View Full Version : cryo times for 'complete' conversion


SteveS
08-10-2004, 03:08 PM
When using liquid nitro what's your recommended soak times?

I'm sure the austentite/martensite conversion percentage is asymptotic and after a while the soak time really doesn't make an appreciable difference.

I've heard everything up to 12 hours. The Crucible data sheets don't list a time, just a minimum temp of -112 (or something like that).

I had one S30V blade soaked for about an hour and got the same results as over night. At least from a HRC measurement.

Steve

nate d.
08-10-2004, 04:09 PM
the conversion wait let me start over the remaining part of austenite that you are able to convert to martensite in the cryo quench process happens as soon as the material's temperature goes below the Martensite finish line on the TTT curve diagram. I have asked Crucible the fine and helpful folks i might add for a TTT diagram for 3V and both times they don't have one and as a result of this i just dunk blades in LIN and let them come to euqlibrium in the LIN and leave then in as long as i feel like it. I though the same thing you did that the final martensite comversion was time dependent till my proffessor who was helping me HT sat me down and calmly ask me a few questions and that SET ME STRAIGHT!!!!!!!!!!!

SteveS
08-10-2004, 04:30 PM
Nate,

No kidding? It happens when the steel reaches temperature? It'll take me a while to digest that.....

Uum, Let's see during the 'real' quench the conversion is incredibly fast (I forgot, but it travels thru the steel in fractions of a second.) SO I suppose the continuing conversion in sub-zero is also very fast?

Is that what the proffessor's little chat was about?

Steve

RJ Martin
08-10-2004, 10:39 PM
Steve: That's my understanding as well. Conversion is complete when the parts equalize at temp.

Quenchcrack
08-11-2004, 08:15 AM
The transformation does start to occur as soon as the austenite is cooled below the Ms temperature. Note I said "cooled below", it does take some undercooling to get things started. The percentage of conversion of retained austenite to martensite is a function of temperature and NOT quench velocity. Soak only long enough to get the blade cooled down to the temperature of the cryo bath, then you can pull it out. It is usually recommended that the blade be given a quick, low temperature temper prior to cryo treating, something on the order of heating to 250F in the forge and air cooling. This will minimize the danger of cracks and distortion in the cryo bath. However, this snap draw will also decompose some of the retained austenite to things like lower bainite and pearlite. This will slightly reduce the hardness.

SteveS
08-11-2004, 10:58 AM
However, this snap draw will also decompose some of the retained austenite to things like lower bainite and pearlite. This will slightly reduce the hardness.

OH!!!!!! That explains it, well part of it. Long story, but on the last 2 batches, I wasn't getting the same (any) jump in hardness after the cryo as described in the . However, I was doing a snap draw. Hmmm.

Thanks,

Steve

rlinger
08-11-2004, 12:17 PM
I leave mine in there 10 to 12 hours minimum. Many times up to 17 - 18 hours because I sometimes am not here to pull after 12 hours. Once upon a thread Mete suggested 10 hours is plenty long enough.

RL

RJ Martin
08-11-2004, 01:56 PM
Steve: Well, turns out I was wrong. Even though diffusion is very slow at -320F, it does still occur, and it takes time. This is why 24 hours is generally recommended as a soak time for the cryo treatments.

Also, remember that the better the initial heat treatment, the less apparent effect the cryo will seem to have. But, it is still working it's magic on your steel.

When I first started heat treating A2, I oversoaked a few blades just above the high end of the Austenitizing range. After quench, they were only about 56 rockwell, which pointed out immediately that they were oversoaked-Cryo brought them up about 6 points! After tempering, they were right at 59 Rc.
Of course, I didn't sell the,-Just turned them into beaters for the shop, and, they worked fine. That's the great benefit of cryo-It tends to equalize minor inconsistencies in HT that you might not even know are present.

So, leave those blades in there for 24 hours, bacause that's best!

SteveS
08-11-2004, 02:43 PM
Thanks RJ,

Looking at the CM154 data sheet, it shows what you experienced if you use 2000 degrees. My assumption is that the entire blade is austentite, but the quench brings it down so fast thru critical that very little (by comparison) austentite converts to martensite. The cryo becomes the major quencher.

Always stuff to learn!

Thanks again,

Steve

Quenchcrack
08-11-2004, 07:30 PM
RJ, with all due respect, I must politely disagree with your comments about soaking at cryogenic temperatures. Tempering is a diffusion controlled process. The transformation from austenite to martensite is a diffusionless shear process that is dependant only upon temperature, not time. However, leaving it for 24 hours will certainly guarantee the blade has been sufficiently refrigerated and will do it no harm. :)

Remember that the quench velocity does not have any influence on retained austenite. Retained austenite is caused by high carbon content (and alloy content) that impedes the shear transformation to martensite.

RJ Martin
08-11-2004, 09:02 PM
Quenchcrack: I have read published data that stated both cases as being correct. So, today, I called Scott Devanna. Scott is one of the CPM gurus over at Crucible, and I wanted to hear his answer. He says soak time in the LN2 definitely matters, particularly for some of the very highly alloyed CPM steels. Apparently, the MF temperatures for these alloys can be very low, and, even with the soak you can't get 100% Martensite, but you can reach well into the 90's.
So, the second answer I gave is the one I got straight from him. I'm inclined to stick with the 24 hour deep freeze. Like you say, it can't hurt. As an Engineer, I'm fine with that. If I were a Scientist, I'd probably want absolute proof......

fitzo
08-11-2004, 09:15 PM
Do you guys feel there is any truth to the claims of other things besides conversion of retained austenite going on that may be more time dependent? I read an e-paper on a site called "cryogenius" or something like that which spoke of things like "eta-carbide rearrangements" and didn't know if it was gibberish-science or based in fact. I believe the author was speaking specifically about high alloy steels.

Thanks for any opinions.

Quenchcrack
08-12-2004, 08:25 AM
RJ, well, I learn something every day! I wonder if it has anything to do with the way the CPM is made? I looked this up in 4 different books and all of them said time at low temperature was not an issue ONCE YOU GOT THE PIECE DOWN TO CRYOGENIC TEMPERATURES. I wonder if it just takes time to get the blade down to -300F? Although, the CPM grades are extremely high in alloys known to retard the shear transformation. So I guess what I should have said was that for carbon and low alloy steel, soak time is not critical. For very high alloys, soak time is critical. Sound right?

Eta-carbides: I believe these are the carbides that knifemakers have been precipitating for thousands of years but nobody could see. Eta carbides are formed at low tempering temperatures and are so small they can only be resolved with a Scanning Electron Microscope. They are a slighly different chemical composition from the Fe3C found in pearlite, etc.

Ms and Mf temperatures: The Ms temperature for a given steel is usually known fairly accurately. The Mf is much more ambiguous as it is difficult to know when the transformation is actually complete. Some books us the M99 temperature which is a more conservative temperature that represents a 99% transformation. There are empirical equations to calculate Ms, M50, M90, and M99 but they are probably only good estimates...

Mike Stewart
08-12-2004, 08:52 AM
Hi Guy's,

I have been Cryogenically Treating my blades since 1987.

In every test I have ever done the 24 hour process has yielded a better and stronger blade that holds an edge better. I do 500 blades at a time on the average batch and get on average a 1 point increase in rockwell. I then do a low heat stress relief at about 275F for an hour. I don't get broken blades and for semi-production knives I get exellant results.

I really don't think that there are too many folks out there that have been doing Cryo-Processing longer than I have. I've had years to test this stuff and I'm not a good debater. I'm going to keep doing it the same way. I never tell anyone how to make their knives but I have never had a problem with the long soak method. If it ain't Broke...........

Mike..........

RJ Martin
08-12-2004, 10:02 AM
Mike: Sounds like you have a good track record. I have been cryo treating almost as long as you, but, if you're doing 500 blades at a time, you have lots more data than I do!
Generally, 300F is suggested as a stress relief for the newly formed Martensite, so, 275 is right there. I do my tempering after the cryo.
Quenchcrack: Yes, I am wondering if it doesn't take quite a while for those blades to actually reach -320F. And, the CPM alloys probably complicate the process a whole bunch. For simple steels, the soak time is probably not critical. And, yes, my understanding of the eta-carbides is that those are ultra-small carbides that precipitate during cryo. They help wear resistance and toughness.

shgeo
08-12-2004, 10:44 AM
The martensite transformation is a diffusionless shear-related recrystallization that moves at ~1 KM/sec through simple FeC steels. I have not seen figures for the phase transformation rates in high alloys, but I would expect it to be slower through the more complex systems.

Crucible and Bucorp (Bohler/Uddeholm, NA) both recommend cold treatments at dry ice temperatures (-110F to -112F) for 3 to 4 hours for tool and CPM steels. It will not hurt to go longer. The colder lN2 temperatures give a small extra amount of transformed retained Austenite, but the relationship is asymptotic as mentioned above.

I have not seen any published data that claims anything other than retained Austenite transformation for cryo treatment..other than from companies involved in cryo.

Mike Stewart
08-12-2004, 06:06 PM
Over the years I have used a number of steels and all have had noticable benifit from Cryo-Treating.

I have used 1095,5160, 440A, 12C27,440C,52-100,0170-6, 154CM,S30V and A-2.

In side by side tests all the blades performed at a higher level of edge retention and lateral strength with the process.

Mike.........

mete
09-10-2004, 05:44 PM
" cryogenically treating since 1987" ? that makes me feel 1000 years old. In the old days we called it subzero quench or treatment. Since Roger already quoted me I'll stand by my comment that 10 hours is more than enough.Much of cryo is nonsense ,at this point in time cryo has been proven to reduce retained austenite anything else is still conjecture . There is a research paper that talks about eta carbides and that has been quoted by many cryo companies who imply many things. If we are looking at edge retention and wear resistance we have the large carbides that haven't been dissolved in austenitizing [high carbon steels], smaller carbides from tempering martensite and still smaller eta carbides from cryo. Obviously the larger carbides will have a greater effect on wear. The existance and effect on eta still is in question. ......The use of cryo to make up for poor hardening is certainly not recommended - do it right the first time. Improper austenitizing will produce more retained austenite which cryo will reduce ,but do it right the first time.

Mike Stewart
09-14-2004, 01:14 AM
Mete,

Good to see you have been doing the process that long. In the OLD days we all did sub-zero quench. I still do a sub-zero quench. I also do a 24 hour after the third temper and after the blades are ground.( I grind hard). I don't need to have a bunch of Cryo salesmen tell me anything and I agree with you that the guys who sell the service and the equipment imply a lot. I ask them nothing and just tell them what I want done. My favotire was the guy who told me that he was going to ultrasonically -magneto -wave length migrate my carbides. I'm just not sure how much snake oil is needed for that process. All I know is that my blades are stronger and hold an edge better the way I have them processed. That's really all I need to know.

Thanks,

Mike........

mark23
09-21-2004, 12:10 PM
... My favotire was the guy who told me that he was going to ultrasonically -magneto -wave length migrate my carbides. I'm just not sure how much snake oil is needed for that process. All I know is that my blades are stronger and hold an edge better the way I have them processed. That's really all I need to know.

Thanks,

Mike........

Mike, in case you have your knives processed this way, can you give further information on the "ultrasonically-magneto-wave length migration" of carbides? Do you happen to know whom to ask for further information?

Thanks!

Best regards

Mark23