While it doesn't answer why the pain is occuring, I would suggest
trying to find some relaxation, distraction techniques for this mom
to use.  It is only natural to anticipate the pain, however, that
anticipation can lead to less than effective latching techniques.

Moms who have had some nipple trauma, for example, will often
continue to have some "residual" discomfort for a few seconds after
latching while that injury heals, even when the initial latching
problem has been assessed and corrected.  Mom may, anticipating that
initial discomfort, move baby to breast just a little slower which,
for some babies who close their mouths quickly, means not as much
areolar tissue in the mouth as would be ideal.  I will point this
out to a mom whose nipples are healing and remind her to try to
consciously "override" this natural protective tendency to move a
little slow.  I have also found that for some moms, rubbing an ice
cube over the nipple just before latching will "dull" the nerve
endings for a few seconds and that may be long enough to get past
the discomfort of the first few sucks.  (Of course, I remind her if
it feels like "new" pain, then the latch may not be the best yet.  I
find that most moms, once they think about it, can distinguish
between the new and the residual discomfort.  Also, if the
tenderness isn't inproving, or if it increases, she is asked to call
us for an immidiate reassessment of what's happening.)

Again, this doesn't sound like what you are describing, but mom may
find it helpful to try the ice cube trick, especially if the pain is
more surface than deep inside.  I would think of possible vasospasm,
which means warmth would be helpful, but it sounds like you have
already tried this to no avail.  Breathing techniques (such as
childbirth breathing) and any visualization techniques that help her
relax will both help her through that brief painful time and may
actually help the MER come sooner.  Her tension in anticipation of
the pain may be inhibiting MER and making the problem even worse.

Good luck with this puzzling case, and please let us know what you
finally figure out about it.

Winnie

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