To avoid having the password available in memory as plain text at any point, I provide the value as a parameter to my command.
<Label>User Name</Label>
<TextBox Text="{Binding UserName}" />
<Label>Password</Label>
<PasswordBox Name="PasswordBox" />
<StackPanel Orientation="Horizontal" HorizontalAlignment="Right" Margin="0 16 0 0">
    <Button Margin="0 0 8 0" MinWidth="65" 
            Command="{Binding LoginAccept}" 
            CommandParameter="{Binding ElementName=PasswordBox}">
        Login
    </Button>
    <Button MinWidth="65" Command="{Binding LoginCancel}">Cancel</Button>
</StackPanel>
Then in my view model.
public DelegateCommand<object> LoginAccept { get; private set; }
public DelegateCommand<object> LoginCancel { get; private set; }
public LoginViewModel {
    LoginAccept = new DelegateCommand<object>(o => OnLogin(o), (o) => IsLoginVisible);
    LoginCancel = new DelegateCommand<object>(o => OnLoginCancel(), (o) => IsLoginVisible);
}
private void OnLogin(object o)
{
    var passwordBox = (o as System.Windows.Controls.PasswordBox);
    var password = passwordBox.SecurePassword.Copy();
    passwordBox.Clear();
    ShowLogin = false;
    var credential = new System.Net.NetworkCredential(UserName, password);
}
private void OnLoginCancel()
{
    ShowLogin = false;
}
While it would make sense to provide the SecurePassword directly from the binding, it always seems to provide an empty value.  So this does NOT work:
    <Button Margin="0 0 8 0" MinWidth="65" 
            Command="{Binding LoginAccept}" 
            CommandParameter="{Binding ElementName=PasswordBox, Path=SecurePassword}">