Boron Nitride

What is boron nitride? What makes it a good separator?

Boron nitride is a heat resistant refractory compound of boron and nitrogen with the chemical formula BN. It is also chemically stable at elevated temperatures.  It exists in various crystalline forms that are similar to a structured carbon lattice. The hexagonal form corresponding to graphite is the most stable and soft among BN forms.  It is the form most useful in kiln forming as a smooth release separator, especially for steel.  It is also used as a high temperature lubricant, and has a wide use in cosmetic products.

There is a cubic form that is similar to diamond (called c-BN), but softer.  It has a superior thermal and chemical stability.  There is a harder form called wurtzite, but which is rare. Neither of these is of much use in kiln forming.

Hexagonal BN

Hexagonal BN (h-BN) is the most widely used form of boron nitride. It is a good lubricant at both low and high temperatures (up to 900C, even in an oxidizing atmosphere). Another advantage of h-BN over graphite is that its lubrication properties do not require water or gas trapped between the hexagonal sheet layers. So, h-BN lubricants can be used even in vacuum, e.g. in space applications. The lubricating properties of fine-grained h-BN are used in cosmetics, paints, dental cements, and pencil leads.  In kiln forming, the high temperature lubricating properties are made use of as separator between metal, ceramic and other supporting materials for the glass.

“Hexagonal BN was first used in cosmetics around 1940 in Japan. However, because of its high price, h-BN was soon abandoned for this application. Its use was revitalized in the late 1990s with the optimization h-BN production processes, and currently h-BN is used by nearly all leading producers of cosmetic products for foundations, make-up, eye shadows, blushers, kohl pencils, lipsticks and other skincare products.”   
https://en.wikipedia.org/wiki/Boron_nitride

It has wide application in materials to give them self-lubricating properties.  Boron nitride has the properties of stabilisation of materials, reducing expansion and resistance to electrical conduction, making for wide use in plastics and electronics among a wide variety of other products.

Health and Safety

There are some health issues related to its use.  It is reported to have a weak association with the formation of fibrous material in the lungs and so result in pneumoconiosis when inhaled in quantity in particulate form.  It is best to wear a dust mask when applying and to do it outdoors, as simple ventilation will not prevent dust settlement indoors.

Mandrels for Screen melts

In creating screen melts, the steel or other support left in the project can leave such a degree of stress that the piece will began to fracture over time.  The use of thin stainless steel rods as used in mandrels for bead making is an alternative, as they can be pulled out.

The separator used on the mandrel can be bead release.  If you have it that will work very well. This illustration shows a bead maker coating a mandrel from a bottle of mixed bead release.

If you do not have bead release on hand, you can use kiln wash.  To give the thick coating required to easily pull the steel out you need to mix the kiln wash differently. 

The normal mix of kiln wash would be 5 parts water to one of powdered kiln wash.  As you want this to be thicker so it will stay on the mandrel, you can mix it in a 3:1 ratio.  This will be sufficiently thick to keep it running off the mandrel and be able to extract it after kiln forming.

Mandrels prepared for bead making.  In coating them for a melt, you need to have the whole length coated.

To avoid the mess of pouring the wash over the mandrel, you can fill a stringer tube with the mixture and dip the mandrel into it. You can place the end of the mandrel into a polystyrene insulation block or a bit of clay to let it dry as done by bead makers.

Once dry, you can arrange these coated mandrels in any shape of grid you choose.  Lay them across your supports whether fibre board or brick with about 25mm on the support at each end.  Lay all of one direction down first and the follow with the second, or more layers.  Place you glass on top of the grid created and fire.

Kiln Washing Kiln Lids

It is frequently recommended that the bottom of the kiln should be kiln washed to prevent any spilled glass from sticking to the kiln brick.  You should remember that this is applicable to brick lined kilns.

This in itself is a little clue.  You do not need to kiln wash any insulation fibre in the kiln. If any glass were to stick to the fibre, it would come away easily.  In any case, most insulation fibre blanket will not stick to the glass.

The recommendation often goes on to advocate kiln washing the sides.  There is a caution that the side elements (if any) should not be kiln washed. The caution comes from the knowledge that water and electricity should not be mixed.  The kiln should not be on when applying kiln wash anyway.  If kiln wash is splashed onto the elements, it is simply a matter of letting the whole kiln dry naturally with the lid open before firing.

The extension to this series of recommendations is that the whole of the kiln should be kiln washed, including the lid.  This is not a good idea.  The wash on the lid will soon fail and drop dust and debris onto and into your work.  The glass should never touch the top of the kiln anyway.  If the elements are in contact with the glass, the glass will either stick to them or break.  You have to ensure you do not put glass nearer than about 20mm to the elements or lid. In any case, the glass will fall to the bottom of the kiln, not the top or sides – unless the kiln is not level.

BUT

The whole idea of kiln washing the interior of the kiln is suspect in some ways.  Anyone who has had glass drip off the shelf and onto the brick during an over-firing will know the glass eats into the brick through the kiln wash.  Kiln wash will only protect the brick at full fuse or less temperatures. But it is a good precaution to keep the pieces of frit that fall off the shelf from sticking to the brick. It does not do much more than that.

The application of kiln wash to the kiln creates another source of dust within the kiln.  Dust and general uncleanliness in the kiln is a main potential source of devitrification. Thus, the application of kiln wash should be the minimum necessary and does not need to go up the side beyond the elements or the lowest shelf height, whichever is less.

There is a strong argument to be made that laying a sheet of 0.5 mm fibre blanket on the floor of the kiln will provide better protection of the kiln than any amount of kiln wash.  It is less likely to fail, it is not a source of additional dust, it provides a better protection during any kiln runaway, and it is easily replaceable.

Carved Fibre Moulds

The question of whether you can use carved moulds more than once will arise.

This refers to moulds made from refractory boards or materials.  Once fired, refractory boards and materials become more fragile as they have lost their binders.  If the carving is simple with lots of support, and the mould is kept supported in a container of some sort, rigidising is not essential.  The life of the mould may be short though.

To make a longer lasting mould, you can rigidise the refractory material using this method.  This can apply to board as well as blanket.  The process will make a much longer lasting mould that is light weight, and is not affected by rapid changes in temperature.

Do the fibre moulds need kiln wash?

This depends on both the nature of the material and whether hardened or not.  Refractory fibre boards – often called ceramic fibre – do not need kiln wash to separate the glass from the mould.  However, putting powdered kiln wash and smoothing it with a piece of glass or plaster’s float can give a less grainy finish.  If applied wet, the dried kiln wash can be gently sanded to give a very smooth surface.

Other refractory boards such as calcium silicate or vermiculite do need kiln wash to separate the glass from the mould.

Any refractory mould which has been hardened with colloidal silica will need to be coated with kiln wash to keep the glass from sticking.  The kiln wash needs to be re-applied each time the mould is used above tack fusing temperatures.  Otherwise it does not need renewal until or unless the kiln wash is chipped, scratched or in other ways damaged. 

Another popular separator is boron nitride.  It is sold under various brand names.  This must be applied each time the mould is used.

Reversibility of Boron Nitride

After using Zyp/MR97, can I sand it off and use kiln wash?

Some people are applying boron nitride to ceramic moulds for the "smoother" surface.  Boron nitride is an excellent separator for metal moulds and casting moulds whether metal or ceramic. But it has limitations, including the price and requirement for a repeated application at each firing.  Some are beginning to wonder if they can go back to kiln wash after having used the boron nitride. Some say you cannot unless you sand off the separator.

The general experience has been that you can't apply kiln wash on top of the boron nitride. It just beads up and flows off, because the boron nitride creates a non-wetting surface that survives relatively high temperatures.  The water in the kiln wash mixture merely beads up or washes away. This means the kiln wash in suspension has no opportunity to adhere to the mould.

The most accepted way to get rid of the boron nitride is by sandblasting. Then apply kiln wash as normal. The sandblasted ceramic mould previously coated accepts kiln wash with no difficulty. In the absence of a sandblaster, you can use a sanding pad. You do need to be cautious about taking the surface of the mould when using abrasive removal methods, as the ceramic is relatively soft in relation to the abrasive materials.

The difficulty of removal of the boron nitride means that you have to think carefully about which moulds you put it onto.  If the mould has delicate or fine detail, removing the boron nitride risks the removal of some of the detail.  This indicates that this kind of mould, once coated, should not be taken back to the bare mould to change the kind of separator.

Another use of boron nitride is to spray a very small amount on a fiber strip to be used for damming. This will give you fewer needles as it provides a non-wetting surface at relatively high temperatures. This allows the glass to slide down the fibre paper without hanging up and creating the needles.

One advantage of kiln wash over boron nitride is that you do not have to reapply every firing as with boron nitride. With the boron nitride you need to apply before every firing.  It is best to use a paint brush to dispose of any lose material before giving a light re-coating. Not a whole lot is required on subsequent coatings.

If you are using boron nitride to get a smoother surface to the object, consider using a lower slumping or draping temperature, as this will also minimise mould marks.  

Steel Pipe for Slumping

Steel pipe as opposed to stainless steel can be used for slumping. It will spall, so there will be a need to clean up the flakes of rust after firing. But since there is so much spalling, putting kiln wash or boron nitride is a waste of effort. Each firing will flake off any separator painted onto the metal. Cover the pipe with fibre paper instead - 0.5 mm at least.

You need to advance in temperature slowly as the pipe drains the heat from the glass where it rests. My practice is to advance the temperature at 100C/hr to 100C with a 20 minute soak, followed by 50% increases in rate to 250, and to 500 with 20 minute soaks before proceeding to the next segment. This probably is more cautious than necessary on all but the first segment.

Diagnosing Fractures

What does the nature of the fracture tell about the reason for the break?

• incompatibility
• annealing
• adhesion
• splits
• lamination

Incompatibility

Fractures that follow the outline of a glass are normally indicators of incompatibility. The fracture starts at the incompatible glass and then - usually – goes directly to the nearest edge. Occasionally, the stress is not so great, so it only breaks around the offending glass without proceeding to the edge.

Annealing

A sinuous break – often with a hook at the edge – across the whole of the piece is generally an indication of one caused by an annealing stress. Inadequate annealing builds up stress within the glass that breaks through the whole piece in a lazy “S” pattern, rather than a straight line or following outlines of glass pieces.

Adhesion

Another kind of fracture occurs that is most often seen in ceramics. It is a kind of crazing that leaves the glass in granules. I call these adhesion fractures. This is indicative of the glass having stuck to the surface it is resting upon. This can be ceramic, steel or any other rigid refractory material. This comes from inadequate amounts of separator, often at high temperatures.

Split

Sometimes during slumps the piece can develop a tear or split in the lower surface without the upper breaking. This kind of split comes from heating the top of the glass more rapidly than the heat can penetrate the whole thickness. The weight of the relatively plastic upper surface overcomes the resistance of the lower surface by splitting it on the bottom face.

Lamination

Occasionally, a break will have both of the characteristics of incompatibility and annealing stress. The break is relatively straight and goes through differing colours rather than skirting them. This seems to happen most often on tack fused pieces and so is likely to be inadequate annealing. The annealing requirements of tack fused glass are much greater than flat fused glass, as the pieces are to some extent still reacting separately. If the whole piece is not given enough time for each piece to settle with the others they will contain unrelieved annealing stresses, which may have be too great to be held within the whole.

Applying Kiln Wash

Kiln wash, or batt wash as used in the ceramics field, is largely made up of alumina hydrate, kaolin (china clay), and often some colouring to indicate an unfired shelf.

These solids are heavy and settle to the bottom of the container quickly. So, you have to agitate the contents with each dip of the brush onto the liquid. To provide adequate - and even – coverage of the shelf, mould or other refractory material, you should paint in four directions. Up, down and the diagonals. You need to apply just enough that you do not see the shelf surface.

Alternatively you can spray the solution onto the surface. This is an easier way to get an even covering, but it sometimes is overly stippled.

A tip I was given for the smoothest kiln shelf is to level the damp prepared shelf and spray a layer of warm water over the wash to form a very shallow puddle. As the water is absorbed into the shelf, the only limitation to the smoothness of the surface is the granular nature of the kiln wash.

Thinfire as a Separator on Moulds

"I was told that it was possible to put a piece of thinfire paper under a circular piece of glass that is to be draped over a mould....  Has anyone done this or heard of doing it?"

Yes this can be done. Some caveats are in order though.

It is important to put a separator on the mould -normally kiln wash - before using it. Once coated, it will not need to be re-coated unless the surface is damaged, scratched, etc., for a very long time. If the kiln wash seems to be rough you can smooth it in various ways as noted in this tip.  The advantage of kiln wash is that it does not cost much and lasts a long time. The thinfire or similar is a one-time-use product.

The binder in the thnifire burns away during the heat up and allows the now unbound separator to drift down to the mould before the glass begins to conform to the mould. In that way it is very similar to a fine dusting of kiln wash powder over the mould surface before firing.

I don't see the point of using Thinfire or similar during slumps (although I can see that there are occasions where this method would be useful). For drapes, placing a bit of thinfire over the mould - especially if it is metal – is an additional precaution.

My view is that you have to kiln wash the mould anyway. KIln wash is cheap and long lasting while thinfire needs to be replaced after each firing.

Moulds for Bottles

One of the many styles of commercially prepared moulds

An alternative to buying moulds for slumping bottles is to use a sand bed. You can place the bottle into the sand and roll it a little from side to side to create a depression in the sand that then becomes the mould.

I use a fine sand (not builder's or garden) and coat it with alumina hydrate (slaked alumina). I use about 1 part alumina to 5 sand, but the mix is not critical, just enough alumina to coat the sand particles. It can go directly on your kiln floor if you have an easy way to pick it back up, as it is re-usable. Or you can put it in a stainless steel tray or any open topped box that will withstand the temperature.



Make your depressions and then sprinkle or sift a fine layer of alumina over the area - I use an old sock to hold some and dust it over the sand. Then lay the bottle in the depression.

The amount of sand impression you get is dependent on the temperature you use - the higher, the more sand texture you get. 





This way of slumping bottles eliminates the need for a mould and it is variable for different sized bottles.

Removing Kiln Wash

Kiln wash can get stuck on items for a variety of reasons. 

A variety of ways to remove the kiln wash are:

Grind the kiln wash off with diamond hand pads, or small rotary tool with wet sandpaper. You can then proceed to continue to grind with successively fine grits until a polish is achieved, or you can fire polish after a thorough cleaning.

Example of scrubbing kiln wash off

You can sandblast off the kiln wash and then proceed in either of the fashions above.

You can soak small pieces in tri-sodium citrate and then if necessary scrub with a wire brush – a brass wire brush is preferable to steel one to avoid scratching the glass.

Another solution is to place small items in an ultrasonic cleaner basket with water and a little soap or proprietary cleaner. Leave for an hour or two and they should be free of the kiln wash.

A link to some methods of cleaning shelves is here.

Avoiding Large Bubbles

“I tried small projects and they turned out fine. I have a 12" square with an emblem in the centre and a border set in slightly from the sides. Most of the glass is only the one layer. Both firings produced huge bubbles in the areas where the glass was only one thickness.”

Scale does matter. What can be done at a small scale does not always directly transfer to a larger scale.

The first problem this project created was using only one layer as the base. Glass has a surface tension which means that it tries to become 6-7 mm thick. One layer is only half that. As it thickens at the edges, it traps the air under the other parts of the glass, and as the glass continues to soften the expanding air bubbles come up through the thin parts of the glass.

Using two layers of glass with the design on top will ease the problem.

The design is the second problem. The weight of the border makes it even more difficult for the air to get out from under the glass.

Although having two layers of glass will reduce the problem, think about ways to make the border incorporated with the second layer of glass, so the weight of the glass at the perimeter is not greater than the interior.

The third problem is that there is not a bubble squeeze in the schedule (elsewhere in the query). The soak of 10 minutes at 538C is not necessary. You do need a soak at a point between 650C and 677C - this is the bubble squeeze temperature range. It is also the slump temperature, so you can determine what the bubble squeeze should be for your glass by what the slump temperature is.

The bubble squeeze can be accomplished by a half hour soak at the slump temperature, or by a slow rise from 50C below the slump temperature – taking an hour or so, depending on the size of the piece.

A fourth problem is the separator is batt (kiln) wash, the edges of the glass conform to the batt wash, resisting the movement of air from under the glass.

You may need to change to fibre paper for single layer pieces, as that allows more air out. Thinfire may be enough, but you can put it over 0.5 mm fibre paper. For a smoother finish, sprinkle powdered batt wash over the fibre paper and smooth it with a plasterer's float or a piece of window glass if you don't want to use Thinfire.

Lastly, don't use the pre-programmed schedules in your kiln's controller.

Look at the glass manufacturer's website. Bullseye, Spectrum and Uroboros give basic firing schedules that work with minimal adjustment. I don't understand why kin manufacturers don't simply refer to the sites to give their customers good advice, instead of the pre-programmed stuff.

Mould preparation

The preparation of a mould is more than adding a separator to it, although that is essential.

The glass will always take up the mould texture if it touches. So start with smoothing the mould itself. You can do this by wrapping very fine wet and dry sandpaper round a flexible sanding block. You can use this wet or dry, although wet is more healthy. When you get the desired surface texture you can let the mould dry or immeidately apply kiln wash. When this is dry you can again sand the kiln wash but with dry paper only this time and very lightly. Alternatively you can ball up nylon stockings to provide a soft abrasive action. If you sand through to the mould surface, simply apply the kiln wash again.

You can minimise mould marks by slumping at the lowest temperature which can achieve the slump you want.

If you want to avoid mould marks altogether, do an aperture drop and cut off the rim. There is no mould contact with this technique, so the glass retains the surface it had in fusing.

Separators for Steel

Steel moulds, whether stainless or other steel, require separators as glass will stick to hot metal.

The preparation of steel is a little different from ceramic or fibre moulds. First the steel has to have the oil coating removed. This can be done by sanding, sandblasting or by heating to about 550C.

The separators can be just normal kiln wash, boron nitride, or fibre. When using kiln wash or boron nitride, the steel needs to be heated – about 200C should be enough. Too hot and the water will boil leaving gaps in the coating. If the metal is too cool, the kiln wash will drip. A little experimentation will be needed to find the right temperature for your purposes. Remove the mould from the kiln and brush or spray on the separator. Return to the kiln to heat up again and apply the separator again. Continue this until an even complete covering of the metal has been achieved. It does not have to be thick.

Fibre paper works best on cylinder or wave moulds with curves in one plane only.  Bowl shapes lead to wrinkling of the fibre papers and marking of the glass with wrinkles.  This applies to the Bullseye Thinfire too.

Just as on shelves and ceramic moulds and as long as you fire below 700C, you can use the coated mould over and over with no problems. Once you fire hotter than 700C, it is best to remove the old kiln wash and put a fresh coating on before firing again.