Enhancing the Program
Understand the numerous UI choices that the Blend components have to offer by changing display attributes and examining the XAML modifications made to the source code. Append additional controls within existing design surfaces and see how these are nested within the host control and can bubble UI changes accordingly. Once comfortable with the power that WPF imbues, research the WPF examples and documentation included in the .NET 3.0 SDK. There is also an excellent book entitled Windows Presentation Foundation Unleashed (Sams, 2007) that's written by WFP Program Manager Adam Nathan.
Conclusion
While ultimately best-suited for graphic designers with some coding experience, Blend is also a XAML programming tool that offers Windows application developers one of the fastest ways to realize and explore the combined power of XAML and the Windows Presentation Foundation. Additionally, Blend offers programmers a headstart on their own WPF application ideas because the XAML it produces will be interchangeable with the WPF form-rendering functionality that future versions of the Visual Studio IDE will supply.
Several Blend-related web sites featuring additional code samples and XAML tips and tricks have begun to sprout on the Web, including www.expressionblend.com, by-expression.com, and even the Expression team's own blog at blogs.microsoft.com/expression. Also on Dr. Dobb's Portal, you can find a multipart interview with Brad Becker, Senior Product Manager for Microsoft Expression Blend; see www.ddj.com/mediaCenter.