Monday, 30 December 2024
Glass Volume for a Frit Mould
Saturday, 28 December 2024
Devitrification
Dr. Jane Cook states that devitrification is not a category (noun), but a verb that describes a process. Glass wants to go toward devitrification; a movement toward crystallisation.*
Mild devitrification is the beginning of crystallisation on the surface of the glass. It can look like a dirty film over the whole piece or dirty patches. At its worst, the corners begin to turn up or a crackling can appear on a granular surface. This is distinct from the effects from an unstable glass or the crizzling as in a ceramic glaze. Devitrification can occur within the glass, but normally is a surface effect as oxygen is required.
Differences in the surface of glass promotes precipitation of the crystal formation of silica molecules. This fact means that two defences against the formation of crystals are smooth and clean surfaces. There are other factors at play also. The composition of the glass has an effect on the probability of devitrification. Opaque glass, lime, opalising agents, and certain colouring agents can create microcrystalline areas to "seed" the devitrification process. One part of the composition of glass that resists devitrification is the inclusion of boron in the composition of the glass, acting as a flux.
Visible devitrification generally occurs in the range of approximately 720°C – 830°C/1330F - 1525F, depending to some extent on the type of glass. This means that the project needs to be cooled as quickly as possible from the working (or top) temperature to the annealing point, which is, of course significantly below this range.
There is evidence to show that devitrification can occur on the heat up by spending too long in this devitrification range, and that it will be retained in the cooling. Normally this is not a problem as the practice in kilnforming is for a quick advance on the heat up through this range, causing movement in the glass and so working against any crystallisation. The quick advance does not (and should not for a variety of reasons) need to be as fast as possible. A rate of 300°C per hour will be sufficient, as time is required for devitrification to develop.
Medical research into using a glass matrix to grow bone has shown that devitrification begins around 650C/1200F, but only becomes visible after 700C/1290F. This has implications for multiple slumps. Devitrification is cumulative, so the devitrification that may have begun on the flat piece will be added to in the slumping process and may become visible. For me this has appeared as a haze on the edge of the slumped piece. Avoidance of this effect is by thorough cleaning of the piece before placing it in the mould.
The devitrification seen in typical studio practice results more often from inadequately cleaned glass than from excessive time at a particular temperature, up or down, through the devitrification range. It is often seen as a result of grinding edges to fit. Even though the ground edge is cleaned, it may still be rough enough to promote devitrification. The edge must be prepared for fusing by grinding to at least 400 grit (600 is better). Alternatively, use a fine coating of clear powder to give a new surface to the whole piece.
Dr. Cook suggests three approaches to devitrification:*
Resistance through:
- Schedules
- Flux
Dealing with it:
- Cold work
- Acids
Embrace it:
- Allow it
- Use it
Other sources of information:
Temperature range for devitrification
Homemade devitrification solution
Frit to fill gaps
Low Temperature Kilnforming at Etsy and Bullseye
* From a lecture given by Dr. Jane Cook at the 2017 BECON
[entry revised 28.12.24]
Sunday, 10 December 2023
Sealing MEMS Devices with Glass
Krista Grayson
•
However, the success of MEMS devices often hinges on maintaining a hermetic environment to protect their delicate internal components. This is where glass frit sealing technology comes into play, providing a superior solution for achieving reliable hermetic seals in precise applications like MEMS manufacturing and packaging.2
Understanding Hermetic Sealing and its Importance
Hermetic sealing involves creating an airtight barrier around a device to prevent the entry of contaminants, moisture, and other external elements. This sealing technique is crucial for MEMS devices as even minute environmental influences can alter their performance or lead to premature failure. In applications where stability, precision, and reliability are paramount, such as in the aerospace, medical, and telecommunications industries, achieving a hermetic seal is essential.2
Glass Frit Sealing: The Ideal Solution for MEMS
Among the various methods available to achieve hermetic seals, glass frit sealing stands out as a versatile and high-yield approach, particularly suited for MEMS applications. This technique leverages the unique properties of glass to create a reliable, robust, and precise encapsulation for MEMS devices while imposing minimal stress on the bonding surface. In a three-step process, a glass paste is screen-printed on a capping wafer, which is then bonded to the subject device through thermocompression for 10 minutes. During this process, 1000 mBar of force and 440 °C are applied to the material under a vacuum. Capable of bonding both hydrophobic and hydrophilic surfaces, this technique can be applied to almost all commonly used microsystem surface materials, such as aluminum, silicon, and glass.3,4
Tailoring Precision Using the Coefficient of Thermal Expansion (CTE)
As the name implies, glass frit sealing makes use of glass particles, known as frit, which can be precisely formulated to match the coefficient of thermal expansion (CTE) of different materials.4 The CTE of a material refers to how its dimensions change with temperature fluctuations. By tailoring the glass frit’s composition, its CTE can be adjusted to closely match that of the MEMS device and the encapsulating material. This compatibility ensures that, when subjected to temperature variations, the seal remains intact without compromising the structural integrity of the device.2
Mo-Sci, a pioneering glass technology company, has been at the forefront of developing and perfecting glass frit sealing solutions for various high-tech applications, including MEMS devices. Its expertise lies in creating sealing glasses with customizable thermal expansion coefficients. With a diverse range of glass-metal and glass-ceramic seals that are meticulously matched in terms of CTE and are capable of enduring temperatures as high as 1600°C, Mo-Sci is an ideal partner for MEMS manufacturers seeking reliable hermetic sealing solutions.2,5
The Versatility of Glass Frit Sealing
The applications of glass frit sealing extend beyond MEMS devices and encompass a range of cutting-edge technologies:
1. Solar Cells
Sealing glasses find utility in encapsulating perovskite photovoltaic elements. These elements are promising alternatives to traditional silicon solar cells due to their high efficiency and lower production costs. However, perovskite cells are highly sensitive to moisture, whereby even small amounts can completely prevent function. Laser-assisted bonding of glass frit sealing guarantees a durable hermetic barrier, shielding perovskite cells from moisture exposure and locking in lead-containing chemicals.2
2. Metal Ion and Thermal Batteries
In the evolving landscape of energy storage solutions, glass frit sealing plays a pivotal role in enhancing the reliability and longevity of metal ion batteries, including lithium-ion and sodium-ion batteries. These batteries require seals that can withstand high temperatures and resist chemical corrosion. Sealing glasses provide a resilient barrier that enables the efficient operation of these advanced battery technologies.
Sealing glass is also a viable solution for molten salt batteries. These batteries are highly dependent on sodium salts, including sodium-nickel and sodium-sulfur chloride, to achieve remarkable energy and power densities. For this reason, they are an appealing option for large-scale industrial and energy storage applications.
Sealing glasses are classed as a high-energy alternative to conventional polymeric or metal seals as they exhibit excellent resilience against demanding chemical environments but also against the rigorous operating temperatures inherent to molten salt batteries, which can range from 300 °C to 350 °C.2
3. High Temperature Sensors
Glass frit sealing also finds applications in high-temperature environments, such as automotive systems and chemical processing plants. The predictable thermal expansion and corrosion-resistant nature of sealing glass ensure the longevity and stability of sensors operating in extreme conditions.2
4. Solid Oxide Fuel Cells (SOFCs)
SOFCs hold tremendous promise for clean and efficient power generation, but their high operating temperatures present engineering challenges. To create high-temperature sealant materials for SOFCs, Mo-Sci currently utilizes two methods. One relies on a traditional glass-ceramic seal, wherein the glass undergoes crystallization to establish bonds with the sealing components.
The second approach involves the development of viscous-compliant glass seals. These seals remain vitreous throughout application and can self-heal, mitigating the risks associated with thermal stresses and ensuring the long-term stability of SOFCs.This groundbreaking technology is anticipated to play a pivotal role in facilitating the commercialization of SOFCs and driving their widespread adoption.2,6
Embracing the Future with Glass Frit Sealing
Glass frit sealing technology has emerged as a transformative solution for achieving hermetic seals in MEMS devices and a wide array of other advanced applications. By precisely engineering the properties of sealing glasses, companies like Mo-Sci enable manufacturers to create highly reliable and robust encapsulation systems.
As industries continue to push the boundaries of technological innovation, the role of glass frit sealing in safeguarding sensitive components and ensuring optimal device performance becomes increasingly vital.
References and Further Reading
- Forbes. Why Timing Must Be Tough Enough For Our Digital World. Available at: https://www.forbes.com/sites/forbestechcouncil/2021/09/02/why-timing-must-be-tough-enough-for-our-digital-world/ (Accessed on 10 August 2023).
- Mo-Sci. Sealing Glass Applications. Available at: https://mo-sci.com/sealing-glass-applications/ (Accessed on 10 August 2023).
- Chang H-D, et al. (2010). High hermetic performance of glass frit for MEMS package. 2010 5th International Microsystems Packaging Assembly and Circuits Technology Conference. https://doi.org/10.1109/IMPACT.2010.5699539
- Knechtel R. (2015). Chapter 31 – Glass Frit Bonding. Handbook of Silicon Based MEMS Materials and Technologies (Second Edition). https://doi.org/10.1016/B978-0-323-29965-7.00031-2
- Mo-Sci. Matching Coefficient of Thermal Expansion in Glass Seals. Available at: https://mo-sci.com/matching-cte-in-glass-seals/ (Accessed 10 August 2023).
- Mo-Sci. Sealing Glass. Available at: https://mo-sci.com/products/sealing-glass/ (Accessed on 10 August 2023).
Wednesday, 25 October 2023
Spikes on Frit Castings
It is frequent to have castings from frit with spikes, needles, or prickles around the edges.
Causes
These spikes result from the glass touching the edge of the mould or separator during the hottest part of the firing. The glass particles first begin to compact as the glass rises toward the fusing temperatures. As the temperature increases toward the casting temperature it begins to expand both horizontally and vertically from that compact mass. As it cools, the glass sinks down and retreats from the edge. This movement leaves some small bits of glass stuck to the sides. The glass contracts as it cools, leaving the spikes as it contracts from its hottest state.
Avoidance
The usual recommendation is to mound frit in the middle and let it flow to the outside. Still, the glass flows to the outside of the mould at casting temperature and it touches the sides. Leaving the risk of creating spikes. Accurate measuring of the amount of glass to charge the mould with is important. With the right amount of glass, the mould will not be overfilled and so, reduce the spiking.
Measuring the weight of glass for the mould is not difficult. In many cases, the manufacturer of the mould has done the work for you. If you need to calculate the weight of glass required for the mould, it is not difficult. A method is given here. In short, you use a dry fill of the mould. Measure the volume (using the metric system) and multiply by the specific gravity to get the weight in grams.
Larger chunks of glass tend to produce fewer spikes than smaller frit. Usually longer soaks at top temperature are required to fully form the glass with smaller frit. It is also possible to drip glass into the mould from a pot suspended above the mould. Accurate measurement of the weight will still be important. But add 100gms/4oz. to the amount to allow for the glass that will stick to the pot.
My view is that with dams, it is better to use a straight sided shape with fibre cushioning around the outside. When annealed and cool, clean it well. Then fire polish with a slow ramp to 540°C/1000°F followed by a quick ramp to the fire polish temperature. This will polish the sides of the piece that were in contact with fibre paper.
Wednesday, 27 September 2023
Homemade Glass Powder
Summary of a question: Frit made in an electric coffee grinder and cleaned with magnet still produced black specks in the finished piece. What’s happening?
Most coffee
grinders use stainless steel blades. Most culinary stainless is not magnetic. So, you
are left with flecks of steel in your powder that the magnet cannot remove.
The contamination
in home-made glass powders make it best to buy powders and make your own frit.
Wednesday, 29 March 2023
Frit Additions to Shaped Pieces
It is possible to stick frit to slumped pieces. But soaking for a long time – several hours - at 650°C/1200°F is required to stick the frit. The added pieces will remain relatively sharp. You need to observe frequently from 600°C/1111°F to make sure that the form of the glass is not distorting.
Credit: Pyramid Gallery, Smyth and Zebrak |
Although it is possible, adding pieces to already shaped objects is not best practice, nor will it frequently give satisfactory results. If the slump is shallow, it is more possible to do this successfully than steep or highly shaped forms. But the most suitable practice is to flatten the piece, then tack fuse the pieces onto it. Follow this fusing with the new slump or drape. This flattening process will not be possible with all shapes.
The best results will be achieved by accepting what you have and make a new piece with the planned additions from the start.
This process will not be suitable for draped glass as the
glass will drape further during this low temperature soak.
I've a book that
gives more detail. Low Temperature Kilnforming, an evidence based approach to scheduling or at Bullseye
Wednesday, 14 September 2022
Home Made Frit Maker
Recently, when looking for a small frit maker, no shop had one
in stock. Having heard of making one
from plumbing pipes, I went in search of material. I came across stainless steel pipe and caps.
The practical size seemed to be 50mm. Short sections of threaded pipe were available with matching caps. That forms the containment cylinder.
A threaded 25mm pipe and cap can be fitted loosely into the
larger one, and so forms the plunger or piston.
There needs to be a handle. It could be a turned piece of wood to fit the inside of the pipe. In this case, I obtained a reducing connector to fit a 12mm pipe to the plunger and topped it with another cap.
The completed frit maker |
Galvanised pipe would be cheaper but carries the possibility
of introducing zinc into the frit.
Stainless steel risks introducing non-magnetic particles into the frit. As I sieve out powder from my own frit making
before washing, I am not too concerned about steel contamination. If you want powder, use uncoated mild steel so
the contamination can be drawn out with a strong magnet.
Wednesday, 24 November 2021
Playing in the Sandbox
Pouring the frit into the sandbox |
Moving the frit with a skewer |
Using a jewellers scoop to add the frit. |
A thick copper wire being used to poke down from an upper layer to the lower ones. |
Two sandboxes placed on separate shelves |
A corner of the shelf with the 6mm fibre spacer |
Pressing shelf placed on top of the glass sandbox |
- · Even with this additional mass, you can fire quickly. This is because the glass is in small pieces and that the mass of the shelves gains heat slowly.
- · The greater mass does require longer soaks than a normal fuse firing.
- · The upper temperature for a full fuse is required to get the glass to a sufficiently low viscosity to allow the glass to move.
- · The long soak at the top temperature does not promote devitrification as in normal fusing. My speculation is that the glass is not exposed to the air, so the devitrification cannot form.
- · A further difference in a pressing firing is that the annealing can be at the rate for the final thickness of the glass. The mass of the shelf and weights above the glass means the glass is cooling evenly from both sides, unlike normal fusing. The glass may be cooling more slowly than programmed, but the programmed rates limit any possibility of too rapid a cooling.
Untreated result of pressing |
This shows on the lower left a loosened piece of sellotape on the edge of the sandbox. |
Wednesday, 5 May 2021
Colour Dilution of Powders
Credit: www.warm-glass.co.uk |