/X_xN_m systems (Me = Ti, W, V, (TiAl)N,…; X = Si, B). More recently, this has been confirmed experimentally for TiN-Si₃N₄ heterostructures and by first principle density functional theory calculations. We present a consistent understanding of the formation of the nanocomposites with one monolayer Si₃N₄ interface by spinodal phase segregation. This interface is energetically stabilized as compared to bulk Si₃N₄, which results in an enhanced bond strength and corresponding cohesion energy. Such an enhancement appears to be of a general validity in nano-sized solids with well-ordered interfaces. The paper concludes a brief summary of the recent progress of the understanding of the mechanical properties of these nanocomposites.     

Thermal shock behavior of Si3N4-TiN nano-composites

Si₃N₄-TiN nano-composites were fabricated by hot press sintering nano-sized Si₃N₄ and TiN powders. The microstructure, mechanical properties and thermal shock behavior of Si₃N₄-TiN nano-composites were investigated. The addition of proper amount TiN particles can significantly increase the flexural strength and the fracture toughness. Si₃N₄-TiN nano-composites showed both higher critical temperature difference and higher residual strength compared with those of monolithic silicon nitride nano-ceramic when the amount of TiN is less than 15 wt.%. But a further increase in the amount of TiN leaded to a decrease in the thermal shock resistance.     

Brazing of 6061 aluminum alloy/Ti-6Al-4V using Al-Si-Cu-Ge filler metals

Al-8.4Si-20Cu-10Ge and mixed rare-earth elements (Re) containing Al-8.4Si-20Cu-10Ge-0.1Re filler metals were used for brazing of 6061 aluminum alloy/Ti-6Al-4V. The addition of 20 wt.% copper and 10 wt.% germanium into the Al-12Si filler metal lowered the solidus temperature from 586 °C to 489 °C and the liquidus temperature from 592 °C to 513 °C. The addition of 0.1 wt.% rare-earth elements into Al-8.4Si-20Cu-10Ge alloy caused remarkable Al-rich phase refinement and transformed the needle-like Al₂Cu intermetallic compounds into block-like shapes. Shear strengths of the 6061 aluminum alloy/Ti-6Al-4V joints with the two brazing filler metals, Al-8.4Si-20Cu-10Ge and Al-8.4Si-20Cu-10Ge-0.1Re, varied insignificantly with brazing periods of 10-60 min. The average shear strength of the 6061 aluminum alloy/Ti-6Al-4V joints brazed with Al-8.4Si-20Cu-10Ge at 530 °C was about 20 MPa. Rare-earth elements appeared to improve the reaction of the Al-8.4Si-20Cu-10Ge filler metal with Ti-6Al-4V. The joint shear strength of the 6061 aluminum alloy/Ti-6Al-4V with Al-8.4Si-20Cu-10Ge-0.1Re reached about 51 MPa.     

First melting stages during isothermal brazing,of Ni/BNi-2 couples

Ni/BNi-2 brazing couples were continuously heated at 25 °C/min and their melting temperature range was determined by differential thermal analysis (DTA). Samples were cooled down from different temperatures in the melting domain. Their microstructures were observed and quantitatively characterized through image analysis. Melting proceeds in two steps: The first one (lower temperatures) involves the filler metal being only partially melted, and boron diffusion in pure Ni leading to the precipitation of fine Ni₃B borides at the initial interface between the filler alloy and the base metal. In the second step (higher temperatures), melting completes and thermodynamic equilibration requires significant dissolution of nickel, which also involves the dissolution of the borides already formed. Afterwards, transient liquid bonding can proceed as described in the usual models, involving re-precipitation of Ni₃B borides on the new fresh interface between liquid alloy and solid metal. High heating rates allow avoiding the first step (direct melting of brazing alloy then dissolution of base metal), whereas very low heating rates can result in brazing without significant dissolution of base metal (no second step).     

采用Ti/Ag-Cu/Cu中间层钎焊连接Si3N4陶瓷和TiAl合金的界面结构及性能

采用Ti/Ag-Cu/Cu中间层实现了Si₃N₄陶瓷与TiAl合金的钎焊连接,获得了良好的接头.利用SEM,EDS等微观手段,分析了接头界面结构和元素分布情况.结果表明,Si₃N₄陶瓷/Ti/Ag-Cu/Cu/TiAl典型界面微观结构可能为:Si₃N₄/TiN/Ti-Si/Cu-Ti+Ag（s,s）+Cu（s,s）/AlCuTi/TiAl.在连接温度1 133 K、保温时间30 min、接头压力0.040 MPa时,接头四点弯曲强度达到最大值170 MPa.     

Strong bonding of infrared brazed α2-Ti3Al and Ti–6Al–4V using Ti–Cu–Ni fillers

Infrared dissimilar brazing of α₂-Ti₃Al and Ti–6Al–4V using Ti–15Cu–25Ni and Ti–15Cu–15Ni filler metals has been performed in this study. The brazed joint consists primarily of Ti-rich and Ti₂Ni phases, and there is no interfacial phase among the braze alloy, α₂-Ti₃Al and Ti–6Al–4V substrates. The existence of the Ti₂Ni intermetallic compound is detrimental to the bonding strength of the joint. The amount of Ti₂Ni decreases with increasing brazing temperature and/or time due to the depletion of Ni content from the braze alloy into the Ti–6Al–4V substrate during brazing. The shear strength of the brazed joint free of the blocky Ti₂Ni phase is comparable with that of the α₂-Ti₃Al substrate, and strong bonding can thus be obtained.     

Cu + TiB2 composite filler for brazing Al2O3 and Ti-6Al-4V alloy

Al₂O₃ and Ti-6Al-4V alloy were brazed using Cu + TiB₂ composite filler, which manufactured by mechanical milling of Cu and TiB₂ powders. Typical interface microstructure of joint was Al₂O₃/Ti₄(Cu,Al)₂O/Ti₂Cu + Ti₃Al + Ti₂(Cu,Al)/Ti₂(Cu,Al) + AlCu₂Ti/Ti₂Cu + AlCu₂Ti + Ti₃Al + Ti₂(Cu,Al) + TiB/Ti(s.s) + Ti₂Cu/Ti-6Al-4V alloy. Based on temperature- and time-dependent compositional change, the formation of intermetallics in joint was basically divided into four stages: formation of interfacial Ti₄(Cu,Al)₂O in Al₂O₃ side, formation of Ti₂Cu, Ti₃Al, TiB, Ti₂Cu, and AlCu₂Ti in layers II and IV, formation of Ti₂(Cu,Al) and AlCu₂Ti in layer III, formation of Ti + Ti₂Cu hypereutectoid organization adjacent to Ti-6Al-4V alloy. TiB in situ synthesized in joint not only acted as low thermal expansion coefficient reinforcement to improve the mechanical properties at room temperature, but also as skeleton ceramic of joint to increase high temperature mechanical properties of Al₂O₃/Ti-6Al-4V alloy joint increasing. When the joint containing 30 vol.% TiB brazed at 930 °C and 10 min of holding time, the maximum room temperature shear strength of joint was 96.76 MPa, and the high temperature shear strength of joint was 115.16 MPa at 800 °C.     

3R and 14M martensitic transformations in as-rolled and annealed Ni64Al34.5Re1.5 shape memory alloy

Martensitic transformation of as-rolled and 1323 K × 1 h annealed Ni₆₄Al_34.5Re_1.5 (NiAl-1.5Re) shape memory alloy (SMA) is investigated. For as-rolled NiAl-1.5Re alloy, TEM and EPMA results indicate both 14M and 3R martensites are observed at the room temperature. 14M is formed in the precipitate-free zone which is a Ni-depletion region and 3R is formed in the matrix which is a Ni-enrichment region. XRD and partial-cycle DSC testing results show that the higher temperature peak of the DSC cooling curve is B2 → 14M and the lower one is B2 → 3R. Hardness tests show that 14M hardness is higher than that of 3R. For annealed NiAl-1.5Re alloy, only B2 ↔ 3R can be observed. The critical value for the formation of 14M martensite in NiAl-1.5Re alloy is about 63.6 at.% Ni, as compared to 63.0 at.% Ni for Ni-Al binary SMAs.     

Ti40Zr25Ni15Cu20非晶钎料钎焊Si3N4陶瓷的界面结构及强度

采用Ti40Zr25Ni15Cu20非晶钎料进行了Si3N4陶瓷真空钎焊连接,利用SEM、EDX等微观分析手段,研究了钎焊界面的微观结构,得出界面反应层有两部分组成,接头界面微观结构为Si3N4/TiN/Ti-Si,Zr-Si化合物/钎缝中心;在相同钎焊工艺条件下,研究对比了晶态和非晶态钎料钎焊接头的强度,发现非晶态钎料钎焊的接头强度大大超过用晶态钎料钎焊的接头.     

Nb、Cu金属层厚度对Si3N4/Nb/Cu/Ni/Incone l600接头组织和性能的影响

采用Nb／Cu／Ni作中间层，在连接温度为1403K、连接时间为50min、连接压力为7．5MPa的条件下，采用不同尺寸的中间层进行了Si3N4陶瓷与Inconel 600高温合金的部分液相扩散连接。通过改变Nb层、Cu层厚度，研究了Cu层、Nb层厚度变化对Si3N4／Nb／Cu／Ni／Inconel 600接头的组织和性能的影响。研究发现，当Cu层厚度小于0．05mm时，随着Cu层厚度的增加，接头中的Cu—Ni合金层厚度增加，接头强度快速增加；当Cu层厚度超过0．05mm时，接头中的Cu—Ni合金层厚度由于压力的作用不明显增加，接头强度增加缓慢。随着Nb层厚度的增加，反应层厚度增加，接头的强度先增大后减小。     

纳米Si3N4 对TC4钛合金微弧氧化层微观结构和性能的影响

在基电解液中加入氮化硅纳米颗粒,对TC4钛合金进行微弧氧化（MAO）处理,研究了Si₃N₄浓度对微弧氧化层表面形貌、耐蚀性和耐磨性的影响。添加Si₃N₄的MAO层呈现多孔结构,当Si₃N₄浓度为1 g/L时,涂层厚度最大,且经过7 d的酸腐蚀试验,该涂层的耐蚀性良好,腐蚀速率最低,约为0.057 mg·cm^-2·d^-1。随着Si₃N₄的加入,MAO涂层的抗菌性能先升高后降低。当Si₃N₄的添加量为1 g/L时,该MAO层的抗菌性能最好。Si₃N₄的加入能明显提高涂层在模拟海水中的耐磨性。当Si₃N₄的添加量为3和4 g/L时,所得涂层的摩擦系数低且稳定,且添加3 g/L Si₃N₄制备来的MAO涂层表现出优异的耐磨性。     

Densification, microstructure, and fracture behavior of TiC/Si3N4 composites by spark plasma sintering

TiC/Si₃N₄ composites were prepared using the β-Si₃N₄ powder synthesized by self-propagating high-temperature synthesis (SHS) and 35 wt.% TiC by spark plasma sintering. Y₂O₃ and Al₂O₃ were added as sintering additives. The almost full sintered density and the highest fracture toughness (8.48 MPa·m^½) values of Si₃N₄-based ceramics could be achieved at 1550°C. No interfacial interactions were noticeable between TiC and Si₃N₄. The toughening mechanisms in TiC/Si₃N₄ composites were attributed to crack deflection, microcrack toughening, and crack impedance by the periodic compressive stress in the Si₃N₄ matrix. However, increasing microcracks easily led to excessive connection of microcracks, which would not be beneficial to the strength.     

Crystal structures and magnetic properties of iron (III)-based phosphates: Na4NiFe(PO4)3 and Na2Ni2Fe(PO4)3

Crystal structures from two new phosphates Na₄NiFe(PO₄)₃ (I) and Na₂Ni₂Fe(PO₄)₃ (II) have been determined by single crystal X-ray diffraction analysis. Compound (I) crystallizes in a rhombohedral system (S. G: R-3c, Z = 6, a = 8.7350(9) Å, c = 21.643(4) Å, R₁ = 0.041, wR₂=0.120). Compound (II) crystallizes in a monoclinic system (S. G: C2/c, Z = 4, a = 11.729(7) Å, b = 12.433(5) Å, c = 6.431(2) Å, β = 113.66(4)°, R₁ = 0.043, wR₂=0.111). The three-dimensional structure of (I) is closely related to the Nasicon structural type, consisting of corner sharing [(Ni/Fe)O₆] octahedra and [PO₄] tetrahedra forming [NiFe(PO₄)₃]⁴⁺ units which align in chains along the c-axis. The Na⁺ cations fill up trigonal antiprismatic sites within these chains. The crystal structure of (II) belongs to the alluaudite type. Its open framework results from [Ni₂O₁₀] units of edge-sharing [NiO₆] octahedra, which alternate with [FeO₆] octahedra that form infinite chains. Coordination of these chains yields two distinct tunnels in which site Na⁺.The magnetization data of compound (I) reveal antiferromagnetic (AFM) interactions by the onset of deviations from a Curie-Weiss behaviour at low temperature as confirmed by Mössbauer measurements performed at 4.2 K. The corresponding temperature dependence of the reciprocal susceptibility χ⁻¹ follows a typical Curie-Weiss behaviour for T > 105 K. A canted AFM state is proposed for compound (II) below 46 K with a field-induced magnetic transition at H ≈ 19 kOe, revealed in the hysteresis loop measured at 5 K. This transition is most probably associated with a spin-flop transition.