Nanostructure, mechanical properties and oxidation resistance of understoichiometric ZrB2-x films deposited by high power impulse magnetron sputtering

IF 5.3 2区材料科学 Q1 MATERIALS SCIENCE, COATINGS & FILMS Surface & Coatings Technology Pub Date : 2025-01-30 DOI:10.1016/j.surfcoat.2025.131860

Viktor Šroba , Tomáš Roch , Martin Truchlý , Leonid Satrapinskyy , Branislav Grančič , Katarína Viskupová , Peter Švec Jr , Peter Kúš , Grzegorz Greczynski , Marián Mikula

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Abstract

Diborides of transition metals from group IVB (TMB₂, TM = Ti, Zr) are desirable materials in demanding industrial conditions due to their excellent mechanical properties. Direct current magnetron sputtering (DCMS) leads to the growth of overstoichiometric (TMB_x, x > 2) film with nanocomposite structure consisting of crystalline hexagonal TMB₂ nanocolumns surrounded by a thin, amorphous boron-rich rich tissue phase. At elevated temperatures, the presence of the tissue phase has a negative effect on the films' mechanical properties and oxidation resistance. An innovative approach using effective ionization of sputtered species during high-power pulsed magnetron sputtering (HiPIMS) growth of ZrB₂ films is presented.

While layers grown using the conventional DCMS method are overstoichiometric (B/Zr = 2.2), the films grown by HiPIMS are understoichiometric, with a B/Zr ratio ranging from 1.6 to 1.9. In understoichiometric ZrB_1.9 and ZrB_1.6 films, detailed structural analysis using transmission electron microscopy revealed a nanocrystalline structure comprised of densely packed 10–20 nm wide nanograins. In addition, the understoichiometric films exhibit high hardness values above 42 GPa and improved high-temperature oxidation resistance compared to the ZrB_2.2 film deposited by DCMS.

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IVB 族过渡金属二硼化物（TMB2，TM = Ti、Zr）因其优异的机械性能而成为苛刻工业条件下的理想材料。通过直流磁控溅射（DCMS）技术，可以生长出具有纳米复合结构的超全度（TMBx, x > 2）薄膜，这种纳米复合结构由结晶六方 TMB2 纳米柱组成，周围环绕着一层薄薄的无定形富硼组织相。在高温条件下，组织相的存在会对薄膜的机械性能和抗氧化性产生负面影响。在高功率脉冲磁控溅射（HiPIMS）生长 ZrB2 薄膜的过程中，采用有效电离溅射物的创新方法。采用传统的 DCMS 方法生长的薄膜层具有超化学计量性（B/Zr = 2.2），而采用 HiPIMS 方法生长的薄膜则具有低化学计量性，B/Zr 比率在 1.6 到 1.9 之间。利用透射电子显微镜对低计量 ZrB1.9 和 ZrB1.6 薄膜的详细结构分析表明，其纳米晶体结构由 10-20 纳米宽的纳米晶粒密集组成。此外，与通过 DCMS 沉积的 ZrB2.2 薄膜相比，低计量薄膜具有高于 42 GPa 的高硬度值和更好的耐高温氧化性。

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来源期刊

Surface & Coatings Technology 工程技术-材料科学：膜

CiteScore

10.00

自引率

11.10%

发文量

921

审稿时长

19 days

期刊介绍： Surface and Coatings Technology is an international archival journal publishing scientific papers on significant developments in surface and interface engineering to modify and improve the surface properties of materials for protection in demanding contact conditions or aggressive environments, or for enhanced functional performance. Contributions range from original scientific articles concerned with fundamental and applied aspects of research or direct applications of metallic, inorganic, organic and composite coatings, to invited reviews of current technology in specific areas. Papers submitted to this journal are expected to be in line with the following aspects in processes, and properties/performance: A. Processes: Physical and chemical vapour deposition techniques, thermal and plasma spraying, surface modification by directed energy techniques such as ion, electron and laser beams, thermo-chemical treatment, wet chemical and electrochemical processes such as plating, sol-gel coating, anodization, plasma electrolytic oxidation, etc., but excluding painting. B. Properties/performance: friction performance, wear resistance (e.g., abrasion, erosion, fretting, etc), corrosion and oxidation resistance, thermal protection, diffusion resistance, hydrophilicity/hydrophobicity, and properties relevant to smart materials behaviour and enhanced multifunctional performance for environmental, energy and medical applications, but excluding device aspects.