The overflow valve as you termed it is operated by two factors. Temperature which would mean that the Bottom thermostat may be malfunctioning. Pressure which is not as likely, Lifts at about 150 PSI. Check water temperature. If the temperature is to high the problem is with the setting or the themostatic control may need to be replaced.
When you draw hot water the top thermostat takes control and cuts power to the lower thermostat. When the top thermostat is satisfied the control is changed to the bottom thermostat. The contacts on the bottom thermaostat could be welded together.
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