Comparison of Citric Acid and Trisodium Citrate.

These two substances are useful means of removing kiln wash and refractory mould material from glass. They are important where abrasive methods such as sand blasting are not available or appropriate.

My recent experience with both citric acid and trisodium citrate shows differences in performance. This makes each more suitable in different contexts.

credit: Amazon

Trisodium citrate is the safest option when long soaks are required to remove refractory mould material. The trisodium citrate removes any risk of etching the glass on long soaks. It has been shown by Christopher Jeffree that two-day soaks in this will not etch the glass. It is most suitable for casting work.

Items cleaned with citric acid and vinegar
credit: Christopher Jeffree

Citric acid acts quickly on kiln wash, making long soaks less necessary. Depending on the thickness of the stuck kiln wash and the amount of agitation of the stuck kiln wash, the time required may be only a dozen minutes. It rarely takes more than a few hours.  Citric acid does not work quickly on refractory materials. This makes the trisodium citrate the better choice for long soaks.

 More on citric acid as a cleaner

 More on citric acid

More on trisodium citrate

Muriatic acid as a cleaner of kiln wash

Muriatic acid is a common name for hydrochloric acid.   Let’s look at what is being cleaned off first.

The main components of kiln wash are hydrated aluminia, kaolin, and colouring. Colouring burns away, hydrated aluminum is inert at kilnforming temperatures, Kaolin begins a non-reversable change from hexagonal plates to a crystalline form at about 600C/1100F and completes it by 900C/1650F. Now consider the characteristics of each element. 

Aluminium Oxide

Aluminium oxide is widely used for its hardness and strength. It is only slightly softer than diamond. In its hydrated form it is a separator between glass and supporting structures. It has excellent refractory characteristics with a melting point of 2,072 °C/3,762 °F. But it is insoluble in water and all solvents. It is largely impervious to acids. 

Kaolin

Kaolinite structure, showing the interlayer hydrogen bonds in white.
Source: Wikipedia

 

Compared with other clay minerals, kaolinite is chemically and structurally simple. It consists of layers, each bound together by shared oxygen ions. The layers are bonded via hydrogen bonding between oxygen on the outer face of one sheet and the other. … The close hydrogen bonding between layers also hinders water molecules from infiltrating between layers, accounting for kaolinite's non-swelling character.

When moistened, the tiny plate-like crystals of kaolinite acquire a layer of water molecules that cause crystals to adhere to each other and give kaolin clay its cohesiveness. The bonds are weak enough to allow the plates to slip past each other when the clay is being moulded, but strong enough to hold the plates in place and allow the moulded clay to retain its shape.   Source: https://en.wikipedia.org/wiki/Kaolinite

It is this slipperiness that makes it a good carrier of the aluminium hydrate. However, kaolin begins a non-reversable change from hexagonal plates to a crystalline form at about 600C/1100F and completes it by 900C/1650F. It is the crystalline form that sticks to glass. So, it is the clay (kaolin) that needs to be removed from the glass.

Hydrochloric acid as a cleaner of kiln wash

Glass is almost impervious when it has a minimum of modifiers. Glass which has a minimum amount of [modifiers] and is almost entirely SiO2 is remarkably chemically inert and reacts only with very strong alkaline (bases) materials.   Source: https://www.quora.com/How-come-hydrochloric-acid-does-not-burn-through-the-glass-bottle-that-its-stored-in

Note that coloured and fusing glass have a significant level of sodium and potassium modifiers. This means that fusing glass is subject to attack by hydrochloric acid. 

Safety notes on hydrochloric acid

Being a strong acid, hydrochloric acid is corrosive to living tissue and to many materials, but not to rubber. Typically, rubber protective gloves and related protective gear are used when handling concentrated solutions. Solutions of less than 25% cause skin irritation, serious eye irritation and respiratory irritation. Over 25% causes severe skin burns and eye damage. It is also a precursor of many illegal drugs. Serious safety gear is required to handle even 10% solutions. 

Even then:

“Clays are not truly soluble in HCl acid, [but] exposure to HCl acid does affect the structure of clay minerals. Hydrochloric acid cleans clay minerals by removing free iron oxide from the surface. … The dissolution of kaolinite clay in hydrochloric acid solutions has been carried out in the presence of fluoride ions. Leaching in the presence of fluoride ions activates the clay for leaching, making higher extractions possible at lower roasting and leaching temperatures. Acetic acid [vinegar] is less effective.”   Source: Stability of Clay Minerals in Acid, by D E Simon and M S Anderson. https://onepetro.org/SPEFD/proceedings-abstract/90FD/All-90FD/SPE-19422-MS/68436 

This piece of research shows that hydrochloric acid is most effective in combination with fluoride and heat.

Other reported research from Researchgate shows:

“Kaolin and other clays are partly soluble in acidic solutions (organic or inorganic acids in water) but the … solubility is never complete. Increasing the acid content doesn't … increase the solubility.” Philip G Jessop, Queen's University. 

       “Potassium hydroxide … will get kaolinite dissolved with a white residue for selective leaching. … The most aggressive solvent is hydrofluoric acid which "kills" almost all silicates [including kaolin]. … For the kaolinite group … use hydrazine as solvent.” Harald G. Dill, Leibniz Universität Hannover. 

Hydrazine is highly toxic unless handled in solution. Hydrofluoric acid may dissolve the kaolin, but it also dissolves the minerals in glass. Both these chemicals are extremely dangerous. 

Conclusion

It is not advisable to use hydrochloric (muriatic) acid as a cleaner of the kaolin in kiln wash from glass. 

There are other much safer methods which use a chelating action rather than attempting to dissolve the almost insoluble kaolin. These are citric acid for brief (less that 24 hours) soaking, or trisodium citrate for longer periods.

Cleaning Kiln Wash from Glass without Etching

 This is a note from Christopher Jeffree on a piece of research he did on the effects of three chemicals to remove kiln wash and investment residue from glass.  These are the common vinegar soak, my preferred citric acid soak and a tri-sodium citrate soak.  

This latter is a neutralised citric acid. It is widely used in the food, and engineering industries. It is an anti-oxidant. It is used to remove limescale also. Clearly it is an all around useful chemical.  It is edible, widely available, and cheap.

Christopher informs me that "One interesting application for it is for retarding the setting of gypsum plaster, so it is sold by plasterers and building merchants."  It is also available through Amazon, Ebay and sellers of food making supplies.  Typically, it is sold as tri-sodium citrate dihydrate.

Without more introduction, here is Christopher's research and conclusions.

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Which etches glass more – 6% vinegar or 6% citric acid? To cut a long story short, a quick experiment shows that it depends on the glass.

·         Both acids etch opal glasses, especially some reds, oranges and yellows, when soaked for 48h, but citric acid etches the same colours more in the same time.

·         Most transparent colours and clears are very resistant to etching, even when exposed for much longer times.

·         The neutralized form of citric acid, tri-sodium citrate, is just as effective as citric acid for cleaning glass of mould material and kiln wash but does not etch either transparents or opals during extended soaks of several days.

·         Bottom line:  to avoid glass etching, long soaks should be carried out in trisodium citrate, not in vinegar or citric acid

 

Samples containing mainly opal yellows and oranges.

Samples containing mainly opal blues and greens. Due to a slight difference in angle of illumination, the etch pits appear bright in this set of sample, but dark in the yellow set above.

 

©Chris Jeffree, December 2021

Pickling

Pickling Silver

This term relates to the removal of firescale from silver by use of chemicals, often slightly warmed.

When heated, silver blackens on the surface. It is common in silversmithing to pickle the object, bringing the shine back.

There are several methods.

Hydrochloric acid is the most common chemical used. It normally is used in concentrations of 10% or less and often is slightly warmed in a soup warmer or other similar temperature controlled container

Hydrogen peroxide (sparex) solutions can be used, but are a bit slower. This also is used in a soup warmer.

Acetic acid, available from most chemists and home-brew suppliers, can be used but is so much slower that significantly long soaks are required.

The best solution for this is a 5% solution of citric acid or similar concentration of tri-sodium citrate.  This latter is best for glass, as it chelates the corrosion or stuck kiln wash, but does not etch the glass even after 48 hours soaking.

Revised 6.1.2022