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1.
Superhard nanostructured coatings, prepared by plasma-assisted chemical vapour deposition (PACVD) and physical vapour deposition (PAPVD) techniques, such as vacuum arc evaporation and magnetron sputtering, are receiving increasing attention due to their potential applications for wear protection. In this study nanocomposite (TiAl)BxNy (0.09 ≤ x ≤ 1.35; 1.07 ≤ y ≤ 2.30) coatings, consisting of nanocrystalline (Ti,Al)N and amorphous BN, were deposited onto Si (100), AISI 316 stainless steel and AISI M2 tool steel substrates by co-evaporation of Ti and hot isostatically pressed (HIPped) Ti-Al-B-N material from a thermionically enhanced twin crucible electron-beam (EB) evaporation source in an Ar plasma at 450 °C. The coating stoichiometry, relative phase composition, nanostructure and mechanical properties were determined using X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), in combination with nanoindentation measurements. Aluminium (∼ 10 at.% in coatings) was found to substitute for titanium in the cubic TiN based structure. (Ti,Al)B0.14N1.12 and (Ti,Al)B0.45N1.37 coatings with average (Ti,Al)N grain sizes of 5-6 nm and either ∼ 70, or ∼ 90, mol% (Ti,Al)N showed hardness and elastic modulus values of ∼ 40 and ∼ 340 GPa, respectively. (Ti,Al)B0.14N1.12 coatings retained their ‘as-deposited’ mechanical properties for more than 90 months at room temperature in air, comparing results gathered from eight different nanoindentation systems. During vacuum annealing, all coatings examined exhibited structural stability to temperatures in excess of 900 °C, and revealed a moderate, but significant, increase in hardness. For (Ti,Al)B0.14N1.12 coatings the hardness increased from ∼ 40 to ∼ 45 GPa.  相似文献   

2.
Hard TiAl(B)N coatings were deposited by radio-frequency magnetron sputtering in reactive mode in an argon and nitrogen environment using a TiAlB target with 12 at.% of boron. The deposition was carried out under ion bombardment at various negative bias voltages in the range of 0 to 170 V, and at substrate temperatures between 453 and 523 K. The internal stress in the coatings was studied at room temperature as a function of annealing temperatures in ambient air up to 1123 K. The heating duration was 2 h followed by annealing for 1 h. The microstructure, phase composition and hardness were also studied prior to and after annealing.We found that the TiAlBN coatings consist of TiAl3 and TiN phases. With increasing ion bombardment, the structure of the coatings changes from columnar to nano-scale features. Prior to annealing we also observed a correlation between the residual stress and hardness. After annealing, the compressive stresses of the TiAl(B)N coatings decreased from 1.0 GPa to less than 0.2 GPa, while the hardness remained constant or increased from ∼ 10 GPa to ∼ 25 GPa. The hardness increase of the coatings after annealing is related to a self-hardening effect.  相似文献   

3.
Ti-Zr-N coatings were formed by the method of vacuum arc deposition using combined Ti and Zr plasma flows in a N2 atmosphere at different ratios of arc currents of Ti and Zr cathodes. After deposition, obtained samples were annealed in vacuum at the temperature of 850 °C. The element and phase composition, residual stresses and nanohardness were studied by Auger-Electron Spectroscopy, X-ray diffraction (XRD) and nanoindentation, respectively.XRD analysis reveals the formation of ternary Ti-Zr-N nitride coatings with the structure of solid solutions. It is shown that Ti-Zr-N coatings possess high hardness in comparison with TiN and ZrN binary nitrides. An increase in hardness is observed with increasing Zr content. However, it is established that after annealing coatings keep better stability of hardness with decrease of Zr content. The intrinsic stress in the as-deposited coatings is found to be largely compressive (− 4 GPa) and almost independent of Zr content, but much higher than in ZrN and TiN binary nitrides (− 2 GPa). After annealing, a significant stress relaxation is observed in all coatings due to relief of growth-induced point defects. Stress analysis on as-grown and annealed samples enabled us to determine the stress-free lattice parameter a0. This latter is expanded by ∼ 0.4-0.7% as compared to Vegard's law.The thermal stability of Ti-Zr-N coatings will be discussed in terms of evolution and interdependence between structure, composition and hardness after annealing.  相似文献   

4.
A comparative investigation of the structure and properties of TiAlC(N), TiCrAlC(N), and CrAlC(N) coatings deposited by sputtering of МАХ-phase Ti2 − хCrхAlC targets (where x = 0, 0.5, 1.5, and 2) in an Ar atmosphere or in a gaseous mixture of Ar + N2 is presented. The coatings were characterized in terms of their structure, elemental and phase composition, hardness, elastic modulus, elastic recovery, thermal stability, friction coefficient, wear rate, corrosion, and high-temperature oxidation resistance. The structure of the coatings was studied by means of X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, glow discharge optical emission spectroscopy, electron energy loss spectroscopy, and Raman spectroscopy. To evaluate the thermal stability and oxidation resistance, the coatings were annealed either in vacuum or in air at temperatures 600-1200 °C. The results obtained show that the TiAlCN coatings possess high hardness of 32-35 GPa, low friction coefficient against WC-Co well below 0.25, high thermal stability up to 1200 °C, and superior performance in dry milling tests against high Cr steel. Meanwhile, the coatings with high Cr content demonstrated improved oxidation resistance up to 1000 °C and superior electrochemical behavior, but their mechanical and tribological properties were deteriorated.  相似文献   

5.
In this work, Ti-N-B coatings have been deposited by thermal chemical vapor deposition (CVD). The effect of boron varying between 0 and 35.1 at.% on coating structure, mechanical and tribological properties was investigated. The coatings reveal a dual-phase structure of TiN and TiB2 above 1 at.% B. The addition of boron causes grain refinement and changes the structure from columnar for TiN to fine-crystalline. Coating hardness increases continuously from 20 GPa for TiN to 45 GPa at 35.1 at.% B. Ball-on-disc tests against alumina were conducted at 25, 500 and 600 °C. At 25 °C the friction coefficients increase from 0.75 for TiN to about 1.0 for boron contents up to 13.1 at.%, while values down to 0.26 were measured at 35.1 at.% B. The friction coefficients at 500 and 600 °C increase from 0.55 for TiN to 0.8-1.0 for the highest boron content. At 25 °C the lowest wear rates were obtained for the highest boron contents, while the opposite behavior was found for 500 and 600 °C. Extensive coating oxidation resulted in the highest wear rate at 500 °C for 35.1 at.% B, but the wear resistance improved at 600 °C. Raman spectroscopy of the oxide layer revealed the preferred formation of anatase at the expense of rutile for high boron concentrations.  相似文献   

6.
《Surface & coatings technology》2007,201(24):9476-9484
Nano-sized clusters consisting of strongly preferentially oriented, partially coherent nanocrystallites were observed in Cr-Al-N and Cr-Al-Si-N coatings deposited using cathodic arc evaporation. Microstructure analysis of the coatings, which was done using the combination of X-ray diffraction (XRD) and transmission electron microscopy with high resolution (HRTEM), revealed furthermore stress-free lattice parameters, size and local disorientation of crystallites within the nano-sized clusters in dependence on the aluminium and silicon contents, mean size of these clusters and the kind of structure defects. Within the face-centred cubic (fcc) Cr1 − x − yAlxSiyN phase, the stress-free lattice parameter was described by the equation a = (0.41486 − 0.00827 · x + 0.034 · y) nm. The size of individual crystallites decreased from ∼ 11 nm in Cr0.92Al0.08N to ∼ 4 nm in Cr0.24Al0.65Si0.10N. These nanocrystallites formed clusters with the mean size between 36 and 56 nm. The mutual disorientation of the partially coherent nanocrystallites forming the clusters increased with increasing aluminium and silicon contents from 0.5° to several degrees. The disorientation of neighbouring nanocrystallites was explained by the presence of screw dislocations and by presence of phase interfaces in coatings containing a single fcc phase and several phases, respectively.  相似文献   

7.
Transition metal (TM) boron nitrides are promising candidates for protective coatings with self-lubricating abilities as they can combine properties of TM diborides with the lubricity of hexagonal boron nitride (h-BN). Here, we report on Cr-B-N coatings prepared by unbalanced DC magnetron sputtering of a CrB2 target in argon/nitrogen atmosphere at 450 °C. By varying the nitrogen partial pressure (pN2) between 0 and 64% of the total pressure (pAr + pN2), the N-content in our coatings could be increased from 0 to 47 at.%. The results obtained from X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy show that for pN2 ≤ 11% a CrB2-based structure type develops, whereas with increasing pN2 the microstructure becomes then X-ray amorphous and finally CrN is detected as the sole crystalline constituent. With increasing pN2 from 0 to 11%, the hardness and indentation modulus rapidly decrease from 40.6 and 397 GPa for CrB2 to 13.4 and 108 GPa for CrB2.0N0.5. All coatings investigated yield only a moderate friction coefficients between 0.5 and 0.7. Based on detailed high-resolution TEM studies, we can conclude that the missing h-BN based lubricity is due to a lack of a significant long-range order.  相似文献   

8.
Binary Nb-N coatings, ternary Ti-Nb-N and Zr-Nb-N, and multi-layer TiN/NbN coatings consisting of up to 100 alternating TiN and NbN layers, were deposited onto WC-Co substrates, using two different vacuum arc deposition (VAD) systems: with and without magnetic guiding of the metal plasma flow. Binary Nb-N coatings were fabricated by deposition of metal plasma produced by a Nb cathode in a background of reactive nitrogen gas at different pressures, P. Ternary coatings were fabricated at co-deposition of plasmas originating from two different cathode materials. Multilayer coatings were fabricated by alternatively depositing plasmas of Ti and Nb in reactive nitrogen gas. The crystalline coating structure, phase composition, hardness and critical load for coating failure were studied.For binary Nb-N coatings fabricated using both deposition systems, the phase composition, the Vickers hardness, HV, and the critical load strongly depended on the deposition pressure. Using VAD with magnetic plasma guiding, the highest HV of ∼ 42 GPa was measured for coatings deposited at low nitrogen pressure. These coatings contained a hexagonal β-Nb2N phase and had a relatively low critical load. The highest critical load and HV ∼ 38 GPa were obtained for coatings consisted of a single phase NaCl-type cubic δ-NbN structure, deposited at a higher nitrogen pressure. The structure and properties of Nb-N coatings deposited using VAD without magnetic plasma guiding had a similar correlation with the deposition pressure, however, their hardness values were lower.Ternary Ti-Nb-N and Zr-Nb-N coatings fabricated by both deposition processes had a single phase cubic NaCl-type structure and the hardness higher than that of the binary nitrides TiN, ZrN and NbN. The hardest coatings, HV ∼ 51.5 Pa, deposited with magnetic plasma guiding had a single-phase cubic δ-(Ti,Nb)N structure and a Ti:Nb ratio of ∼ 50:50 (at.%).Multilayer coatings TiN/NbN consisting of 20-40 alternating TiN and NbN layers with total thickness of 4-5 μm increased the life time of cemented carbide cutting inserts at turning tough Ni-base alloys by 2-7 times relative to uncoated cutting tools, while conventional vacuum arc deposited TiN coatings were not effective in machining of these alloys.  相似文献   

9.
By means of a surface plastic deformation method a nanocrystalline (NC) intermetallic compound was in situ synthesized on the surface layer of bulk zirconium (Zr). Hardened steel shots (composition: 1.0C, 1.5Cr, base Fe in wt.%) were used to conduct repetitive and multidirectional peening on the surface layer of Zr. The microstructure evolution of the surface layer was investigated by X-ray diffraction and scanning and transmission electron microscopy observations. The NC intermetallic layer of about 25 μm thick was observed and confirmed by concentration profiles of Zr, Fe and Cr, and was found to consist of the Fe100 − xCrx compound with an average grain size of 22 nm. The NC surface layer exhibited an extremely high average hardness of 10.2 GPa. The Zr base immediately next to the compound/Zr interface has a grain size of ∼ 250 nm, and a hardness of ∼ 3.4 GPa. The Fe100 − xCrx layer was found to securely adhere to the Zr base.  相似文献   

10.
Mechanical properties (Young's modulus E, hardness H, degree of plasticity) of all three components of thermal barrier coatings systems, prepared by electron beam physical vapour deposition (EB PVD), have been investigated by nanoindentation. The power-law exponents n and m, describing the shapes of the loading and unloading nanoindentation curves, increase with peak load for the yttrium-stabilized zirconia top coat (TC), containing 4 mol% Y2O3, and the NiCoCrAlY bond coat (BC). The variations of m are correlated to the degree of plasticity. Decrease of the hardness with increasing peak load, generally known as indentation size effect (ISE), is observed only for the TC and the BC. The ISE in the TC is explained using a new empirical equation based on the concept of elastic recovery. The average Young's moduli of the Ni-based superalloy substrate, the BC and the TC are 189 ± 11 GPa, 166 ± 7 GPa, and 126 ± 25 GPa, respectively. The corresponding average hardness values are 3.3 ± 0.3 GPa, 5.5 ± 0.2 GPa, and 6.2 ± 1.7 GPa, respectively. The mechanical properties of the TC show complex behaviour upon annealing at 1000°°C in air, which can be explained by changes in the porosity and the residual stresses.  相似文献   

11.
In this study, a combination of nanocomposite and multilayer coating design was investigated in an effort to reduce the coefficient of friction (COF) while maintaining good mechanical properties of the TiBCN coatings. The TiBCN:CNx coatings consist of TiBCN and CNx nanolayers which were deposited alternately by reactive sputtering a TiBC composite target (80 mol% TiB2 + 20 mol% TiC) and a graphite target in an Ar:N2 mixture using a pulsed closed field unbalanced magnetron sputtering system. Low angle X-ray diffraction and transmission electron microscopy characterizations confirmed that the coatings consist of different bilayer periods in a range of 3.5 to 7.0 nm. The TiBCN layers exhibited a nanocomposite structure, whereas the CNx layers were in an amorphous state. The mechanical properties and wear resistance of the TiBCN:CNx multilayer coatings were investigated using nanoindentation and ball-on-disk wear test. The TiBCN:CNx coatings exhibited high hardness in a range of 20-30 GPa. The highest hardness of 30 GPa was achieved in the coating with a bilayer period of 4.5 nm. A low COF of 0.17 sliding against a WC-Co ball was obtained at a bilayer period of 4.5 nm, which is much lower than those of the single layer TiBCN and TiBC nanocomposite coatings (0.55-0.7).  相似文献   

12.
The paper will present the state-of-art in the process, structure and properties of nanostructured multifunctional tribological coatings used in different industrial applications that require high hardness, toughness, wear resistance and thermal stability. The optimization of these coating systems by means of tailoring the structure (graded, superlattice and nanocomposite systems), composition optimization, and energetic ion bombardment from substrate bias voltage control to provide improved mechanical and tribological properties will be assessed for a range of coating systems, including nanocrystalline graded Cr1−xAlxN coatings, superlattice CrN/AlN coatings and nanocomposite Cr–B–N and TiC/a-C coatings. The results showed that the superlattice CrN/AlN coating exhibited a super hardness of 45 GPa when the bilayer period Λ was about 3.0 nm. Improved toughness and wear resistance have been achieved in the CrN/AlN multilayer and graded CrAlN coatings as compared to the homogeneous CrAlN coating. For the TiC/a-C coatings, increasing the substrate bias increased the hardness of TiC/a-C coatings up to 34 GPa (at −150 V) but also led to a decrease in the coating toughness and wear resistance. The TiC/a-C coating deposited at a −50 V bias voltage exhibited an optimized high hardness of 28 GPa, a low coefficient of friction of 0.19 and a wear rate of 2.37 × 10−7 mm3 N−1 m−1. The Cr–B–N coating system consists of nanocrystalline CrB2 embedded in an amorphous BN phase when the N content is low. With an increase in the N content, a decrease in the CrB2 phase and an increase in the amorphous BN phase were identified. The resulting structure changes led to both decreases in the hardness and wear resistance of Cr–B–N coatings.  相似文献   

13.
It is important to evaluate the thermal stability of hard coating because at high working temperatures the mechanical and tribological properties are deteriorated. The temperature operating on the cutting tool tip during work may reach temperatures as high as 1000 °C. Environmental considerations limiting the use of lubricants and coolant liquids, increase the necessity of finding coatings that can function at such high temperature.Coatings can be differentiated by their hardness, H, into three main categories: hard with H < 40 GPa; superhard with H > 40 GPa; and ultra-hard coatings with H > 80 GPa.There are two main reasons in the high hardness coatings: either high compressive stresses or nano-scale structure. The application of high biaxial compressive stress acts as a driving force for recovery, i.e. the higher the compressive stress, the lower is the thermal activation energy needed to initiate recovery. High biaxial compressive stress increases superhardness, but reduces the coating thermal stability. Dislocations increase the micro-scale compressive stress inside the coating and consequently, enhance recovery. In nano-scale coatings, the small nanometric scale grain size restricted grain growth and boundaries sliding, and therefore the thermal stability is enhanced.This study treats the thermal stability of several types of superhard materials, i.e. nanocomposite coatings and those consisting of a hard transition-metal nitride and a soft metal. It focuses on formation mechanisms, materials and phase composition.  相似文献   

14.
The monolayered TiSiN and multilayered TiSiN/CrN were synthesized by cathodic arc evaporation. The Ti/Si (80/20 at.%) and chromium targets were used as the cathodic materials. With the different I[TiSi]/I[Cr] cathode current ratios of 1.8, 1.0, and 0.55, the multilayered TiSiN/CrN coatings possessed different multilayer periods (Λ) of 8.3 nm, 6.2 nm, and 4.2 nm. From XRD and TEM analyses, both the monolayered TiSiN and multilayered TiSiN/CrN revealed a typical columnar structure and B1-NaCl crystalline, no peaks of crystalline Si3N4 were detected. Among the multilayered TiSiN/CrN coatings, the multilayered coating with Λ = 8.3 nm possessed higher hardness of 37 ± 2 GPa, higher elastic modulus of 396 ± 20 GPa and the lower residual stress of − 1.60 GPa than the monolayered (Ti0.39Si0.07)N0.54 coating(− 7.25 GPa). Due to the higher Cr/(Ti +Cr + Si) atomic ratio, the multilayered TiSiN/CrN with Λ = 5.5 nm possessed the lowest friction coefficient. But the lowest of wear rate was obtained by the multilayered TiSiN/CrN with Λ = 8.3 nm, because of higher H3/E?2 ratio of 0.323 GPa. The monolayered TiSiN possessed the highest wear rate of 2.87 μm2/min. Therefore, the mechanical and tribological property can be improved by the design of multilayered coating.  相似文献   

15.
Ta-Si-N thin films were applied as diffusion barriers for Cu interconnections or hard coatings in mechanical application. The resistivity, hardness and thermal stability were the important issues in the interconnections and hard coatings, respectively. In this paper, we investigated the relationship between the microstructures, resistivity, nanohardness and thermal stability of the Ta-Si-N thin films at different nitrogen flow ratios of 0-30% (N2% = N2 / (Ar + N2) × 100%) by magnetron reactive co-sputtering. The Ta-Si-N films were annealed at 600, 750 and 900 °C at about 6 × 103 Pa for 1 h, respectively, to examine their thermal stability. The microstructures of Ta-Si-N films at low N2% of 2-10% still retained the amorphous-like phase with nanocrystalline grains in an amorphous matrix at annealing of 600-900 °C. The nanohardness of amorphous-like Ta-Si-N film at N2% of 3% was measured to be 15.2 GPa much higher than that of polycrystalline film of 10.1 GPa at N2% of 20%. The average nanohardness of both films is stable up to 900 °C and varied in the range of 0.43-0.83 GPa. The resistivity of the as-deposited Ta-Si-N films increase with increasing N2 flow rate. It is small around 220-540 μΩ cm for low N2% of 2-10% while it increases abruptly to about 7700-43,000 μΩ cm at high N2% of 20-30%. The best thermal stability of resistivity of Ta-Si-N film occurs at the N2% of 2% in the range of 220 to 250 μΩ cm from RT to 900 °C.  相似文献   

16.
TiB2-C preforms formed with different compositions and processing parameters were reactively infiltrated by Si melts at 1450 °C to fabricate TiB2-SiC-Si composites. Phase constituent and microstructure of these composites were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The resulting composites are generally composed of TiB2 and reaction-formed β-SiC major phases, together with a quantity of residual Si. Unreacted carbon is detected in the samples with a starting composition of 2TiB2 + 1C formed at higher pressure and in all of the ones at the composition of 1TiB2 + 1C. The distribution of these phases is fairly homogeneous in microstructure. TiB2-SiC-Si composites show good mechanical properties, with representative values of 19.9 GPa in hardness, 395 GPa in elastic modulus, 3.5 MPa m1/2 in fracture toughness and 604 MPa in bending strength. The primary toughening and strengthening mechanism is attributed to the crack deflection of TiB2 particles.  相似文献   

17.
The aim of this work was to understand the reasons for the exceptionally high thermal stability of the TiAlSiCN coatings. The hardness of the coatings increased from 41.5 to 43 GPa between 25 and 900 °C, reached a maximum value of 49 GPa at 1000 °C, and then decreased to 37 GPa at 1300 °C. The structural investigations performed before and after annealing at 1000, 1200, and 1400 °C using X-ray diffraction, scanning and transmission electron microscopy (TEM), and high-resolution TEM showed that the as-deposited “comb” like nanocomposite structure, in which (Ti,Al)(C,N) columnar grains, 10–30 nm wide, were separated by a well developed amorphous tissue, possessed a very high thermal stability as its dominant cubic phase was stable in the temperature range of 25–1400 °C. Further thorough characterization by means of energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy revealed structural modifications inside crystalline and amorphous phases during annealing in vacuum. Such modifications associated with a short-range rearrangement of elements are shown to be responsible for the high hardness of the TiAlSiCN coatings observed up to 1300 °C, with peak hardness at 1000 °C.  相似文献   

18.
The simultaneous synthesis and densification of TiN/TiB2 ceramic composites via reactive spark plasma sintering (RSPS) was investigated. Different component ratios (TiH2/BN (TiN, B)) and heating rates (112.5-300 °C/min) were used to initiate the chemical reaction for TiN/TiB2 synthesis. The omit RSPS process was revealed to have three stages, which are described separately. The relationships between the RSPS conditions, the microstructure and the properties of sintered ceramic composites were established. A Vickers hardness of 16-25 GPa and a fracture toughness of 4-6.5 MPa m1/2 were measured for various compositions. Sintered ceramic composites containing 36 wt% TiB2 with the highest relative density of 97.4 ± 0.4% and an average grain size of 150-550 nm have been obtained.  相似文献   

19.
ZrN/W multilayered coatings with different nanoscale modulation periods have been synthesized at different deposition time using ion beam assisted deposition. XRD, AES, Nanoindenter and profiler were employed to investigate the influence of modulation period on microstructure and mechanical properties of the coatings. The results showed that all superlattice coatings almost revealed higher mechanical property than the monolithic ZrN and W coatings. At modulation period of 8.6 nm, XRD pattern showed a significant mixture of strong ZrN (111), W (110), as well as weak ZrN (220) textures. It possessed the highest hardness (∼ 26 GPa), elastic modulus (∼ 310 GPa), and fracture resistance (∼ 80 mN), compared with the ones with other modulation period.  相似文献   

20.
NiAl-TiB2 composite coatings with 0, 10 and 20 wt.% TiB2 were synthesized on the Ni-based superalloy substrate using electro-thermal explosion ultrahigh speed spraying technology. The microstructure analysis shows that the coatings consist of submicron grains. The bond between coatings and substrate is metallic cohesion. TiB2 as a powerful reinforcement is doped in NiAl for increasing its hardness. The isothermal oxidation test is carried out for the composite coatings at 1100 °C in air. The result shows that the oxidation resistance of NiAl coating is higher than that of NiAl-10TiB2 and NiAl-20TiB2 coatings. The phases of oxides on the coatings during the process at high temperature have been analyzed by X-ray diffraction. The results show that Al2O3 and Cr2O3 coexistence on surface of NiAl coating, while Al2O3, Cr2O3, TiO2 and a small amount of NiO form on surface of NiAl-10TiB2 and NiAl-20TiB2 coatings after oxidation for 4 h.  相似文献   

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