NAudio has a Network Chat Demo within the Examples if you download the source code, which does a good job of showing how to implement a very simple Chat application.
Basically though what you want the client to do is this:
void Initialize()
{
waveIn = new WaveIn();
waveIn.BufferMilliseconds = 50;
waveIn.DeviceNumber = inputDeviceNumber;
waveIn.WaveFormat = codec.RecordFormat;
waveIn.DataAvailable += waveIn_DataAvailable;
waveIn.StartRecording();
...
}
void waveIn_DataAvailable(object sender, WaveInEventArgs e)
{
//Encode and send e.Buffer
}
With this you get a byte array every 50 ms (or however long you set you buffer to) and send it to the server. You'll need to encode it however, since sending the sound un-encoded will take up too much bandwidth. NAudio has codecs of its own, so that shouldn't be much of a problem. See here for NAudio's network chat demo.
Another thing to consider, if you plan to implement a client to client voip (either via p2p or streamed through the server itself) is a good networking library to handle all the communications. I've used Lidgren on a similar project which worked pretty well. It's open source, but can easily be set up to fit your needs.