闭合场非平衡脉冲磁控溅射沉积碳氮化铬薄膜结构与性能研究
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摘要
采用闭合场非平衡脉冲磁控溅射沉积碳氮化铬薄膜,利用EPMA、XPS、GIXRD、FESEM和HRTEM表征了薄膜的成分与结构,纳米压痕仪、Rockwell C硬度计、划痕仪和球盘式磨损实验机分别表征碳氮化铬薄膜的力学和摩擦学性能,分析薄膜成分、结构及其性能之间的关系,探讨复合薄膜性能改善机制。采用等离子体质量和能量分析仪探测闭合场非平衡脉冲磁控溅射沉积薄膜时的离子质量和能量分布,讨论等离子体特性对薄膜结构与性能的作用规律。
脉冲直流纯氩和氮氩混合气磁控溅射铬和碳时52Cr+、40Ar+、12C+和28N2+的离子能量分布均包括3个能量区域：峰值为4-5 eV的低能能量峰、能量峰为20-40 eV的中间区域和80-200 eV的高能区域。脉冲频率100 kHz时,随着占空比由90%降至50%,最大离子能量由90 eV拓宽至量程极限200 eV；脉冲频率提高至200 kHz,最大离子能量却逐渐由90 eV减至50 eV,占空比为50%时又突然增至130 eV,且均小于相同占空比条件下100 kHz时的能量。
脉冲直流磁控溅射沉积碳氮化铬薄膜,厚度约为2-3μm,在不锈钢和单晶Si基体与薄膜之间沉积了厚约100 nm的金属铬附着层,工作气压0.27 Pa,铬靶和碳靶共溅射,溅射功率分别为500-1000 W和600-1400 W,脉冲频率0-200 kHz,占空比50-90%,氮气分压0-60%。氮气分压、铬靶和碳靶溅射功率是控制碳氮化铬薄膜成分的主要参数,覆盖的成分范围为47.0-58.9 at.%Cr,15.5-38.9 at.%C和36.3-55.9 at.%N。碳氮化铬薄膜由纳米晶体相和非晶相组成,非晶相的含量随着碳、氮含量的增加而提高。固定铬靶溅射功率1000 W、碳靶1400 W,随着氮气分压fN2由20%增至50%,C／Cr原子比为0.29-0.39,而N／Cr原子比由0.41增至0.92。Cr靶700 W,FN2为20%-60%时,C／Cr原子比为0.23-0.90,而N／Cr原子比由0.37增至1.90。保持20%氮气分压和1000 W铬靶溅射功率,逐渐提高碳靶功率至1000 W, N/Cr原子比为0.54-0.62,而C／Cr原子比由0.26增至0.44。氮化铬薄膜为密排六方Cr2N结构,C进入密排六方Cr2N点阵中N的亚点阵位置,形成复合化合物Cr2(C,N),随着碳和氮的不断增加,最终转变为面心立方Cr(C,N)。铬靶溅射功率降至500 W时,薄膜中Cr含量进一步降低,组成为CrC1.47N1.30,薄膜结构为含Cr非晶C(N)。Cr靶和C靶的脉冲参数对碳氮化铬薄膜的成分与相结构没有明显影响,组成为CrC0.23-0.35N0.83-0.91,均为面心立方Cr(C,N)。
随着(C+N)/Cr原子比由0.81增至2.77,碳氮化铬薄膜中观测到3种微结构：横向晶粒尺寸为20-50 nm的纳米柱状晶Cr2(C,N)或Cr(C,N),纳米晶Cr(C,N)/非晶C(N)复合结构和含Cr非晶C(N),对应的薄膜组成为：CrC0.26N0.55或CrC0.29N0.74,CrC0.35N0.91和CrC0.90N0.88,以及CrC1.47N1.30。
闭合场非平衡脉冲直流磁控溅射沉积碳氮化铬薄膜的硬度为11.0-30.9 GPa, H/E比值0.058-0.102,摩擦系数0.31-0.59,磨损量1.28-18.2×10-6 mm3N-1m-1,膜基结合性能HF1-3,薄膜开始失效的临界载荷(LC3)5-23 N,具有很好的力学和摩擦学性能。碳氮化铬薄膜微结构为纳米柱状晶时,随着晶体结构由hcp-Cr2(C,N)转变为fcc Cr(C,N),硬度由17.5 GPa增至25.4 GPa,摩擦系数为0.52-0.56,磨损量为1.28-1.76×10-6 mm3N-1m-1;具有纳米晶Cr(C,N)／非晶C(N)复合结构的碳氮化铬薄膜硬度达30.9 GPa, H/E比值0.102,摩擦系数和磨损量分别为0.31和3.67×10-6 mm3N-1m-1,随着非晶含量的增加,硬度和H／E比值降至19.7 GPa和0.089,摩擦系数升至0.45；薄膜结构转变为含Cr非晶C(N)结构时,硬度仅为11.0 GPa, H/E比值0.059,磨损量高达18.20×10-6mm3N-1m-1。
等离子体质量和能量分析表明高功率调制脉冲磁控溅射铬时产生了高束流低能多价金属铬和气体原子,离化率随着靶峰值功率和电流的增加而提高,氩气溅射时产生的等离子体中包含52Cr+、40Ar+、52Cr2+、40Ar2+离子,而氮氩反应溅射时由Cr1-3+、Ar1-3+、N+1-2、N2-4+、CrN+和CrN2+组成,峰值能量均为3-4 eV。随着平均功率由1 kW增至3.5kW,直流磁控溅射沉积铬的沉积速率由67.9 nm min-1线性增至163.0 nm min-1,高功率调制脉冲磁控溅射沉积时,同样随着平均功率在0.8-4 kW范围内线性增加,为53.7-230.3nm min-1。高功率调制脉冲磁控溅射和直流磁控溅射沉积氮化铬的沉积速率相当,氮气分压50%、平均功率1-4 kW条件下,沉积速率为30-220 nm min-1。
平均功率为1-4 kW时,高功率调制脉冲磁控溅射沉积的铬薄膜为纳米柱状晶a-Cr,晶粒尺寸为60-100 nm,硬度为9-15 GPa,而直流磁控溅射的晶粒尺寸随着平均功率增加而增至微米级,硬度为8.2-4.3 GPa。氮气分压50%条件下,直流、脉冲直流和高功率调制脉冲磁控溅射沉积氮化铬薄膜为纳米柱状晶CrN结构,晶粒尺寸分别为105 nm、78 nm和45-60 nm,硬度、摩擦系数、磨损量分别为16.0 GPa、0.58、8.75×10-6 mm3N-1m-1, 21.0 GPa、0.45、3.65×10-6mm3N-1m-1和24.5-26 GPa、0.33-0.36、2.43×10-6 mm3N-1m-1。随着氮气分压由10%增至30%,高功率调制脉冲磁控溅射沉积的碳氮化铬薄膜由a-Cr+β-Cr2(C,N)逐渐演变为Cr(C,N),硬度为23.2-24.6 GPa,摩擦系数0.4-0.6,磨损量1.2-3.7×10-6mm3N-1m-1。高功率调制脉冲磁控溅射改善了薄膜的结构,提高了所沉积薄膜的力学和摩擦学性能。
Chromium carbonitride (Cr-C-N) coatings were deposited by pulsed closed field unbalanced magnetron sputtering (P-CFUBMS). The composition and microstructure of the coatings were investigated using electron probe micro-analysis (EPMA), x-ray photoelectron spectroscopy (XPS), glancing incident angle x-ray diffraction (GIXRD), field-emission scan electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). Mechanical and tribological properties of the coatings were measured by nanoindentation, Rockwell C test, scratch test and ball-on-disk wear tests. A correlation was pursuit between the composition, microstructure and properties of the coatings. A diagnostic of the ion species and their energy distribution generated during P-CFUBMS deposition was performed by electrostatic quadrupole plasma analyzer (EQP) to understand the improved structure and performance.
When chromium and carbon targets were pulsed asynchronously in Ar and Ar+N2 atmospheres, the 52Cr+、40Ar+\12C+ and 28N2+ ion energy distributions (IEDs) were measured by EQP. The basic characteristics of these typical IEDs are similar and reproducible, which present three energy regions in all ion species:a low energy peak at 4-5 eV, a middle energy region at 20-40 eV, and a high-energy region at 90-200 eV. The reduction of duty cycle 90% to 50% led to the increase of maximum ion energy from 90 eV to 200 eV when pulsed at 100 kHz, whereas at 200 kHz, the maximum ion energy decreased firstly from 90 eV to 50 eV, and then suddenly increased to 130 eV under 50% duty cycle.
The Cr-C-N coatings were deposited by pulsed direct current magnetron sputtering (PMS) under 0-200 kHz frequency and 50-90% duty cycle at 0-60% nitrogen flow rate ratio (fN2) and working pressure of 0.27 Pa. The chromium and graphite targets were respectively powered at 500-1000 W and 600-1400 W. The thickness of Cr-C-N coatings was 2-3μm and a chromium adhesion layer (about 100 nm) was firstly deposited onto the substrates. The concentration of coatings was controlled by the nitrogen flow rate ratio and the power on chromium and graphite targets, which was varied in the range of 47.0-58.9 at.%Cr,15.5-38.9 at.%C, and 36.3-55.9 at.%N. The Cr-C-N coatings consist of nanocrystalline embedded in an increased amorphous matrix as the carbon and nitrogen content were improved in the coatings. With an increase in fN2 from 20% to 50%, the atomic ratio of nitrogen to chromium (N/Cr) was increased from 0.41 to 0.92 as well as the C/Cr in the range of 0.29-0.39 when the chromium and graphite target was powered at 1000 W and 1400 W respectively. Decreasing the power on chromium target to 700 W, the N/Cr was also increased from 0.37 to 1.90, whereas the C/Cr varied in the range of 0.23-0.90 as the fN2 was increased from 20% to 50%. Under a 20% fN2 and 1000 W on chromium target, (N/Cr) in the Cr-C-N coatings was 0.54-0.62, whereas the C/Cr ratio was increased from 0.26 to 0.44 as the power on the graphite target was increased from 600 to 1000 W. The carbon occupied the sublattice positions of nitrogen in hcp-Cr2N to form the multi-compound Cr2(C,N), which transferred into fcc-Cr(C,N) with the increase of carbon and nitrogen content in the coatings. At a low chromium target power of 500 W, no crystalline phase but the Cr-containing amorphous C(N) phase was detected in the CrC1.47N1.30 coating. There were no effect of the pulse configuration on the composition and structure, which had the compositions of CrC0.23-0.35N0.83-0.91 and fcc-Cr(C,N) phase structure.
A nanostructure transition from nano-columnar Cr2(C,N) or Cr(C,N) with the diameter of 20-50 nm to nanocomposite nc-Cr(C,N)/amorphous-C(N), and then to Cr-containing amorphous C(N) was detected in the Cr-C-N coatings with an increase in (C+N)/Cr from 0.81 to 2.77, which possessed the corresponding compositions of CrC0.26N0.55/CrC0.29N0.74, CrC0.35N0.91 and CrC0.90N0.88.
The PMS Cr-C-N coatings exhibited a wide range of mechanical and wear resistance properties:the hardness of 11.0-30.9 GPa, the H/E ratios of 0.058-0.102, the coefficient of frictions (COF) of 0.31-0.59, the wear rates of 1.28-18.2×10-6 mm3N-1m-1, and the adhesion properties of HF1-3 and 5-23 N(LC3), which is dependent on the microstructure of the coatings. An increase of hardness from 17.5 GPa to 25.4 GPa was observed accompanied by the microstructural evolution from nano-columnar hcp-Cr2(C,N) to fcc-Cr(C,N), both of which possessed the COF of 0.52-0.56 and the low wear rates of 1.28-1.76×10-6 mm3N-1m-1. For nanocomposite nc-Cr(C,N)/amorphous-C(N) with the composition of CrC0.26N0.55, the highest hardness and H/E ratio of 30.9 GPa and 0.102 were evaluated with the lowest COF of 0.31 and the wear rate of 3.67×10-6 mm3N-1m-1 in the coatings. When the fraction of the amorphous C(N) phase increased with the further increase of carbon and nitrogen content to CrC0.29N0.74, the hardness and H/E ratio decreased to 19.7 GPa and 0.089, and the COF increased to 0.45. The poor mechanical and wear resistance properties, i.e. the lowest hardness and H/E ratio of 11.0 GPa and 0.059, and the highest wear rate of 18.20×10-6 mm3N-1m-1, were found in the Cr-C-N coating with the Cr-containing amorphous-C(N).
By EQP diagnostics, the plasma generated by MPP sputtering chromium contain the ion species of 52Cr+,40Ar+,52Cr2+ and 40Ar2+ in Ar, and that of Cr1-3+, Ar1-3+, N+1-2, N2-4+, CrN+ and CrN2+ in Ar+N2, all of which exhibited a peak energy of about 3-4 eV and their intensity improved with the increase of the peak power and current. For dcMS, the deposition rate of Cr coatings increased almost linearly from 67.9 to 163.0 nm min-1 as the average power was increased from 1 to 4 kW. The deposition rates of MPP sputtered Cr coatings are in the range of 53.7-230.3 nm min-1, which are lower than the dcMS rates when the the average power is less than 2.5 kW and exceed the dcMS deposition rates as the Pd is higher than 2.5 kW. The deposition rates of MPP sputtered Cr coatings are comparable with that by dcMs, and increased almost linearly from 30 to 220 nm min-1 as an increase in the average power of 1-4 kW.
The MPP Cr coatings exhibited a nano-columnar a-Cr in a diameter of 60-100 nm and possessed the hardness of 9-15 GPa, which is higher than 8.2-4.3 GPa for dcMS under the average power of 1-4 kW. A denser nano-columnar fcc-CrN microstructure showing the interruption of the columnar grain growth and a finer grain size of 45-60 nm was found in the CrN coatings deposited by MPP at 50% fN2 as compared to those of the dcMS and PMS CrN coatings. The improved microstructure in the MPP CrN coatings led to high hardness of 24.5-26 GPa, excellent wear resistance with COF of 0.33-0.36 and wear rates of 2.4-2.43 X 10-6 mm3N-1m-1. The MPP Cr-C-N coatings transited from a-Cr+13-Cr2(C,N) to Cr(C,N) with increasing the fN2 from 10% to 30%. The coatings possessed the high hardness of 23.2-24.6 GPa and the COF of 0.4-0.6. The wear rates of the coatings are in the low range of 1.2-3.7×10-6 mm3N-1m-1. The MPP technique was shown to improve the coating microstructure, and then enhance the mechanical and the wear resistance properties of the coatings.
脉冲直流纯氩和氮氩混合气磁控溅射铬和碳时52Cr+、40Ar+、12C+和28N2+的离子能量分布均包括3个能量区域：峰值为4-5 eV的低能能量峰、能量峰为20-40 eV的中间区域和80-200 eV的高能区域。脉冲频率100 kHz时,随着占空比由90%降至50%,最大离子能量由90 eV拓宽至量程极限200 eV；脉冲频率提高至200 kHz,最大离子能量却逐渐由90 eV减至50 eV,占空比为50%时又突然增至130 eV,且均小于相同占空比条件下100 kHz时的能量。
脉冲直流磁控溅射沉积碳氮化铬薄膜,厚度约为2-3μm,在不锈钢和单晶Si基体与薄膜之间沉积了厚约100 nm的金属铬附着层,工作气压0.27 Pa,铬靶和碳靶共溅射,溅射功率分别为500-1000 W和600-1400 W,脉冲频率0-200 kHz,占空比50-90%,氮气分压0-60%。氮气分压、铬靶和碳靶溅射功率是控制碳氮化铬薄膜成分的主要参数,覆盖的成分范围为47.0-58.9 at.%Cr,15.5-38.9 at.%C和36.3-55.9 at.%N。碳氮化铬薄膜由纳米晶体相和非晶相组成,非晶相的含量随着碳、氮含量的增加而提高。固定铬靶溅射功率1000 W、碳靶1400 W,随着氮气分压fN2由20%增至50%,C／Cr原子比为0.29-0.39,而N／Cr原子比由0.41增至0.92。Cr靶700 W,FN2为20%-60%时,C／Cr原子比为0.23-0.90,而N／Cr原子比由0.37增至1.90。保持20%氮气分压和1000 W铬靶溅射功率,逐渐提高碳靶功率至1000 W, N/Cr原子比为0.54-0.62,而C／Cr原子比由0.26增至0.44。氮化铬薄膜为密排六方Cr2N结构,C进入密排六方Cr2N点阵中N的亚点阵位置,形成复合化合物Cr2(C,N),随着碳和氮的不断增加,最终转变为面心立方Cr(C,N)。铬靶溅射功率降至500 W时,薄膜中Cr含量进一步降低,组成为CrC1.47N1.30,薄膜结构为含Cr非晶C(N)。Cr靶和C靶的脉冲参数对碳氮化铬薄膜的成分与相结构没有明显影响,组成为CrC0.23-0.35N0.83-0.91,均为面心立方Cr(C,N)。
随着(C+N)/Cr原子比由0.81增至2.77,碳氮化铬薄膜中观测到3种微结构：横向晶粒尺寸为20-50 nm的纳米柱状晶Cr2(C,N)或Cr(C,N),纳米晶Cr(C,N)/非晶C(N)复合结构和含Cr非晶C(N),对应的薄膜组成为：CrC0.26N0.55或CrC0.29N0.74,CrC0.35N0.91和CrC0.90N0.88,以及CrC1.47N1.30。
闭合场非平衡脉冲直流磁控溅射沉积碳氮化铬薄膜的硬度为11.0-30.9 GPa, H/E比值0.058-0.102,摩擦系数0.31-0.59,磨损量1.28-18.2×10-6 mm3N-1m-1,膜基结合性能HF1-3,薄膜开始失效的临界载荷(LC3)5-23 N,具有很好的力学和摩擦学性能。碳氮化铬薄膜微结构为纳米柱状晶时,随着晶体结构由hcp-Cr2(C,N)转变为fcc Cr(C,N),硬度由17.5 GPa增至25.4 GPa,摩擦系数为0.52-0.56,磨损量为1.28-1.76×10-6 mm3N-1m-1;具有纳米晶Cr(C,N)／非晶C(N)复合结构的碳氮化铬薄膜硬度达30.9 GPa, H/E比值0.102,摩擦系数和磨损量分别为0.31和3.67×10-6 mm3N-1m-1,随着非晶含量的增加,硬度和H／E比值降至19.7 GPa和0.089,摩擦系数升至0.45；薄膜结构转变为含Cr非晶C(N)结构时,硬度仅为11.0 GPa, H/E比值0.059,磨损量高达18.20×10-6mm3N-1m-1。
等离子体质量和能量分析表明高功率调制脉冲磁控溅射铬时产生了高束流低能多价金属铬和气体原子,离化率随着靶峰值功率和电流的增加而提高,氩气溅射时产生的等离子体中包含52Cr+、40Ar+、52Cr2+、40Ar2+离子,而氮氩反应溅射时由Cr1-3+、Ar1-3+、N+1-2、N2-4+、CrN+和CrN2+组成,峰值能量均为3-4 eV。随着平均功率由1 kW增至3.5kW,直流磁控溅射沉积铬的沉积速率由67.9 nm min-1线性增至163.0 nm min-1,高功率调制脉冲磁控溅射沉积时,同样随着平均功率在0.8-4 kW范围内线性增加,为53.7-230.3nm min-1。高功率调制脉冲磁控溅射和直流磁控溅射沉积氮化铬的沉积速率相当,氮气分压50%、平均功率1-4 kW条件下,沉积速率为30-220 nm min-1。
平均功率为1-4 kW时,高功率调制脉冲磁控溅射沉积的铬薄膜为纳米柱状晶a-Cr,晶粒尺寸为60-100 nm,硬度为9-15 GPa,而直流磁控溅射的晶粒尺寸随着平均功率增加而增至微米级,硬度为8.2-4.3 GPa。氮气分压50%条件下,直流、脉冲直流和高功率调制脉冲磁控溅射沉积氮化铬薄膜为纳米柱状晶CrN结构,晶粒尺寸分别为105 nm、78 nm和45-60 nm,硬度、摩擦系数、磨损量分别为16.0 GPa、0.58、8.75×10-6 mm3N-1m-1, 21.0 GPa、0.45、3.65×10-6mm3N-1m-1和24.5-26 GPa、0.33-0.36、2.43×10-6 mm3N-1m-1。随着氮气分压由10%增至30%,高功率调制脉冲磁控溅射沉积的碳氮化铬薄膜由a-Cr+β-Cr2(C,N)逐渐演变为Cr(C,N),硬度为23.2-24.6 GPa,摩擦系数0.4-0.6,磨损量1.2-3.7×10-6mm3N-1m-1。高功率调制脉冲磁控溅射改善了薄膜的结构,提高了所沉积薄膜的力学和摩擦学性能。
Chromium carbonitride (Cr-C-N) coatings were deposited by pulsed closed field unbalanced magnetron sputtering (P-CFUBMS). The composition and microstructure of the coatings were investigated using electron probe micro-analysis (EPMA), x-ray photoelectron spectroscopy (XPS), glancing incident angle x-ray diffraction (GIXRD), field-emission scan electron microscopy (FESEM) and high resolution transmission electron microscopy (HRTEM). Mechanical and tribological properties of the coatings were measured by nanoindentation, Rockwell C test, scratch test and ball-on-disk wear tests. A correlation was pursuit between the composition, microstructure and properties of the coatings. A diagnostic of the ion species and their energy distribution generated during P-CFUBMS deposition was performed by electrostatic quadrupole plasma analyzer (EQP) to understand the improved structure and performance.
When chromium and carbon targets were pulsed asynchronously in Ar and Ar+N2 atmospheres, the 52Cr+、40Ar+\12C+ and 28N2+ ion energy distributions (IEDs) were measured by EQP. The basic characteristics of these typical IEDs are similar and reproducible, which present three energy regions in all ion species:a low energy peak at 4-5 eV, a middle energy region at 20-40 eV, and a high-energy region at 90-200 eV. The reduction of duty cycle 90% to 50% led to the increase of maximum ion energy from 90 eV to 200 eV when pulsed at 100 kHz, whereas at 200 kHz, the maximum ion energy decreased firstly from 90 eV to 50 eV, and then suddenly increased to 130 eV under 50% duty cycle.
The Cr-C-N coatings were deposited by pulsed direct current magnetron sputtering (PMS) under 0-200 kHz frequency and 50-90% duty cycle at 0-60% nitrogen flow rate ratio (fN2) and working pressure of 0.27 Pa. The chromium and graphite targets were respectively powered at 500-1000 W and 600-1400 W. The thickness of Cr-C-N coatings was 2-3μm and a chromium adhesion layer (about 100 nm) was firstly deposited onto the substrates. The concentration of coatings was controlled by the nitrogen flow rate ratio and the power on chromium and graphite targets, which was varied in the range of 47.0-58.9 at.%Cr,15.5-38.9 at.%C, and 36.3-55.9 at.%N. The Cr-C-N coatings consist of nanocrystalline embedded in an increased amorphous matrix as the carbon and nitrogen content were improved in the coatings. With an increase in fN2 from 20% to 50%, the atomic ratio of nitrogen to chromium (N/Cr) was increased from 0.41 to 0.92 as well as the C/Cr in the range of 0.29-0.39 when the chromium and graphite target was powered at 1000 W and 1400 W respectively. Decreasing the power on chromium target to 700 W, the N/Cr was also increased from 0.37 to 1.90, whereas the C/Cr varied in the range of 0.23-0.90 as the fN2 was increased from 20% to 50%. Under a 20% fN2 and 1000 W on chromium target, (N/Cr) in the Cr-C-N coatings was 0.54-0.62, whereas the C/Cr ratio was increased from 0.26 to 0.44 as the power on the graphite target was increased from 600 to 1000 W. The carbon occupied the sublattice positions of nitrogen in hcp-Cr2N to form the multi-compound Cr2(C,N), which transferred into fcc-Cr(C,N) with the increase of carbon and nitrogen content in the coatings. At a low chromium target power of 500 W, no crystalline phase but the Cr-containing amorphous C(N) phase was detected in the CrC1.47N1.30 coating. There were no effect of the pulse configuration on the composition and structure, which had the compositions of CrC0.23-0.35N0.83-0.91 and fcc-Cr(C,N) phase structure.
A nanostructure transition from nano-columnar Cr2(C,N) or Cr(C,N) with the diameter of 20-50 nm to nanocomposite nc-Cr(C,N)/amorphous-C(N), and then to Cr-containing amorphous C(N) was detected in the Cr-C-N coatings with an increase in (C+N)/Cr from 0.81 to 2.77, which possessed the corresponding compositions of CrC0.26N0.55/CrC0.29N0.74, CrC0.35N0.91 and CrC0.90N0.88.
The PMS Cr-C-N coatings exhibited a wide range of mechanical and wear resistance properties:the hardness of 11.0-30.9 GPa, the H/E ratios of 0.058-0.102, the coefficient of frictions (COF) of 0.31-0.59, the wear rates of 1.28-18.2×10-6 mm3N-1m-1, and the adhesion properties of HF1-3 and 5-23 N(LC3), which is dependent on the microstructure of the coatings. An increase of hardness from 17.5 GPa to 25.4 GPa was observed accompanied by the microstructural evolution from nano-columnar hcp-Cr2(C,N) to fcc-Cr(C,N), both of which possessed the COF of 0.52-0.56 and the low wear rates of 1.28-1.76×10-6 mm3N-1m-1. For nanocomposite nc-Cr(C,N)/amorphous-C(N) with the composition of CrC0.26N0.55, the highest hardness and H/E ratio of 30.9 GPa and 0.102 were evaluated with the lowest COF of 0.31 and the wear rate of 3.67×10-6 mm3N-1m-1 in the coatings. When the fraction of the amorphous C(N) phase increased with the further increase of carbon and nitrogen content to CrC0.29N0.74, the hardness and H/E ratio decreased to 19.7 GPa and 0.089, and the COF increased to 0.45. The poor mechanical and wear resistance properties, i.e. the lowest hardness and H/E ratio of 11.0 GPa and 0.059, and the highest wear rate of 18.20×10-6 mm3N-1m-1, were found in the Cr-C-N coating with the Cr-containing amorphous-C(N).
By EQP diagnostics, the plasma generated by MPP sputtering chromium contain the ion species of 52Cr+,40Ar+,52Cr2+ and 40Ar2+ in Ar, and that of Cr1-3+, Ar1-3+, N+1-2, N2-4+, CrN+ and CrN2+ in Ar+N2, all of which exhibited a peak energy of about 3-4 eV and their intensity improved with the increase of the peak power and current. For dcMS, the deposition rate of Cr coatings increased almost linearly from 67.9 to 163.0 nm min-1 as the average power was increased from 1 to 4 kW. The deposition rates of MPP sputtered Cr coatings are in the range of 53.7-230.3 nm min-1, which are lower than the dcMS rates when the the average power is less than 2.5 kW and exceed the dcMS deposition rates as the Pd is higher than 2.5 kW. The deposition rates of MPP sputtered Cr coatings are comparable with that by dcMs, and increased almost linearly from 30 to 220 nm min-1 as an increase in the average power of 1-4 kW.
The MPP Cr coatings exhibited a nano-columnar a-Cr in a diameter of 60-100 nm and possessed the hardness of 9-15 GPa, which is higher than 8.2-4.3 GPa for dcMS under the average power of 1-4 kW. A denser nano-columnar fcc-CrN microstructure showing the interruption of the columnar grain growth and a finer grain size of 45-60 nm was found in the CrN coatings deposited by MPP at 50% fN2 as compared to those of the dcMS and PMS CrN coatings. The improved microstructure in the MPP CrN coatings led to high hardness of 24.5-26 GPa, excellent wear resistance with COF of 0.33-0.36 and wear rates of 2.4-2.43 X 10-6 mm3N-1m-1. The MPP Cr-C-N coatings transited from a-Cr+13-Cr2(C,N) to Cr(C,N) with increasing the fN2 from 10% to 30%. The coatings possessed the high hardness of 23.2-24.6 GPa and the COF of 0.4-0.6. The wear rates of the coatings are in the low range of 1.2-3.7×10-6 mm3N-1m-1. The MPP technique was shown to improve the coating microstructure, and then enhance the mechanical and the wear resistance properties of the coatings.
引文
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