I don't think they're using different dielectric materials -- tempco and age would be affected then. Material should be pretty consistent as long as it says "X7R" or what have you.
(There are some quirky effects at very low voltage ratings. That is, for very thin dielectric layers, where the electric domain size is comparable to dielectric thickness, k goes down. This, incidentally, limits the feature size of FeRAM devices, because each capacitor has to be some 200nm across, or whatever, for the ferroelectric effect to manifest. I don't think you can buy MLCCs /this/ low in voltage, though, so we don't have to worry about this.)
It would be interesting if they specified how much of the internal volume is occupied by electrodes and active dielectric. Alas, they don't, so we'd have to do a lot of cut-and-polish to figure that out...
I don't see it as a puzzle, it's just hidden information: they don't tell you how much of the chip they're using, so it's anyone's guess.
They do seem to land between two "reasonable" limits:
The lower limit assumes the same dielectric thickness, across all parts in a given series and given voltage rating.
E.g., all 25V rated caps in a series of parts use the same spacing between electrodes. Filler makes up the rest of the height of the chip (since the finished chip needs a minimum height).
The upper limit is a chip stacked to maximum height, made only of active dielectric (i.e., it's completely full of electrodes).
Parts on the upper limit are the easiest to say something about, because they're pushing the maximum energy density the material can offer. For these, you can say: when you need some amount of CV or CV^2, you need a part that's so-and-so large.
Between these two cases, the manufacturer has a degree of freedom: for values below the upper limit, they could use thicker dielectric. This would lead to higher effective voltage ratings (defining the effective voltage rating as, say, the -30% C(V) point), because more internal volume is active (surrounded by electrodes).
I'm assuming the lower limit is actually a limit; there's nothing hard and physical about it, but it would be very disingenuous of them to sell capacitors with even less active dielectric than you expect from the ratings.
Then, what about different voltage ratings? They could use proportional thickness dielectric, but this seems not to be the case, because higher voltage parts have worse C(V/Vrated). It's also not the same thickness, because the C(V) curve is better... just not proportionally better.
So the conclusion is, since we don't have any of this internal design information, and we'd have to examine a ton of parts to see what a given manufacturer is actually doing -- we can't go this deep, and must fall back to the one thing the manufacturer does provide (...when they do..), which is the C(V) curves themselves.
Between the C0805C105K3RAC and C0805C105K5RAC, it sure as hell looks like they screwed up big time (violating my supposed lower limit)...
Ya know... they could've transposed the curves. Got 'em backwards.
If I compare C0805C475K3PAC and C0805C475K4PAC, I see the '3' (16V) has -30% at 7.3V, while the '4' (25V) has -30% at 8V. This implies the 25V part has 10% thicker dielectric, but not 56% thicker (despite the 56% higher voltage rating).
Tim