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Hegi
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[*] posted on 10-7-2019 at 08:15
Mechanochemistry - is it a way?


Dear members of SM,

I´ve been wondering lately if anyone of you has ever come into contact with mechanochemistry? :) I have been working in this field since 2016 and I find it highly innovative and green technique. We used solid-state ball milling for successful synthesis of many oxides and sulfides (mostly naturally also occurring in a form of minerals). Especially sulfides can be used for photovoltaic and thermoelectric applications due to their electrical and optical properties. Our group has published several papers in CC journals lately. To mention a few of compounds we prepared directly from elements:

mohite - Cu2SnS3
stannite - Cu2FeSnS4
kesterite - Cu2ZnSnS4
mawsonite - Cu6Fe2SnS8
colusite - Cu26V2Sn6S32

There are much more examples of mechanochemistry being utilized also for organic reactions, reductions, alloy formation and so on... there are many types of milling equipment available (plantery mills, shaker mills, vibratory mills, different materials of chambers and milling balls - WC, SiO2, ZrO2, steel, plastics..)

I started project last year with couple of my friends and now we are finishing our prototype of low-cost mixer mill which we are willing to use for inorganic halide perovskite nanodots synthesis. I am attaching few schemes from software (I do not have photo of actual prototype in my PC yet). We are now looking for some programmer to help with electronic part (should be ARDUINO based). Anyone willing to contribute to this project will be rewarded by authorship on very first paper .)

Also, if anyone has any experience in this field I would be glad to discuss it. I think there should exist topic on mechanochemistry on SM.



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MrHomeScientist
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[*] posted on 10-7-2019 at 08:26


Interesting, I hadn't heard of that field. So you simply mill together mixtures of powdered elements in the correct ratios, and it forms those compounds? How do you confirm that a reaction happened?
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[*] posted on 10-7-2019 at 08:48


Quote: Originally posted by MrHomeScientist  
Interesting, I hadn't heard of that field. So you simply mill together mixtures of powdered elements in the correct ratios, and it forms those compounds? How do you confirm that a reaction happened?


Dear MrHomeScientist,

thanks for your question. Actually, it is not that straightforward process. It all depends on thermal parameters of proposed reactions. Mostly these reactions run through more steps - firstly binary sulfides are formed and then they react together to form more complex. In most cases you can follow the mechanism by measuring XRD patterns for mixtures milled for different times (check out attached figure). Raman spectra can be helpful as well. In the end, the only mineral we did not prepare successfully was tetrahedrite - Cu12Sb4S13 but its synthesis by solid-state approach was published. So conditions play a key role here (RPMs, volume of chamber, material, time).

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[*] posted on 10-7-2019 at 10:07


Very cool, thanks for the info. What is the advantage of this method? Are these compounds difficult to make with other routes, like aqueous chemistry?
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[*] posted on 10-7-2019 at 13:02


Awesome! I've been trying to set up a ball mill of my own lately, actually. I'm trying to make a (novel) hydraulic cement, and I want to mill the powder to be finer. For a cementitious mixture the literature seems to indicate I want a particle size of about 50 um.

I've tried a couple of different variations on a "rolling can" technique where the ball mill is just a can that rolls on the ground, but it turns out to be nearly impossible to control the can (it turns/flips/catches the strings pulling it), so I need a different approach.

So do you have any experience setting up a cheap ball milling setup with minimal materials? Is it more practical just to buy one -- and which one?




[Edited on 04-20-1969 by clearly_not_atara]
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[*] posted on 10-7-2019 at 18:21


There is actually quite a bit published in the organic field related to reaction run by grinding reactants in a mortar and pestal. It seems that much of this type of chemistry originates in India, at least that which I have stumbled on. I have run across quite a bit of it, some believable some not so much. I have not seen any organic chemistry run in a ball mill but that is not something I seek out - it could well be out there.

In any event, mechanochemistry is an interesting area. Thanks for bringing up the topic.

AvB
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[*] posted on 10-7-2019 at 20:50


Quote: Originally posted by MrHomeScientist  
Very cool, thanks for the info. What is the advantage of this method? Are these compounds difficult to make with other routes, like aqueous chemistry?


The main advantage is that you eliminate a need for using solvents (thus it is considered green chemistry). Also you do not need high temperature or pressure for synthesis. You can also induce formation of metastable polymorphs of compounds..




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[*] posted on 10-7-2019 at 21:03


Quote: Originally posted by clearly_not_atara  
Awesome! I've been trying to set up a ball mill of my own lately, actually. I'm trying to make a (novel) hydraulic cement, and I want to mill the powder to be finer. For a cementitious mixture the literature seems to indicate I want a particle size of about 50 um.

I've tried a couple of different variations on a "rolling can" technique where the ball mill is just a can that rolls on the ground, but it turns out to be nearly impossible to control the can (it turns/flips/catches the strings pulling it), so I need a different approach.

So do you have any experience setting up a cheap ball milling setup with minimal materials? Is it more practical just to buy one -- and which one?


Interesting idea. Even though I do not know anything about hydraulic cements.. I guess you can set up your own mill. Commercially available mills are generally expensive (thousands of euros). We spent approximately 1000 euros for the whole setup, which is still a lot. But in case you own Reciprocating Saw you can simply attach a jar with material and balls in it. It will have the same effect as a shaker mill.




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[*] posted on 11-7-2019 at 11:35


Quote: Originally posted by AvBaeyer  
There is actually quite a bit published in the organic field related to reaction run by grinding reactants in a mortar and pestal. It seems that much of this type of chemistry originates in India, at least that which I have stumbled on. I have run across quite a bit of it, some believable some not so much. I have not seen any organic chemistry run in a ball mill but that is not something I seek out - it could well be out there.

In any event, mechanochemistry is an interesting area. Thanks for bringing up the topic.

AvB


Yeah, that was the oldest technique used centuries ago and applicable also now. There are many examples of organic reactions run in ball mills. Just use correct keywords in Google search .)




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[*] posted on 11-7-2019 at 12:06


Very Interesting. I am curious what change different medias would have. For instance- attrition grinding, vs a ring and puck pulverizer, vs rod mill, vs even a SAG mill. If the reaction is caused by the energy of ball impact, then it stands to reason that other mills would do the same.



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[*] posted on 11-7-2019 at 15:44


Have you investigated combing ultrasound with ball milling (especially in damp mixtures, to possible assist in compound creation)?

The effect of ultrasound as an energy source which acts on water forming radicals, and therefrom other reactions are possible. For example, the formation of the hydrogen atom radical and the hydroxyl radical from water:

H2O ---Ultrasound--> .H + .OH

You may find my acidic radical thread of interest http://www.sciencemadness.org/talk/viewthread.php?tid=94166 .
----------------------------------

Caution: On ball milling transition and post-transition metals, the dust could be particularly problematic relating to lung disease (see, for example, "Generation of Hydroxyl Radicals from Dissolved Transition Metals in Surrogate Lung Fluid Solutions" by Edgar Vidrio, et al at http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2626252/ ).

I would recommend melatonin as a supplement to suppress undesirable REDOX chemistry in the body. To quote from a source (https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4657108/ ):

"The antioxidants within the body are composed of antioxidant enzyme defenses (Table 2) and additional antioxidant compounds such as melatonin and glutathione that are internally synthesized."

Also: "Melatonin is an endogenous antioxidant that plays an important role in protecting against free radical-induced oxidative damage [59]."

And reference [33] citation:

Poeggeler B., Saarela S., Reiter R. J., et al. Melatonin—a highly potent endogenous radical scavenger and electron donor: new aspects of the oxidation chemistry of this indole accessed in vitro. Annals of the New York Academy of Sciences. 1994;738:419–420.

[Edited on 12-7-2019 by AJKOER]
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[*] posted on 11-7-2019 at 16:12


I got interested in mechanochem a few months ago, and I could have sworn I downloaded a bunch of interesting stuff... I can only find this one on mechanochemistry of fullerenes, though.

Zhu, S.-E., Li, F., & Wang, G.-W. (2013). Mechanochemistry of fullerenes and related materials. Chemical Society Reviews, 42(18), 7535. https://doi.org/10.1039/c3cs35494f



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[*] posted on 12-7-2019 at 00:00


Nice! Hegi, do you have a good review on the topic?

Also we good have a chat about the programming part, I can write C++.
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[*] posted on 12-7-2019 at 21:39


Quote: Originally posted by Tsjerk  
Nice! Hegi, do you have a good review on the topic?

Also we good have a chat about the programming part, I can write C++.


There are good review by prof. Friscic from Canada and also prof. Balaz (Slovakia). I tried attaching it here but it does not work.




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[*] posted on 12-7-2019 at 23:50


Here´s the link for the video of the first reaction we performed in our mill. Check it out. MIXER MILL PROTOTYPE

You will see an explosion at some point. That´s exactly the point at which the elements reacted. This time it was copper and sulfur to form CuS.




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[*] posted on 9-8-2019 at 08:57


Just for your information.. one interesting link.

SUZUKI COUPLING - SOLID STATE




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[*] posted on 9-8-2019 at 14:52


Nice
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[*] posted on 10-8-2019 at 04:56


Quote: Originally posted by MrHomeScientist  
Interesting, I hadn't heard of that field. So you simply mill together mixtures of powdered elements in the correct ratios, and it forms those compounds? How do you confirm that a reaction happened?


MrHomeScientist:

You should be more of a reader of my threads!

A search on 'mechanochemical' under AJKOER returns 6 citations dating back to 2014 on this forum!!

[Edited on 10-8-2019 by AJKOER]
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[*] posted on 10-8-2019 at 15:56


Quote: Originally posted by AvBaeyer  
There is actually quite a bit published in the organic field related to reaction run by grinding reactants in a mortar and pestal. It seems that much of this type of chemistry originates in India, at least that which I have stumbled on. I have run across quite a bit of it, some believable some not so much. I have not seen any organic chemistry run in a ball mill but that is not something I seek out - it could well be out there.

In any event, mechanochemistry is an interesting area. Thanks for bringing up the topic.

AvB


There was a thread on here a few years back about making metal hydrides that way by ball-milling lithium in a hydrogen atmosphere.

Meltonium, I think, but I can't find it now.

I have heard a recipe for a solventless organic synthesis, but assumed it was total BS because it was for the dry reduction of ephedrine into meth, which really doesn't sound like a happening deal.

Sounded more like an incendiary than an organic reaction.

I got it from a big, twitchy biker-type with really bad psoriasis and inverted crucifix tattoos.

The (aqueous) purification/isolation step (standard acid/base deal for amines) was backward, so I assumed he was an idiot and it was all total fantasy stuff.




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[*] posted on 10-8-2019 at 22:37


In my undergrad advanced O-chem lab we did a mechanochemical Diels-Alder reaction by grinding anthracene-9-methanol and N-methylmaleimide. The reaction can also be performed by refluxing in water, with slightly better yields (at least when I did it). But "solventless organic synthesis" definitely works for some reactions. Not sure about ephedrine reduction, though.

[Edited on 2019-8-11 by Metacelsus]




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