To use it in the Format method, you use numbers corresponding to the indexes of the params array.
Also, don't reassign Sb, just call Append or AppendFormat:
Sb.Append(String.Format("{0,5}", myObj[i].ToString()));
//or
Sb.AppendFormat("{0,5}", myObj[i].ToString());
If you're fortunate enough to be on the latest and greatest C# version, you can skip Format and do it with the new string interpolation syntax:
Sp.Append($"{myObj[i],5}");
Or since all you're doing is padding, then you can also do:
Sb.Append(myObj[i].ToString().PadLeft(5));
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