Log in

View Full Version : Cobalt Oxide Coated Anodes


jpsmith123
December 6th, 2007, 05:21 PM
For the last few weeks I've been trying to make a cobalt oxide coated titanium anode for chlorate and perchlorate production; so far without much luck. (There is a detailed discussion about it at sciencemadness).

Most of my attempts so far have involved anodic electrodeposition from both cobalt (II) sulfate and acetate solutions. (If I get any good results I will post them here, since I know many people here may be interested).

The problem is that, regardless of how the surface is prepared, the product just doesn't seem to adhere very well. Most of the deposited material can be wiped off with a rag, and if that's not done beforehand, it seems to come off like slime after a short period of exposure to the salt brine.

Anyway, I'm wondering if anyone might have access to the following papers? These sound like they may have some useful information.

###################################

A new cobalt oxide electrodeposit bath for solar absorbers
Solar Energy Materials and Solar Cells, Volume 51, Issue 1, 1 February 1998, Pages 69-82
Enrique Barrera, Ignacio González and Tomás Viveros

A study was carried out in a Hull cell in order to optimize the deposition conditions of cobalt oxide (black cobalt) in an electrolytic bath, which uses cobalt nitrate for direct obtention of black cobalt. Thermal stability of the material was surveyed on several samples of black cobalt prepared on stainless-steel with a thickness of approximately of 2.5 μm. It was found that the optical properties change, in respect to the initial values, with time of treatment until an equlibrium is reached. This equilibrium depends on the substrate and the temperature of the treatment used.

################################################## ############################

Black cobalt solar absorber coatings
Solar Energy Materials, Volume 22, Issue 4, August 1991, Pages 293-302
S. John, N. Nagarani and S. Rajendran

A new electrolyte has been proposed for the deposition of black cobalt selective absorber coatings. These coatings are used in solar collectors for photothermal conversion of solar energy. We have studied the influence of electrolyte composition and operating parameters on the properties of the black cobalt coatings including optical (α, ε;) and electcical properties. Thermal stability and corrosion resistance tests showed good durability of black cobalt selective coatings for high temperature applications.

################################################## ################################

Preparation of selective surfaces of black cobalt by the sol-gel process
Renewable Energy, Volume 9, Issues 1-4, September-December 1996, Pages 733-736
E. C. Barrera, T. G. Viveros and U. Morales

Black cobalt, Co3O4, thin solid coatings on stainless steel and glass substrates have been prepared by the dip coating technique via the sol-gel route using a CoCl2 precursor. The coatings produced on substrates exhibit a blue to black colours as a function of the film thickness. Sols have been made from a cobalt acetate precursor 0.1 M, and for such conditions, the dip coating process gives 0.08–0.25 μm thick uniform films per dipping, depending on the viscocity of the sol.


################################################## #################################

Cobalt oxide thin films prepared by chemical vapor deposition from cobalt (II) acetate
Solar Energy Materials, Volume 23, Issue 1, November 1991, Pages 25-29
Toshiro Maruyama and Tsuyoshi Nakai

Cobalt oxide thin films were prepared by a low-temperature atmospheric-pressure chemical vapor deposition method. The raw material was cobalt (II) acetate which is non-toxic and easy to handle. Polycrystalline films were obtained at a reaction temperature above 300°C. From near-normal reflection measurements it follows that the films have solar absorptance α = 0.73 and thermal emittance ε = 0.089.

Bacon46
December 6th, 2007, 09:47 PM
I’m not an authority on plating but I don’t think Al or Ti are good substrates. For that reason those metals are usually painted, polished, brushed or anodized if anything other than a mill finish is desired.

The articles referenced in your post use stainless steel or glass as a substrate. In my opinion Type 316 and Nitronic 60 stainless steel would both be good candidates for this particular experiment. Both of these types of stainless steel are commonly used in the chemical industry where resistance to corrosion is the main concern.

jpsmith123
December 7th, 2007, 02:18 AM
Hello Bacon46,

I'm wondering, what makes you think that Ti is not a good substrate?

Thermiteisfun
December 7th, 2007, 10:34 AM
If you had to choose just one or two of those... What would it be?
The reason I'm asking is because a friend has access to the UF archives, I would not like to step on any toes

jpsmith123
December 7th, 2007, 11:20 AM
Thanks for the thought, but I just got them a little while ago.

I also posted the request on the sciencemadness forum and someone came through.

The two papers on electrodeposition look very promising.

Apparently, I was unknowingly quite close to the result I was looking for already.

If anyone is interested in any of these papers, let me know, and I will upload them here.

Bacon46
December 7th, 2007, 06:52 PM
Hello Bacon46,

I'm wondering, what makes you think that Ti is not a good substrate?

I have no reason based on science. I have seen many things plated with titanium nitride (drill bits etc.) but I just can't recall ever seeing titanium plated with another metal. Then again I may have held it in my hand and not known it.

I’m not saying that you can’t plate it, or that the titanium substrate is your problem. I was merely throwing it out there as a possibility, since you were having trouble and the articles in your post refer to stainless steel and glass as substrates.

I would be interested in reading the papers you have on this subject.

jpsmith123
December 7th, 2007, 07:04 PM
I should say that I've been able to plate cobalt metal onto titanium, and it looks like a million bucks; it's smooth and highly adherent. The trick is to either cathodically hydride the titanium for a few minutes at a modest current density, and then electroplate immediately thereafter.

I've also done it, as I recall, by putting a very thin TiO2 layer down by anodizing at a low voltage in 10% oxalic acid solution. I just got two papers that claim to have developed new electrolyte solutions that can plate out an adherent cobalt oxide layer. I'll upload them a little later.

Bacon46
December 7th, 2007, 09:44 PM
It took very little research to discover that Ti is the preferred substrate for plated chlorate anodes.

Open mouth insert foot!:o

I’m anxious to see your results. I’m getting tired of filtering out graphite.

Thanks in advance for uploading the documents.

jpsmith123
December 7th, 2007, 10:34 PM
This paper describes an electrolyte comprising Co Sulfate and Ammonium Acetate.

jpsmith123
December 7th, 2007, 10:37 PM
This paper describes an electrolyte containing the nitrate, sulfate and chloride of cobalt and some boric acid.

Bacon46
March 25th, 2008, 10:25 AM
Here are two patents pertaining to the application of metal oxide coatings. They are very similar methods and both seem feasible on an amateur or improvised level.