What is retained austenite? How does martensite form?

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Larrin

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After the recent thread on cryogenic processing, I thought I would give a short description of what retained austenite is. Retained austenite cannot be understood without explaining how martensite forms.

First, at room temperature annealed steel we have ferrite and carbides. Ferrite is a crystal structure call Body Centered Cubic (BCC). This is a description of the repeating arrangement of atoms, here primarily iron atoms. Above the austenite transformation temperature the ferrite transforms to austenite. The austenite crystal structure in Face Centered Cubic (FCC). You can see the unit cells for BCC and FCC here (Edit: this image only shows austenite with extra atoms on three of the cube faces, but there are atoms on all six faces)

Picture1.png


Unit cells are the smallest possible graphical representation of the crystal structure. For brevity I won't describe the process whereby ferrite transforms to austenite. The image above also has a phase diagram showing temperature vs carbon content. Alpha is ferrite, gamma is austenite, and Fe3C is the cementite, or carbides.

Heating the steel to austenite is called austenitizing, and it the first primary step when hardening steel. Also during this step some (or all) of the carbides dissolve and carbon becomes part of the crystal structure. Because carbon atoms are much smaller than iron atoms, the carbon atoms fit into the gaps in the iron atoms. These small atoms are called interstitial atoms:

fetch.php


Here is a diagram of where we are at the austenitizing temperature:

24phzxg.gif


At this point we have austenite with carbon dissolved into it. If we cooled slowly from here the carbon would have time to diffuse and we would get ferrite and carbides again. If we cool quickly, however, the carbon doesn't have time to diffuse and it is "locked in." Then we have a situation where at low temperature the steel wants to be ferrite but we have carbon trapped into interstitial sites. This leads to the formation of martensite. Martensite is Body Centered Tetragonal (BCT) as opposed to BCC ferrite. The reason it is tetragonal is because the carbon strains the lattice in one direction more than the other which elongates the unit cell. The high strength of martensite comes because of this strained lattice. This can be seen in the following image:

3_1.jpg


The "Bain model" is FCC austenite with carbon interstitial atoms in it, which then transforms to BCT martensite on cooling.

Because martensite transforms on fast cooling it is a diffusionless transformation. So the transformation occurs through displacement of the existing austenite atoms rather than through a rearrangement of those atoms. So martensite atoms always maintain a relationship with the parent austenite:

Picture22.png


Therefore at grain boundaries where the atomic arrangement is no longer regular the martensite can no longer grow. Martensite plates/laths are limited in size by the original grain size of the austenite, where here martensite is the black ovals:

Picture25.png


So back to our earlier diagram here is where we are currently after cooling to some temperature below Martensite start (Ms):

ets6d4.gif


Which hopefully has brought us a little closer to explaining retained austenite. These martensite plates grow very rapidly, so their formation is controlled almost entirely by temperature. The lower the temperature below Ms the more martensite we form. The plates form and stop growing when they hit another martensite plate or an austenite grain boundary. Therefore we would expect the largest plates to form first and smaller plates to form later. The more plates that form the smaller are the gaps between plates, these gaps being retained austenite.

So why cryo then? The martensite start (Ms) and martensite finish (Mf) temperatures are related, and those temperatures are controlled by various alloying elements, including carbon and chromium. Higher carbon reduces the Ms and Mf temperatures, until the Mf temperature can be lower than room temperature. You can see this in the following two images:

3_2.jpg

ih0409-mct-fig7-lg.gif


The first image shows hardness vs carbon content in martensitic steel, with hardness increasing with carbon content. At high carbon, though, you see two diverging lines. One line is the hardness going down and one has hardness going up. The line with hardness still increasing is with the use of cryo to convert retained austenite to martensite. The second image shows retained austenite fraction with carbon. Where you can see that retained austenite increases with increasing carbon. Since kitchen knife steels are high in carbon (just look at White #1) we would expect there to be retained austenite without cryo. Again, this is because the Mf temperature has been reduced below room temperature. Other alloys such as chromium also reduce the Mf temperature.

Here is an awesome video of martensite formation:

[video=youtube;OQ5lVjYssko]https://www.youtube.com/watch?v=OQ5lVjYssko[/video]

Is retained austenite bad? No. However, as you can see from the hardness vs carbon plot above, retained austenite does reduce hardness. That's because austenite is lower strength than martensite. However, austenite is also a much tougher and more ductile phase than martensite, so steels with retained austenite exhibit greater toughness than steels that are fully martensitic.

I hope this all makes sense and it's too long winded.
 
Awesome Larrin! Thanks for the explanation - that was very straight forward and easy to follow.
 
Thanks for taking the time to write that up, really interesting
 
I need to re-read this at least another couple of times to fully soak in the details but I want to thank you for taking the time to make such an awesome post.

I'm moving this to the Knowledge section so that it doesn't get pushed away into oblivion.
 
Great write up. Makes me want to go out and start smelting some dirt. JK wouldn't know were to start.
 
Great stuff. Love the video. All that is missing now to understand heat treatment is what tempering does to the material structure...
 
DUDE!!!! Fantastic post.

You explained a lot of high-level science in a way that was possible for us enthusiastic lay-persons to understand.

It answered a lot of questions as to the "why" and "what's actually happening" that I've had ever since learning about the concept of heat treating steel.

Thanks for taking the time to put that together!
 
Thank you for all the positive feedback. I look forward to any questions.
 
How can I cite these fascinating information? is there any book or paper in this regards?
Thanks


After the recent thread on cryogenic processing, I thought I would give a short description of what retained austenite is. Retained austenite cannot be understood without explaining how martensite forms.

First, at room temperature annealed steel we have ferrite and carbides. Ferrite is a crystal structure call Body Centered Cubic (BCC). This is a description of the repeating arrangement of atoms, here primarily iron atoms. Above the austenite transformation temperature the ferrite transforms to austenite. The austenite crystal structure in Face Centered Cubic (FCC). You can see the unit cells for BCC and FCC here (Edit: this image only shows austenite with extra atoms on three of the cube faces, but there are atoms on all six faces)

Picture1.png


Unit cells are the smallest possible graphical representation of the crystal structure. For brevity I won't describe the process whereby ferrite transforms to austenite. The image above also has a phase diagram showing temperature vs carbon content. Alpha is ferrite, gamma is austenite, and Fe3C is the cementite, or carbides.

Heating the steel to austenite is called austenitizing, and it the first primary step when hardening steel. Also during this step some (or all) of the carbides dissolve and carbon becomes part of the crystal structure. Because carbon atoms are much smaller than iron atoms, the carbon atoms fit into the gaps in the iron atoms. These small atoms are called interstitial atoms:

fetch.php


Here is a diagram of where we are at the austenitizing temperature:

24phzxg.gif


At this point we have austenite with carbon dissolved into it. If we cooled slowly from here the carbon would have time to diffuse and we would get ferrite and carbides again. If we cool quickly, however, the carbon doesn't have time to diffuse and it is "locked in." Then we have a situation where at low temperature the steel wants to be ferrite but we have carbon trapped into interstitial sites. This leads to the formation of martensite. Martensite is Body Centered Tetragonal (BCT) as opposed to BCC ferrite. The reason it is tetragonal is because the carbon strains the lattice in one direction more than the other which elongates the unit cell. The high strength of martensite comes because of this strained lattice. This can be seen in the following image:

3_1.jpg


The "Bain model" is FCC austenite with carbon interstitial atoms in it, which then transforms to BCT martensite on cooling.

Because martensite transforms on fast cooling it is a diffusionless transformation. So the transformation occurs through displacement of the existing austenite atoms rather than through a rearrangement of those atoms. So martensite atoms always maintain a relationship with the parent austenite:

Picture22.png


Therefore at grain boundaries where the atomic arrangement is no longer regular the martensite can no longer grow. Martensite plates/laths are limited in size by the original grain size of the austenite, where here martensite is the black ovals:

Picture25.png


So back to our earlier diagram here is where we are currently after cooling to some temperature below Martensite start (Ms):

ets6d4.gif


Which hopefully has brought us a little closer to explaining retained austenite. These martensite plates grow very rapidly, so their formation is controlled almost entirely by temperature. The lower the temperature below Ms the more martensite we form. The plates form and stop growing when they hit another martensite plate or an austenite grain boundary. Therefore we would expect the largest plates to form first and smaller plates to form later. The more plates that form the smaller are the gaps between plates, these gaps being retained austenite.

So why cryo then? The martensite start (Ms) and martensite finish (Mf) temperatures are related, and those temperatures are controlled by various alloying elements, including carbon and chromium. Higher carbon reduces the Ms and Mf temperatures, until the Mf temperature can be lower than room temperature. You can see this in the following two images:

3_2.jpg

ih0409-mct-fig7-lg.gif


The first image shows hardness vs carbon content in martensitic steel, with hardness increasing with carbon content. At high carbon, though, you see two diverging lines. One line is the hardness going down and one has hardness going up. The line with hardness still increasing is with the use of cryo to convert retained austenite to martensite. The second image shows retained austenite fraction with carbon. Where you can see that retained austenite increases with increasing carbon. Since kitchen knife steels are high in carbon (just look at White #1) we would expect there to be retained austenite without cryo. Again, this is because the Mf temperature has been reduced below room temperature. Other alloys such as chromium also reduce the Mf temperature.

Here is an awesome video of martensite formation:

[video=youtube;OQ5lVjYssko]https://www.youtube.com/watch?v=OQ5lVjYssko[/video]

Is retained austenite bad? No. However, as you can see from the hardness vs carbon plot above, retained austenite does reduce hardness. That's because austenite is lower strength than martensite. However, austenite is also a much tougher and more ductile phase than martensite, so steels with retained austenite exhibit greater toughness than steels that are fully martensitic.

I hope this all makes sense and it's too long winded.
 
You can find it in a material science and engineering book.
 
This is a great post! Excellent Cliffs Notes of some very complex concepts that allows a dummy like me to generally conceptualize how/why/what occurs during the smithing process that transforms a piece of iron alloy into the knife steels that we obsess over. Understanding the science behind the art is definitely something I envy!
Either way, lots here, and if anyone, without a background in molecular chemistry/geometry and calculus based physics, pretends to fully understand the referenced crystalline structures and concluding model outputs, well...
 
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