What causes the secondary diode to be reverse biased during tON? Is it to do with the opposing trafo polarity?
During tON, the MOSFET is on and current flows from the input through the primary inductor, linearly charging the coupled inductor and creating a magnetic field around it. In the secondary inductor, the rectifier diode is reverse-biased, which means the transformer is disconnected from the output.

https://www.monolithicpower.com/en/primary-side-vs-secondary-side-regulation
During tON, the MOSFET is on and current flows from the input through the primary inductor, linearly charging the coupled inductor and creating a magnetic field around it. In the secondary inductor, the rectifier diode is reverse-biased, which means the transformer is disconnected from the output.

https://www.monolithicpower.com/en/primary-side-vs-secondary-side-regulation
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