Refractory transition-metal (TM) diborides have high melting points, excellent hardness, and good chemical stability. However, these properties are not sufficient for applications involving extreme environments that require high mechanical strength as well as oxidation and corrosion resistance. Here, we study the effect of Cr addition on the properties of ZrB2-rich Zr1-xCrxBy thin films grown by hybrid high-power impulse and dc magnetron co-sputtering (Cr-HiPIMS/ZrB2-DCMS) with a 100-V Cr-metal-ion synchronized bias. Cr metal fraction, x = Cr/(Zr + Cr), is increased from 0.23 to 0.44 by decreasing the power PZrB2 applied to the DCMS ZrB2 target from 4000 to 2000 W, while the average power, pulse width, and frequency applied to the HiPIMS Cr target are maintained constant. In addition, y decreases from 2.18 to 1.11 as a function of PZrB2, as a result of supplying Cr to the growing film and preferential B resputtering caused by the pulsed Cr-ion flux. ZrB2.18, Zr0·77Cr0·23B1.52, Zr0·71Cr0·29B1.42, and Zr0·68Cr0·32B1.38 films have hexagonal AlB2 crystal structure with a columnar nanostructure, while Zr0·64Cr0·36B1.30 and Zr0·56Cr0·44B1.11 are amorphous. All films show hardness above 30 GPa. Zr0.56Cr0.44B1.11 alloys exhibit much better toughness, wear, oxidation, and corrosion resistance than ZrB2.18. This combination of properties makes Zr0·56Cr0·44B1.11 ideal candidates for numerous strategic applications.@en

We study microstructure, mechanical, and corrosion properties of Zr1-xCrxBy coatings deposited by hybrid high-power impulse/DC magnetron co-sputtering (CrB2-HiPIMS/ZrB2-DCMS). Cr/(Zr + Cr) ratio, x, increases from 0.13 to 0.9, while B/(Zr + Cr) ratio, y, decreases from 2.92 to 1.81. As reference, ZrB2.18 and CrB1.81 layers are grown at 4000 W DCMS. ZrB2.18 and CrB1.81 columns are continual from near substrate toward the surface with open column boundaries. We find that the critical growth parameter to achieve dense films is the ratio of Cr+-dominated ion flux and the (Zr + B) neutral flux from the ZrB2 target. Thus, the alloys are categorized in two groups: films with x < 0.32 (low Cr+/(Zr + B) ratios) that have continuous columnar growth, rough surfaces, and open column boundaries, and films with x ≥ 0.32 (high Cr+/(Zr + B) ratios) that Cr+-dominated ion fluxes are sufficient to interrupt continuous columns, resulting in smooth surface and dense fine-grain microstructure. The pulsed metal-ion irradiation is more effective in film densification than continuous Ar+ bombardment. Dense Zr0.46Cr0.54B2.40 and Zr0.10Cr0.90B1.81 alloys are hard (>30 GPa) and almost stress-free with relative nanoindentation toughness of 1.3 MPa√m and 2.3 MPa√m, respectively, and remarkedly low corrosion rates (∼1.0 × 10-6 mA/cm2 for Zr0.46Cr0.54B2.40 and ∼ 2.1 × 10-6 mA/cm2 for Zr0.10Cr0.90B1.81).@en