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Can't advise regarding the PTFE release agent, don't know anything about it or what it is normally used for. If it is a composite release agent then it should be fine, if it's normally a casting release agent or concrete release agent or something like that then it may or may not work. Realistically, there's so many excellent release agents available for composites use that I just wouldn't bother messing around experimenting.
The trouble with silicones is they contaminate things, especially spraying them. You will get silicone overspray all around your shop and start finding weird issues with contaminated surfaces and materials. If you spray paint anything yourself, don't ever spray anything silicone in the same area. You'll have endless trouble with paint fisheyeing.
As for wax, PVA, and semi-perms; occasionally there is a benefit to combining them. For example if I'm making a mould, I generally treat the pattern with a semi-permanent and then do a coat or two of release wax. This just adds a layer of security, as there are often several different materials being used on the pattern (ie. the pattern surface itself, barrier materials, filleting wax or plasticine, etc) and the wax may provide an easier release from one of those surfaces that the chemical release agent may not have. Certainly not necessary at all, one would normally get away with just a semi-perm on its own, just something I like to do personally.
PVA on the other hand is pretty old-school, but still has it's uses. For me, it protects anything that may be chemically incompatible. For example, trying to make a fibreglass mould off a surface that has been coated with a single pack paint, or perhaps even a rubber surface. The gelcoat would attack those surfaces if you just used a wax or a semi-perm, you need PVA to form a physical barrier between the two. Alternatively you may have a mould made with polyester tooling gelcoat and plan to layup an epoxy component in it, and in this case using just a wax or a semi-perm on their own could result in a stick and PVA is a good idea.
For the most part though, there's no need to combine them.
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