Does the ionosphere only reflect radio waves at large angles?

No. Radiosonds routinely send radio signals in a nearly vertical direction into the ionosphere to probe the reflectivity of the returned signal at normal incidence. By scanning in frequency from kilohertz to 10s of megahertz, the return signal provides 'ionograms' which can be translated into plots of density versus altitude.

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All answers are provided by Dr. Sten Odenwald (Raytheon STX) for the
NASA IMAGE/POETRY Education and Public Outreach program.