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.

Hazards of Flux Fumes

Note:  These health risks are those associated with industrial exposure – frequent and for extended periods.  They do not apply directly to occasional and shorter periods of exposure.

Risks are assessed as acute and chronic.  Acute means immediate reaction.  Chronic means the effects are cumulative and may take years to appear.
 

Composition of Flux

The major components of commercial flux are varying combinations and proportions of zinc chloride (or ammonium chloride), hydrochloric acid, phosphoric acid, citric acid, and hydrobromic acid.  It comes in many forms and many brand names.  It is important to use water soluble flux in stained glass work to enable thorough cleaning.
 
 

 

Zinc Chloride Risks

Zinc chloride inhalation from smoke screen generators or smoke bombs may cause transient cough, sore throat, hoarseness, a metallic taste, and chest pain.  Exposure to high zinc chloride concentrations produces a chemical pneumonitis with marked dyspnoea, a productive cough, fever, chest pain and cyanosis. Pneumothorax and the adult respiratory distress syndrome (ARDS) have been reported. Fatalities have occurred….
http://www.inchem.org/documents/ukpids/ukpids/ukpid86.htm#:~:text=Toxicity%20Zinc%20chloride%20is%20corrosive,anorexia%2C%20fatigue%20and%20weight%20loss.
 

Ammonium Chloride Risks

Exposure to Ammonium Chloride is moderately hazardous, causing irritation, shortness of breath, cough, nausea, and headache. Most exposure is a result of contact with the fume form of this chemical (Ammonium Muriate Fume and Sal Ammoniac Fume), which is a finely divided particulate dispersed in the air. The fumes are capable of causing severe eye irritation. Consistent exposure can cause an asthma-like allergy or affect kidney function.
 
In the event of accidental contact, get immediate medical attention and follow these first aid measures:
·        Skin Contact: Immediately flush skin with water and disinfectant soap and use an emollient on irritated area.
·        Eye Contact: Rinse eye(s) with water for at least 15-20 minutes. Protect unexposed eye.
·        Ingestion: Rinse mouth thoroughly with water. Do NOT induce vomiting.
·        Inhalation: Move to fresh air and administer artificial respiration if needed.
https://www.msdsonline.com/2017/05/05/chemical-spotlight-ammonium-chloride/#:~:text=Exposure%20to%20Ammonium%20Chloride%20is,particulate%20dispersed%20in%20the%20air.
 
 

Hydrochloric Acid Risks

Hydrochloric acid is corrosive to the eyes, skin, and mucous membranes.  Acute (short-term) inhalation exposure may cause eye, nose, and respiratory tract irritation and inflammation and pulmonary edema in humans.  Acute oral exposure may cause corrosion of the mucous membranes, oesophagus, and stomach and dermal contact may produce severe burns, ulceration, and scarring in humans.
 

Acute Effects: 

Hydrochloric acid is corrosive to the eyes, skin, and mucous membranes.  Acute inhalation exposure may cause coughing, hoarseness, inflammation and ulceration of the respiratory tract, chest pain, and pulmonary edema in humans.  Acute oral exposure may cause corrosion of the mucous membranes, oesophagus, and stomach, with nausea, vomiting, and diarrhoea reported in humans.  [Skin] contact may produce severe burns, ulceration, and scarring…. Acute animal tests in rats, mice, and rabbits, have demonstrated hydrochloric acid to have moderate to high acute toxicity from inhalation and moderate acute toxicity from oral exposure.

 

Chronic Effects: 

(Non cancer): Chronic occupational exposure to hydrochloric acid has been reported to cause gastritis, chronic bronchitis, dermatitis, and photosensitization in workers.  Prolonged exposure to low concentrations may also cause dental discoloration and erosion.  Chronic inhalation exposure caused hyperplasia of the nasal mucosa, larynx, and trachea and lesions in the nasal cavity in rats.  The Reference Concentration (RfC) for hydrochloric acid is 0.02 milligrams per cubic meter (mg/m 3) … The RfC is an estimate … of a continuous inhalation exposure to the human population (including sensitive subgroups) that is likely to be without appreciable risk of deleterious noncancer effects during a lifetime.  It is not a direct estimator of risk but rather a reference point to gauge the potential effects.  At exposures increasingly greater than the RfC, the potential for adverse health effects increases.  Lifetime exposure above the RfC does not imply that an adverse health effect would necessarily occur.
https://www.epa.gov/sites/production/files/2016-09/documents/hydrochloric-acid.pdf
 

 
Phosphoric Acid Risks

Phosphoric acid can be very hazardous in the case of skin contact, eye contact, and ingestion. It can also cause irritation if vapours are inhaled. This chemical can cause damage to the skin, eyes, mouth, and respiratory tract. Because of the potential hazards posed by this chemical, it is important to use care when handling it.
 
Repeated or prolonged exposure to phosphoric acid mist can lead to chronic eye irritation, severe skin irritation, or prolonged respiratory tract issues.  In case of accidental exposure to phosphoric acid, follow these first aid guidelines:

Inhalation — Seek fresh air and immediate medical attention.

Eye Contact — Remove contact lenses if present. Immediately flush eyes with plenty of water for at least 15 minutes and get medical attention.

Skin Contact — Wash skin with soap and water. Cover any irritated skin with an emollient. Seek medical attention. 

Ingestion — Do NOT induce vomiting. Never give anything by mouth to an unconscious person. Seek medical attention if any adverse health symptoms occur.
https://www.msdsonline.com/2015/06/17/phosphoric-acid-safety-tips/
 
  

Citric Acid

Citric acid can be a minor skin irritant, causing itchy skin and even minor burns to those that are sensitive to it. Hands should be washed immediately if citric acid comes into contact with bare skin. Protective gloves should be worn during handling to avoid any accidental contact. The acid can also irritate the walls of the throat if ingested or burn the lining of your stomach if ingested in large quantities.
 
Eye Irritation - Citric acid is a severe eye irritant. Accidental contact with the eyes can occur … by touching the eyes after the acid has contacted the fingertips. …  Protective eyewear should be worn when working with citric acid under laboratory conditions. Eyes should be flushed with water immediately if they happen to come in contact with the acid.
https://sciencing.com/hazards-citric-acid-8165149.html

Remember that this irritation is equivalent to squirting lemon juice into your eye.  It is not a chronic risk.
 

Hydrobromic Acid (HBr)

Hydrobromic acid and hydrogen bromide gas are highly corrosive substances that can cause severe burns upon contact with all body tissues. The aqueous acid and gas are strong eye irritants and [tear producers]. Contact of concentrated hydrobromic acid or concentrated HBr vapor with the eyes may cause severe injury, resulting in permanent impairment of vision and possible blindness. Skin contact with the acid or HBr gas can produce severe burns. Ingestion can lead to severe burns of the mouth, throat, and gastrointestinal system and can be fatal. Inhalation of HBr gas can cause extreme irritation and injury to the upper respiratory tract and lungs, and exposure to high concentrations may cause death. … Hydrogen bromide has not been found to be carcinogenic or to show reproductive or developmental toxicity in humans.
https://web.stanford.edu/dept/EHS/cgi-bin/lcst/lcss/lcss47.html#:~:text=The%20aqueous%20acid%20and%20gas,gas%20can%20produce%20severe%20burns.
 
 
 

Precautions to be taken by glass workers

The risks outlined above are related to dealing with concentrated amounts of the materials in industrial settings.  Risk levels are much reduced in the craft setting.  The risks are mainly centred on breathing and eye exposure. 
 
It is important to wear masks of the quality that will deal with inorganic fumes.  In Europe these are designated as FFP2.  In general masks rated at N95, P95, or R95 are the level required for filtering out 95% of particles that are larger than 3microns.  Dust masks are not sufficient protection. 
 

Usually overlooked is eye protection.  The risks outlined here show that risks to eyes are equal to - or in some cases greater than – respiratory ones.  Eye protection is as important as breathing filters.  To fully protect the eyes, goggles of some sort are the minimum requirement.  Glasses will not be sufficient to prevent fumes reaching eyes.

 
For a “one stop solution” a full-face mask may be the simplest solution.  The filters on these are long lasting and replaceable.  They can be put on as one unit and are available in various face sizes.
 

At soldering temperatures, there are no lead or tin fumes created.  It is the fumes from the flux that are the risks in soldering.  These risks are small and can be dealt with by using adequate ventilation, masks, and goggles.

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.

---    ---    ---    ---    ---    ---    ---    ---    ---    ---    

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

Cleaning masses of pieces

Are there any easy tips on how to clean off the cutting oil without having to wipe each of 168 pieces individually?

There are a variety of approaches. Some put multiples into a basin of water as they are cut.  Some with soap added, some with window cleaner or vinegar.  When all are cut, the pieces are swirled around in the water/additives solution and laid out on kitchen towels to drain while each is polished with clean towels.  Some put the glass in a bag into the dish washer.  This leaves the glass with the residue of a number of corrosive chemicals on the surface.

If you must put additives into the soaking water, I suggest you use a combination of 1 part water, 1 part isopropyl alcohol, and 1 part 5% citric acid.  Avoid the use of vinegar. There is a significant risk of etching the glass, leaving a dull surface. Citric acid will not affect the glass, nor leave residues after rinsing.  The alcohol will speed the drying.  But see this post on another better chemical than Citric acid. You can leave glass soaking in tri-sodium citrate for up to 48 hours without etching.

Essentially these practices are to soak the pieces until all are cut to have a mass cleaning and drying session.

But I don’t use oil in my cutter and so I can follow this procedure:

clean the glass sheet first,

score with no oil in the cutter,

break,

set aside to assemble.

Prior to assembly I clean each piece with isopropyl alcohol and a polish with paper towel.

Cleaning glass for fusing is much simpler if you do not use oil in the cutter.  There is no absolute necessity to do so.  The glass will score and break very well without oil.

More Information on Citric acid

Vinegar is not recommended for cleaning of glass, and especially not to soak glass in to remove kiln wash or investment materials.

The reasons for avoiding vinegar are that

·        Dilute vinegar - as culinary vinegar is - attacks glass, giving a mild etch to the surface similar to devitrification.  Concentrated vinegar – oddly - does not attack glass as strongly.

·        It is of variable quality – due to uncontrolled strength, various culinary additives, etc.,

·        It has a strong odour, and

·        It takes a long time to work.

Citric Acid

However, there is an acid which works very well to remove investment materials and kiln wash without affecting the glass.  It is the humble citric acid.

Citric acid is a weak organic acid that has the chemical formula C₆H₈O₇. It occurs naturally in citrus fruits, although that is not the best source for cleaning purposes.

More than two million tons of citric acid are manufactured every year. It is used widely as anacidifer, as a flavouring agent and chelating agent. It is the last that is of most interest to kilnformers.

Chemical characteristics

A citrate is a derivative of citric acid. There are many formulations. Two examples are a salt that is named trisodium citrate (also known as sodium citrate); and an ester called triethyl citrate. We are more interested in the first as it is cheap and widely available.

The citrate ion forms complexes with metallic cations.  It forms complexes even with alkali metal cations. This makes citric acid an excellent chelating agent, especially of interest in removing kiln wash and refractory materials from glass.

Chelation 

This is a type of bonding of ions and molecules to metal ions. The agents are usually organic compounds. Chelation is useful in applications such as providing nutritional supplements, in chelation therapy to remove toxic metals from the body, in MRI scanning, in chemical water treatment to assist in the removal of metals, and in fertilisers, among other things. 

Citric Acid as a Cleaning and chelating agent

Citric acid is an excellent chelating agent, binding metals by making them soluble. Among many cleaning uses are:

    to remove and discourage the build-up of lime scale, from boilers and evaporators. 

    to treat water by chelating the metals in hard water, cleaners produce foam and work better without need for water softening. Citric acid is the active ingredient in some bathroom and kitchen cleaning solutions. 

    A solution with a 6% concentration of citric acid will remove hard water stains from glass without scrubbing. 

    Citric acid can be used in shampoo to wash out wax and colouring from the hair. 

    In industry, it is used to dissolve rust from steel and to form a coating on stainless steels to resist corrosion.

Its use in kiln forming is to make use of the chelation properties when dealing with kiln wash and investment material residues.  Aluminium hydrate is the main ingredient of all kiln washes.  When it becomes bound to glass, it is impervious to almost all chemicals.  The chelating property of citric acid enables the bond between the glass and the kiln wash to be broken by incorporating the molecules within its own, making a colloidal solution.  This process is approximately 6 times faster than any vinegar solution and without the odour and etching risks.

A sample of the affected glass followed by 4 hours in citric acid and 24 hours in vinegar.
Credit: Christopher Jeffree

A 5% solution made up with 50gm of granular citric acid in 1 litre of water is all the strength that is required. The affected glass can be soaked in this solution for the time required to complete the chelation without the risk of etching, and without needing ventilation to remove smells.  Unless you are using a lot of cleaner, it is better to make up much smaller amounts as mould can grow on this organic solution.

A 5% solution made up of 50gms citric acid in 500ml of water and 500ml of isopropyl alcohol makes an inexpensive and effective glass cleaner. However, if left for a length of time, it becomes sticky.  Apply the solution, scrub the glass and immediately wipe off the solution.  Then polish the glass dry. The alcohol in the solution makes keeping large quantites possible. 

This post was compiled with the assistance of Wikipedia, Christopher Jeffree and my own experience.

Although this post remains valid, there is another chemical for long soaks to remove mould material or kilnwash.

Citric Acid Cleanser

Christopher Jeffree has kindly outlined the reasons for the effectiveness of citric acid as a cleaner for removing refractory mould residue and acting on kiln wash stuck to glass.  This is his work (with a few personal notes removed).

"Citric acid works well for removing the plaster scale that builds up in vessels used to mix plaster, and it helps to remove traces of investment plaster and kiln wash from glass.  Its metal-chelating properties probably help with dissolution of calcium deposits, but I am less clear why it is so good at removing kiln wash.  The constituents of kiln wash are kaolin and alumina hydrate, neither of which I would expect to be soluble in dilute acids.  Equally, the refractory materials in investment formulae I would expect to be insoluble.  However, kaolin forms layered structures in which flakes, molecular layers, of alumina hydrate and silica interact through hydrogen bonding. It is possible (I am guessing here) that citric acid can disrupt those hydrogen bonds, thereby disaggregating the clay.  All we can say is that empirically, it works.

"I prefer to use citric acid partly because it has a defined composition, but also because it is safe and pleasant to handle – no odour, and comes in the form of easily-dissolved dry crystals like granulated sugar.  Vinegar stinks, and glacial acetic acid is  an aggressive flammable, corrosive liquid with a chokingly acrid smell.

"Calcium sulfate has low solubility, but is not completely insoluble in water - gypsum (calcium sulfate dihydrate) has a solubility of about 2.5g per litre (0.25%)  from 30-100 C. Its solubility is retrograde, meaning that it decreases, rather than increasing, with temperature.  Natural gypsum is an evaporite, a type of rock that often forms by evaporation of lake water in a geological basin with little or no outflow. It can also be produced hydrothermally in hot springs, when water containing sulfuric acid passes through limestone.  

"Calcium citrate is not very soluble either, only in the order of about 0.85g per litre, but the important thing from our point of view is not to get the material into solution but to separate its crystals and make it detach from the glass.

"In other contexts, warm citric acid is used by jewellers and silversmiths as a pickle for dissolving copper oxide (firestain) from silver and gold alloys  after heating / soldering.  It is a safer alternative to the traditional jeweller's pickle of 10% H₂SO₄.

"Citric acid also dissolves rust from iron, without much etching the iron itself, so is good for cleaning rust off tools etc.

"These pictures show a plaster mixing bowl with (presumably) CaSO₄-rich deposit on the surface, cleaned by soaking with 5% citric acid for 4 hours,

and flash from the pate de verre castings with tightly adhering kiln wash, cleaned using 5% citric acid soaked for 4 hours, and vinegar (white wine) soaked for 24 hours.

"I'm not sure about reaction products - I was speculating a lot there, running through hypotheses that I can't support. We don't really have data on the composition of the layers that are stuck to the glass, or a clear idea of why they sometimes stick and sometimes don't (e.g. the differences between transparent and opal glasses in this respect). Maybe this would be a topic to discuss with technical people at Bullseye."

Hope this helps
Best wishes

Chris Jeffree

Subsequent to this work Christopher has done more work and found that Tri-sodium citrate is an even better chemical for cleaning glass of kiln wash and mould material.

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