Rendering → V-Ray Scene Converter → Material Library tab → Set path to the installed folder.
Once you've downloaded the material library, follow these steps for offline installation: vray 6 material library download offline install
He plugged it into the workstation.
Do not drag materials directly from the ZIP. V-Ray needs a specific folder structure. Rendering → V-Ray Scene Converter → Material Library
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If your workstation is permanently offline, you can download the library on an online machine and transfer it via a USB drive.