Hypix 3000

The solid state of the drug in the samples was investigated by X-ray powder diffraction (XRPD) with a Rigaku SmartLab diffractometer equipped with a 9 kW rotating anode and a HyPix-3000 detector (Rigaku Corporation, Tokyo, Japan). Bragg–Brentano optics were set as follows: 5.0 degree (deg) incident parallel Soller slit, 1/8 mm incident slit, 10 mm length limiting slit on the incident arm of the goniometer and 4 mm receiving slit #1, open parallel slit analyzer, 5.0 degree receiving parallel Soller slit, and 13 mm receiving slit #2 on the receiving arm of the goniometer.
The samples were exposed to X-rays of Cu wavelength (1.541 Å) and measured in 1D detection mode in a θ/2θ range of 2–60 degree with a step size of 0.01 deg and a 1 deg/min scanning speed.

XRD experiments were performed using SuperNova (Rigaku Oxford Diffraction, Oxford, UK), Single source at offset/far, HyPix3000 (for 1·1,3,5-FIB and 2·2(1,3,5-FIB)) and XtaLAB Synergy (Rigaku Oxford Diffraction, Oxford, UK), Single source at home/near, HyPix (for 3·2(1,3,5-FIB)) diffractometers with monochromated CuKα radiation. All crystals were kept at 100 K during data collection. The structures were solved using ShelXT [74 (link)] structure solution program and refined by means using ShelXL [74 (link)] incorporated in Olex2 version 1.5 [75 (link)] program package. Empirical absorption correction was accounted for using spherical harmonics implemented in SCALE3 ABSPACK scaling algorithm (CrysAlisPro 1.171.41.122a; Rigaku Oxford Diffraction, 2021). The structures can be obtained free of charge via CCDC database (CCDC numbers 2280076, 2280077, and 2281032).

The X-ray reflectivity (XRR) was measured on a 2-circle diffractometer (Rigaku SmartLab) equipped with a 9 kW rotating Cu anode source and parallel beam multilayer optics for monochromatic Cu-Kα radiation (λ = 1.54 nm). Reflected intensities were recorded on a 2-dimensional single photon counting hybrid pixel detector (Rigaku HyPix-3000, 775 × 375 pixels, 100 µm × 100 µm pixel size). Specular reflected X-ray intensities were recorded in the scattering angle range of 0^o ≤ 2θ ≤ 10^o with 0.01^o step width and 60 s counting time per data point. For quantitative analysis using the software Motofit [40 (link)], scattering angles were converted to a momentum transfer $q=\frac{4\pi }{\lambda }sin\left(\theta \right)$ .

The surface and cross-sections and wear track of the sample, and also wear scar of the counter surface ball were observed by a scanning electron microscope (SEM) along with an energy-dispersive X-ray spectroscope (EDX) was used (JSM-6610LA, JEOL, Tokyo, Japan). The surface roughness and hardness were measured 3–4 times by using a profilometer (SJ-210, Mitutoyo, Tokyo, Japan) and a micro-Vickers tester at 300 gf and 12 s (MVK E3, Mitutoyo, Tokyo, Japan), respectively. Microstructural changes were analyzed using an X-ray diffraction (XRD: D8 ADVANCE, Bruker, Karlsruhe, Germany) with a chromium (CrKα) radiation (2.2897 Å) at a wavelength of 0.210. Compressive residual stress was measured by an X-ray method (HyPix-3000, Rigaku, Tokyo, Japan). Grain size refinement was analyzed by a transmission electron microscope (TEM: Titan Themis Z, FEI, Hillsboro, OR, USA) operated at 300 kV and the size of at least 20 nano-grains were measured by using an ImageJ version 1.51 (NIH, Bethesda, MD, USA) software. The samples were washed in a solution of 90% ethanol and 10% nitric acid at a voltage of 5 V for 3 min to keep surfaces visibly clean and free from contaminants. Wear tracks generated on the surface of the samples after tribological testing were analyzed with the help of Vision64 software provided by 3D stylus profilometry (Dektak XT, Bruker, Karlsruhe, Germany).