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Starting to construct my Salamanders and wondering about a few things.

What are the best weapons to take advantage of the free master-crafting on characters?
What goes well with the different sergeants (tac/dev/ass/term)?

If taking Vulkan do I just load up as much melta as possible, i.e. combi-melta, melta speeders, melta pintles?
Does this change if I run him in a Flameblade detachment with the boosted flamers?

If I want to run some FW units in a CAD like an Achilles, Predator infernus, would I be better running vulkan in the CAD instead and loading up on melta/assault cents in pods, mm devs in pods and twin-melta speeders?

I’m going to start by giving you the stock “It depends” answer. There is no right/wrong way, and there are pros and cons for pretty much every choice.

MCing makes everything better. Well, not your flamers, as they already get the re-roll from the CT. Or Meltas in Vulcan’s detachment, as they get TL'd from him. So figure out what a squad needs, and equip the sarge as normal.

Tac sarges should still probably get a combi to match the squad. C-plas is a little more attractive, as the MC helps with the gets hot.
Assaults should get a power weapon. Sword/maul/axe, depending what you are worried about, and if there is a HQ in the unit to soak challenges.
Dev sarges should probably just MC their bolt pistol if in a traditional camping squad. If doing some drop pod trickery, a combi works. Melta/grav to match what the squad is doing.
Terminator sarges don’t have a huge number of options. Assaults should probably go TH/SS. Tactical the sword. Capheract start with a MC sword, so switching it out for a better weapon that you get to MC for free is an easy call.

While tempting and rewarding to load up on melta with Vulcan, do try to keep a balanced list in mind. If not, you end up unable to affect anything more then 12” away, and high mobility armies will just run circles around you. Melta is great at it’s job (popping vehicles) but there are more threats on the battlefield then those.

Vulcan works on everything in his detachment. You are going to have to look at your army and weigh the pros/cons of where that benefit is best placed. No easy answer to that, as it’s very list dependent.