Lehigh Summer IMI for Advanced Glasses

Luminescent Borosilicates
& the 3D Printing of Glasses
Vicarte Institute of Glass and Ceramics for
the Arts, Universidade Nova Lisboa, Lisbon,
Portugal
Penn State University, State College PA

Rachel Guarriello
Department of Materials Science and Engineering
Penn State University
 Lehigh Summer IMI for Advanced Glasses

The Projects:

While at Vicarte over the summer, I worked with 2 different projects concerning glass. The first

was the production of a luminescent borosilicate glass for lamp working. Borosilicate glasses are high

temperature glasses with low coefficients of thermal expansion such as Corning’s Pyrex or Schott’s

Duran. These glasses are very resistant to thermal shock, and melt at extremely high temperatures

relative to other glasses; usually around 1250 C. While these thermal properties make the glass

extremely useful, they also make borosilicates much more difficult to process relative to other glasses.

UV luminescence due to the presence of rare earth ions had already been achieved and studied in more

commonly used glasses such as the soda-lime glasses used in windows and glass blowing, but not in

borosilicates for lamp working. Lamp work is the form of glass art typically used in Murano, Italy to

create glass beads and free-form delicate structures from glass rods and a small, hot torch. The main

goal of my project was to create a clear glass that luminesced in UV light that was still workable in the

torch with regular Duran borosilicate rods.

The second project I worked on was the 3D printing of glass. In this case, Vicarte already had a

3D printer, specific binder, and some glass frits from Ferro to work with. However, almost no work has

been done to date with the 3D printing of glass, severely limiting the background information I could

find to work with. The goal was to use the printer, binder, and frits to print an object using glass that

could then be sintered. Unfortunately, there was almost no information on what the actual composition

of the glass frits were, so extensive testing had to be done to determine basic thermal properties of

each frit. Then, I had to figure out how to make the inorganic glass powders compatible with the

organic binders for use in the 3D layer printer. Once all that was figured out, I had to determine a

burnout and sintering cycle for the printed objects. Both of these projects were very interesting for me

since they were artistically motivated rather than more scientifically based.

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Guarriello, Rachel
 Lehigh Summer IMI for Advanced Glasses

UV Luminescent Borosilicates:

When I started working on the project, the scientists at Vicarte had already figured out a

borosilicate composition that was compatible with the Duran rods typically used in flame working. The

Rare earths used to create luminescent colors were Europium for pink and blue, Terbium for green,

Samarium for red, and Dysprosium for yellow. However, the addition of the rare earth oxides to this

composition altered its thermal expansion, and also created a lot of bubbles within the glass which is an

undesirable trait for most art since they’re difficult to remove. Additionally, the glass couldn’t be re-

melted multiple times since the rare earth oxides would vaporize out of the melt, and the glass would

lose its luminescence.

After trying many different methods for fining to minimize and remove the bubbles, I finally

found that NaCl, common table salt, worked wonderfully to get rid of the bubbles. Below, I’ve included a

picture of the glass before the bubbles were removed, and then the clear piece where the salt was used

to get rid of the bubbles (Figure 1).

Figure 1: Luminescent glass with bubbles (left) and fined with NaCl (right) without bubbles

Since the processing issue with the bubbles was fixed, the next challenge was to tailor the

thermal expansion so that the luminescent glass was compatible with the commercial glasses. To do

this, I had to adjust the amounts of rare earth oxide, aluminum oxide, and potassium oxide in the glass

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Guarriello, Rachel
 Lehigh Summer IMI for Advanced Glasses

melt. The rare earths and aluminum lowered the thermal expansion of the glass while the potassium

increased it slightly. I finally came to the conclusion that the best composition had only 1%, rather than

2%, of the rare earth oxide by weight with the difference made up using the potassium oxide. This

composition worked best with the commercial glasses, and all four rare earth elements that I tested.

The different colors are shown below in Figure 2.

Figure 2: Luminescent borosilicate glasses. Left to right: Europium, Dysprosium, Terbium, Samarium

3D printing glass:

My main project for the extent of the IMI experience was the luminescent borosilicates, and so

the 3D printing of glass began as a sort of side project. Regardless of its start, this project grew to

become much more interesting and lengthy than the luminescent glasses. It was an idea that the

scientists at Vicarte had been toying with for a while, but never got around to pursuing, so I was able to

jump right into the project since all the materials were already there. The goal of the project was to use

glass powder in Vicarte’s 3D inkjet layer printer with the printer’s standard binder. There were plenty of

glass frits from Ferro laying around, so we decided to start working with that.

I first conducted a melting test with each of the frits to figure out a rough melting temperature.

Then, using a recipe from the University of Washington, I milled together a frit with a combination of

dextrene and powdered sugar to assist in the adhesion of the powder to the binder. Then I had to figure

out a good ratio of the mixed powder to the binder. To do this, I mixed them together until I was able to

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Guarriello, Rachel
 Lehigh Summer IMI for Advanced Glasses

shape the mixture by hand into a bar as shown in Figure 3. These bars were then used in more furnace

tests to develop a burnout cycle and sintering/ glass transition temperatures for the frits I had chosen to

work with.

Figure 3: Hand-shaped bars for testing 3D glass powder and binder combinations

Eventually, I narrowed down the powders I was going to work with and filled the 3D printer bed

with the glass/ powdered sugar/ dextrene mix. Unfortunately, however, due to the heat and humidity

in Portugal, the dextrene agglomerated overnight before we were able to print anything, but we tried

anyways. The resultant green parts were exceptionally fragile, and most broke as we tried to remove

them from the printer or clean the extra powder off. The two pieces that survived were placed in a

furnace to burnout the organic binders, sugar, and dextrene, and then were started in a sintering cycle.

Due to the low green density though, the parts didn’t sinter properly as shown below in Figure 4. I’m

continuing this work now as my senior thesis using a slurry typically used for ceramic tape casting as a

way to get better green density and hopefully, fully sintered parts.

Figure 4: 3D printed pieces from glass after sintering

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Guarriello, Rachel
 Lehigh Summer IMI for Advanced Glasses

Working in Portugal:

This past summer was not my first time going overseas for research as I’d gone to China the

summer after my freshman year. However, it was a very different experience in that I was mostly on my

own this summer. During my trip to China, I was with a Doctoral student and a post-doctoral student

from Penn State, whereas this summer, I was the only American student in the lab, and the only

undergraduate as well. This forced me to be very independent and figure things out on my own. One of

the biggest challenges for me was the language. I had to get around and go grocery shopping on my

own, so I had to learn enough Portuguese to do so which was fairly difficult since it’s barely similar to

Spanish at all aside from a few words. That sort of immersion in a completely different culture was very

new to me, and forced me to adapt. Additionally, being the only undergraduate researcher at Vicarte

had some interesting challenges of its own. Unlike at Penn State, I was not allowed to use most of the

scientific equipment by myself, so I had to work my schedule around the researchers that were certified

to work the equipment. There was a very different set of standards for research there than at Penn

State, a combination of being at a different institution and working mainly with artists.

However, aside from the challenges that came with being abroad and working in a new

environment, I learned a great deal at Vicarte and had the amazing opportunity to witness some truly

great works that came from the marriage of science and art at the institute. I was able to meet and

work with the Conservators that had worked on and repaired the beautiful stained glass windows at the

Peña Palace, shown below in Figure 5, as well as learning some basic glassblowing from the resident

artist. Some of the conservators there were working with tiles and pieces that have been around since

before North America was even discovered by Columbus through the assistance of the Portuguese

monarchs.

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Guarriello, Rachel
 Lehigh Summer IMI for Advanced Glasses

Figure 5: Peña palace Sinatra, Portugal

All things considered, the IMI was an amazing opportunity and learning experience for me, not

to mention that in the end, the glass samples from my experiments were sent to Murano, Italy for

further testing and use in some artistic pieces. To me, it’s amazing that my scientific work will be able to

contribute so much to various facets of art and historical conservation.

Figure 6: Me in the gardens of Peña Palace

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Guarriello, Rachel