You touched on one issue that I think deserves it's own topic so I will only briefly mention it here. The ease with which comparable Unique and Untradeable gear is obtained diminishes the value of all crafted and melded gear of both comparable and superior quality. When given the choice to either do dungeons for a week or so or spend several million gil for similar quality equipment, most people will simply take the dungeon gear.
Now, the purpose of the Materia System was not to enhance gameplay whatsoever - it merely gives players the ability to spend lots of time 'improving' their character; the real purpose of materia is purely destruction. To eliminate equipment by both conversion into materia and by loss through the melding process itself. When you frame your view of the materia system, it is quite ingenious.
However, the degree to which this system is effective is, in part, related to how much it is used. Unique Untradeable gear, especially the superior quality pieces, directly diminish the use of the materia system as a whole. By giving such an easy alternative, it becomes quite obvious that the pursuit of multi-melded gear is a fool's task.
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As for the rate of successful melds, I think it is important to recognize that it is an arbitrary decision what % is adequate. I think the best measure of how often melds should succeed should be in proportion to the actual benefits that are granted. If someone with 5x melded gear in all available slots is 5x as powerful; there should be a steep price to pay. But supposing they are only 1.25x as powerful, very few will pay very steep prices to even attempt such melds.
There is also another factor, as I alluded to before; the amount of destruction the materia system introduces is based upon these rates of success. The developers have to introduce an arbitrary amount of 'wanted destruction' that fits their vision of how much gear should be in demand.
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My suggestion would be to:
Modify dungeon gear by allowing them to all be converted into materia (could introduce rare materia or simply have dungeon gear provide higher probability of high grade materia) and melded. There would be little need for this gear to be Unique or Untradeable at this point, as those who run dungeons multiple times would have a great advantage in obtaining the most melds for their equipment; and, thus they can be distinguished from others by their superior melded equipment.
At this point, we could have materials be dropped from bosses instead of gear. This would allow groups of players to make HQ dungeon equipment with multiple pieces of materia attached as well. The materials from these dungeons and also the materials obtained from outside dungeons could be incorporated into recipes and even into future recipes which would then keep dungeons relevant.


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