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You can gain until Exceptional is at 100%.
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Err, wrong...
You can gain until your Success rate is equal to your scrolled skill cap (which for a 120 PS is 120% success). However, amounts over 100% aren't displayed.
From 0-95 skill, your chance to make exceptional (with out a talisman) is Success chance - 60%. So you can see your success chance over 100% by adding 60% to the exceptional chance to see your actual Success chance that isn't rounded down to 100%.
From 100 skill, up, your Exceptional chance is Success chance -45%. So, add 45% to the Exceptional chance to see your actual Success chance.
from 95.1 to 99.9, as an artifact of the pre-powerscroll system, the exceptional chance rate of advancement goes up 2.5 times the rate of the Success chance. Instead of both advancing 0.2% every 0.1 skill, Exceptional chance goes up 0.5% each 0.1 skill in this stretch, so figuring your actual success chance is a bit more difficult.
It is this bit of math on which the skill gain guides are based on for smith & tailor.
Quick chart.
Provided one does not have a talisman equipped....
Up to 95 skill
One can gain on an item as long as its chance of exceptional quality is...
No PS / 105 / 110 / 115 / 120 PS
40% / 45% / 50% / 55% / 60%
Above 100 skill
One can gain on an item as long as its chance of exceptional quality is...
No PS / 105 / 110 / 115 / 120 PS
55% / 60% / 65% / 70% / 75%
This is a rough treatment for items that hit 100% success between 95 & 100 (these items are few, if they exist at all). numbers assume no PS used (add 5% per 5 points over 100 for power scroll used)
95.0 skill: 40% Exceptional as above for 95.0 skill. add +0.3% for each 0.1 skill above the whole number (95.5 would be 41.5%, for example)
96.0 skill: No scroll gain visual check is 43% exceptional (add value of PS over 100 for scrolled amounts). Increment as needed, as described in the 95.0 skill line for values between whole numbers of skill.
97.0 skill: 46% Exceptional (see 95.0)
98.0 skill: 49% Exceptional (see 95.0)
99.0 skill: 52% Exceptional (see 95.0)
100.0 skill: 55% Exceptional, and Success and Exceptional gain rates fall back into synchronized advancement at 0.2% per 0.1 skill.
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Studded Hiro Sode hit 100% chance of success (55% chance of exceptional) at 110 skill, and 120% (75% chance of exceptional) at 120 skill. So, they can be gained on all the way to 120 skill, but the gains will be VERY slow going as one approaches 120. Be sure to use a salvage bag for the 1 extra leather back from each bonus of the bag.