cryogenics for the home shop?

Smallshop

KNIFE MAKER
Okay....So I've tried to gain some knowledge on this technique and it is hard to determine how much is witchcraft and how much is science. I'm not going to ask what folks think about the necessity since some of the steel manufacturers recommend it as part of the steel treatment process for certain steels.

My questions are:

What do you use? Liquid nitrogen, Dry ice with which liquid, what?

What temps can you achieve? How have you calibrated or determined that you are actually there?

Shouldn't ramp to temp be an issue? or is just getting it to temp enough? Soak times? Some guys leave blade in cryo for a long time, even overnight? Okay? Damaging? Lessen hardness? or once the structures been affected doesn't really matter?

How do you store/handle your materials? How long do they last? Where do you get them?

What steels do you find really benefit by this. Sometimes the steel manufacturer just says to cryo to a temp. But when? before temper(s) in between 1st and second temper? It does seem that some of the steels that want cryo also need two or more tempers?

Thanks for any thoughts you have on this.

Ted
 
seems to be needed most for high alloyed and/or stainless like your cpm's, d-2, 440C. it seems that low alloyed tool steel(01, 1084,L6) may show improvements but usually means original HT wasn't controlled right. will find my links to articles in Industrial Heating that talked on the subject. best results came from ramping and soaking, probably a 4 to 6 hour operation. the end of each article had the same conclusion, yes we gained 1 to 2 Rc numbers, but was it really worth the headaches.
 
Thanks Scott. My questions are kind of geared towards trying it. But if at the home shop level it is really only a placebo why bother? But, many makers do it and can tell a difference on some steels. On the technical side I would think the lack of control over ramp, the relaxed soak time, and the high temp of dry ice (-70F?) would all be a concern. Kevin C made a distinction between cold treatments (Which may be what most makers are really doing?) and Cryo as far as what is really happening to the metal. Cryo is seemingly a wonderland of theory right now.

Sometimes when you are bouncing around on the internet getting facts to line up to make a determination is difficult which is why I'm asking all my questions here.
 
Ted, you are probably wise about not getting too much into the necessity or science vs. witchcraft (although I would replace that word with “marketing”), as it rarely settles the matter with most folks. However, most of your questions are tied to the necessity part of the topic.

The trouble is that one needs to separate the effects into two categories. Those that are definitively established, understood and explained. And then the effects that are controversial, not entirely understood or the jury is still out on.

On the former- yes it is worth it, and it does make a difference, but that mostly depends on the steel you are using. As we have recently discussed in other threads when you harden a piece of steel you heat it a temperature at which the carbides will begin to dissolve and fill the iron matrix with carbon atoms that will make a new, hard phase of steel when the carbon atoms are trapped there during the quench. The soft, hot phase where you have dissolved the carbide is called austenite and it has an atomic arrangement that only wants to occur at high temperature, not room temp. When you quench the steel that arrangement will want to change to a new one and this is what traps the carbon and makes hardened steel.

But, here is the catch, you only want enough trapped atoms to make the steel hard and not enough to reinforce the austenite’s atomic stacking so that it becomes stable, because then you would have hardened steel mixed with the very soft austenite phase that remains at room temperature. There are two major culprits in this reinforcing effect, carbon in excess of.8% and many of the alloying elements, nickel or chrome being two of the biggest. If the austenite becomes stable, the answer is to keep cooling the steel below room temperature until the rest of the austenite is transformed. This is what the freezing cold treatment definitively do they convert retained austenite.

So if you are working with steels that have no alloying like chrome or nickel, all you have to worry about is carbon in excess of .8%, and this is what the recommended hardening (austenitizing) temperatures are for, they are designed to get just enough carbon into solution for full hardness without putting enough into solution to stabilize austenite. If you notice a gain in Rockwell with a 1095, W2, or 52100 blade from cold treatment, you can save all your effort and money that would be spent on the cold stuff and simply keep your hardening temperature in the proper range.

If, however, you are working with steel that has alloying that is higher, like stainless or semi-stainless steels, then you are going to have retained austenite regardless of how carefully you heat it, since these atoms are going to reinforce the stacking anyhow. These steels will almost always benefit from some cold treatment to some degree, and that is why you get those manufacturing recommendations.

Now there are a lot of those other claims about cryo that is based upon the idea of precipitation of special carbides and other such that could affect abrasion resistance, but the science is still out on that. One of the main problems is that the vast majority of the research on it has been done or sponsored by folks who are already making money from the process, which technically makes it advertising rather than legitimate research.

How long should you freeze it? That is an interesting question that is based on if you are looking at retained austenite or of you are looking to explore some of the other claims. The other claims normally involve intricate soaks and ramp times that require very specialized equipment that only the guys selling the service have, another red flag in my opinion. But retained austenite is much simpler. The austenite to martensite (hardened steel) transformation is very quick, in fact it occurs at the speed of sound, and it is driven solely by temperature, not by time. Other transformations require time for the carbon atoms to move through the matrix, but since you are trapping the carbon atoms right where they are time isn’t a factor. When you super cool a piece of austenitic steel the strain from the cooling action drives the transformation, if you stop the cooling the transformation stops as it doesn’t care about time, only the temperature. So if you want to convert retained austenite with cold all that is required is that you achieve the target temperature throughout, at the given temperature the conversion will be complete, you may need to go colder if it is not complete, but the time is irrelevant to zapping retained austenite.

Retained austenite can also be converted by tempering. The precipitation of tempering carbides will destabilize the matrix and it will transform to something else. It is that “something else” that can be worrisome because you want martensite. So the guys that I know, who really know their stuff in industry, recommend not going to a full temper before cryo, but instead do a low temperature stabilizing temperature (around 300F-350F) first to keep the cold shock effects down.
 
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Thanks Kevin. A lot of new info for me there.

Below is one of the steels that is available from AKS as a "for instance". The carbon is below 8.0% but has a lot of Chromium. The AKS folks recommends a cryo of -95F degrees. My question here is can I do this at home? Are they over stating the need for cryo? would -20 be enough? After quenching should you do a quick low heat temper on this one? Now, the data below is what AKS puts out yet it differs a bit from the mfg data sheet (see attachment View attachment 14C28N-DS.pdf) as far as Cryo requirements.

It seems on ANY steel I search, heat treat methods are very subjective among different craftsmen and different material suppliers. Almost as if guys sneak up on a method that gives them what they think is ideal even though it may vary from MFG recommendations. What's tough on us new guys is learning how to interpret the variance in methodology. At the back of my thinking I get the nagging suspicion that many guys are not getting exactly the results they think they are yet are making very good blades. Proved out by their personal testing. And confidently repeated by consistent methodology. (I am specifically referring to heat treating not blade design or forging technique)

I am using this steel as an example because it and AEB-L are very similar, reasonable and available. I have decided to begin my knife making joyride with a folder and a steel like this one seems very suitable. Smaller blades are cheaper and the mechanics of a folder are not worrisome to me as much as heat treating a good blade is.(or...I'd rather not be scrapping full tang chef's knives )I would like to use a stainless for the obvious aesthetic reasons.But if -95 is really a do-or-die I don't think I could pull that off. Yet once again the mfg data sheet doesn't mention -95......

While some of you are artists when it comes to understanding the alloying materials and amounts, many of us are merely painting by numbers. We can't look at % and alloy content and see the interplay enough to know what we would change in process to give us a little better result than even the mfg has devised.

I plan on learning what manganese or phosphorus or silicon does and why nitrogen reduces the formation of Chromium carbides, etc. But before I have that all figured out I can still make excellent blades by following in others footsteps...no?

I'm probably not even making a good "for instance" here but trying to apply good advice to different materials is difficult (for me).






Tbl--Elements.gif
Tbl-14C28N.gif
Tbl-13C26.gif
Tbl-AEBL.gif

Kershaw asked Sandvik to develop an alternative to 13C26 with better corrosion resistance. 14C28N is the result. Kershaw was the exclusive buyer of the steel for a few years. Now it is available to everyone.
The primary difference between 13C26 and 14C28N is the addition of more chromium and a small amount of nitrogen. The changes result in a steel that has no chromium carbides like AEB-L/13C26, but better corrosion resistance. This steel gets very hard, has excellent edge stability and corrosion resistance.
13C26 and AEB-L are shown in the table above for comparison purposes.
Data Sheets:

Heat Treating Information:
Preheat: Heat to 1560° and equalize.
1920°F Austenitize: Ramp to 1920°F and hold at temperature for 15 minutes. Oil or plate or air quench as quickly as possible.
1975°F Austenitize: Ramp to 1975°F and hold at temperature for 5 minutes. Oil or plate or air quench as quickly as possible.
Cryogenic Treating: To get the most from 14C28N you must cryo. Cool to -95 °F. No soak is required.
Temper: Temper immediately after hardeneing or cryo. Temper at least 2 times for two hours each time. Use the table below to achieve desired hardness.
AEBL-TC.gif

 
I can't pretend to even come close to Kevin C's knowledge of heat treating. In any matter where we disagree, I would go with his opinion with out hesitation over mine.

I can offer some comments from my own experience:

I did quite a bit of research and experimentation on this several years ago. My thought was cryo treatment was hooey and hucksterism and I was determined to prove that. Boy was I wrong -- in the case of stainless knife steels.

In my opinion, it is worth doing and there is a definite performance improvement on many (not all) steels by soaking in liquid nitrogen for at least 8 hours. Alternatively, you can soak in RV antifreeze/dry ice for 8 hours and see nearly as much improvement. It's been kicked around for years to soak in acetone/dry ice. I find acetone too flammable for my comfort so I suggest RV antifreeze. The nontoxic kind of antifreeze if there are pets around.

I did some cutting and hardness tests on stainless and high carbon steel with and with out cryo (liquid nitrogen).
I see an average of 1.5HRC jump in nearly any stainless steel.
I saw only occasional lift in HRC on "simple" carbon steels and that I attribute to poor quenching technique on my part.

in stainless steel I thought I saw finer grains but that was subjective and I probably didn't.
in cutting tests with stainless, I saw at least a 20% improvement in edge retention. These weren't blind cutting tests so it's likely some confirmation bias slipped into my testing but I do recall the difference was clearly noticeable.

in any stainless knife that I make that I know edge retention matters (and what knife doesn't?), I would absolutely cryo treat it.
in any carbon knife, I would make sure I understand the heat treating basics and quench that steel likes and do it right that way and I would probably not cryo it.
 
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Liquid Nitrogen runs around minus 280F, dry ice runs around minus 90-95. The actual temps for both are slightly colder but transfer temps are slightly warmer.

All the data I read (a long time ago) suggested the benefits of cryo treatment starts at minus 100. The minus 100 was more or less a nice round number to use in "research data" so the minus 95 or dry ice is right there. The data suggested colder than minus 100 gave some additional improvement but not all that much.

Eight hours at temp was the most commonly referenced soak time.
 
Smallshop,
This is not a area of my expertise or to put it in plain speak, I don't know S&*T about how to apply a Cryo treatment properly.

However I do know the benefits as I have been having all of my Air hardening stainless steels Hted to my requests by Paul Bos Heating in the Buck knives company for over 15 years. The man that runs it currently is Paul Farner."? spelling on last name?" This man know's how cryo is applied for our cutlery applications. He has always been very polite, and has called me if their was any concerns on my order.

I have great respect for Kevin & Bossdog and If I was trying to duplicate Liquid cryo at my shop with Dry Ice etc for my knives Paul Farner would be the man I would call to tell me if it was feasible or was I wasting my time? If you call and leave a message for him at Buck knives in Idaho I am sure he has a few minutes to share with you.

1800.326.2825
660 South Lochsa Street
Post Falls, ID 83854-5200

By the way, A great comparison would be to have Paul Bos Ht & Cryo a few of your knives and then see if you could do the same at your shop?
 
I thought about bringing Paul Bos up but didn't, however now that it's in the thread...

During my research on this, I called and talked to Paul about cryo.

He had obviously answered the same question about a million times but was gracious and polite and his answer basically was: "It's worth doing for stainless steels or I wouldn't do it. The steel picks up about a point in hardness and we anneal back to 59 or what ever the customer asks for. "
 
Thanks guys! Tracy, those temps are real helpful.

Do any of you use liquid nitrogen? Is it practical on a small scale? $$/storage/use? It seems as if dry ice is on the edge for actual "cryo" yet I think Kevin is saying there is still much benefit doing cold treatment on the stainless steels. So I'm guessing that dry ice is more than adequate to provide some improvement in changing stack up. I have commercial freezers that go to -20F. I wonder how much that would help after HT and before temper(s)?

Still it would be nice to be able to be overkill on the cryo stuff as I haven't seen any warnings about "too cold" or "too long". I have done more reading the last month on tech stuff than I have in years....and I still feel like I'm failing the course! LOL.....

I'm not worried about implementation as I understand how to weed out/minimize variables. production machining is highly dependent on killing variables and it becomes second nature for any shop rat that wants to survive. With heat treating it seems that much wrong info abounds and that some of it is just truly subjective.


It is probably a blessing that Paragon is taking their sweet time to build my furnace. I'm learning by reading rather than by the scrap bin (I'm sure I'll learn a bit there also!)

Thanks for all the info being shared here!

Ted
 
I can't pretend to even come close to Kevin C's knowledge of heat treating. In any matter where we disagree, I would go with his opinion with out hesitation over mine...

No disagreement at all Tracy, your results are exactly what I have seen as well. Nickel or chrome, are huge substitutional atoms, particularly nickel, that result in outrageous distortion of the lattice. In enough volume the effects on austenite stabilization is unavoidable and undeniable. With M-90%+ (what used to be called Mf) pushed that far below room temp, freezing the stuff is the only way to get a fully hard blade. Simpler steels lacking the substitutional alloying should see a lot less dramatic benefit from it with the effects decreasing even more as you drop to .8% carbon or less and eventually negligible with lower carbon contents and tighter heating controls. Nothing is 100% and any steel will have some retained austenite but the simpler steels should be able to keep it below 6%-8% if the heat treating parameters are all good and tight. If the austenitizing heat drifts a little high, retained austenite will increase, as it will if soak time goes a little long, although the heat is much more critical.

If retained austenite in the alloyed stuff reaches greater amounts, like 20%, one could see different effects in the fractured grain appearance as the slip/shear involved fracturing makes a rougher look. Converting this to martensite would result in a finer appearance. But since grain size is based on prior austenite grain, it is beyond the scope of any cold treatment to actually refine grain as that is determined by the austenitizing heat alone.

There is no question that cold and cryo treatments are invaluable in zapping retained austenite, and I even do not dismiss the other possibilities out of hand, I just think some of the theories need better substantiation before I can accept them as fact. Some of the folks selling cryo have shot themselves in the foot with the pyramid power type claims they have made regarding the panacea effects of freezing everything from speaker wires to women’s stockings. But I find the improved lattice/super-lattice theories very intriguing and not impossible. I have reviewed a lot of the stuff about eta carbide precipitation, and the problem I have with it is that back in 2000 I had the opportunity to discuss it, over a pleasant dinner, with a well-known PhD who did some of the ground breaking work in that area. He simply shook his head and laughed at the way some of his work has been used in cryo marketing, and gave me some insights about the realities of those precipitates. This was not an isolated incident. I have been privileged to know some of the best in the metallurgy field, and the top guys, who are not involved in selling cryo, range from being cautiously dubious to calling many claims “snake oil”. However, none of them have any doubts that the effects on retained austenite are proven and quite beneficial.
 
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Liquid nitrogen is for is for sale at any welding gas supply store. I have 30liter dewar I bought used on eBay some time ago for a couple hundred bucks. There are probably dozens of used dewars for,sale on eBay at any time currently but the prices have about doubled in the last ten years. Knifemakers keep buying them so they keep the prices higher than they used to be. I would buy a 20liter today if I had to do it over. The stuff will last from 5 weeks to 8 weeks depending on how well your dewar holds temps. Every time I buy it they charge me a different price but it averages around $75 to fill my dewar.
-100F is the threshold for minimum temperature researched and proven austenite to martinsite, at least to my memory, of what was demonstrated to be effective. -20 might do something and it can't hurt but you would need to test it yourself by measuring the hardness in a side by side test.

Many Knife makers in Scandinavia routinely put their knife blade outside (in the winter) overnight as part of their heat treat regimen. Many old time custom makers put theirs in the freezer over night. That practice has largely been replaced with dry ice or liquid N.

Thanks guys! Tracy, those temps are real helpful.

Do any of you use liquid nitrogen? Is it practical on a small scale? $$/storage/use? It seems as if dry ice is on the edge for actual "cryo" yet I think Kevin is saying there is still much benefit doing cold treatment on the stainless steels. So I'm guessing that dry ice is more than adequate to provide some improvement in changing stack up. ...

Ted
 
Ted,
here a link that has more links.
http://www.industrialheating.com/articles/91311-the-deep-cryogenic-treatment-question. the magazine is pretty good, you can subscribe free.
IMHO, I would get more bang for the buck putting the money($300 will get you a used 5 liter dewar) into another thermocouple and good controller or a seperate kiln for tempering

Scott,
Thank you for posting those links, I find that article very interesting and informative. I found that Yamaha doing DCT on their brass musical instruments very interesting.
 
I'll just agree with everyone else, that on high alloy steels it almost always gains a point or two - which of course, we temper back anyhow. I believe that it is probably beneficial and more importantly, generally meets the test of "do no harm".

I don't cryo simple tool or carbon steels.

I do cryo as a continuation of the quench for maximum effect. If someone sent me something really complex just begging for fractures, I'd probably flash temper first.

I have used both dry ice and liquid nitrogen. My choice of liquid nitrogen is based mostly on retention time - as Tracey mentioned 4 - 8 weeks - compared to dry ice at about 24 - 48 hours.

Check dairy operations and their suppliers for used dewars. Check their suppliers for Liquid nitrogen. Almost always cheaper than welding shops - and might even deliver to you.

As for ramp speed. you just dropped the blade temperature nearly 2000 degrees in 60 seconds in the quench plates. I doubt the rate is much different for the last few hundred degrees.

I believe cryo can be done to good effect in the home shop and at reasonable cost. Home heat treat problems are going to come from your oven, long before they come from your cryo.

I'm going to be meeting Kevin Cashen in a few weeks. My mind is open. :biggrin:

Rob!
 
Thanks Scott. Here's another article from the same site that I thought was interesting for a couple of reasons.

http://www.industrialheating.com/ar...ogenic-treatment-on-properties-of-tool-steels

This second article as an almost "oh...by the way" states: " Tempering is a very important process in forming useful tool-steel properties because most have secondary-hardening capabilities. This is why all studies that deal with CT should also consider optimizing the tempering process." Which is what you have just suggested.(Less the "forget about Cryo" direction you are suggesting)

Okay, the first article addressed some of the questions that have been niggling at me. And exactly the direction that I have questioned. BUT....I'm not willing to throw out the baby with the bath water here (yet). So lets make a few observations on article 1.(which I also enjoyed) These are not necessarily good or bad or how I feel about what I read, just observations that could be pertinent to how I evaluate an article like that. I indulge myself in a combination of skepticism/sarcasm when re-reading something like this. Not as a means of being intentionally disrespectful, It's how I keep from letting myself get sucked into a frame of thought without challenging the assertions. (We all have some method of doing this or we'd buy everything every salesman ever tried to sell us.)

Author(s)/credentials/sources: One individual authored this. He is the president of a company that does Cryo treatments. Is he a scientist? Or a marketing genius that knows how to utilize his metallurgists to write cool articles? He listed a single source as support. Nothing too alarming here as this is more of an general article than a scientific brief. But the potential for bias is very high.

Ask why the article was written. Two things jump out to me there. First is, this article is damage control by a president of a cryo service company against some of the speculative claims made by industry peers/competetitors. Second is, there is very specific weight given to the importance of the one area the home guys cannot control...ramp time. Subtle message there is "don't waste your time" case for proof is wire treatment. Diagram makes special note of fact that many companies are now treating down to -450 degrees. more subtle message..."Not only can you not control the ever so important ramp time you also can't get it cold enough". Dispatching wild claims lends credence to the author's sense of only advancing truth, which would definitely make a person want to use that company to do their work.


Which statements seem top heavy or exaggerated?:
"Many researchers try to circumvent the timing of the process by immersing materials in liquid nitrogen or liquid helium. At best, there is no change in the performance of the material; at worst, there is catastrophic failure. Unfortunately, the results of these experiments are usually cited as proof that DCT does not work." If this statement were true darn near every blade that A knifemaker cryo'd on his own would fail. The thinness of the material we use coupled with the hardness we are attaining should almost always prove out on the "catastrophic failure" end of things. Yet this isn't so. Enough makers have gone through their own anecdotal testing observing favorable results to give credence to home treatments. If every time I eat bell peppers they disagree with me and my solution of not eating them makes my upset stomach go away. I don't need to find a more scientific reason why I shouldn't eat them. In a similar fashion, No knifemaker is going to routinely do home cryogenic treatments if he has a high degree of failure with no observable improvements "at best". Hopefully the cost, hassle, and lack of any discernible improvements would weed out the temptation to do this just to tell a customer, "Oh yes! It's been treated cryogenically!...."

In fact, rather than saying DCT doesn't work, most knifemakers say it does. This would lead me to question the importance of ramp time. ( I instinctively think that it matters, but, which of us are giving our knives 6-40 hours soak time in the furnace? Maybe heat and cold are apples and oranges when it comes to what matters) Since something is changing that is observable on the home shop front in direct opposition to the "At best, there is no change in the performance of the material" portion of his statement, I have to wonder if the ramp time issue is being overstated. It is interesting that in the second article, written by four authors, supported by multiple citation of other experts, no mention of ramp time is mentioned in their testing.( I question these guys as to how scientific they were also, though)



Here's another claim that absolutely has my BS meter clanging like a fire alarm:
"Another item holding DCT back is that it is rarely taught in colleges and universities. It is not unusual for metallurgists to state that they have never heard of the process. And again, many are sure that it is just cold treating using colder temperatures and then try to explain it will do nothing." So let me get this straight....This "hidden" technique that I first heard about in trade school 38 years ago is still not being addressed at the university level. And, the droves of metallurgical engineers coming from these myopic universities, who generally are very fact/science driven, have collectively been able to turn a blind eye for the better part of their careers to one of the important exciting areas of advancement in their field. Thank goodness for knife makers as apparently they are carrying the torch of metallurgical discovery forward for the next generation.(actually, sarcasm aside, I think this is true in the area of forging...especially the Damascus stuff.) Then when I read a statement like the above one I ask, how many metallurgists did you survey? How many universities did you contact about course content? How many tried to explain to you that DCT will do nothing?

I did like the article. He went after the key point that I have been puzzling over but that only means I need to be cautious to not internally think, "Yep, an expert agreed with my guess. Must all be smoke and mirrors....".

I would like to hear what Kevin C. thought about that article.

Sorry for the philibuster....coffee and keyboards don't mix....:biggrin:
 
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I was involved in the conversation where one very qualified metallurgist called some claims “snake oil” to the consternation of the author of that article you linked to Scott. In the spirit of full disclosure I would mention that the author of that article stated that the reason he was defensive about the criticism was that he made his living off from doing cryo. This is not to say that he is not an honest guy, just that all of us have our biases and they can creep into our objectivity at any point without our even realizing it, and they can be very pervasive when our livelihood is on the line.

...I'm going to be meeting Kevin Cashen in a few weeks. My mind is open. :biggrin:

Rob!

Rob, I am in such a total Blade Show mode right now I keep forgetting that the very next weekend I will be up with you folks in Alberta. I look forward to seeing you there and chatting about whatever you would like. I will probably be preparing some of my lectures on my way to and back from Atlanta. Fortunately I have a heat treating Power Point that is already in Celsius from a talk I did in Quebec last year.:3:
 
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