PHP has a mail function which allows you to send emails from your code, but in order for it to work you will need to install and configure something like Simple Mail Transfer Protocol (SMTP)
Additionally you might need to setup NAT forwarding on your router for SMTP to work correctly
http://php.net/manual/en/function.mail.php
http://www.serversmtp.com/en/smtp-configuration
If you need more help PM me and I'll see if I can point you on the right direction
Quick edit: One issue with running your own mail server is that most mail providers will mark it as spam unless you properly configure your ssl certificate and DNS records, and even then you might still be marked as spam
> Am I right in saying though, if my PCB has the correct primary smtp settings and is sitting on a network with Internet it should send emails?
Yes. Here is smtp info for hotmail. You should have no problem getting this to work. SMTP can be very basic. Just note the other 2 factor auth response here
Except that is pretty much what happens with e-mail as well, in a standard mail exchange you send to a server, that sends to the destination server, that then delivers to the recipient. When you send this the receiving server indicates to the sending server that things went all A-OK (250 Message Received) or that it didn't (http://www.serversmtp.com/en/smtp-error )
It is rare that a mail exchange record will not actually point to the final destination, in the same way that it is rare that a fax machine will not be at the final destination of a message.
While it is possible for a server to forward messages, this is no different from a faxing service receiving a fax and then forwarding it. The only difference here is that one is presumed by lawyers to work in a certain way and the other is presumed to be voodoo magic.
We use http://mandrill.com/ at work, although we have also used http://www.serversmtp.com/ for delivering email from our web app.
If you require a server for hosting mailboxes google apps is easy to use, as well as Office 365. I have also heard good things about FastMail
Coming IN, but, when I send mail, I'm still contacting my mail server (Either gmail, my company's, or, my ISP's (I personally use none of them, but, you get the point)).
Example, it's one of the default options in Thunderbird (Sue me, I'm using Windows 7 in /r/linux, I still use Linux, just not on this PC):-
http://i.imgur.com/FDz68PK.png
Hotmail still uses it as it's SMTP port (For sending mail):- http://www.serversmtp.com/en/smtp-hotmail
Yahoo and Gmail seem to only accept SSL now (on port 465), although, if your ISP is blocking SMTP non-SSL, they'll also be blocking the SSL port too:-
https://en.wikipedia.org/wiki/List_of_TCP_and_UDP_port_numbers
>465 - TCP - SMTP over SSL - Official
Want to know why? There's such a small difference between sending an email to a server (I.E. Gmail) to be relays for you (As what everyone is doing now-er-days), or, sending an email to a server (I.E. Gmail) for them to save for one of their users. ISPs (At-least, where I live, no idea about other countries) simply can't cut off support for ALL SMTP based SMTP interfaces. Sure, majority of people use HTTP to interface SMTP (such as gmail.com, yahoo.com/mail, etc...), but, quite a lot of people still don't, so, they can't just firewall port 25 incoming and outgoing.