Glass: an old material for the future of manufacturing

Susanne Klein, Fraser Dickin, Guy Adams, Steven Simske

HP Laboratories
HPL-2012-230
Keyword(s):
colloids; extrusion; 3D printing

Abstract:
Traditional assembly line manufacturing is speculative, costly and environmentally unsustainable. It is
speculative because it commits substantial resourcesenergy, materials, shipping, handling, stocking and
displayingwithout a guaranteed sale. It is costly because each of these resourcesmaterial, process,
people and placeinvolves expense not encountered when a product is manufactured at the time of sale. It
is environmentally unsustainable because, no matter how much recycling is done, not using the resources
unless actually needed is always a better path. Three-dimensional printing is currently of great commercial
interest as it can be employed to manufacture parts on-demand economically and without the significant
cost & environmental downsides, i.e. inventory and waste, associated with traditional manufacturing
processes. Herein, we describe the formulation of a novel water-based material which can be used in a
traditional 3D printer extrusion process to create optically transparent glass-based objects. Such objects
have a wide range of applications including, but not wholly limited to: security printing using color &
coating effects, protective films and coatings, electronic codes readable by smartphones, tablets or touch
screens. Additional all glass objects traditionally manufactured by the so called kiln glass method can be
generated by this type of 3D printing making it interesting for the high end market of art objects.

External Posting Date: November 21, 2012 [Fulltext]

Internal Posting Date: November 21, 2012 [Fulltext]

Approved for External Publication

Copyright 2012 Hewlett-Packard Development Company, L.P.

Glass: an old material for the future of manufacturing

Susanne Klein1, Fraser Dickin1, Guy Adams1, Steve Simske2
1
HP Labs, Long Down Avenue, Bristol BS34 8QZ, UK
2
HP Labs, 3404 E Harmony Rd, Ft. Collins, Colorado, 80528-9544, USA
ABSTRACT
Traditional assembly line manufacturing is speculative, costly and environmentally
unsustainable. It is speculative because it commits substantial resourcesenergy, materials,
shipping, handling, stocking and displayingwithout a guaranteed sale. It is costly because each
of these resourcesmaterial, process, people and placeinvolves expense not encountered
when a product is manufactured at the time of sale. It is environmentally unsustainable because,
no matter how much recycling is done, not using the resources unless actually needed is always a
better path. Three-dimensional printing is currently of great commercial interest as it can be
employed to manufacture parts on-demand economically and without the significant cost &
environmental downsides, i.e. inventory and waste, associated with traditional manufacturing
processes. Herein, we describe the formulation of a novel water-based material which can be
used in a traditional 3D printer extrusion process to create optically transparent glass-based
objects. Such objects have a wide range of applications including, but not wholly limited to:
security printing using color & coating effects, protective films and coatings, electronic codes
readable by smartphones, tablets or touch screens. Additional all glass objects traditionally
manufactured by the so called kiln glass method can be generated by this type of 3D printing
making it interesting for the high end market of art objects.

INTRODUCTION
Even after 30 years, the 3D printer market is still a niche market for prototyping and the
major obstacle inhibiting its market expansion is the limited number of materials which can be
printed and printed together. At present, 3D printing is mostly based on organic materials such as
ABS plastics or UV curable monomers. The functionality of the printed objects is constrained by
that of the underlying material, e.g. most printed plastic parts are not robust enough to withstand
daily usage. Consequently, the main application of 3D printing has been prototyping, and as such
it has not yet reached additive manufacturing. To transform 3D printing into a viable method for
additive manufacturing, it is necessary to expand the material choice.
The Ragnarok (Research on Advancing Glass & Nonorganic Applications to Recreate
Objects & Kinetics) project in HP Labs is targeting the more obvious of the replaceable
manufacturing processes using 3D printing methods. Casting, molding and sintering are the first
three processes receiving our attention.
We identified glass as a promising material for additive manufacturing. Glass is a silicabased material and with 90% of the Earths crust composed of silicate minerals there is no
shortage of silica resources. Glass is easy to recycle and is environmental friendly. With regards
to health and safety, inhaling glass dust without the appropriate EHS equipment can lead to
silicosis, but the consumer does not usually come into contact with glass dust. Otherwise glass

shows no ill health effects. Glass is a cheap material but looks precious, is pleasant to the touch
and its behavioral characteristics are well known such that customers will intuitively know what
applications it is most appropriate for.
Glass 3D printing has been attempted in the recent past but the results published [1] lack
both the smooth appearance and the optical transparency of traditionally made glass. A
photograph showing an example of glass printing by a group in Washington University is shown
in Figure 1 below.

Figure 1: 3D printed glass using a powder bed method and sugar as binder. The objects do not
look like glass as a result of the powder bed method and the resulting matt surface. There is also
discoloration caused by caramelization of the binder material

EXPERIMENTAL DETAILS
To stay as environmentally friendly as possible and to avoid health and safety issues
during production, we concentrated on water as the solvent and bio-polymers as binders for our
glass pastes. We used binders from the following groups: saccharides, clays, collagens and
cellulose. Glass powder, binder and water were worked into a paste which was then extruded
through an Auger print head mounted in a RapMan 3D printer, as shown in Figure 2.

Figure 2: Printing of glass paste with a modified RapMan 3D printer

After printing, the objects were thoroughly dried and the so called greenware was then fired in a
kiln.
DISCUSSION
Printing by extrusion generates a glossy, that is glassy, surface appearance since the
printed object does not come into contact with any powder. Reduction of binder content prevents
caramelization. Between 110C and 180C all saccharides transform into polymeric caramel.
Above 250C caramel decomposes into carbon mon- and di-oxide, hydrocarbons, alcohols,
aldehydes, ketones and several furan derivatives (for more detail see [2]) which are volatile and
evaporate from the samples as long as they are not trapped or do not undergo chemical reactions
with the glass surface. We have found that reducing the saccharide content of the glass paste to 5
to 10wt% on the weight of glass frit resolves the problem of discoloration. In table 1 we show
the minimum binder content for a printable glass paste as a function of the type of saccharide and
the resulting discoloration. The required binder percentage for cellulose, collagen and clay
binders is on average below 10 wt% and discoloration has not been observed.
Saccharide

Minimum percentage on
weight of glass powder

Discoloration

Dextrin
Dextrin/fructose
Pectin from citrus peel

40 wt%
25/25 wt%
10 wt%

Yes
Yes
No

Chitosan
Xanthan gum

5 wt%
5wt%

No
No

Table1: Minimum saccharide content for printable pastes.

In addition, extrusion printing allows the combination of different colors in one printing
process, as can be seen in Figure 3.

Figure 3: multiple color glass object.

From a traditional glass production process, kiln glass, it is known that the finer the powder, the
finer the detail, but the less transparent the final object. We tested powders with grain sizes in the

range from 200 nm up to 200 m. We have found that glass powders with grain sizes larger than
38 m samples are translucent. Powders with smaller grain sizes lead to opaque samples (figure
4).

Figure 4: Optical appearance as a function of particle size.

The shift in color indicates that the opaque appearance is caused by scattering from glass/air
interfaces, but density measurements did not confirm this assumption. The spread of densities
within sample groups of the same size is as big as the overall spread over all sizes, as can be seen
in figure 5. All samples were processed following the same procedure and firing schedule.

Figure 5: Densities of glass samples as function of the grain size in the extruded glass paste.

CONCLUSIONS

We have developed several formulations for printable glass pastes which were tested with
a modified RapMan 3D printer. The best recipes lead to translucent objects which are shape and
color true and have the appearance of classic glass. True optical transparency has not yet been
reached. Experiments with submicron grain sizes have led to opaque objects with very fine
detail, but lacking the required glass-like finish (see also [3]). More research is needed to explain
that kind of behavior. To reduce the production time, we have also started exploring paste
formulations which allow to the firing step to be skipped without adversely compromising the
mechanical integrity of the object. As can be seen in Figure 6, the firing step is the most timeconsuming aspect of the process.

Figure 6: For fired glass, fusing and cooling (summarized as firing shown in green) is the most time consuming
part of the production process. Skipping the firing stage would reduce production time radically.

First results show that greenware with cellulose binders show enough structural stability to
replace fired glass in certain applications where the optical appearance is not the most important
consideration.

REFERENCES
[1] http://open3dp.me.washington.edu/2009/09/3dp-glass-recipe/
[2] J. Claude, J. Ubbink, Food Chemistry 96, 402-410 (2006)
[3] S. Klein, et al., PG 336, Proceedings of NIP and Digital Fabrication 2012