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3D Printing With Polymers Challenges Among Expanding Options and Opportunities
3D Printing With Polymers Challenges Among Expanding Options and Opportunities
ScienceDirect
a r t i c l e i n f o a b s t r a c t
∗
Corresponding author at: Department of Craniofacial Biology, School of Dental Medicine, University of Colorado Anschutz Medical
Campus, 12800 East 19th Avenue, MS 8310, Aurora, CO 80045, USA. Tel.: +1 303 724 1044; fax: +1 303 424 1945.
E-mail addresses: jeffrey.stansbury@ucdenver.edu (J.W. Stansbury), mike.idacavage@cpspolymers.com (M.J. Idacavage).
http://dx.doi.org/10.1016/j.dental.2015.09.018
0109-5641/© 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 54–64 55
Curing light
Inkjet heads
Leveling blade
Part
Support
casting applications, which is often encountered in dentistry controlled additional energy input by a high-power CO2 laser,
and in jewelry design applications. Much work has already which traces the 2D layer design that fuses exposed particles
developed a range of UV-curable inkjet inks for 2D printing together within the layer as well as connects it to the previ-
applications. These formulations are typically composed of ously scanned underlying layer (Fig. 5). The laser power (up to
monomers, oligomers, colorants (pigments or dyes dispersed 20–50 W), beam size (typically about 0.5 mm), beam speed and
or dissolved in the reactive carrier), photoinitiator(s) and spacing between scans (both physical, known as hatch spac-
other additives. A UV-curable ink applied as an oil-in-water ing, and temporal) needs to be carefully controlled to balance
emulsion has been used to create intentional well-controlled effective sintering while avoiding polymer property degrada-
porosity in parts upon curing followed by evaporation of the tion that comes with overheating [22]. The sintering steps are
aqueous phase. With a co-continuous phase structure in the interspersed with application of an incremental layer of pre-
ink, interconnected pores can be obtained in printed parts that polymer powder of approximately 100 m applied by a roller or
permit infiltration to achieve, for example, conductive mate- blade. Since the polymer powders are approximately 30–90 m
rials [19]. Inks can contain nano-fillers such as silica, clay of in dimension, this means only about 2–4 particles represent a
suitable dimension to be accommodated within a jetted ink layer thickness. This minimizes the extent of indirect heating
droplet to provide both viscosity control during deposition as based on thermal conductivity to provide effective sintering.
well as reinforced mechanical properties in the final part [20]. The particles must be free flowing since layers receive no
A leveling blade can be used between layers to assure uni- further compaction. Therefore, particle size, shape and free
form build layers prior to exposure to the UV curing lamp packing density are critical factors in the material design along
and z axis stage translation in preparation for the next layer. with the thermal behavior. Spherical particles flow more eas-
The parts produced are dimensionally accurate and can be ily and pack more densely than irregular shapes so ground
robust in their mechanical properties; however, the build ori- polymer processing is problematic since it creates irregular
entation can significantly affect elastic modulus and fracture particle shape and a broad distribution of particle size. Par-
stress but tensile strength is relatively insensitive to print ticles that are too small create processing difficulties due
direction [21]. However, as with all 3D printing approaches, to either excessive cohesion or electrostatic repulsive forces.
the degree of isotropic mechanical property character can vary After the part is completed, the entire building chamber is
greatly based on the material used with any given building cooled slowly to maximize polymer crystallization to provide
process. added strength as well as to reduce stress development and
Selective laser sintering (SLS) was introduced soon after improve dimensional accuracy, which can be improved fur-
the SLA technique but it employs primarily semi-crystalline, ther by incorporation of shrinkage modeling into the initial
particulate thermoplastic prepolymer as the building mate- part design [23,24]. The unsintered powder serves as the phys-
rial. The technique relies on two energy sources accomplish ical support for the part throughout the process. The free
part production. First a bed of polymeric particles is preheated powder is removed at the end of the build cycle and it can
close to the melting transition and above the temperature generally be reused albeit with concerns of material alter-
necessary for recrystallization during the cooling cycle. The ation related to oxidation (which can be mainly avoided by an
preheated powder bed limits the energy input necessary inert gas purging), thermal degradation and even increases in
from the laser to cause sintering, which avoids large thermal polymer molecular weight (with changes in many properties
differentials that would otherwise result in part distortion. including reduced polymer crystallinity) during the extended
Localized thermal sintering of the particles is achieved by the heating process. This means that recycled polymer typically
d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 54–64 59
is mixed with virgin powder for subsequent use [25]. Rather may be desired so that a secondary infiltration with an epoxy
than the aging effects associated passive heating, a separate resin or wax can be used to provide parts with much enhanced
study investigated PA12 material alterations resulting from mechanical properties or varied surface finish [14]. While
the higher temperatures as a result of direct laser exposure at poly(methyl methacrylate) is used widely in dentistry and
varied power levels. The results were that higher laser power many other amorphous commodity polymer applications,
resulted in PA12 chain scission as evidenced by lower viscosity PMMA has only recently been adapted for use in 3D prin-
and lower values for elongation at break [26]. ting [35]. As with all the polymer powders, very rigorously
The scanned laser produces a melt zone within the polymer controlled, high-grade material stocks are required. So while
powder bed that has a comparable radius in both the horizon- the palate of polymers for use in SLS is growing, it is orders
tal and vertical dimensions. Within this zone, depending on of magnitude smaller than the choices of polymers available
particle size and laser power, adjacent particles may be com- for injection and extrusion molding applications. A range of
pletely melted or just liquefied at the particle surface with fillers, such as silica, aluminum, carbon fiber and glass can
gravity and capillary forces serving to produce consolidation also be incorporated into the powdered polymer to further
[27]. In addition to the more dense core within the scanned modify the appearance and properties of the printed parts.
beam path, the sintered zone extends to a more loosely One study has demonstrated that the SLS processing intro-
bound and less dense boundary layer that was exposed to duces an orientation bias of micro-scale carbon fiber filler in PA
less power and lower temperatures based on thermal conduc- parts [36]. Silica can be added separately to polymer powders
tivity [28]. When the processing conditions are well matched to improve flow properties. Achieving uniform distribution of
to the polymeric material [29], including the hatch spacing filler in a mixed powder system where differences in particle
between adjacent scans in the x/y plane, reasonable mechani- size and density are involved makes this nontrivial. The fac-
cal strength and good toughness can be achieved with certain tors that govern a successful material are quite complex in
materials. One approach to reaching increased part den- terms of both the polymer powder production and its inter-
sity, minimizing defects and improving mechanical properties action with the SLS process [37]. The current state-of-the-art
involves the application of pressure in the build chamber [30]. in SLS is that a given material will have significantly different
Polyamide (PA12 or nylon 12) represents the vast majority mechanical properties based on how it is oriented [38], and
of the current commercial SLS materials market. Alterna- processed within a given device and that because of the sen-
tive materials include other polyamides (PA6, PA10, PA11), sitivity of the materials to the process conditions, the same
poly(acrylonitrile/butadiene/styrene) (ABS), polystyrene (PS), material used on different devices can produce quite varied
polycarbonate (PC) and work continues to develop polypropyl- results [27]. Certain materials, PA12 being a good example, are
ene, high-density polyethylene, polyether ether ketone (PEEK) more forgiving in that regard but the transition from printed
among others for use in polymer powder form. Significantly structures used mainly as models toward 3D printed func-
higher powder bed heating temperatures are necessary to tional parts remains a challenge; however it is a target toward
allow use of high performance polymers such as PEEK. These which definite progress is being made. A technology known
high powder processing temperatures (∼350 ◦ C) limit poten- as Selective Heat Sintering (SHS) utilizes a thermal printhead
tial recycling of the non-fused PEEK powder, which greatly rather than a laser to fuse the surface of a powdered thermo-
increases the production expense, while also excluding its use plastic into patterned, layered structures analogous to the SLS
with most commercial SLS devices [27]. approach.
Semi-crystalline polymers are primarily used with the Another AM technique that relates to both SLS and MultiJet
intrinsic selection criteria ideally including a broad process printing is the binder jetting process. This method originally
temperature window between polymer melting upon heating gave rise to the term “3D printing” that subsequently has
and recrystallization upon cooling, a narrow melt transition, been broadened to include all the additive manufacturing
and a high melting enthalpy to minimize unwanted sinter- approaches described here. A liquid binder is delivered with
ing associated with thermal conductivity [31]. The surface high spatial resolution to a powder bed surface from a print
tension of the particle must also be sufficient to avoid inter- head. The binder connects just the exposed particles together
particle fusion even though the powder is maintained far either through solvent welding or chemical reaction with no
above its glass transition temperature for extended inter- thermal processing necessary, which improves building effi-
vals. The polymers can be selected to yield parts that are ciency since no cooling cycle is involved and the unexposed
glassy or elastomeric. The preheating and laser sintering con- powder stock can be freely reused. The powder can be poly-
ditions can be empirically modified to account for differences mer or many other materials and a range of binders can be
in melting temperatures of materials as well as also being employed based on the powder used. With some materials, a
able to work with amorphous polymers that display elevated dilute polymer solution is used as the binder. The layers need
glass transition temperatures. Amorphous polymers such as to remain small to allow effective binding between incremen-
polycarbonate or polystyrene tend to yield weaker, more tal layers while also achieving reasonable x/y resolution. The
porous structures than the semi-crystalline polymer pow- choice of polymeric powder materials can be much broader
ders [32], although relatively brittle polystyrene parts can be than that associated with SLS since the constraints involved
strengthened and toughened by substitution of poly(styrene- with thermal processing windows are largely avoided; how-
acrylonitrile) or ABS [33]. However, amorphous polymers do ever, for solvent welded parts or in applications with solvent-
not undergo the significant dimensional contraction associ- carried adhesives, there are obvious solvent resistance con-
ated with polymer crystallization as the process temperature siderations. The ability to use multi-print heads dispensing
is reduced [34]. In some situations, a more porous structure binder of different colors provides a means to produce blended
60 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 54–64
to print the car was significantly less than that associated patterns for fixed prosthodontics, surgical guides, and com-
with typical auto manufacturing practices. plete removable dentures. Based on individual patient data,
A recent marriage between filament deposition 3D printing implant drill guides [61] as well as thermo-formable orthodon-
and electrospinning has further expanded the possibilities tic patterns [62] and aligners are also in use in dental offices
for the preparation of reinforced tissue engineering scaffold with additive manufacturing devices designed exclusively for
structures among other applications. By moving the collec- dental and medical applications being very actively promoted
tor plate in the same fashion as FFF techniques, the random to the dental profession. Models of mandibles and other com-
coiling nature of the electrospinning process can be cir- plex tissue structure can be realized relatively rapidly based on
cumvented to form very well defined continuous patterned the 3D data obtained by digital scanning techniques including
structures [47–49]. Laminated object manufacturing (LOM) is laser scanning, computerized tomography (CT) and magnetic
yet another layered manufacturing technique that uses a resonance imaging (MRI) [63–65]. Materials have been specifi-
variety of materials including polymer-based foils in layer- cally designed to produce life-like colors and textures for teeth
by-layer application process interspersed with cutting with a and gingiva in models. Recent advances in 3D printing speed
blade or laser to achieve spatial patterning within each of the while retaining the potential for high spatial accuracy and res-
laminated film layers [50]. Thus, this approach represents a olution will only further expand these opportunities. One such
compromise between additive and subtractive manufacturing opportunity is demonstrated by the option to make printed
strategies in the building of three dimensional structures. structures that include bioactive components. As an exam-
The areas of 3D printing in bioengineering including bio- ple, a drug (nitrofurantoin) as well as hydroxy apatite were
printing, which involves printing structures that include cells, blended into PLA to obtain an extruded filament with up to a
DNA and other bioactive components as integral parts of the 30% mass fraction of drug that could be processed by FFF to
building process, are growing at a remarkable rate [51,52]. Labs create a device that prevented surface-associated and plank-
everywhere are printing prototypic organs including heart tonic growth of Staphylococcus aureus [66]. The development
valves, ears, artificial bone, joints, menisci, vascular tubes of 3D printed drug delivery devices with spatial variations in
and skin grafts. The structural and compositional complexity drug loading and material properties is an area of growing
associated with many types of tissue mimics greatly compli- interest that will likely find application in dentistry [67]. The
cates both the programming and the printing [53]. Even the accuracy of 3D printed dental models relative to plaster casts
tremendous challenge of achieving viable vascularized tissue has been documented [68]. However, a recent study focused on
constructs is potentially enabled by the additive processing the dimensional fidelity of printed die spacers relative to the
approach [54,55]. In tissue engineering, the ability to repro- input computer-aided design parameters for crown fabrica-
ducibly print the physical aspects of a tissue scaffold or other tion demonstrated some inaccuracies and inconsistencies in
constructs for use in complex cell-based studies means that print-producing these sub-100 m details [69]. As the materi-
this physical parameter can be removed as a variable while als, the 3D build design software and the hardware associated
the chemical, mechanical or other properties of a scaffold are with the building processes continue to improve, obviously
systematically probed. Alternatively, physical features such as more mainstream as well as specialized applications of 3D
pore structure in a given scaffold material can be manipulated polymer-based printing in dentistry will continue to develop
at will [56]. Poly(latic acid) is commercially available for SLS with further expansion into both dental labs and dental
and FFF printing applications and because of the widespread practices.
use of PLA in other forms in human, animal and cell-based It should also be noted that there are well-designed studies
studies, it is a popular choice for biomedical related poly- to compare the dimensional accuracy, mechanical proper-
mer printing [57]. Polycaprolactone is also being evaluated as ties, surface roughness, build speed and materials cost across
a biodegradable printed scaffolding material [58]. Due to the multiple 3D printing platforms [70]. This demonstrates that
specific material requirements associated with scaffolds for there are advantages and disadvantages associated with each
bioengineering, microfluidic devices, drug delivery vehicles approach. As the penetration of additive manufacturing con-
and many other biological applications, the medical field has tinues to grow and evolve in the industrial world as well as in
actually significantly expanded the number of new polymers the varied arenas of dental/biomedical materials and tissue
that have been examined for use in 3D printing applications engineering, quality standards associated with the wide array
[59]. of 3D printing processes and materials becomes of greater con-
Additive manufacturing of polymeric biomedical materi- cern. To address this issue, ASTM International Committee
als are also being applied to dentistry with patient-specific F42 on additive manufacturing technologies has been engaged
constructs used in clinical applications beginning to emerge and there is an ASTM standard (F2792-12a) on the standard ter-
[60]. This type of hard and soft tissue repair will certainly minology for additive manufacturing technologies [71]. The
expand and there are predictions of printed replacement National Institute for Standards and Technology has pro-
teeth but as with the other organ printing considerations, posed a standard AM test artifact [72]. This artifact would
implementation of these prospects remains an aspiration on permit independent, objective assessment of build quality
the horizon. Current mainstream polymer-based 3D printing based on standardized measurements. The proposed arti-
applied to clinical dental practice include dental wax-ups, fact would be large enough to provide features near edges of
orthodontic patterns, crown and bridge molds, which can offer build platforms as well as central locations and contain prac-
quicker turnarounds along with local control of the model tical features such as flat surfaces, ramps, arcs, thin walls,
processing. Presently, 3D printing is being used in dental labo- holes and protruding features over a broad range of length
ratories around the world. Restorative labs are using it to make scales.
62 d e n t a l m a t e r i a l s 3 2 ( 2 0 1 6 ) 54–64
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