Columbia, no. They were still too fast for any current-technology space suit to protect them from the impinging plasma.
In other words, whatever heat shield you have simply
has to work. Meaning it must be as small and simple as possible, and preferably protected from damage until right before use.
Challenger, yes. At breakup they were at ~50k feet and Mach 2, conditions less severe than the 1966 SR-71 ejection. However, the space shuttle design would have made ejection seats for all occupants very difficult if not impossible (three of the seven occupants sit in the mid deck, deep in the crew compartment).
Doesn't the B-52 eject two crew members downward? If the Shuttle had been laid out so that some of the occupants sat just above the bottom skin, maybe it would have been possible. But this would have required punching a hole through the silica tiles on the underside, complicating an already difficult piece of technology.
But even if you can get the crew quickly away from the orbiter, you have the problem of protecting them from a hydrogen/oxygen fireball and two still-burning SRBs that are flying without guidance. Those plumes are pretty wicked, and you don't have to get directly hit by one to be fried by the noise and thermal radiation.
Launch abort survivability is not easy. Remember the Aries-1 was sunk by an Air Force analysis showing that the Orion's parachutes would be fried by chunks of burning solid propellant were an abort to occur as a result of a first stage failure (which for solid rockets usually means "a sudden, dramatic explosion" -- the Challenger SRB failure was a very unusual mode).