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First time using Thermal Compound for CPU/Heatsink tips needed

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I used to use the spread method, but after watching the video Earth _ Dog posted. Never again.
 

This.

I've used Arctic Silver's recommended spread methods for my past 3 CPUs (and have done multiple cooler swaps/reseats), and I've always had great results.

Honestly, thermal paste has always freaked me out a bit. I don't want to bake my CPU, so I roll with whatever the manufacturer says.

I'm sure someone else answered your second question about whether you have to wait or not, but no. You don't have to wait. In fact, you'll want to get the system going and jump into a benchmark program to begin "breaking in" the thermal compound. Page 6 of this document gives you more info on the break-in period for Arctic Silver 5 (200 Hours).
 
Those using the razer or pre spread method... look a this vid (about 2M in is the prespread method):

That dude applied maybe 1/4 to 1/2 the amount of AS3 as he did the silicone stuff, then complained it didn't spread well.

Well, duh. If you don't put much of any on there, there isn't much to spread around.

I used the spread + rice method once. Worked well for me, but every other mount I've done has either been line or grain of rice (it's like a very short, but thick, line). Results have always been good.
 
Actually with the new cooler that came in a couple days ago I kinda just ran a straight line of NT-H1 in the middle and plopped it on there as I had replaced the TRUE copper once recently on TIM when I got the L5639 and had a pretty nice spread there, after looking at it a bit and was a bit small.

I just put a bit more on the same way in a line.

*shrug*
 
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