During deployment the database is synchronized, during which the index is created. So it is available for use when the application has been started. As fas as I can tell Mendix only uses indices that are maintained during create and update of the table records.
Whether the index is used depends on the requests sent to he database. For small tables the db engine might prefer a table scan (read entire table and pick the record(s) that match the selection) over index access. For thousands or more the index becomes more interesting for the engine. Especially an index that has many different values.