This way is very simple, but it doesn't protect against the source value being longer than the specified length and it doesn't account for trailing SPACEs in the source value.
DECLARE @W INTEGER
SET @W = 10
DECLARE @X NVARCHAR(MAX)
SET @X = 'VALUE'
DECLARE @Y NVARCHAR(MAX)
SET @Y = '#'
DECLARE @Z NVARCHAR(MAX)
SET @Z = @X + REPLICATE(@Y,@W-LEN(@X))
SET @Z = REPLICATE(@Y,@W-LEN(@X)) + @X