$\newcommand{\psym}{\operatorname{P}_{\ge 0}}$
Let $\psym$ be the set of symmetric positive semidefinite (real) matrices.
Let $\sqrt \cdot :\psym \to \psym $ be the unique positive semidefinite square root.
Let $A \in \psym$ be a matrix on the boundary, i.e $\det A=0$. Let $B$ be a symmetric matrix such that $A+tB$ is positive semidefinite for $t>0$ small enough**.
Quesion: Characterize all such pairs $A,B$ where the one sided directional derivative
$$ (d\sqrt{\cdot})_A(B)=\left. \frac{d}{dt}\right|_{t=0} \sqrt{A+tB}:=\lim_{t \to 0^+} \frac{ \sqrt{A+tB}-\sqrt{A}}{t} \, \, \text{ exist.}$$
Partial results:
(1) For $A=0$ the limit exists only for $B=0$.
(2) For every $A=B$ the limit exists (and equals $\frac{1}{2}\sqrt{A}$).
(3) For every $A$, there are a "lot" of matrices $B$ for which the limit does not exist (see the answer of loup blanc):
By orthogonal diagonalization, after noting that
$(d\sqrt{\cdot})_A(B)$ exists $\iff (d\sqrt{\cdot})_{V^TAV}(V^TBV)$ exists for every $V \in O_n$,
we reduce to the case $A=diag(0,a_2,\cdots,a_n)$ where $a_i\geq 0$: For every matrix $B$ of the form $B=diag(\lambda,C)$ where $\lambda > 0,C\in M_{n-1}$ is symmetric s.t. $diag(a_2,\cdots,a_n)+C\geq 0$, $(d\sqrt{\cdot})_A(B)$ does not exist.
In this question, it is shown that $\sqrt{\cdot} $ is not differentiable in the standard sense. In fact, this answer shows $\psym$ is not a manifold (with boundary) at all, so "standard differentiability" does not really make sense here.
** Actually, as noted by loup blanc, if $B$ is a symmetric matrix such that $A+B \in \psym$, then $A+tB \in \psym$ for small enough $t$. Indeed,
$A,A+B \in \psym$ and $\psym$ is convex, hence $(1-t)A+t(A+B)=A+tB \in \psym$.
Note that the reverse implication is false in general; It can happen that $A+tB \in \psym$, but $A+B \notin \psym$, see here.