1 s2.0 S0079670018303265 Main

Progress in Polymer Science 97 (2019) 101144
Contents lists available at ScienceDirect
Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci
Polymer Design for 3D Printing Elastomers: Recent Advances in

Structure, Properties, and Printing
Jana Herzberger a,1,2 , Justin M. Sirrine a,2 , Christopher B. Williams b , Timothy E. Long a,∗
a
Department of Chemistry, Macromolecules Innovation Institute, Virginia Tech, Blacksburg, VA 24061, USA
b
Department of Mechanical Engineering, Macromolecules Innovation Institute, Virginia Tech, Blacksburg, VA 24061, USA
a r t i c l e i n f o a b s t r a c t
Article history: Elastomers are a unique and important class of polymers that enjoy applications in virtually every
Available online 26 July 2019 industry, including healthcare, aerospace, automotive, and apparel. However, due to inherent physi-
cal, thermal, and mechanical properties of elastomers, the additive manufacturing (AM) of elastomers
Keywords: remains challenging. These challenges are discussed in the context of various AM processes, includ-
3D Printing ing powder bed fusion, material extrusion, and vat photopolymerization. This review provides an
Elastomers
in-depth discussion of the current state of silicone and polyurethane polymers for AM, and also dis-
Vat Photopolymerization and Additive
cusses polyesters/polycarbonates, liquid crystalline elastomers, and monomer compositions that provide
Manufacturing
elastomeric properties upon photocuring. Finally, the current state of common, commercially-available
elastomers for AM is provided, as well as an outlook for this rapidly progressing field. We expect this
review to be useful for any research involved with the additive manufacturing of elastomers.
© 2019 Elsevier B.V. All rights reserved.
Abbreviations: 2D, two dimensional; 2PP, two-photon polymerization; 3D, three dimensional; ABS, acrylonitrile butadiene styrene; AM, additive manufacturing; AUD,
aliphatic urethane diacrylate; BDI, 1,4-diisocyanatobutane; BDO, 1,4-butanediol; BPO, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide; CAD, Computer-aided design;
CL, caprolactone; CLIP, continuous liquid interface printing; CO2 , carbon dioxide; CTA, chain transfer agent; DABCO, 1,4-diazabicyclo[2.2.2]octane; DBB, 1,2-dihydroxy-4-
tert-butylbenzene; DCM, dichloromethane; DEA, dielectric elastomer actuators; DIW, direct ink writing; DLP, digital light processing; DLS, dynamic light scattering; DMA,
dynamic mechanical analysis; DMD, Digital Micromirror DeviceTM ; DMF, dimethylformamide; DMPA, 2,2-bis(hydroxymethyl)propionic acid; DSC, differential scanning
calorimetry; e-3D printing, embedded 3D printing; EAA, epoxy aliphatic acrylate; EDDT, 2,2’-(ethylenedioxy) diethanethiol; EGTG, ethylene glycol bisthioglycolate; EGVE,
ethylene glycol vinyl ether; ETCH, 1-ethynyl-1-cyclohexanol; ETLA, ethyl lactate; FDA, food and drug administration; FDM, fused deposition modeling; FFF, fused filament
fabrication; FRE, freeform reversible embedding; G’, shear storage modulus; G”, shear loss modulus; GPC, gel permeation chromatography; H12 MDI, hydrogenated methy-
lene diphenyl diisocyanate; HDI, 1,6-hexanediisocyanate; HEA, hydroxyethyl acrylate; HEMA, hydroxyethyl methacrylate; HMDI, hexamethylene diisocyanate; HS, hard
segment; HTV, high-temperature vulcanization; IPDI, isophorone diisocyanate; LC, liquid crystal; LCE, liquid crystalline elastomer; LDI, lysine diisocyanate; LOPP, low one-
photon polymerization; LSR, liquid rubber silicone; MA, monoacrylate; Mc , molecular weight between crosslinks; MDI, methylene diphenyl diisocyanate; Me , entanglement
molecular weight; Mn , number average molecular weight; MSDS, materials safety data sheet; MW, molecular weight; NA, not available; NaOH, sodium hydroxide; NP,
nanoparticle; NSC, neural stem cells; O2 , oxygen; Oh , Ohnesorge number; PA, polyamides; PBF, powder bed fusion; PBS, buffered saline solution; PC, polycarbonate; PCL,
polycaprolactone; PDLLA, poly(D,L-lactide); PDMS, polydimethyl siloxane; PDMSDMAA, ␣,␻-dimethacrylamide polydimethylsiloxane; PDMS-E, ␣,␻-dimethacryloxypropyl
PDMS; PDMS-S, poly(methacryloxypropyl siloxane-co-dimethylsiloxane); PDPS, diphenylsiloxane; PEG, poly(ethylene glycol); PEGDA, polyethylene glycol diacrylate; PEO,
poly(ethylene oxide); PEU, poly(ester urethane); PGS, poly(glycerol sebacate); PhEA, 2-phenoxyethyl acrylate; PHMS, polymethylhydrosiloxane; PLA, polylactic acid; PLBSI,
poly(lactate/butanediol/sebacate/itaconate) copolyester; PLLA, poly(L-lactide); PMMA, polymethyl methacrylate; PS, polystyrene; Pt, platinum; PTMC, polytrimethylene
carbonate; PTMO, poly(tetramethylene oxide); PU, polyurethane; PUD, polyurethane dispersion; PUU, poly(urethane urea); PVA, polyvinyl alcohol; RM82, 1,4-bis-[4-(6-
acryloyloxhexyloxy)benzoyloxy]-2- methylbenzene; Rmax , maximum end-to-end distance; RTV, room temperature vulcanization; SAXS, small angle x-ray scattering; SDS,
sodium dodecyl sulfate; SEBS, poly(styrene-block-ethylene/butylene-block-styrene); SEM, scanning electron microscopy; SEPS, poly(styrene-block-ethylene/propylene); SL,
stereolithography; SS, soft segment; Tc , clearing temperature / isotropic transition temperature; Td , thermal decomposition temperature; TDI, toluene diisocyanate; TEA,
triethylamine; TEM, transmission electron microscopy; Tg , Glass transition temperature; Tm , melting temperature; TMC, trimethylene carbonate; TPE, thermoplastic elas-
tomer; TPO-L, ethyl (2,4,6-trimethylbenzoyl) phenylphosphinate; TPP, two-photon polymerization; TPU, thermoplastic polyurethane; TPV, thermoplastic vulcanizate; UDA,
urethane diacrylate (e.g. Genomer 4215); UV, ultraviolet; VPP, vat photopolymerization; WDPU, water dispersible polyurethane; ZP, zeta potential; , viscosity.
∗ Corresponding author.
E-mail address: telong@vt.edu (T.E. Long).
1
Current institution: Department of Chemical and Materials Engineering, University of Kentucky, Lexington, KY 40506, USA
2
These authors contributed equally to the work.
https://doi.org/10.1016/j.progpolymsci.2019.101144
0079-6700/© 2019 Elsevier B.V. All rights reserved.
2 J. Herzberger, J.M. Sirrine, C.B. Williams et al. / Progress in Polymer Science 97 (2019) 101144
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Elastomer Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Overview of 3D Printing Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.1. General overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2. Vat photopolymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.3. Fused filament fabrication (FFF) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.4. Direct ink writing (DIW) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.5. Inkjet printing / material jetting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.6. Polymer powder bed fusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
4. Challenges of 3D Printing Elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
5. Silicone Elastomers – Synthesis and Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5.1. Properties of silicone elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5.2. Synthesis of silicone elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5.3. Traditional processing of silicone elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
6. Additive Manufacturing of Elastomeric Architectures using Silicone Precursors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
6.1. Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
6.2. Direct ink writing of silicone elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
6.3. Two-photon absorption microstereolithography of PDMS-based elastomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
6.4. Vat photopolymerization/SL to yield elastomeric polysiloxanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
6.5. Inkjet printing of silicones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
7. Polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
7.1. Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
7.2. Chemistry of polyurethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
7.3. Traditional polyurethane printing in solution (material extrusion, inkjet printing) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
7.4. Waterborne polyurethane dispersions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
8. Photopolymers for Vat Photopolymerization or Inkjet Printing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
9. Additive Manufacturing Using Polymer Emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
10. Liquid Crystalline Elastomers (LCE) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
11. Polyesters and Polycarbonates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
12. 3D Printing of Commercially Available Elastomer and Elastomeric-Like Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
13. Conclusions and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
1. Introduction
tire companies recently released their vision of the future tire. [4,5]
Thermoplastic elastomers and crosslinked rubbers remain an Starting from recycled or bio-based materials, they propose 3D
extremely important polymer class and enjoy a global demand printing airless and lightweight tires. Their design would provide
expected to rise 5.2 % annually to a total of 6.7 million metric tons improved shock-absorbing properties and enhance the safety of a
in 2019. [1,2] Their versatile properties render them ideal materials tire, due to improved wet grip and puncture resistance. One of these
for everyday usage in products that include car tires and footwear, companies also envisions a customized tread pattern, enabling
medical tubing in health care applications, automotive and aircraft the customer to reprint the tread pattern at a service station for
sealants, and soft robots. Named as a portmanteau of the words demanding weather conditions such as ice or snow. [4] Both con-
“elastic” and “polymer,” elastomers are composed of long polymer cepts demonstrate the importance of AM and materials design for
chains that undergo shape recovery after being subjected to often- a more sustainable future.
large applied strains. While crosslinked rubbers permanently retain This review highlights the recent achievements in additive man-
their shape as a result of their covalent crosslinks, thermoplastic ufacturing of elastomers and elastomeric-like materials. It aims
elastomers may be re-shaped, often by heating and subsequent re- to elucidate synthetic strategies and required material properties
forming above their highest transition temperature. Both classes that enable 3D printing of elastomers with a focus on silicone- and
of materials possess unique strengths and are suited to individual polyurethane-based materials. A brief introduction of relevant AM
applications. techniques and synthetic methods to prepare elastomers provide
The advent of additive manufacturing (AM), also known as the reader with the proper background information for the detailed
three-dimensional (3D) printing, inspired academic and industrial sections that discuss 3D printing of elastomers. Finally, a short per-
researchers to combine elastomeric properties with design free- spective outlines potential future work and inspires the reader to
dom and the potential for facile mass customization. This enabled solve ongoing challenges.
the production of customized articles, e.g. headphone or hearing aid
inserts, dental retainers, and footwear. For example, in 2015, a large 2. Elastomer Properties
footwear manufacturer reported the first 3D printed shoe sole uti-
lizing selective laser sintering of thermoplastic polyurethanes. [3] Elastomers are crosslinked polymer networks which exhibit
Due to its reliance on polymer deposition only at the desired 3D low crosslinking density and possess high molecular weight poly-
pixels (voxels) in a 3D design, instead of reliance on standard sub- mer strands between crosslinks. When an external stress is
tractive manufacturing methods, AM significantly reduces material applied to an elastomer, the long polymer strands alter their
waste, enables lightweight design through printing of low-density, chain conformation and enable a large deformation of the net-
high-strength truss geometries, and provides the ability for mass work, while the crosslinks prevent flow. A typical elastomer
customization where each part remains customized to the needs of may be stretched up to 10 times its original length, reach
the individual. Inspired by the potential of 3D printing, two major extremely high elongation at break (e.g. ≥ 400-1000 %), and recov-
J. Herzberger, J.M. Sirrine, C.B. Williams et al. / Progress in Polymer Science 97 (2019) 101144 3
Scheme 1. Shore hardness scale of everyday products.
ers its shape when the stress is released. [2,6] The crosslinks are
either chemical or physical in nature. While chemical crosslinks
are permanent, physical crosslinks are reversible and can be
disrupted upon swelling or heating to elevated temperatures.
Examples of physical linkages are small crystallites, coalesced
ionic centers or glassy bonds, or adsorbed polymer chains onto
the surface of fillers. [6] Most thermoplastic elastomers (TPEs)
are based on microphase-separated networks, meaning that a
glassy or crystalline region acts as the hard phase (crosslinks)
and a low Tg polymer provides chain flexibility and mobil-
ity (soft phase). In this latter case, the Tg must be below the
desired use temperature. Examples of TPEs are polyurethanes,
styrene triblock copolymers (poly(styrene-butadiene-styrene) or
poly(styrene-isoprene-styrene)) and polyester elastomers, e.g.
with polybutylene terephthalate as hard phase and a polyether as
soft phase. In contrast, PDMS elastomers typically consist of chemi-
cal crosslinks and are thermosets, although in certain cases a PDMS
can form the soft block of a TPE, resulting in PDMS TPEs. [6]
Important characterization techniques for elastomers include
tensile testing (e.g. stress-strain behavior), hardness measure-
Fig. 1. Typical stress-strain behavior for a(n) (A) brittle polymer, (B) thermoplastic,
ments, compression testing, shear and flexural measurements, tear
and (C) elastomer.
testing, and friction/abrasion property measurements. [7] Dynamic
stress/strain measurements, including dynamic mechanical anal-
ysis (DMA) of solid-like samples or melt rheology of liquid-like
close to 0 or 100 for a Shore A hardness measurement, care must
samples, also provide important viscoelastic information. Fatigue
be taken to select the proper hardness scale.
measurements remain important for any object that may undergo
Tensile testing also provides a large quantity of useful informa-
repeated cycling, while creep, relaxation, and set measurements
tion for the characterization of elastomer behavior. [7,8] Typically
probe the elastomer behavior as a function of deformation and
performed in uniaxial tension, an instrument pulls on a sample and
time. Gas permeability and electrical property measurements also
measures force (with a load cell) as a function of extension. This
remain important for select applications. Details for these methods
data is later normalized according to sample cross-sectional area
are provided elsewhere, while two common techniques are briefly
and original sample length to provide stress (e.g. MPa) vs. strain
discussed below. [7]
(e.g. [l-l0 ]/l0 , unitless) behavior as a function of testing environ-
Shore durometer measurements represent one type of hard-
ment, which includes strain rate, temperature, and atmosphere.
ness measurement and an overview of materials and their Shore
[8] Typical data for a thermoplastic elastomer is shown in Fig. 1
hardness are depicted in Scheme 1. [7] The durometer mea-
as curve C. [8] As mentioned above, elastomers typically possess
sures the resistance of a polymer to mechanical indentation of a
large, recoverable strains with accompanying low stress levels.
spring-loaded steel rod and is frequently employed for hardness
Primarily entropic in nature, ideal polymer chains possess stored
determination of elastomers. The spring force and type of inden-
elastic energy in the form of free energy. [9] As elastomers undergo
ter ranges with the type of polymer (soft vs. hard), with higher
elongation, the original Gaussian distribution of polymer chain
numbers representing harder than softer materials. Extremely soft
end-to-end distances becomes elongated up to the point of non-
materials are measured using a Shore 00 durometer, whereas
Gaussian behavior, where the finite extensibility of polymer chains
harder materials are characterized using a Shore D durometer.
induces strain hardening (e.g. an increase in stress at high strain).
Values from 0 to 100 indicate maximum indentation and almost
[9] The Young’s modulus of elastomers, which is defined as the ratio
no indentation, respectively. Most elastomers typically fall on the
of the stress to the strain in the linear elastic regime, is typically on
Shore 00 and Shore A ranges. Due to the decrease in sensitivity
the order of several MPa or lower, which makes elastomers attrac-
of various hardness scales at the bounds of the measurement, e.g.
tive to mimic biological tissue. [10] Furthermore, the area under a
Fig. 2. Schematic of three common types of vat photopolymerization. (a) Stereolithography. (b) Digital light processing vat photopolymerization. (c) Two-photon polymer-
ization. [13] Copyright 2015. Reproduced with permission from Springer New York.
tensile stress-strain curve is known as toughness, which represents platform lowers further into the photopolymer vat (z direction),
the work done to fracture the material. [8,11] Thus, tensile testing permitting recoating of the previously printed layer with uncured
provides a multitude of useful information with only one test. photopolymer. The UV laser is then scanned across the second layer
in the x-y plane. This process repeats itself until completion of
3. Overview of 3D Printing Techniques the print, after which the printed object lies encased in the vat of
uncured photopolymer. Isolation of printed objects simply requires
3.1. General overview removal from the build platform, removal of uncured resin and an
optional post-cure in a UV chamber, which converts any remaining
Here, we introduce the types of additive manufacturing (AM) UV-responsive functionality within the part. Digital light process-
that are most employed in the 3D printing of elastomers. A general ing (DLP) VPP, shown in Fig. 2b, occurs in a similar manner to vector
overview of various types of AM technologies is provided in more scan SL, except that the UV light is reflected onto an unmoving Dig-
detail elsewhere. [12] ital Micromirror DeviceTM (DMD) that exposes entire layers with
masked UV light all at once. VPP remains a popular AM method
for elastomer production, typically when processed in a top-down
3.2. Vat photopolymerization apparatus, though challenges exist and are discussed below. In the
case of two-photon polymerization (TPP), shown in Fig. 2c, two
Vat photopolymerization (VPP) involves directed energy depo- independent scanning laser sources are focused on a single 3D pixel
sition upon the surface of a photocurable mixture of monomers, element, or voxel, within the build volume. Polymerization occurs
oligomers, and/or polymers, termed a photopolymer, inside a con- only at the intersection of the laser sources, thus enabling a high
tainer, or vat. [12,13] Multiple literature reports discuss this and degree of control over print resolution. Additionally, TPP removes
other types of additive manufacturing in great detail, elsewhere. the need for recoating and the movement of a build platform, as the
[12] A recently published review also discusses photopolymers for laser source intersection is controllable in the x-y-z build volume.
3D printing in general terms. [14] In brief, Fig. 2a depicts top- However, in addition to characteristically small build volumes, TPP
down vector scan stereolithography (SL), where top-down refers requires highly customized, femtosecond laser sources and printing
to the direction of UV light impingement. Top-down SL avoids the apparatus remain relatively expensive, thus limiting applications
repeated delamination step from the UV-transparent window that primarily to tissue engineering. [12,14] Typical resolution for laser-
is common with bottom-up SL. This helps prevent damage of the based VPP is in the range of a few microns in the x-y build plane,
soft, delicate features that are common with 3D printed elastomers. while DMD-based VPP possesses x-y resolution in the 10-50 ␮m
In top-down SL, the energy source, typically ultraviolet (UV) light, is range, due to limitations in the number of pixels/micromirrors in
reflected off a scanning galvanometer onto the photopolymer sur- the DMD. [12] Resolution in the z-direction remains controlled by
face and initiates polymerization. After photopolymerization of the the capabilities of the build platform stepper motor, as well as resin
first layer in the plane of the build platform (x-y plane), the build
Fig. 3. Schematic of continuous liquid interface printing (CLIP). [15] Copyright 2015.
Reproduced with permission from the American Association for the Advancement
of Science.
chemistry (e.g. UV absorber concentration). [12] Resolution in the Fig. 4. Fused filament fabrication (FFF) process depicting a movable build platform
x-y plane in the case of TPP remains unrivaled, with feature sizes (a), a movable build head (b) with attached filament spool (e), and polymer deposi-
tion occurring from the main filament head (c) and the support material head (d).
below 100 nm for multi-photon lithography. [12] [13] Copyright 2015. Reproduced with permission from Springer New York.
Fig. 3 depicts a relatively new type of vat photopolymeriza-
tion termed continuous liquid interface printing (CLIP), a process
designed by DeSimone and commercialized in 2015 by CarbonTM . 100-150 ␮m is achievable. [12] Unfortunately, elastomers typically
[15,16] CLIP improves upon traditional bottom-up VPP through suffer from filament buckling through the extrusion head, an extru-
elimination of the repeated delamination steps from the bottom, sion failure mechanism that arises from insufficient filament elastic
UV-transparent window. An oxygen-permeable window (Teflon® modulus. [17] The most common, commercially available polymers
AF 2400) allows diffusion of molecular O2 into the bottom of the for FFF are thermoplastics and include poly(lactic acid), acryloni-
photopolymer vat, retarding free radical polymerization in the so- trile butadiene styrene (ABS) random copolymer, polycarbonate
called “dead zone.” Fine tuning of the “dead zone” thickness occurs (PC), and polyamides (PA), none of which are elastomers. However,
through control of the photoinitiator type and concentration, inci- commercially available TPE filaments are becoming increasingly
dent photon flux, and resin curing dosage. [15] Elimination of the common, such as thermoplastic polyurethanes. A plethora of exam-
delamination process enables continuous elevation of the build ples of TPE printing also exist in the academic literature and are
support plate, resulting in print speeds up to 100x faster than discussed below.
an equivalent, traditional bottom-up VPP process would provide.
Though this is a bottom-up VPP approach, processing of elastomers 3.4. Direct ink writing (DIW)
with CLIP presents no issue as no adhesion to the bottom, O2 -
permable window occurs. CarbonTM currently sells at least two Direct ink writing (DIW) is a materials extrusion process, which
elastomeric photopolymer compositions that include Silicone (Car- enables printing of viscoelastic materials at ambient temperatures.
bonResin SIL 30) and Elastomeric Polyurethane (CarbonResin EPU It is also known by the name robocasting. Lewis et al. provided
40), both of which possess a tensile strain at break > 250 %. two outstanding reviews describing the concept of DIW and dis-
cussed suitable materials. [18,19] Here, we aim to only provide a
3.3. Fused filament fabrication (FFF) short overview on the concept of DIW AM and we will highlight the
required materials properties to enable printing briefly. Scheme 2
Fused filament fabrication (FFF), otherwise known as fused illustrates a common DIW set-up, including a syringe with an ink-
deposition modeling (FDM) and a member of the material extrusion deposition nozzle and a computer-aided positioning stage. The
AM class, involves the directed deposition of a thermoplastic poly- apparatus continuously extrudes material out of the nozzle, gen-
mer filament in a layer-by-layer fashion. Shown in Fig. 4, a feeding erating 3D architectures layer-by-layer. Suitable materials for DIW
system forces the spooled filament through a heating element in a should possess specific rheological properties to be processable.
process similar to a hot melt adhesive (hot glue) gun. The heating The material should be shear thinning to enable extrusion out of the
element, attached to a series of motors that enable spatial control in printing nozzle. It should also possess a shear yield stress. To induce
the x-y-z build volume, rasters first in the build platform plane (x- flow, a shear stress above the yield stress of the resin is applied.
y), depositing an entire layer of polymer. The printer then moves to Subsequently, the shear stress is released, and the resin recovers
the next layer (z), and the process continues. The incorporation of its rigidity when placed on a substrate. Polymer resins are com-
multiple build heads permits multi-material extrusion. This allows monly blended with fillers, e.g. silica particles or nano-clay to afford
creation of multi-material objects or objects with complicated the described rheological properties. The fillers induce shear thin-
geometries in the case of simultaneous extrusion of the desired ning flow behavior and at optimal resin/filler compositions, afford
and sacrificial (support) materials. Build head diameter and poten- a material which possesses a shear yield stress. These rheological
tial die swell issues limit typical feature resolution with material properties enable shape retention of the printed object, rendering
deposition, but despite these issues a typical feature resolution of self-standing structures. The Herschel-Bulkley model is frequently
Scheme 2. Schematic of DIW apparatus. [21] Copyright 2016. Reproduced with

permission from the Royal Society of Chemistry.
used to describe such yield-stress fluids, with = y + K˙ n where

= shear stress, K = consistency factor, ˙ = shear rate and n = flow
Scheme 3. Schematic of inkjet printing technique. [23] Copyright 2010. Reproduced
index with n < 1 for shear-thinning fluids. [20]
with permission from Annual Reviews.
Alternative solidifying processes include subsequent UV-curing
of the printed layer, thermal cure or extrusion into a support bath.
The latter holds the printed structure in place until the deposited
ink is converted into a solid. This process is often called “freeform
reversible embedding” (FRE) or embedded 3D printing (e-3D print-
ing). Angelini et al. recently described this concept in detail and
provided an overview of the required rheological properties of the
support material. [22] Overall, the minimum printing resolution for
viscous polymer resins using DIW range from hundreds of microns
to the sub-microns range and is usually dictated by the nozzle
dimensions. [18]
3.5. Inkjet printing / material jetting
Inkjet printing is another ink-based technique and utilizes the

deposition of fluid droplets on a substrate (Scheme 3). Subsequent
solvent evaporation renders the solid pattern or UV-curing trans-
forms the liquid into a solid. Details on the required ink parameters
are given in recent reviews by Derby[23] and Ma et al. [24] The
Fig. 5. Polymer powder bed fusion (PBF) process. [29] Copyright 2015. Reproduced
solution viscosity, surface tension, density, pH and particle size of with permission from Springer New York.
the ink determine its printability. For conventional printers, suit-
able inks must possess low viscosities (0.5 - 40 mPas), surface
tensions in the range of 20-70 mNm-1 and should enable stable 3.6. Polymer powder bed fusion
droplet formation. These values are summarized in the Fromm
1
(d) 2 −1
Fig. 5 depicts the polymer powder bed fusion (PBF) process,
equation (Z = = Oh ) with the dimensionless number Z, which is also described in great detail elsewhere. [12,29] Here,
which equals to the inverse Ohnesorge number (Oh), and d = diam- the entire apparatus exists inside an oven set to a temperature
eter of the nozzle aperture, = surface tension of the liquid, = just below the glass transition temperature (Tg ) for amorphous
density, = viscosity. [25] Values of Z ranging from 1 to 10 indicate polymers or the melting temperature (Tm ) for semi-crystalline
ideal droplet formation. [20] polymers. After initial polymer loading into the feed cartridges,
Overall, inkjet printing is a low-cost technique, requires small the feed cartridge raises slightly, followed by a L-R motion of the
amounts of material, enables fast and multi-material printing and counter-rotating, powder leveling roller, depositing an initial layer
is highly attractive to print organic thin-film transistors, sensors, of powder onto the build platform. A CO2 laser then rasters in
microfluidic channels or organic-solar cells. [26] The minimum lat- the x-y plane, providing the remaining thermal energy required
eral printing resolutions range from 20 ␮m to 70 ␮m with printing to raise the polymer temperature above Tm , after which the molten
heights around 100 nm to 1 ␮m. [18] New generations of jetting powder fuses together. The build platform then lowers by one-
printheads enable printing of highly viscous inks with viscosities layer thickness and the process repeats itself. Traditionally, the vast
of up to 100,000 mPa·s. [27,28] majority of PBF powders remain in the nylon (polyamide, or PA)
Scheme 4. Crosslinking of polysiloxanes via hydrosilylation reaction utilizing a transition metal catalyst. Details on the curing mechanism are provided in reference [65].
Scheme 5. Crosslinking of acetoxy-functional polysiloxanes via condensation reaction.
Scheme 6. Crosslinking of polysiloxanes using alkoxysilane groups and subsequent release of n-propyl alcohol.
Scheme 7. Free-radical curing mechanism of polysiloxanes. Further details can be found in reference [66].
family, with PA11 and PA12 representing the two most popular block polyamide chemical structure that is likely synthesized via
compositions,[12] although a handful of elastomeric PBF powders catalyzed (e.g. Ti(OR)4 ), melt esterification of diacid-terminated
exist (e.g. DuraForm Flex, Luvosint X92A-2, PrimePart ST PEBA polyamide oligomers and hydroxyl-terminated polyether poly-
2301). [12] The latter example, PEBA 2301 contains a polyether ols, then finally processed into powder form. [30] Typical print
Fig. 6. A) Sher-rate dependent, apparent viscosity of Dow Corning SE1700 (uncured). B) Oscillatory stress sweep of DC SE1700 (uncured) showing storage and loss moduli.
[72] Copyright 2014. Reproduced with permission from John Wiley and& Sons Inc.
Fig. 7. Image of DIW process using a blend of DC SE1700 (85 wt%) and Sylgard 184 (15 wt%). [74] Copyright 2015. Reproduced with permission from John Wiley and Sons Inc.
Fig. 8. Embedded 3D printing utilized to incorporate conductive inks into the silicone elastomer to manufacture elastic electronics. [94] Copyright 2014. Reproduced with
permission from John Wiley and Sons Inc.
resolution for the PBF process is on the order of 100 ␮m, while ity often results in slower print times at best,[15] or warpage of
post-processing steps help improve surface finish. [12] the printed objects at worst. [32] A practical upper photopoly-
mer viscosity limit is 5 Pa·s,[33] though rapid developments in
printer technology often make previous restrictions obsolete. For
4. Challenges of 3D Printing Elastomers example, recently, the use of a custom-built VPP with a recoat-
ing blade enabled selective UV-curing of a photopolymer with a
Challenges related to elastomer processing with various AM viscosity of 18 Pa·s. [34] However, the use of a recoating blade
technologies are highly dependent on the printing technology. is often challenging when working with elastomers because the
Therefore, many challenges remain specific either to the printer low storage moduli of the cured networks might not withstand
or the combination of the polymer and the printer. One major the shear forces during the recoating process and printed struc-
challenge with vat photopolymerization relates to photopolymer tures might deform or collapse. One common method for viscosity
viscosity. [31] Processing of photopolymers with too high viscos-
Fig. 9. A: Apparent viscosity versus shear rate for the ink, reservoir material and filler fluid, utilized for embedded 3D printing. B: Shear elastic modulus versus shear stress
for the same materials. [94] Copyright 2014. Reproduced with permission from John Wiley and Sons Inc.
in photopolymer compositions, the affine and phantom network

models apply. [9] Here, the relative deformation in a network
strand is relative to the macroscopic, relative deformation for the
entire part. Upon application of a force, e.g. stretching an elastomer,
polymer chains uncoil but are limited by their finite extensibil-
ity, e.g. when reaching their maximum end-to-end distance (Rmax ).
As Rmax = bN, where b is the monomer length and N the number
of monomers, it is apparent that Rmax increases with increasing
number of monomers, or molecular weight. [9] This corroborates
the high extensibility observed in elastomers, which is primarily
entropic in nature. [9,40] Unfortunately, the melt viscosity of a
linear polymer is proportional to the molar mass M for unentan-
gled melts but is proportional to M3.4 , for polymer melts above
the critical molar mass (2-3 x Me ),[41] so it would seem elas-
ticity and precursor viscosity inherently oppose one another. In
practice, this remains true, though a number of strategies exist to
circumvent this issue, which include printing in the presence of
chain extenders,[36,42,43] or a post-processing, chain extension
step with blocked isocyanates. [44,45]
As described in section 3.5 and in detailed reviews[23], the vis-
cosity and surface tension of an ink are important parameters which
determine its printability for inkjet printing. [46] High molecular
Fig. 10. Principal of extruding two-part PDMS (Sylgard 184) into Carbopol® weight polymers must be diluted and their viscoelasticity makes
medium. [97] Copyright 2016. Reproduced with permission from the American
printing of solutions above > 1 wt% challenging. [47,48] This also
Chemical Society.
complicates fluid line drying and highly diluted polymer solutions
tend to form non-uniform printing patterns due to the coffee-ring
reduction involves the addition of reactive diluents, or monomers, effect. [23] One strategy to print high molecular weight polymers
to the photopolymer composition. These small molecule additives while reducing their impact on the fluid properties is printing of
polymerize along with other reactants and become part of the polymer emulsions, which is discussed in more detail in section
crosslinked network. [35] Though these often impart unique func- 7.4 and 1.9. Alternatively, the ease of multi material printing using
tionality onto the printed object, issues of volatility and toxicity inkjet printing allows to print polymer precursors separately and
during printing must be managed. [35,36] Unreactive diluents, or to react them after ink deposition to form a polymer network. [49]
solvents, often enable the processing of polymers that are not liquid Printing elastomers with FFF involves a set of unique challenges,
at room temperature. [37,38] However, potential issues of volatil- some specific to the printing technology and others specific to elas-
ity and toxicity also exist, in addition to the added complication tomers. Complications specific to FFF include interlayer adhesion
of solvent removal, after printing, from the resulting organogel or (e.g. weld line strength), object/bed adhesion, complex geometries
hydrogel. [38] Some printers also possess the ability to heat the (e.g. overhangs), and extrusion failure mechanisms (e.g. improper
photopolymer vat, which can reduce photopolymer viscosity, but filament diameter, filament buckling, and annular backflow). Upon
raises the risk of potential thermopolymerization, in the case of extrusion, deposited polymer cools to ambient temperature rela-
(meth)acrylates. [39] tively quickly due to a low surface area to volume ratio. Seppala
One added complication with VPP involves the fundamentals et al. examined polymer temperature as a function of time after
of rubber elasticity and its implications on viscosity. For non- deposition and employed infrared thermography of welding zones
associating, unentangled, linear polymer chains, which is typical while printing acrylonitrile butadiene styrene (ABS). They found
for VPP due to the prevalence of low molecular weight precursors that ABS remains above Tg for approximately 1 s under typical
Scheme 8. Complex resin formulation to yield silicone elastomers with tunable stiffness. Further details can be found in reference [82].
Scheme 9. UV-initiated thiol-ene reaction of tetrafunctional thiol and ␣,␻-divinyl PDMS yielded silicone elastomers. Further details can be found in reference [86].
Scheme 10. Synthetic scheme to formulate PDMS suspensions. [100] Copyright 2017. Reproduced with permission from John Wiley and Sons Inc.
Fig. 11. Self-assembly of SEBS triblock and SEP diblock copolymers in mineral oil to yield jammed micro-organogels. [98] Copyright 2017. Reproduced from the American
Association for the Advancement of Science.
printing conditions (e.g. 230 ◦ C head temperature, 100 mm/s fila- elastomers remain hygroscopic (e.g. polyurethanes), which induces
ment speed, and a 110 ◦ C build platform). [50] Because interlayer void formation in printed objects during steam formation. A simple
adhesion depends on polymer entanglement formation, interlayer drying step prior to printing eliminates this issue.
adhesion often suffers due to the insufficient time for wetting, chain For DIW, the ink must possess specific rheological properties to
reptation, and entanglement formation processes to occur before flow through the print nozzle and rapidly solidify after placement
the extruded polymer crystallizes or falls below Tg . [51] Printing on the substrate, as outline in section 3.4. [52] This requires care-
of complex geometries is often solved through the co-extrusion of ful resin design and fillers are often indispensable. For elastomers,
support material, a second filament that acts as a temporary sup- the curing of the precursors often requires extended time and the
port surface for geometric features such as overhangs, bridges, etc., resulting networks possess low storage moduli. The latter might
and is later removed after the printing. Annular backflow occurs cause deformation or collapse of the printed structures under their
when filament diameter is smaller than nozzle inner diameter, own bodyweight. One method to overcome this challenge is the
resulting in polymer flow in the opposite direction of filament flow use of freeform embedded 3D printing. This AM technique utilizes a
in the annular region of the die, which subsequently solidifies above support bath, which holds the printed structure in place during the
the die, resulting in a clogged nozzle. [17] print. However, removal of the support medium from printed struc-
Challenges specific to FFF with elastomers arise primarily from tures, e.g. hollow features remains challenging. Details are given in
a low filament modulus. As shown in Fig. 4, a typical FFF print head section 6.2.
contains a pinch-roller feed system and a heated nozzle tip, which In addition to printing challenges during PBF, powder formation
are separated by a certain distance. Filament buckling occurs when remains non-trivial. Requirements for PBF and powder formation
the resistance to flow at the nozzle (e.g. viscosity) overcomes the are discussed elsewhere. [12] Briefly, PBF powders must possess
ability of the filament to act as a piston to drive the polymer melt high sphericity and well-defined diameter, which contribute to
through the nozzle. Consequently, filament buckling will not occur powder flow and compaction (e.g. bulk density) characteristics.
as long as the ratio of the filament compressive, elastic modulus These powders are typically manufactured via grinding or post-
to viscosity at the relevant shear rate remains above a threshold polymerization precipitation procedures, but can also be produced
value. [17] This remains a particular issue for FFF of elastomers, via direct precipitation during polymerization (e.g. dispersion
which possess much lower modulus than rigid filaments like ABS polymerization). [53] Challenges specific to PBF include powder
or PLA. Buckling can be avoided by reducing the extrusion speed. production via grinding, as some elastomers possess high tough-
Another extrusion challenge during FFF of elastomers includes noz- ness (e.g. thermoplastic polyurethanes) and may resist grinding
zle drool and/or slow refilling of the nozzle after filament retraction, unless cooled below Tg . Polymer powders must also possess a suf-
which is mitigated by turning off retraction and employing contin- ficiently high modulus to prevent tackiness, which would impede
uous extrusion throughout the print. Finally, many thermoplastic powder flow. Despite these challenges, several commercially-
Fig. 12. Variety of geometries consisting of crosslinked PDMS and printed using two-photon absorption microstereolithography. [104] Copyright 2004. Reproduced with
permission from the American Chemical Society.
available PBF elastomer powders exist, which are mentioned in

section 12.
5. Silicone Elastomers – Synthesis and Properties
5.1. Properties of silicone elastomers
Silicone elastomers are biocompatible, optically transparent,

relatively chemically inert, electrically insulating, non-flammable,
non-UV absorbing, exhibit low surface tensions, are water-
impermeable and possess a high oxygen permeability. Further-
more, they are rather inexpensive and maintain their mechanical
and electrical properties over a wide temperature range (−50 ◦ C
to +300 ◦ C). [54] Applications below −50 ◦ C are challenging due to
the melt crystallization of polydimethyl siloxane (PDMS) between Fig. 13. Modulus (Pa) versus UV-illumination time (s) for
-75 ◦ C and-100 ◦ C and melting around −50 ◦ C. [55] Yet, incorporat- poly((mercaptopropyl)methyl-siloxane-co-dimethylsiloxanes) with 2.5 mol%
ing bulkier side groups, such as diphenylsiloxane segments into the and 5 mol% pendent thiols and ␣,␻-divinyl PDMS with molecular weights (Mw ) of
186 g·mol-1 and 6000 g·mol-1 , respectively. [108] Copyright 2017. Reproduced with
silicone backbone prevents cold crystallization, which allows for
permission from the Royal Society of Chemistry.
temperature applications below −50 ◦ C. [56] These unique prop-
erties render silicone elastomers highly valuable for a variety of
applications, such as medical applications for implants or pros- Silicone elastomers are covalently crosslinked networks of
theses, sealants in airplanes and automobiles, or as coatings for polysiloxanes. Polysiloxanes, also called siloxanes, or silicones, con-
electronics. For many applications, fillers are added as reinforcing sist of a -Si(R)2 O- repeat unit and owe most of their properties to
agents to increase the mechanical strength of silicone elastomers. the unique chemical nature of the Si-O bond. The large difference
[57,58] Other additives include processing aids, inert fillers, stabi- in electronegativity between the silicon atom (En = 1.8) and the
lizers and pigments. oxygen atom (En = 3.5) results in a thermodynamically strong
Scheme 11. UV-crosslinking of methacrylate-functional PDMS oligomer yields sil-

icone elastomer with high crosslinking density. Further details can be found in
reference [105].
Si-O bond (452 kJ·mol-1 ) with 50% ionic character. [56,59] Further-
more, the long Si-O and Si-C bond (1.64 Å and 1.90 Å, respectively)
compared to their carbon counterparts (C-O and C-C), combined
with the large Si-O-Si bond angle of 143◦ and absence of sub-
stituents on the oxygen atom provide conformational flexibility to
the polymer chains. Overall, low intermolecular forces, low surface
tensions (e.g. 20.4 mN/m for PDMS) and extremely low glass transi- Scheme 13. Schematic of simultaneous crosslinking and chain extension of low
tion temperatures (Tg ), (ca. −127 ◦ C for PDMS) are characteristic for molecular weight thiol-functional PDMS and acrylamide-functionalized PDMS,
polysiloxanes. [56,60] Silicone elastomers typically possess rather which yielded crosslinked PDMS networks with high molecular weight between
low elastic moduli (max. of several MPa), and they are extremely crosslinks. Further details can be found in reference [36].
stretchable with ultimate strains above 300%. [61]
5.2. Synthesis of silicone elastomers
Skov et al. recently provided a tutorial review on how to tailor

and formulate silicone elastomers. [61] Three major crosslink-
ing strategies yield silicone elastomers/rubber, where details on
these methods are described in literature. [59,62,63] In brief, most
thermally cured elastomers utilize the highly selective hydrosily-
lation reaction to form carbon-silicon bonds through an addition
reaction depicted in Scheme 4. These silicones are marketed as
two-part systems to avoid crosslinking during storage. For exam-
ple, Sylgard 184 from Dow Corning is one of the commonly used
two-part silicone resins in academic literature. Details on the com- Scheme 14. Single components of photoresin to enable 3D printing of transparent
silicone elastomers. [110] Copyright 2018. Reproduced with permission from John
position of Sylgard 184 are provided in literature. [64] Part A, the Wiley & Sons Inc.
so-called “base”, contains long-chain vinyl-functional silicones (e.g.
-Si-CH = CH2 ) and a transition-metal catalyst (e.g. platinum in the
form of the silicone soluble Karstedt catalyst). After mixing, the
vinyl-functional silicones react with Part B, often referred to as sation reaction in the presence of a common condensation catalyst,
“curing agent”, which contains hydride-functional silicones (e.g. - e.g. tin catalyst (Scheme 5).
Si(R2 )H) and additional vinyl-functional silicones. [62] Crosslinking Alternatively, other condensation-based systems utilize
is commonly completed at elevated temperatures. alkoxysilane RSi(OR’)3 groups and release short alkyl chain alco-
This curing reaction does not result in shrinkage or does not pro- hols, e.g. n-propyl alcohol upon contact with moisture (Scheme 6).
duce byproducts. The latter renders this reaction highly valuable This is of importance when the release of acetic acid may cause
for processing silicone elastomers for biomedical or food-related corrosion of the substrate. A drawback of one-part RTV systems is
applications. One drawback of this addition reaction is the sensi- their slow curing processes because curing starts at the PDMS-air
tivity of the platinum catalyst to heavy metals, amines or thiols interface.
which inhibit curing due to catalyst poisoning. Free radical crosslinking of silicones using peroxides to initi-
Acetoxy-functional polysiloxanes crosslink through conden- ate crosslinking is an alternative to the described mechanisms but
sation reaction and belong to the family of one-part room offers less control over cure rates and crosslinking distribution and
temperature vulcanization (RTV) silicone elastomers. Upon expo- produces residual by-products (Scheme 7). This curing technique
sure to atmospheric moisture, the acetoxy groups hydrolyze, is commonly employed for high-temperature vulcanizing (HTV)
release acetic acid, and form silanol groups which react via conden- silicone rubbers. [62]
Scheme 12. Reaction of ␣,␻-diamine PDMS with methacryloyl chloride in DCM in the presence of triethylamine yields ␣,␻-dimethacrylamide polydimethylsiloxane. Further
details can be found in reference [106].
Fig. 14. Additive manufactured monolithic device utilizing thiol- and vinyl-functionalized PDMS and UV-initiated thiol-ene click chemistry. Pressurization or evacuation
enabled contraction or elongation of the actuator. [108] Copyright 2017. Reproduced with permission from the Royal Society of Chemistry.
Fig. 15. Transparent hollow cube, 3D-printed using a PDMS-based photoresin. [110] Copyright 2018. Reproduced with permission from John Wiley and Sons Inc.
5.3. Traditional processing of silicone elastomers (peroxides or Pt-catalyst) are blended into the silicone on a roll
mill before vulcanization. Compression molding, injection mold-
Traditional processing of silicone elastomers differs for HTV- ing, extrusion or calendaring are utilized to process the silicone
silicones and liquid rubber silicones (LSR). HTV-silicones exhibit elastomer. In contrast, LRS consist of lower molecular weight
extremely high viscosities (e.g. 20-100 Mooney viscosity) and are polysiloxanes. They possess viscosities of 10-200 Pa·s, and exhibit
commonly distributed in block form. Additives and crosslinker shear thinning behavior. Commonly, LSR are distributed as two-
shear storage (G’) and loss (G”) moduli (Fig. 6). [72] Oscillatory
stress sweep measurements at room temperature (Fig. 6B) demon-
strated that the material exhibited solid-like behavior at lower
oscillatory stress, which changed to liquid-like behavior at oscil-
latory stresses above the yield stress. Wilson and co-workers were
the first who intensively studied the printability of DC SE 1700
and blends of DC SE 1700 with unfilled PDMS to print complex
architectures. [72] The dilution of DC SE1700 with a blend of
vinyl-terminated PDMS and trimethylsiloxane terminated PDMS-
co-polymethylhydrosiloxane decreased the yield stress and the
viscosity of the ink and allowed for tuning the resulting mechani-
cal properties of the cured elastomers. Ideal printing compositions
ranged from 100-70% DC SE 1700. Increasing the amount of unfilled
Fig. 16. Ink-jet printed ziggurat structure (4 mm x 4 mm) consisting of crosslinked
PDMS-based resin further, may induce mechanical instabilities and
PDMS. [49] Copyright 2017. Reproduced with permission from the Royal Society of cause collapse of the printed structure. [72,73] After the print-
Chemistry. ing process, thermal post-curing at 150 ◦ C transformed the resin
to a crosslinked rubber. The excellent printability of these resins
enabled the authors to print cellular architectures, which possessed
part system (Pt-curing system only) and processed via injection
negative shear stiffness, meaning that the load-deformation curve
molding.
exhibited a negative slope.
Capitalizing on the printability of DC SE1700 and its diluted
6. Additive Manufacturing of Elastomeric Architectures blends, various researchers designed complex architectures pos-
using Silicone Precursors sessing outstanding energy trapping abilities[74], programmable
Poisson’s ratios[75] and shape-memory behavior when combined
6.1. Motivation with gas filled microspheres. [76] Other examples are additive
manufactured foams,[77] vascular tissue constructs,[78,79] or the
AM of silicone elastomers is highly desirable for healthcare design of synthetic spider webs. [80] Ozbolat et al. observed higher
applications, e.g. fabricating microfluidic devices, implants and vas- strains at break of 3D printed structures using DC SE 1700/Sylgard
cular tubes. It would also facilitate the manufacturing of soft active 184 compositions compared to their mold counterparts. [73] The
materials, such as actuators, robots, wearable electronics and sens- authors attributed these differences to a decrease in bubble entrap-
ing devices. For example, conventional molding processes require ment in the printed tensile specimen. A dog-bone specimen printed
individual fabrication steps for each part and subsequent assembly, along the transverse direction using a blend ratio of 9:1 DC SE1700
which are time-consuming iterative steps and hinder automation. : Sylgard 184 exhibited the highest strain at break of 400%, higher
AM of silicone elastomers in combination with other materials, e.g. than the casted mold (max. elongation at break 200%). Intrigu-
conductive materials provides a highly attractive manufacturing ingly, the 3D printed structures also facilitated cell adhesion and
opportunity that enables fast processing and higher throughput, spreading due to the presence of grooves and rougher surfaces than
which saves time and costs. In addition, AM of silicone elastomers cast samples, making these structures attractive for bioengineering
would enable facile customization of devices for consumers, where applications.
customized prostheses and implants become accessible. The higher Crosslinking density, weight percent and type of filler dictate
freedom in design compared to traditional manufacturing further the mechanical properties of silicone elastomers. Varying the blend
enables AM of mechanical metamaterials, e.g. cellular solids, attrac- ratio of DC SE 1700 to unfilled two-part silicone resin or the base
tive for shock absorption and stress mitigation applications. [67] to catalyst ratio impacts the mechanical properties of the result-
We refer the reader to the recently published review by Toyserkani ing silicone elastomers. For example, multi-material printing of
et al. for details regarding processing and printing parameters of different resin compositions enabled the design of architectures
silicones. [68] In the following sections, we highlight the required which possessed gradients in the elastic moduli. [81] Nevertheless,
chemistry and materials properties of silicones to render them 3D the limited commercial availability of silicone resins which exhibit
printable. the required rheological properties for DIW still restricts accessi-
ble materials properties. Addressing this need and expanding the
6.2. Direct ink writing of silicone elastomers tool box of silicones for DIW, Wilson et al. formulated tailored sil-
icone inks to render elastomers with tunable stiffness. [82] The
As outlined in section 3.4, the rheological properties of the poly- fundamental concept relied on platinum-catalyzed hydrosilylation
mer resins determine their printability and have a strong impact chemistry, utilizing vinyl-terminated PDMS-co-(diphenylsiloxane)
on the printing resolution because fast “solidification” of the resin (PDMS-co-PDPS) and trimethylsiloxane terminated PDMS-co-
after deposition is required. First attempts on DIW of silicone polymethylhydrosiloxane (PDMS-co-PHMS), combined with a
elastomers lacked silicone precursors with optimized rheological Karstedt Pt catalyst to promote curing (Scheme 8).
properties. Researchers utilized a RTV silicone from 3 M and silver- The incorporation of hexamethyldisilazane-treated silica and
nanoparticle infused silicone (Silicone Solution, Twinsburg OH) to rheology modifying additives (silicone-polyethers copolymers)
print a bionic ear[69] or quick-curing acetoxy silicone (Loctite 5366 rendered a pseudoplastic ink, suitable for DIW. A reaction inhibitor
bathroom sealant, LOCTITE) to design reaction-ware for chemical (1-ethynyl-1-cyclohexanol, ETCH) prolonged print time and pre-
synthesis. [70] In both cases, the silicone object served as bulk vented early curing events. This core ink was then combined with
structure, and high printing resolutions were not required. two different PDMS-based oligomers. Utilizing a chain extender
Corning (DC) offers one silicone resin, DC SE 1700, which fulfills (hydride-terminated PDMS) resulted in silicone elastomers with
all printing criteria for DIW. [19] DC SE 1700 is a two-part, thermally low stiffness. Alternatively, vinyl-terminated PDMS increased the
curable PDMS-based resin which contains fumed silica nanoparti- crosslink density of the network, rendering stiffer material. These
cles. [71] Due to the presence of fumed silica fillers, DC SE 1700 tailormade inks afforded elastomers with Youngs’ moduli ranging
possesses shear-rate dependent viscosity and stress-dependent from 0.40 MPa to 11.51 MPa and hardness values of Shore 10A to
Fig. 17. (A,B) CAD models of freeze-dried polyurethane 3D vasculature models, (C) 3D printed polyurethane construct, (D) cross-section of construct shown in (C), (E) SEM
micrograph of outer scaffold wall in (C) [133] Copyright 2008. Reproduced with permission from Sage Publications Ltd.
Shore 70A, respectively. Overall, the use of PDMS-co-PDPS made Studart et al. introduced an alternative strategy to tailor
such silicone elastomer attractive for low temperature applications the stiffness of silicone elastomers. [86] The authors formu-
because the bulky PDPS segments suppress undesired cold crys- lated silicone-based inks using a low molecular weight tetra-
tallization of PDMS. In addition, the diphenylsiloxane segments functional thiol-crosslinker (pentaerythritol tetrakis(3-mercapto-
provide greater thermal and radiation resistance. [83–85] This proprionate)), which they dispersed in vinyl-terminated polysilox-
approach demonstrated the opportunities for chemists and mate- anes (Scheme 9). Added photoinitiator enabled UV-curability and
rial scientists to synthesize and develop novel inks expanding the fumed silica served as rheological modifier to yield inks, which
accessible materials properties of 3D-printed silicone elastomers. possessed strong shear thinning behavior and a yield stress. After
Fig. 18. (A-D). Various images of a hierarchical construct created by the DIW co-extrusion process. (E-F) two complex constructs undergoing in-vitro pulsatile culture. [135]
Copyright 2013. Reproduced with permission from Elsevier Ltd.
ink deposition, UV-light irradiation induced thiol-ene reaction and modulus of 1 MPa. Exchanging the Dragonskin 30 A with Sylgard
rendered crosslinked silicone networks. 184 and the addition of 15 wt% flax fibers (300-400 ␮m) yielded a
The choice of vinyl-terminated polysiloxanes determined the stiffer network with a Young’s modulus of 3.4 MPa. Elongation at
stiffness of the network. The authors formulated three different break ranged from 922% for the soft network, to 267% for the inter-
inks to tailor the flexibility of the networks. One formulation used mediate, and 150% for the stiff formulation. Comparable values for
part A of Ecoflex 00-30A and yielded a soft silicone elastomer with printed and casted tensile specimen indicated excellent interlayer
a Young’s modulus of 0.12 MPa. A 1:1 mixture of Dragonskin 30 adhesion. The authors proposed that after UV-curing of one layer,
A and silanol-trimethylsilyl modified Q resin afforded an elastic unreacted thiol-groups are still available on the layer surface to
Scheme 15. Indirect AM of silicone elastomers utilizing a sacrificial scaffold. [111] Copyright 2016. Reproduced with permission from Nature Publishing Group.
Scheme 16. Schematic representation of a segmented polyurethane or polyurea.
Scheme 17. Poly(ester urethane) (PEU) elastomers prepared from polycaprolactone (PCL) diol and lysine diisocyanate. Further details can be found in reference [136].
Scheme 18. Segmented poly(ester urethane) (PEU) elastomers prepared from polycaprolactone (PCL) diol, 1,4-butanediisocyanate, and L-Lysine ethyl ester dihydrochloride.
Further details can be found in references [139–141].
such as additional fillers are completely optional. Vlassak et al. uti-

lized a commercially-available UV-curable silicone resin (Shin-Etsu
Silicones, KER-4690 A/B) with an almost Newtonian flow behavior
(viscosity 4̃.8 Pa·s) to enable printing of elastic conductive struc-
tures. [93] In general, the need of fillers to achieve part fidelity
using DIW diminishes the transparency of printed PDMS-based
elastomers and represents one drawback of this technique. As an
example, Fig. 7 shows an image of the DIW process, which utilized
a blend of 85 wt% DC SE1700 and 15 wt% Sylgard 184 and resulted
in translucent 3D objects.
Scheme 19. Synthesis of thiourethanes from EDDT and HDI. Further details can be
found in reference [119].
The demand for wearable electronics has motivated various
researchers to investigate facile manufacturing strategies to com-
bine soft and elastic materials with electronic devices. Lewis et al.
capitalized on the flow behavior of PDMS possessing different
molecular weights and utilized the latter for embedded 3D print-
ing (e-3D printing). [94] Rheological modified silicones served as
printing matrix and filler fluid, which enabled the embedding of
conductive inks as illustrated in Fig. 8.
The addition of thickening agents to commercially-available
Ecoflex 00-30, rendered the reservoir material possessing shear
thinning properties, while the addition of and thinning agents
yielded the filler fluid, which followed Newtonian-fluid behavior
(illustrated in Fig. 9). In particular, the reservoir material must pos-
sess a yield stress below the depositing ink and a high enough
storage modulus (G’1̃04 Pa), to enable nozzle movement but to also
trap the printed pattern in place. On the other hand, low viscosi-
Scheme 20. Chemical structures of epoxy aliphatic acrylate and aliphatic urethane
diacrylate. Further details can be found in reference [163]. ties are required for the filler fluid because it must readily flow into
voids, which were created by the movement of the nozzle.
After embedding the conductive ink, post-curing converted
participate in the crosslinking step of the next layer. Thus, form- the matrix and the conductive ink into a highly elastomeric sys-
ing covalent bonds between layers, responsible for good interlayer tem, exhibiting max. elongations at break of 900% and softness
adhesion. Multimaterial DIW of the different silicone-inks enabled between Shore Hardness of 00-30. [94] Intriguingly, combining this
to locally tune the stiffness of a printed object and inspired the design principal with molding and soft lithography enabled the
design of soft actuators. manufacturing of a soft, autonomous robot. [71] In addition, soft
Shepherd et al. formulated silicone inks for UV-DIW using two somatosensitive actuators have been fabricated recently. [95]
commercially-available silicones. [87] One component was a high While the strategy described by Lewis et al. utilized the silicone
molecular weight silicone (60 wt % Nuvasil® Loctite 5039) to afford as a bulk material, the idea of printing into a support material is
the necessary flow properties (e.g. shear thinning properties). The highly attractive for additively manufacturing silicone elastomers
other component was a low molecular weight, UV-sensitive sili- in three dimensions. In particular, the matrix holds the printed
cone (40 wt % Wacker® Semicosil 912) to impart crosslinking after objects in place, enabling printing of extremely soft materials with
ink placement. This concept was then utilized to print elastic capac- complex geometries. Such soft silicone elastomers with moduli in
itive sensors harnessing the electrically insulating character of the range of 102 -103 Pa are highly attractive for biomedical appli-
silicones. cations, e.g. to mimic human tissue. [10] Exploiting the rheological
To afford the required rheological properties for DIW, many ink properties of microgels, Angelini and co-workers demonstrated
formulations utilize fillers, e.g. fumed silica. Untreated fumed sil- their use as support matrices for DIW. First, the authors introduced
ica consists of amorphous SiO2 particles (1̃0 nm) which form larger the concept of depositing aqueous solutions of UV-crosslinkable
aggregates (1̃00 nm). Thus, it possesses an extremely high surface polyvinyl alcohol (PVA) into hydrophilic Carbopol® medium. [96]
area and is hydrophilic due to the presence of silanol groups on Carbopol® is a product line of Lubrizol, consisting of high molec-
the particle surface. [88] Hydrogen bonding facilitates the inter- ular weight, crosslinked polyacrylic acid (PAA) polymers. Swollen
actions between silanol groups, which enable the fumed silica to Carbopol particles fluidized upon applied stress and enabled the
form a 3D-network in the silicone elastomer. However, they are injection of the polymer solution. After the stress was released, the
also responsible for undesired creep hardening of silicones, where Carbopol material re-solidified and trapped the PVA in place, pre-
the addition of hydrophobic fumed silica prevents this problem. For venting it from flowing and supporting the 3D-printed shape. The
example, facile silylation (e.g. with hexamethyldisilazane) of the printed PVA object remained embedded during the curing step to
silanol groups renders hydrophobic SiO2 particles. As an alterna- retain the print geometry. This method provided improved layer
tive to silica fillers, Lipton et al. exploited paraffin wax to modify the adhesion because curing of the entire object was performed in
rheological properties of silicone Ecoflex 0050 (by Smooth-On). [89] one step. Utilizing this concept, the authors briefly mentioned the
This strategy did not only result in printable inks, but also added a placement of PDMS into a silicone-based medium, consisting of a
thermoresponsive character to the silicone elastomer. The paraffin Dow Corning 9041 silicone elastomer blend, diluted with 10% sili-
wax melted upon heating, created an internal pressure and caused cone oil. However, the latter did not provide the necessary support
the structure to expand. Incorporation of conductive carbon black to realize defined print structures. Surprisingly, a nonpolar scaffold
into the silicone-wax matrix enabled the fabrication of electrically material is not directly required to support PDMS. Feinberg et al.
actuated hydraulic solids. [90] Other conductive fillers for silicone demonstrated successful extrusion of Sylgard 184 into Carbopol®
elastomers are carbon nanotubes or silver nanoparticles, utilized medium (Fig. 10). [97]
to print elastic electrodes[91] or tactile sensors,[92] respectively. If This approach allowed the continuous printing of complex
no stringent printing resolution is required, rheological modifiers objects (e.g. helical tubes) and their release after thermal curing, by
Fig. 19. Poly(ester urethane) (PEU) scaffolds produced via DIW. [138] Copyright 2015. Reproduced with permission from John Wiley and Sons Inc.
Fig. 20. (A) 3D printed laboratory logo created by fused filament fabrication with thiourethane filaments. (B) scanning electron microscopy of printed objects. [119] Copyright
2018. Reproduced with permission from John Wiley and Sons Inc.
simply dissolving the Carbopol medium using phosphate buffered

saline solution (PBS-buffer). Unfortunately, the polarity differences
of the support bath and the extruded silicone resulted in some chal-
lenges. In particular, trapped Carbopol in the silicone resin limited
the printing resolution and hindered lateral layer fusion.
Currently, no commercially-available nonpolar material pro-
vides the necessary rheological properties to act as support material
for PDMS-based resins. Facing these challenges, Angelini et al.
developed nonpolar microgels exploiting the self-assembly of block
copolymers in mineral oil. [98] In mineral oil, poly(styrene-block-
ethylene/propylene) diblock copolymers (172.6 kg·mol-1 ) self-
assembled into micelles with glassy polystyrene cores. In contrast,
triblock copolymers of poly(styrene-block-ethylene/butylene-
block-styrene) (98.1 kg·mol-1 ) formed macroscopic networks due
to bridging events of ethylene/butylene blocks. Combining both
at an equal 1:1 ratio at low polymer concentration (4.5 wt.%)
resulted in microgels, possessing the required rheological prop-
erties for successful printing using DIW (Fig. 11). This tailored
microgel showed excellent support properties for various sili-
cone inks which possessed shear viscosities ranging from 10 to Fig. 21. Inkjet printing of acetic acid/water solution on a sulfonate-containing PU
100,000 mPa·s. Overall, the authors printed complex architectures substrate, producing patterns via protonation of polyurethane ionomers. (A) sepa-
using RTV silicones (Smooth-on Mold Max 10, Sylgard 184) and rate letters printed on glass slide. (B) O-rings printed on glass slide. (C) Schematic of
UV-curable silicone (Momentive UV Electro 225). Tailoring the acetic acid/water printing and subsequent protonation of polyurethane ionomers,
producing water insoluble structures. [144] Copyright 2008. Reproduced with per-
rheological properties of the microgel system enabled printing of
mission from Elsevier Ltd.
feature sizes of 450 ␮m, which possessed the required strength to
maintain shape after support removal. They also reported the print-
ing of feature sizes down to 250 ␮m, but the parts collapsed upon co-workers developed a sacrificial ink for AM of hydrogels
removal of the support bath. 3D printed tensile specimen revealed consisting of a coumarin-functionalized polyacrylamide copoly-
maximum elongations of 700%, confirming good interlayer mer. [99] Irradiation at 365 nm induced [2 + 2] dimerization of
adhesion. the coumarin groups and subsequent gelation of the copoly-
The removal of support medium (gel) from printed struc- mer. This allowed to deposit and cure the sacrificial ink under
tures, e.g. hollow or porous features remains a major drawback the same conditions as the conventional ink (UV-crosslinkable
of this printing technique. Facing this challenge, Sumerlin and poly(vinyl alcohol)). After the object was printed and cured, a
Fig. 22. Synthesis of water-dispersible polyurethane nanoparticles via the prepolymer emulsification method. Further details can be found in reference [154].
second UV-irradiation step (␭ =254 nm) promoted cyclorever- porous microfilaments. The porosity of these samples dictated their
sion of the coumarin dimers, liquified the sacrificial hydrogel mechanical properties and molded dog-bones showed a maximum
and enabled facile removal. Capitalizing on this concept, the strain at break of 140%. Significantly, the authors demonstrated
authors printed defined tubular structures and hollow spheres, the ability to print in aqueous media (PBS-buffer), making this
whereas the coumarin copolymer served as sacrificial infill. How- approach attractive for biomedical applications.
ever, a 3 h irradiation step at 254 nm and subsequent soaking
of the printed object in DI water overnight to ensure complete 6.3. Two-photon absorption microstereolithography of
removal of the sacrificial ink is rather time consuming. Nev- PDMS-based elastomers
ertheless, a similar concept might be useful for PDMS-based
systems. Direct laser writing based on two-photon absorption pho-
Another intriguing approach to 3D-print PDMS elastomers har- topolymerization is an extremely precise technique and enables
nessed capillary forces. [100] Velev et al. described the concept printing of features down to the size of 100 nm,[101] which renders
of 3D printing silicones using capillary bridging forces in analogy it attractive to manufacture optical waveguides or microflu-
to forming a sand castle, where water binds the sand particles. idic devices for biological applications. In 2004, Ober et al.
Such capillary suspension inks consisted of precured PDMS 10 ␮m reported the first use of two-photon absorption microstere-
microbeads, 2-30 vol% uncured PDMS liquid precursor and water olithography to process PDMS-based elastomers. The authors
medium (Scheme 10). exploited two different crosslinking systems. One utilized (5 -
Here, the uncrosslinked PDMS acted as binder and afforded a cyclopentadienyl-methyl) trimethylplatinum as initiator, which
thixotropic gel-like ink. At low shear stresses, the PDMS microbead decomposed into the active platinum hydrosilylation catalyst upon
suspension exhibited gel-like behavior and showed yielding at UV illumination. The actual crosslinking took place via ther-
high oscillatory shear stresses. 3D printing and drying yielded mal hydrosilylation, which impacted the overall print resolution
Fig. 23. Self-assembly of water dispersible polyurethane (WDPU) nanoparticles (NP)s (a) Processing based on the self-assembly of NPs. (b) The possible mechanisms for
self-assembly of NPs. [154] Copyright 2014. Reproduced with permission from the Royal Society of Chemistry.
and decreased part fidelity due to undesired curing events. As 6.4. Vat photopolymerization/SL to yield elastomeric
an alternative, the authors utilized a radical photoinitiator, e.g. polysiloxanes
isopropyl-thioxanthone to improve photoimaging and enabled fea-
ture sizes of 0.3-0.6 ␮m (Fig. 12). Details on the utilized PDMS Literature on the development of PDMS-based photoresins for
precursor were not provided. This work inspired others to man- vat photopolymerization is rather limited. As discussed in sec-
ufacture movable microstructures,[102] and to improve print tion 3.2, ideal photoresins must possess low viscosities (␩ < 5 Pa·s),
throughput. [103] exhibit stability under ambient temperatures, undergo fast and
Scheme 21. Synthesis of bio-based, green, aliphatic urethane-containing photocurable oligomers. Further details can be found in reference [173].
Scheme 22. Low viscosity, urethane-containing oligomers for vat photopolymerization. Further details can be found in reference [127].
controlled gelation upon UV-exposure, and yield networks with toresins which enable printing and high feature resolution but
high enough storage moduli to withstand the printing pro- yield structures with elastomeric properties remains challenging.
cedure. Most commercial photoresins are (meth)acrylate-based In particular, printing elastomers with low moduli often demands
systems which meet the printing requirements but result in highly support scaffolds to avoid collapsing of the printed object. Further-
crosslinked networks with rather high stiffness. Designing pho- more, the high oxygen permeability of silicones affects UV-curing
Scheme 23. Synthetic strategy to prepare blocked isocyanates. Further details can be found in reference [45].
Boydston et al. reinvestigated the challenge of formulat-

ing elastomeric photoresins for digital light processing (DLP)
AM. [106] First, the authors reacted an oligomeric amine-
terminated PDMS with acryloyl methacrylate, affording a ␣,␻-
dimethacrylamide polydimethylsiloxane (PDMSDMAA) (Mn = 4.5k
g·mol-1 ) (Scheme 12). The latter possessed a viscosity of 0.29 Pa·s
when diluted with toluene (5 wt%).
As expected, UV-crosslinking of PDMSDMAA rendered a highly
crosslinked network, which was reflected in a low tensile strain
at break of 50%. To achieve elastomers with higher elonga-
tions, the authors explored the influence of hydrogen bonding
on materials properties and utilized hydroxyethyl acrylate (HEA)
Scheme 24. Types of different liquid crystalline elastomers: Crosslinked side-group for 3D-printing. Intriguingly, small traces of diacrylate impurities
polymers, crosslinked main-chain polymers and crosslinked combined main- in HEA allowed for crosslinking and the formation of networks,
chain/side-group polymers (not shown). Further details can be found in reference which exhibited maximum strains at break of 348%. The combina-
[180]. tion of HEA (56 wt.%) with small amounts of PDMSDMAA (9 wt.%)
and addition of mono-acrylate (n-butyl acrylate, 27 wt.%) with a
surfactant to enable miscibility, afforded structures with similar
elongation at break (338%). Overall, the most successful composi-
of acrylates and methacrylates due to oxygen inhibition events tion was a mixture of HEA with 2-(2-ethoxyethoxy)ethyl acrylate,
and demands printing under inert gas. Dark-polymerization due to which possessed a maximum failure strain of 472%. While some of
the low glass transition temperature of PDMS is another challenge these photoresins exhibited highly promising elastomeric proper-
known from 2D lithography. [105] ties, the silicone resin yielded a rather stiff material because of the
Various silicones bearing UV-reactive functional groups, high crosslinking density.
e.g. methacrylate groups are commercially available. Because Long et al. reported an innovative solution to print low vis-
vat photopolymerization requires low viscosities, only silicone cosity PDMS-based photopolymers while rendering networks with
oligomers possess suitable properties for printing. Wessling et al. high molecular weight between crosslinks. [36] The authors con-
demonstrated successful vat photopolymerization of oligomeric ducted UV-curing experiments using mixtures of ␣,␻-dithiol PDMS
poly(methacryloxypropy)methylsiloxane-co-PDMS with 7-9 mol% and ␣,␻-diacrylamide PDMS with molecular weights ranging
methacrylate groups and a viscosity of 2-3 Pa·s (Scheme 11). The from 1.2-5.5k g·mol-1 . Upon irradiation, two reactions occurred
oligomeric structure resulted in a silicone elastomer with a Young’s concurrently, thiol-ene reaction led to a chain-extension while
modulus of 11.45 MPa. [105] Maximum elongation at break was not free-radical polymerization of the acrylamides formed a polymer
reported.
Scheme 25. Left: Synthesis of LCE utilizing aza-Michael reaction and subsequent UV-crosslinking of the acrylate-end groups. Details are provided elsewhere. [186] Right:
Schematic of the DIW-UV process and the LCE alignment. [185] Copyright 2017. Reproduced with permission from the American Chemical Society.
Scheme 26. Synthesis of PLBSI unsaturated copolyesters. Further details can be found in reference [190].
Scheme 27. Photocurable poly(glycerol sebacate)s. Further details can be found in reference [193].
network (Scheme 13). The authors explored various molecular chain-extension, crosslinked films possessed a Young’s modulus of
weight compositions and different thiol to acrylamide ratios. Over- 6.8 MPa and a strain at break of 17 %. Addition of 0.75 equiv. chain-
all, a mixture of 0.75 mol ␣,␻-thiol PDMS (1.2k g·mol-1 ) and extender (1,6-hexanedithiol) yielded networks with a Young’s
1 mol ␣,␻-acrylamide PDMS (5.5k g·mol-1 ) yielded networks with modulus of 1.4 MPa and a strain at break of 64 %. Despite chain-
molecular weights between crosslinks of Mc = 12,600 g·mol-1 and extension, the molecular weight between crosslinks was still rather
a gel-state modulus similar to PDMS in the molecular weight low (5.5 kg·mol-1 ) which collaborated to the low elongation val-
range of 11 to 30k g·mol-1 . The utilized composition exhibited ues. While this is a great approach to bypass viscosity limits for
a slightly lower viscosity (0.32 Pa·s) than neat ␣,␻-acrylamide vat photopolymerization, the resulting material does not provide
PDMS 5.5 kg·mol-1 (0.5 Pa·s), which enabled fast material refreshing the elastomeric properties known of triblock copolymers based on
after each printed layer. Tensile test specimen of the neat ␣,␻- hydrogenated polybutadiene.
acrylamide PDMS (Mn =5.5 kg·mol-1 ) showed a maximum strain at Shepherd et al. explored thiol-ene click chemistry using
break of 58% and a Young’s modulus of 1.73 MPa, similar to the value commercially-available materials to additively manufacture
reported by Boydston et al. In contrast, 3D-printed tensile speci- silicone elastomers. [108] Two poly((mercaptopropyl)methyl-
men using the chain extended network exhibited a strain at break siloxane-co-dimethylsiloxanes) with pendant thiol groups of
of 80% and a Youngs’ modulus of 0.4 MPa. Significantly, the same 2-3 mol% and 4-6 mol% and molecular weights of Mw 6̃000-
polymer composition rendered a max. strain at break of 123% when 8000 g·mol-1 were reacted with various ␣,␻-divinyl PDMS (Mw
cured in a mold due to better oxygen exclusion compared to the 2̃00, 800, 6000, 17200, 42000 g·mol-1 ) using UV-initiated thiol-ene
printing vat. The same group applied the concept of simultaneous click chemistry. The authors evaluated 10 different mixtures with
chain-extension and crosslinking to hydrogenated polybutadiene thiol to vinyl ratios of 1:1, which possessed viscosities between
diacrylate oligomers with a Mn of 2100 g·mol-1 . [107] Without 0.044 Pas to 1.88 Pa·s. Photorheology determined gel times below
Fig. 24. Waterborne polyurethane dispersions with PCL diol and PLLA-PEO-PLLA triblock copolymers as soft segments. Further details can be found in reference [155].
Fig. 25. 3DP DIW process. [158] Copyright 2014. Reproduced with permission from John Wiley and Sons Inc.
2 s (1 wt% photoinitiator) and storage moduli on the order of 103 kg·mol-1 and fumed or precipitated silica with particle sizes of 6-
to 105 Pa, varying with the resin composition (Fig. 13). 12 nm and 6-10 ␮m, respectively. Note that the addition of silica
In contrast to (meth)acrylate-based systems, the presence fillers increased the viscosity of the resins dramatically and a DLP
of oxygen does not inhibit thiol-ene click reactions. Photo-DSC setup designed for printing ceramics was needed to tackle such
revealed thiol conversions of 79% to 97%, calculated using an high viscosities (e.g. > 50 Pa·s). Photocrosslinking of resins with 0-
enthalpy of 60 kJ·mol-1 for the thiol-ene reaction. Photo-cured ten- 20 wt% reinforcing silica yielded PDMS elastomers with elongations
sile specimens revealed Young’s moduli ranging from 6-287 kPa, at break ranging from 150-1400% and hardness values ranging from
ultimate stresses in the range of 13-129 kPa and elongations at Shore A 11 to 30.
break between 45% to 400%. In addition, the photopolymerized sys- Folch and Bhattacharjee et al. addressed the need of optically
tems showed good fatigue resistance with little hysteresis. These transparent PDMS elastomers for the additively manufactur-
properties motivated the authors to 3D-print a fluidic elastomer ing of microfluidic devices. [110] Many attempts, such as DIW
actuator utilizing the thiol-functional PDMS (5 mol% thiols) with of silicones using DC SE 1700 and other blends lead to non-
6000 g·mol-1 vinyl-terminated PDMS (Fig. 14). Intriguingly, when transparent objects due to the presence of rheological modifiers
the actuator was punctured, the photopolymer rapidly crosslinked (e.g. fillers), which are required for this type of printing pro-
when exposed to sunlight and re-sealed the actuator, enabling self- cess (see section 6.2). Such additional fillers are not needed
healing. for stereolithographic approaches, which enabled printing of
To increase the toughness of 3D printed silicone elastomers, transparent PDMS-based elastomers and rendered this technique
Huang et al. added reinforcing silica fillers to PDMS-based pho- especially attractive to yield clear structures. The authors for-
toresins. [109] The photoresins consisted of a synthesized branched mulated photoresins using commercially-available polysiloxanes,
thiol-functionalized PDMS (molecular weight not reported), vinyl- e.g. ␣,␻-dimethacryloxypropyl PDMS (abbreviated as PDMS-E) and
terminated PDMS with molecular weights of 22 kg·mol-1 or 4.3 poly(methacryloxypropyl siloxane-co-dimethylsiloxane) (abbre-
Fig. 26. Typical DIW 3D printing procedures. (A) fiber stacking by manual injection, (B) manually-produced construct, (C) 3D printing with custom-designed DIW apparatus,
and (D) two layers of 3D-printed fibers, constructed for the purposes of cell visualization via optical microscopy. [155] Copyright 2015. Reproduced with permission from
the American Chemical Society.
Fig. 27. Schematic of PUD-Veroclear® composite scaffold. [160] Copyright 2016. Reproduced with permission from the Royal Society of Chemistry.
viated as PDMS-S) with the purpose to mimic the properties

of Sylgard 184 (Scheme 14). The silicone soluble ethyl (2,4,6-
trimethylbenzoyl) phenylphosphinate (TPO-L) served as photoini-
tiator and a utilized UV-blocker (e.g. isopropyl-thioxanthanone)
ensured good Z-resolution.
After the print, extraction with isopropanol improved the opti-
cal transparency of the material in the visible spectrum (Fig. 15).
Varying the ratio of PDMS-E vs PDMS-S afforded silicone elas-
tomers with a Young’s modulus of 937 kPa (PDMS-E : PDMS-S = 4) to
520 kPa (PDMS-E : PDMS-S = 19). The softest composition (PDMS-E
: PDMS-S = 19) showed a maximum elongation at break of 153%.
Note that the authors utilized PDMS-E and PDMS-S with different
molecular weights and varying mol% of methacrylate groups. Two
different PDMS-E with molecular weight of 10k and 25k g·mol-1
were utilized and PDMS-E with 31.3k g·mol-1 and 5 mol% methacry-
late groups as well as 57.5k g·mol-1 and 38k g·mol-1 both with
16 mol% methacrylate groups. Unfortunately, no blending ratios or
further details on the composition were provided.
Fig. 28. White-light interferometry image and height profile (inset) of inkjet-
Bypassing the viscosity limitations of silicones for SL, Jiang printed single dots. [162] Copyright 2007. Reproduced with permission from the
and Wang utilized an indirect AM approach. The authors printed Royal Society of Chemistry.
a hollow sacrificial support scaffold first, and back-filled it
with commercial silicone resin (Scheme 15). [111] The silicone trimethylbenzoyl)phosphine oxide as photoinitiator. [112] The
is cured in the scaffold and treatment with alkaline solution methacrylic anhydride acted as crosslinker and enabled degra-
(NaOH, 1 mol·L-1 ) removed the sacrificial network and released dation under alkaline conditions. Using this concept, Jiang and
the free-standing PDMS elastomer. Liska et al. developed the Wang printed tin-catalyzed condensation-based silicones, (Mold
compositions of the sacrificial matrix, which consisted of N,N- Max N14® and T10® Smooth-on) and polyurethane elastomers
dimethylacrylamide, methacrylic acid, methacrylic anhydride, and (PMC-724® , Smooth-on). This procedure enabled manufacturing of
polyvinylpyrrolidone as a water soluble filler and phenylbis(2,4,6- highly elastic, complex lattice structures with 100-1500 ␮m print-
Fig. 29. Cartoon representation of network structure before and after the addition of monoacrylate and dithiol chain transfer agent to a formulation that initially contains
100% of a diacrylate-functional oligomer. [42] Copyright 2011. Reproduced with permission from IOP Publishing.
Fig. 30. Photopolymer composition for the production of a blood vessel substitute via microstereolithography. [170] Copyright 2009. Reproduced with permission from John
Wiley and Sons Inc.
ing resolution, maximum strains at break of 414% and Young’s required to compete with conventional VP or the cost-extensive
moduli ranging between 20-400 kPa. two-photon process.
The authors further applied this strategy to print stretch-
able lattice conductors by coating the PDMS elastomer
with ion-doped conductive hydrogels. [113] Using the same 6.5. Inkjet printing of silicones
sacrificial support material but Sylgard 184 (7:1 base to
crosslinker) as filler, Wessling et al. printed three dimen- In addition to SL and DIW, researchers investigated the print-
sional membranes and demonstrated the suitability of ability of silicones using inkjet printing, which is highly attractive
indirect AM to manufacture biomedical-relevant devices. for manufacturing stretchable electronics or microfluidic devices.
[114] Wildman et al. diluted a commercial two-part silicone (Poly-
In 2016, Kim et al. proposed using low one-photon polymeriza- tek, PlatSil 71-SiliGlass) using octyl acetate to meet the viscosity
tion (LOPP) as an alternative to conventional vat photopolymeriza- requirement of conventional inkjet printers (< 30 mPa·s). [49] In
tion of UV-curable silicones. [115] In LOPP, a specific photoinitiator particular, PlatSil® SiliGlass is a platinum-cured two part silicone
is chosen which possesses low absorption of the utilized printing and enabled the printing of part A and B individually. Printing both
wavelength. This technique enabled focal curing within the resin parts separately prolonged ink stability, avoided clogging of the
without polymerizing along the beam path, similar to the well- nozzle and afforded structures with feature resolutions of 48 ␮m
known two-photon absorption polymerization but offering much (Fig. 16).
lower printing resolution. In contrast to conventional VP, printing Shortly after, Shea et al. studied seven commercially-available
of resins with higher viscosities was possible because the non- silicone inks for their printability in inkjet printing, aiming
cured resin provided the optimal support of the cured structure at fabricating dielectric elastomer actuators (DEA). [116] From
and the process is stationary. The authors utilized a UV-curable sil- those seven formulations, Momentive UV Silopren® Electro 225-
icone from Dow Corning but failed to report materials properties or 1, a UV-curable ink which was printed in one step and NuSil
resulting mechanical properties after printing. LOPP is still rather CF18-2186, a thermally curable ink, which was printed in two
unexplored and overall improvement of the printing resolution is steps provided best results. Jetting of Wacker Silpuran® 6000/05
Scheme 28. Synthesis of poly(␧-CL-b-TMC-b-␧-CL) triblock copolymers. Further details can be found in reference [194].
Scheme 29. Synthesis of photocurable poly(citrate diol) biodegradable elastomers. Further details can be found in reference [197].
afforded poor feature precision due to the high molecular weight 7. Polyurethanes
of the silicone, which consequently required high ink dilution.
Tensile data of printed Nusil CF18-2186 and Momentive UV 7.1. Motivation
Silopren® Electro 225-1 elucidated no differences between print-
ing directions (longitudinal or transversal) and were comparable Like silicone elastomers, the AM of polyurethanes presents
to the blade-casted films. Reitelshöfer et al. utilized aerosol- many advantages for healthcare applications (e.g. implants and
jet-printing to fabricate stacked dielectric elastomer actuators. vasculature), as well as automotive and engineering applications.
[117] A RTV 2-part PDMS served as dielectric material (Wacker Printed objects retain characteristic strengths of bulk thermoplas-
Elastosil P 7670) in which both components possessed a vis- tic polyurethanes (TPUs), namely high elongation at break, elastic
cosity of 1800 mPa·s. Reduced graphene oxide dispersed in a recovery, recyclability, and high wear resistance. For example,
mixture of propanol and terpineol represented the conductive Invisalign® retainers from Align Technologies, Inc. are a series of
ink. polyurethane orthodontic retainers that serve as an alternative to
Fig. 31. Various views of a 3D printed, highly deformable isotropic truss. [163] Copyright 2017. Reproduced with permission from John Wiley and Sons Inc.
Fig. 32. PDMS-Slab with asymmetrically placed LCE (yellow material) enables temperature-induced buckling and demonstrates potential as adaptive optical element. [187]
Copyright 2017. Reproduced with permission from John Wiley and Sons Inc.
metal braces. Patients receive a set of customized, optically clear or two-step (segmented) solution-based processes that reacts
polyurethane retainers that slowly move teeth throughout the low Tg oligomeric diamines or diols (termed soft segments, SS)
course of treatment. These retainers are produced through indirect with monomeric diisocyanates and monomeric diamines or diols
3D printing, where a 3D mold of the patient’s teeth is employed (optional chain extenders). The incorporation of dithiols as din-
for thermoforming of a polyurethane sheet, thus producing the ucleophiles produces thiourethane linkages. [119,120] Urethane
retainers. Although these polyurethanes are not elastomeric, they formation process is typically aided with inorganic (e.g. dibutyltin
represent one of the most commercially successful applications of dilaurate) or organic (e.g. DABCO, DMF) catalysts. In the case
AM of polyurethanes, with more than 100,000 parts manufactured of non-segmented polyurethanes, a monomeric or oligomeric
per day as of 2017. [12] diol/diamine is typically reacted with a diisocyanate, producing
a polyurethane either in bulk (no solvent) or in solution. In the
7.2. Chemistry of polyurethanes case of segmented polyurethanes, as shown in Scheme 16, an
oligomeric diol/diamine is reacted with an excess of diisocyanate
Polyurethanes represent a highly versatile class of polymers and in the first step, resulting in an isocyanate-terminated prepolymer.
enjoy numerous applications ranging from insulation and cushion- As a second step, a chain extender is then added, raising the overall
ing foams to adhesives and coatings. [118] This versatility arises amine/hydroxyl:isocyanate stoichiometry and driving the reaction
from synthetic technique for segmented polyurethanes, where to high molecular weight.
variations in soft segment oligomer type and molecular weight, as In the case of segmented, linear polyurethanes, elasticity arises
well as hard segment (HS) content produce drastic morphological through intramolecular hydrogen bonding physical interactions
differences that influence polymer properties, including thermal and is governed by many parameters. These include hard segment
transitions, modulus, stress at break, and strain at break. [118] content, typically measured in weight percent as a ratio of the SS/HS
Synthetic processes typically follow one-step (non-segmented) repeat unit weights, Hildebrand solubility parameters, strength
is the case with the diisocyanate example, above. In these cases,

innovative polymer chemistry often finds a solution, as is the case
with a polyurethane composition for CLIP that employed blocked
isocyanates during printing and relied upon a post-printing ther-
mal cure to unblock the diisocyanate, which is described in greater
detail below. [44]
7.3. Traditional polyurethane printing in solution (material

extrusion, inkjet printing)
The primary route towards segmented polyurethane block

copolymer AM lies in printing from solution, although a few
examples exist for printing from the melt, with fused filament fab-
rication (FFF), or inkjet printing. Fortunately, many polyurethanes,
poly(urethane urea)s, and polyureas remain soluble in a variety
of organic solvents or binary mixtures thereof, though solubil-
ity remains highly dependent on composition. This article focuses
on the attributes most important for additive manufacturing, as
segmented polyurethanes are reviewed in great detail elsewhere.
[118,124,128,129] Most polyurethanes employ soft segments com-
prised of polyethers [e.g. poly(tetramethylene oxide) (PTMO),
poly(ethylene oxide) (PEO)], polycaprolactone (PCL), PDMS, and
Fig. 33. Additively manufactured LCE film (1 mm in thickness) performing polyolefins [e.g. polybutadiene, polyisobutylene)]. [118] The sol-
temperature-responsive “weight lifting”. Scale bar = 5 mm. [188] Copyright 2017. ubility parameter difference between the aforementioned soft
Reproduced with permission from John Wiley and Sons Inc.
segments [between 15.6 - 20.2 (J/cm3 )1/2 ] and the hard segments
[urethane, 37.2 (J/cm3 )1/2 , and urea, 45.6 (J/cm3 )1/2 ] and hard
of hydrogen bonding interactions, e.g. urea vs. urethane, and the segment content (typically measured in wt %) primarily govern
relevant soft segment polymer structure and molecular weight. solubility. Another important factor for solubility includes the
[118] Polymer isolation after a homogeneous solution synthetic number of urea/urethane functional groups in each hard segment
procedure typically occurs via precipitation or solution casting block,[118] with greater differences in solubility parameter, greater
and vacuum drying. In one report, an investigation of the effect HS content, and longer HS blocks reducing solubility in organic
of odd/even numbers of methylene units in the chain extender solvents, in many cases. Common solvents for polyurethanes
revealed that mechanical properties increased for polyurethanes range from the moderately polar (tetrahydrofuran, chloroform,
synthesized with chain extenders that possessed an even number diethyl ether, isopropyl alcohol) to the more polar, aprotic
of methylene units, which was attributed to improved chain pack- solvents (e.g. N,N’-dimethylformamide, dimethylacetamide, and N-
ing in urethane hard segments. [121] Furthermore, polyurethanes methylpyrollidone) or mixtures thereof. Moderately polar solvents
synthesized with > 50 wt % HS result in copolymers with HS as remain more than adequate for dissolution of polyurethanes with
the continuous phase, limiting elastomeric properties. [122,123] low HS content, whereas highly polar solvents or binary mixtures
To achieve elasticity, soft polyols traditionally possess molecular are required for complete dissolution in cases of higher HS content.
weights between 400-6000 g/mol and HS contents below 50 wt %. [118,130] Synthetic strategy for all segmented polyurethane/ureas
[124] However, recent reports demonstrate elastomeric proper- in this section remains similar, with combinations of oligomeric and
ties (e.g. 300-600 % strain at break) with much higher SS oligomer monomeric diols/diamines/dithiols combined with diisocyanates
molecular weights, employing poly(dimethyl siloxane)s (PDMS) to produce polyurethane/urea in solution.
soft segments (e.g. 32,000 g/mol) and 2-5 wt % HS; these prop- Zhang et al. synthesized a segmented polyurethane with two
erties may arise from both the highly improved HS/SS phase oligodiols, polycaprolactone (PCL) and poly(ethylene glycol) (PEG),
separation for PDMS polyurethanes/polyureas and PDMS chain hexamethylene diisocyanate (HDI), and butanediol (BDO) as a
entanglements. [125,126] chain extender. [131–133] Demonstrating an innovative 3D depo-
There are special considerations for combinations of HS/SS in sition procedure, the authors prepared a polyurethane slurry in
the context of specific printing technologies. For example, vat 1,4-dioxane and printed via direct ink write, freezing the lay-
photopolymerization (VPP) requires that photopolymers remain ered structures onto a refrigerated build platform held at −28 ◦ C.
liquid at room temperature. If printing without solvent or appre- Subsequent lyophilization (freeze drying) afforded the desired 3D
ciable reactive diluent (e.g. monomer), oligomers themselves must vasculature model, shown in Fig. 17. The authors advantageously
possess sufficiently low viscosity for adequate processing. In this built on this procedure in a later report, creating a double-walled
context, the choice of a chain extender with an odd number of structure consisting of a PU outer cylinder and an inner collagen
methylenes could help disrupt chain packing and reduce the physi- surface. [134] Later, Wang, et al. synthesized the same PCL/PEG
cal associations that occur at room temperature, to use an example polyurethane described in their previous reports[131,132] and per-
from above. Another approach might involve the use of asym- formed a co-extrusion employing the same 3D printing setup. [135]
metric diisocyanates, which leads to lower strength products due One syringe contained a cell-laden hydrogel precursor, while the
to the disruption in chain packing,[124] but offers lower viscos- other contained a PU-tetraglycol solution. This DIW co-extrusion
ity oligomers at room temperature. Sinh and Jukka employed process enabled the creation of layered, flexible PU-collagen con-
this approach with isophorone diisocyanate (IPDI) in the synthe- duits, with full printed construct shown in various views in Fig. 18.
sis of urethane methacrylate photocurable oligomers for VPP and In a similar manner but employing an amino acid-based
produced oligomers with low viscosity (2200 mPa·s) at room tem- diisocyanate, Hasirci et al. prepared biocompatible poly(ester
perature that possessed a strain at break of 195 % once photocured. urethane)s (PEUs) from 1:1 molar ratio of 1,250 g/mol PCL
[127] Occasionally, what makes a polymer ‘printable’ might seem diol and lysine diisocyanate, reacting the two in solution
at odds with what provides improved mechanical properties, as (shown in Scheme 17). [136] When employed in biodegradable
Fig. 34. (A) Illustration depicting dynamic vulcanization of an elastomer (PLBSI) and thermoplastic (PLA), resulting in a thermoplastic vulcanizates (TPVs). (B) 3D-printed
PLBSI/PLA TPV. [190] Copyright 2017. Reproduced with permission from Elsevier Ltd.
polyurethanes, diisocyanatobutane (BDI) and lysine diisocyanate polymer around the porogen. Removal of the water-soluble PVA
(LDI) degraded into non-toxic products, as compared to aromatic afforded a PUU scaffold. This indirect 3D printing approach enables
diisocyanates such as toluene diisocyanate (TDI) and methylene the creation of geometries not achievable with a direct approach,
diphenyl diisocyanate (MDI). [137] such as 3D channels in a continuous matrix, such as those pro-
Solution-casted films of these biodegradable poly(ester ure- duced by Lewis and co-workers. [71,94,95] In a previous report,
thane)s achieved a strain at break of 1̃500 %. [136,138] 3D Hernández-Sánchez detailed the synthesis of PCL-containing PUUs
fabrication occurred via DIW and salt leaching, where the former with 14 to 40 wt % hard segment, with a wide variety of mechan-
process involved heating bulk polymer to 105 ◦ C and extruding ical characteristics depending on the hard segment content. [143]
from a syringe. The fabricated scaffolds are shown in Fig. 19. Based on PCL diol as the soft segment, the polyureas contained
[138] When compared to salt-leached sponges made from the HMDI and putrescine as a chain extender. Though the authors did
same poly(ester urethane)s, the DIW scaffolds possessed similar not provide specific mechanical properties for all compositions,
thermal properties to those made via salt leaching, but the DIW they noted that the 23 wt % and 32 wt % HS samples attained 7̃50 %
scaffolds possessed improved rat bone marrow stem cell viability strain at break. [143]
and proliferation rates, likely due to the more interconnected pore Taking a unique approach towards hydrogen bond-containing
morphology afforded by the DIW process. polymers and employing dithiol-containing monomers, Voit et al.
Ciardelli et al. prepared similar PCL-containing polyurethanes leveraged a relatively underutilized family of thiourethanes for
for melt extrusion DIW but instead employed 1,4- fused filament fabrication (FFF), with a 3D fabricated laboratory
butanediisocyanate and L-lysine ethyl ester dihydrochloride logo and SEM of layered structure shown in Fig. 20.
as chain extender (Scheme 18). [139–141] Though the exact ratios The step-growth polymerization of an equimolar mixture
of starting materials were not provided,[139] the authors did of 2,2’-(ethylenedioxy)diethanethiol (EDDT) and hexamethylene
observe microphase-separated behavior as evidenced by DSC and diisocyanate (HDI) in DMF afforded high molecular weight
obtained an elastic modulus of 10.2 ± 2.2 MPa, ultimate tensile thiourethane, as show in Scheme 19. [119] This polymer possessed
strength of 3.3 ± 0.2 MPa, and a strain at break of 693.0 ± 15.0 %. The a Tg of 1̃1 ◦ C, Tm of 111 ◦ C, and a Td,5% of 260 ◦ C, providing a wide
scaffolds also demonstrated elastomer-like behavior as evidenced temperature window with which FFF processing can occur and a
by hysteresis cycles at 10 % strain, with low permanent set (2.5 %) low enough flow temperature for this composition to be printable
on the first cycle and 16 % hysteresis on the final cycle. [139] No in a wide variety of commercially available FFF printers.
3D printing occurred during this work, but similar materials were A bulk film of this composition achieved an ultimate ten-
processed with DIW in separate studies. sile strength of 48.3 ± 7.1 MPa and an elongation at break of
Hernández-Sánchez also published on the indirect printing of 307.8 ± 40.3 %, though the printed objects suffered from a typ-
poly(urethane urea) (PUU), PCL-containing elastomers. [142] This ical reduction on mechanical properties as a result of the
indirect 3D printing approach involves printing a porogen, e.g. layering process. When fabricated into bulk films and sub-
poly(vinyl alcohol) (PVA) in this case, and casting the desired jected to tensile testing, this elastomer outperformed T-Lyne® , a
commercially-available, DuPontTM Surlyn® -based poly(ethylene- or tissue being mimicked and will not be discussed here, as these
co-zinc methacrylate) ionomer filament manufactured by Taul- polymers are reviewed elsewhere in the context of 3D printed bio-
man3D. materials. [33,150–153]
A unique approach to inkjet printing of polyurethanes was Fig. 22 depicts the overall aqueous polyurethane dispersion syn-
recently pursued by Boland et al. [144] The authors employed a thesis process using the prepolymer emulsification method. [154]
modified thermal inkjet printing approach,[145] which requires Shan-hui Hsu and co-workers have done much work in this area
low viscosity for both the building material and the support mate- at the Institute of Polymer Science and Engineering at National
rial, if employed. [12] A biodegradable, polyurethane ionomer Taiwan University. In this work, no printing occurred but the
was synthesized from methylene diphenyl diisocyanate (MDI), group later employed similar compositions for printing. Here, Hsu
530 g/mol PCL diol, and chain extended with a sulfonic acid- et al. demonstrated the versatility of PUDs and employed either
containing diol or its non-charged counterpart, at 50 mol % HS. a PCL diol (Mn 2000 g/mol) alone or a combination of PCL diol
[144] Inkjet printing produced single-layer structures employing with a second oligodiol. This second oligodiol was either an in-
the deprotonated, polyurethane ionomer dissolved in DMF/H2 O at house synthesized poly(L-lactide) diol (PLLA diol, Mn 2000 g/mol),
2 % w/v, while subsequent inkjet printing of a 50 % (v/v) aque- poly(D,L-lactide) diol (PDLLA diol, Mn 2000 g/mol), or a commer-
ous acetic acid solution protonated the polyurethane in selected cially available poly(ethylene butylene adipate) diol. The authors
locations, thus producing 2D patterned structures as shown in advantageously combined these oligodiols with isophorone diiso-
Fig. 21. The 2D-fabricated structures demonstrated adequate ini- cyanate (IPDI), 2,2-bis(hydroxymethyl)propionic acid (DMPA),
tial cytocompatibility and show promise as tissue engineering triethylamine (TEA), and ethylene diamine as a chain extender, all
scaffolds. Mechanical property testing for both neutral and ionic of which are typical reactants for PUD synthesis, producing stable
polyurethanes occurred with solution-cast films and revealed an aqueous dispersions (zeta potential between −55 mV and −60 mV)
elongation at break of 211 % for the ionomer, as compared to the of polyurethane nanoparticles with hydrodynamic diameters rang-
neutral polyurethane at 107 % elongation. ing from 30 – 50 nm. Fig. 23a demonstrates possible applications of
Griesser, et al. demonstrated a unique thermal inkjet printing these so-called water dispersible polyurethane (WDPU) nanopar-
approach for the production of soft, elastomeric optical waveg- ticles (NP)s, while Fig. 23b provides a cartoon depiction of physical
uides via simultaneous photopolymerization and inkjet printing of gelation for hydrogel formation, the dehydration, phase inver-
a urethane-containing, oligomeric photopolymer composition atop sion, and film-forming process, or the freeze-drying process (e.g.
a PDMS substrate. [146] The authors inkjet printed a combination lyophilization) that forms porous microsphere sponges. For the
of Genomer 4267 urethane diacrylate, ethylene glycol vinyl ether aforementioned composition in film form, the Young’s modulus,
(EGVE) (less toxic than hydroxyethyl acrylate), 2-phenoxyethyl tensile strength, and elongation at break ranged from 4.6–125 MPa,
acrylate (PhEA) (for improved optical properties), with 1.5 wt % of a 11– 35 MPa, and 280–778%, respectively. Higher PLLA content was
photoinitiator atop a thermally cured Sylgard 184 PDMS substrate. associated with reduced elongation at break, attributed to PLLA
The authors underwent a rigorous optimization and characteriza- crystallinity, while higher content of the amorphous PDLLA diol
tion process to match the strain at break of both the PDMS substrate in the PU nanoparticles resulted in increased elongation at break.
(143 % alone) and optical waveguides (≥120 % when tested with the Hsu et al. have continued the use of this family of polymers in
PDMS substrate), exemplified by the lack of deformation or detach- their other work. Such polymers have been combined with neu-
ment of the waveguides during the strain experiments. These ral stem cells (NSCs) to create a cell-laden ink for 3D bioprinting.
optical waveguides may find application in soft robotics or biopho- [156] Shown in Fig. 24, Hsu et al. synthesized waterborne PUDs
tonics. with a similar procedure described above except now included
in-house synthesized amphiphilic block copolymers, including a
PLLA-PEO diblock copolymer, a PDLA-PEO diblock copolymer, or
7.4. Waterborne polyurethane dispersions a PLLA-PEO-PLLA triblock copolymer. [155] This process provided
thermoresponsive, amphiphilic polyurethanes, while 3D fabrica-
The synthesis of waterborne polyurethane dispersions (PUDs) tion of the cell-laden PUDs occurred via 3D printing at 25 ◦ C
mostly follows that of traditional polyurethanes, but involve addi- followed by gelation at 37 ◦ C. [155] When processed into film form,
tional steps for the insertion of ionic functional groups into two noteworthy PUDs, PCL100 and PCL90LE10, possessed Young’s
the polyurethane backbone. This generates an ionomer and pro- moduli of 30.9 and 18.6 ± 2.8 MPa respectively, while extending to
vides the ability to form colloidally stable, aqueous polyurethane 535.5 ± 19 and 650.6 ± 10 strain %, respectively. The non-reversible
dispersions if properly processed. These aqueous PUDs provide thermal gelation mechanism for this family of polymers is based
many ‘green’ alternatives to organic-solvent based polyurethane primarily on self-assembly via hydrogen bonding, the dynamics of
solutions, namely the avoidance of potentially toxic and volatile which increase with temperature. [157] Key characterization tech-
solvents. [128,129,147] The two most widely employed PUD syn- niques here include size measurements (DLS, SAXS, and TEM), ZP
thetic processes are the acetone process and the prepolymer measurements, and swelling ratios. [157] Typical scaffold depic-
emulsification process, the details for which are provided else- tion for direct-ink write (DIW) 3D printing is shown as a schematic
where. [147] These polyurethane dispersions do not aggregate in in Fig. 25 and the actual process depicted in Fig. 26. [155,158]
solution and maintain colloidal stability through deprotonation of This class of polyester or polyether-containing PUDs is diverse
the ionic functional groups with an organic base, resulting in elec- and enables the direct incorporation of bioactive ingredients (e.g.
trostatic repulsion between the resulting PU nanoparticles. Zeta growth factors, hyaluronan)[159] or living cells[156] into a DIW
potential (ZP), a measurement of electrokinetic potential, repre- ‘ink’.
sents the potential difference between the dispersion medium and Feng et al. synthesized a series of aqueous PUDs with a 2k g/mol
a stationary layer of fluid surrounding the dispersed particle. It is a PCL soft segment, IPDI, DMPA, and L-lysine chain extender. [160]
strong predictor of colloidal stability. [148] ZP measurements occur Initially developed by a different research group at the same uni-
with a dedicated ZP instrument and/or a dynamic light scatter- versity, Fu et al. synthesized a series of PUDs with 16.7 – 45.0 mol
ing (DLS) instrument. A ZP > ± 2̃5-30 mV is widely accepted as a % PEG soft segment that obtained tensile strengths from 16.1 –
stable colloidal dispersion for most systems. [149] Most biologi- 21.8 MPa, elastic moduli from 2.6 – 4.8 MPa, and elongation at break
cal applications for 3D-printed polyurethanes require high water from 1120 – 1479 % in dry, solvent-cast film form. [161] Feng et al.
swellability and mechanical properties specific to the type of cells repeated this synthesis without PEG oligodiols, employing PCL only,
with a composition that contained molar feed ratios of 3 : 1 : 0.75 Finally, Table 1 provides the polymer backbone chemistry and
: 0.75 IPDI/PCL/DMPA/L-lysine. [160] mechanical properties for the 3D printed polyurethane examples
After inkjet printing a commercially-available, photocurable discussed in this section.
resin (Objet Veroclear® ), Feng et al. manually solution-casted this
PUD dispersion onto the surface of the 3D-printed, photocured
resin, a schematic of which is shown in Fig. 27. [160] After dry- 8. Photopolymers for Vat Photopolymerization or Inkjet
ing the composite structures to remove water, a variety of surface Printing
and mechanical property characterization measurements were
performed. The waterborne PUD film alone achieved an ultimate Most photopolymer compositions for vat photopolymerization
tensile strength and strain at break of 45.6 MPa and 716.2 %, respec- or inkjet printing remain highly formulated and contain a vari-
tively. However, the PUD-coated Veroclear® achieved only a strain ety of reactants, such as photocurable oligomers, reactive diluents
at break of 14.8 %, likely limited by the commercially available (e.g. monomers), solvents (e.g. unreactive diluents), photoinitia-
photopolymer (strain at break of 13.7 % alone) and the potentially tors (e.g. sensitizers), UV absorbers, chain extenders, and radical
weak interface between the Veroclear® and the solution-case PUD. inhibitors (e.g. antioxidants). [12] These components are reviewed
Though the Veroclear® bulk scaffold limited the bulk elastomeric in great depth elsewhere but are briefly discussed here for con-
properties of the coating, the local environment exposed to cells text. [12,150–152] Each component plays a critical role. A cartoon
is likely still soft and suitable for cell growth, which is what the representation of a crosslinked network containing some of these
authors observed. species is shown in Fig. 29. [42] Here, the crosslinking agent, e.g. an
In another notable example of inkjet printing of PUDs, this time oligomeric di(meth)acrylate, possesses two functional groups each
with a commercially-available aqueous PUD and inkjet printer, with an effective functionality of two, as each (meth)acrylate is the-
authors printed BASF LR-9005, an aromatic urethane acrylate oretically covalently linked to two other (meth)acrylate moieties in
dispersion (PUD) that contained 10-15 wt % trimethylolpropane the absence of chain termination. Addition of a monoacrylate reac-
ethoxylate triacrylate and supplied at overall 40 wt % solids in tive diluent increases the distance between crosslink points, while
water, based on information available on the BASF website and further addition of a chain transfer agent (e.g. dithiol)[36,42,164]
safety data sheet for this material. [162] Though the PUD con- adds further distance between crosslink points. Unreactive diluents
tained acrylate functional groups, piezoelectric inkjet printing did reduce viscosity and/or dissolve polymer chains, enabling process-
not employ this functionality during the printing process and fol- ing of polymers normally highly viscous or in solid form at room
lowed with custom printing parameters, with a 5 min drying step temperature. [37,38] The remaining ingredients provide fine tun-
in between layers to ensure proper stacking of successive layers on ing of photochemistry, offering greater control over a variety of
previously printed layers, as shown in Fig. 28. This work demon- parameters including layer thickness, minimum feature size, and
strated promise for 3D manufacturing, due to the high aspect ratio photopolymer shelf life. Photoinitiators provide the propagation
of the printed structures, and also demonstrated color gradients center for polymerization, while radical inhibitors inhibit prema-
through addition of a water-soluble dye. ture polymerization and improve resolution in the x-y build plane
Thermoplastic elastomers based on polyurethanes provide due to polymerization termination on the fringe regions (e.g. laser
highly tunable material properties depending on the chosen back- or image edges). UV absorber control vertical light penetration (z
bone chemistry, e.g. hard segment content, as well as type of soft direction); small amounts of UV absorber greatly improve resolu-
segment. Many biological applications exist and range from simple tion in the z direction. [12] Finally, as oxygen inhibits free radical
cell/tissue scaffolds to full-fleged three-dimensional vasculature polymerization through multiple pathways, including quenching
models. Polyurethanes also find many applications as advanced of photoinitiator excited states or termination of growing polymer
materials. However, these unique materials properties create pro- chains, various small molecules are often added that act to remove
cessing challenges that arise in part due to the large difference in oxygen inhibition. [165]
solubility parameter that sometimes arises between hard and soft Much work has come from Jürgen Stampfl and Robert
segments. Challenges for polyurethane 3D printing include solubil- Liska in the Additive Manufacturing Group at TU Wien in
ity for DIW printing and subsequent solvent removal after printing. Vienna. Much of their work involves the synthesis of pho-
Printing from the melt is a much more efficient option if avail- tocurable monomers or oligomers and incorporation into pho-
able, as post-processing steps are often easier in this case. However, topolymer compositions via formulation. This group has pub-
printing from the melt is not without its challenges, as the polymer lished reviews on biomimetics,[166] new polymers for 3D
filament must act as a piston to drive the melt during FFF printing. printing,[12,166–169] and strategies to reduce oxygen inhibition
TPE filaments must either possess sufficient modulus so as not to of photopolymerization,[165] in addition to dozens of research
buckle during printing,[17] or must be extruded with specialized papers in this field. Here, we cover their work in the area of
equipment capable of handling low hardness materials. elastomeric photopolymers. In one early effort, these authors cre-
Opportunities exist in choosing unique polymer backbones ated a series of photopolymer compositions for the purpose of
for a desired application. For example, Voit et al. leveraging of creating blood vessel substitutes for cardiovascular disease treat-
polythiourethanes provided improved toughness and adhesive ment. Based on previously demonstrated biocompatibility of a
properties as compared to their oxygen-only polyurethane coun- cyanoacrylate-containing reactive diluent,[32] photopolymer com-
terparts. [119] The possibilities are endless for polyurethanes in positions were designed to contain 45-49 wt % cyanoethylacrylate,
terms of new polymer backbone chemical structures, as a wide 48.5 wt % PEG (400 g/mol), 1-5 wt % PEGDA (700 g/mol), and 1.5 wt
variety of low-Tg oligomers can be used as long as they are % Irgacure 819 photoinitiator, shown in Fig. 30. [170] The authors
nucleophile-terminated (e.g. hydroxyl, amine, or thiol). then compared mechanical properties of natural blood vessels
PUDs provide immense benefit in potential elimination of toxic (ovine arteria carotid). While the natural blood vessels possessed
and volatile organic solvents, resulting in polyurethane products elastic moduli of 350-550 kPa, tensile strength of 900-1100 kPa,
that do not carry the typical environmental and safety concerns and strain at break between 100-150 % when tested in tension in
of solvent-borne polyurethanes. In recent decades, PUDs have the circumferential direction, the photocured compositions pos-
replaced many solvent-borne polyurethanes in coatings applica- sessed elastic moduli of 215-410 kPa, tensile strength of 121-151
tions in a variety of industries. kPa, and strain at break of 67-98 %. [170] An increase in elas-
tic modulus and tensile strength and decrease in strain at break
36
J. Herzberger, J.M. Sirrine, C.B. Williams et al. / Progress in Polymer Science 97 (2019) 101144
Table 1
Summary of synthetic polyurethanes employed for 3D printing and mechanical properties for dry films.
Composition Traditional PU Oligodiol Diisocyanate Chain Extender Young’s Modulus Ultimate tensile Strain at Break (for Ref.
acronym (from or PUD, or (MPa) strength (for dried dried film)
relevant pub) other film)
PCL PUD 4.6–125 MPa 11– 35 MPa 280–778% [154]

PCL100 PUD 30.9 ± 7.9 34.9 ± 3.1 535.5 ± 19 [155]
PCL90LE10 PUD 18.6 ± 2.8 18.8 ± 1.2 650.6 ± 10 [155]
PU PU 30.8 ± 2.7 3.64 ± 0.83 > 500% [131–133]
PCL Lysine Diisocyanate - 11.94 ± 1.03 5.74 ± 1.33 1504 ± 291 [136,138]
PU 2k PCL 1,4-butandiisocyanate L-lysine ethyl ester 10.2 ± 2.2 3.3 ± 0.2 693 ± 15 [139]
(BDI) dihydrochloride
PUU23, PUU32 2k PCL HMDI Putrecine - - 7̃50 % [142,143]
WBPU1 PUD, 45 mol % 2.6 ± 0.5 16.1 ± 1.6 1453.3 ± 17.2 [161]
PEG
2k PCL, 1.45k PEG IPDI L-lysine
WBPU2 PUD, 33.3 mol 3.5 ± 0.4 16.7 ± 1.3 1336.8 ± 9.3 [161]
% PEG
WBPU3 PUD, 25 mol % 4.8 ± 1.3 21.8 ± 1.4 1120.1 ± 23.3 [161]
PEG
WBPU4 16.7 mol % PEG 3.3 ± 0.3 17.8 ± 0.9 1479.2 ± 18.1 [161]
MP530B PU PCL, 530 g/mol MDI BES - 24.2 211 [144]
MP530M PU PCL, 530 g/mol MDI MIDE - 3.9 107 [144]
Poly(EDDT-co- PU - HDI EDDT - 48.3 ± 7.1 307.8 ± 40.3 [119]
HDI)
EAA-AUD Urethane-cont. - - - 0.58 – 4.21 0.5 – 7.5 240 - 1100 [163]
mixture oligomer
PU PU 2k PTMO, IPDI - 2.5 3.7 195 [127]
550 g/mol
silanol
Table 2 Magdassi et al. have designed a series of highly elastomeric

Photopolymer compositions employed by Liska and Stampfl, et al. Adapted from
and UV curable photopolymers for vat photopolymerization that
Liska and Stampfl, et al. [42].
employ mixtures of an aliphatic urethane diacrylate (AUD, Ebecryl
Abbr. Chemical name / Structure Function 8413, Allnex) and epoxy aliphatic acrylate (EAA, Ebecryl 113); Ebe-
brand
cryl itself contains 33 wt % isobornyl acrylate, with the remainder
being aliphatic urethane diacrylate. [163] The relevant chemical
UDA Genomer 4215 Di-acrylate structures are shown in Scheme 20, with various optical images
of a 3D printed, isotropic truss shown in Fig. 31. Upon varying the
mixture of AUD and EAA, the authors achieved variation in Young’s
HEA Hydroxyethylacrylate Reactive diluent,
mono-acrylate
moduli between 0.58 – 4.21 MPa, elongation at break between 2̃40
% to 1̃100 %, and stress at break between 0̃.5 MPa to 7.5 MPa. This
EGTG Ethylene glycol Chain transfer agent simple photopolymer system relies only on commercially available
bisthioglycolate materials and vastly improves the characteristically poor strain at
break of non-silicone-containing elastomers, with the highest elon-
BPO Phenylbis(2,4,6- Photoinitiator gation composition containing 100 % Ebecryl 8413. The authors
trimethylbenzoyl) attribute this profound increase in strain at break to physical
phosphine oxide interactions from the aliphatic urethane diacrylate, e.g. hydrogen
(Irgacure® 819) bonding.
While many researchers optimize commercially available
DBB 1,2-dihydroxy-4-tert- Stabilizer
butylbenzene
photocurable oligomers, some decide to synthesize oligomers in-
house, due to the greater diversity enabled through synthetic
ABS CGL097 No information Absorber
available chemistry. Shown in Scheme 21, Chen et al. synthesized a series of
isocyanate-free, urethane-containing photocurable oligomers from
ETLA Ethyl lactate Solvent a cyclic carbonate-containing methacrylate monomer and various
biosourced diamines, in the absence of catalyst or solvent, in a reac-
tion requiring only heat. [173] For 3D fabrication, the authors also
employed a continuous liquid interface printing (CLIP) method sim-
was associated with increasing PEGDA concentration. Though these ilar to that described by DeSimone et al. and currently employed
compositions did not contain urethanes, they faithfully repro- by Carbon. [15,16] Though the authors did not measure tensile
duced the tissue mechanical properties of interest, an objective of properties of the fabricated films or structures, 3D printed squares
paramount importance in biomedical engineering. possessed compressive storage moduli between 20 – 30 MPa deter-
Liska and Stampfl built on this work by printing commercially mined using dynamic mechanical analysis (DMA). [173]
available mixtures of urethane acrylates and various reactive dilu- Jukka et al. synthesized a novel, photocurable urethane acrylate
ents in order to mimic the same blood vessel tissue previously oligomer and demonstrated the ability to 3D print an elastomeric
described. [43] Tear resistance was also considered in this work; object in the absence of reactive diluents. [127] The authors
an optimized urethane acrylate formulation containing a dithiol overcame the typically high viscosity of urethane-containing
chain extender matched the tear strength of blood vessel tissue. oligomers synthesized with symmetric diisocyanates, e.g. 1,6-
A related formulation more formally explored the role of chain hexanediisocyanate (HDI) or hydrogenated methylene diphenyl
extension with a dithiol, providing a highly useful cartoon repre- diisocyanate (H12 MDI) through use of the non-symmetrical
sentation of expected chain-extended network structure, shown isophorone diisocyanate (IPDI), which possess both a primary
in Fig. 29. [42,171] In this representation, a crosslinked network aliphatic and secondary cycloaliphatic isocyanate. The unequal
of 100 % oligomeric diacrylate, e.g. a PEG diacrylate hydrogel, reactivity and resulting sterically hindered hydrogen bonding
received an increase in spacing between crosslink points upon results in the production of relatively low viscosity products.
the addition of a monoacrylate (MA) reactive diluent. The space [174] In data that supports this hypothesis and in a sepa-
between crosslink points was further improved by the addition of rate study, Lai et al. employed infrared spectroscopy to confirm
a monomeric dithiol, which simultaneously increased the distance the relatively low amount of hydrogen bonding present in
between crosslink points by adding in between acrylate moieties, IPDI-containing polyurethanes, vs. the more symmetrical MDI-
and also by decreasing the overall degree of polymerization of containing polyurethanes, which they attributed to a lack of
the polyacrylate chain through abstraction of a hydrogen from structure order and resultant increase in steric effects. [175]
a CTA molecule. Bowman et al. corroborated this observation in Detailed in Scheme 22, Jukka et al. combined 550 g/mol hydroxyl-
a study of thiol-acrylate photopolymerizations, where stoichio- terminated PDMS, 2k g/mol poly(tetramethylene oxide) (PTMO),
metric thiol-acrylate polymerizations were observed to have an IPDI, hydroxyethyl methacrylate (HEMA), and a monofunctional
acrylate propagation constant 1.5 times greater than the rate of alcohol to control both the molecular weight, dispersity, and overall
hydrogen abstraction from a thiol but a postulated lower aver- functionality of the resulting urethane acrylate oligomers. Samples
age degree of polymerization. [164] Photopolymer compositions possessed Mn = 3,600 g/mol and Ð = 3.27 as measured by GPC, a sin-
demonstrated high tunability, with elastic moduli ranging from gle, broad Tg centered at -75 ◦ C (though the authors did not measure
0̃.6 – 4.0 MPa, tensile strength ranging from 0̃.5 – 2.3 MPa, and below −90 ◦ C), with a viscosity of 2.2 Pa·s at room temperature.
elongation at break ranging from 1̃00% – 450%. [42] Though the [127] Photocured films possessed a Young’s modulus, ultimate ten-
mechanical property data for these photopolymer compositions sile strength, and elongation at break of 2.5 MPa, 3.7 MPa, and 195
are not readily obtainable due to the proprietary nature of the %, respectively. [127]
urethane-containing oligomers, Table 2 depicts the publically avail- One unique approach toward the 3D printing of urethanes
able chemical components of these photopolymer formulations. involves blocked isocyanates. Based in academic literature[176]
The authors most recently published on tissue scaffold fabrication and shown in Scheme 23,[45] synthesis of blocked isocyanate-
employing related photoelastomer compositions and two-photon containing photocurable oligomer initially follows the forma-
polymerization (2 P P), producing relatively large scaffolds for the tion of an isocyanate-terminated prepolymer, in this case.
2 P P technique [172]. Here, after endcapping of a poly(propylene oxide) oligomer
with a diisocyanate, tert-butylaminoethyl methacrylate attacks hydrogels, this strategy might enable the 3D printing of elastomeric
the isocyanate end groups, producing a blocked isocyanate- structures starting from an oil-in water emulsion.
containing, photocurable oligomer. [45] After photocuring of
this oligomer in the presence of photoinitiator, diluents,
and chain extenders [e.g. triethanolamine, butanediol, or 4,4’-
methylenebis(cyclohexylamine)], a post-curing annealing process 10. Liquid Crystalline Elastomers (LCE)
deblocked the urethanes in the crosslinked object, providing chain
extension. This chain extension enabled strain at break values of Liquid crystalline elastomers (LCEs) are slightly crosslinked,
376 % for a photocured oligomer containing methyl methacrylate flexible polymers which bear liquid crystalline mesogenic groups
as a diluent and 4,4’-methylenebis(cyclohexylamine) as a chain in their side- or main-chains (Scheme 24). They combine the
extender, while the non-annealed sample only achieved 99 % strain ordered and mobile character of liquid crystals (LC) with rub-
at break. Though this work did not involve AM, it did inspire a new bery elasticity of polymers. [180,181] Details on the synthesis and
photopolymer chemistry at Carbon, for use in their CLIP process, as use of LCEs for harnessing macroscale mechanical responses was
indicated by a recent patent. [44] recently reviewed by White and Broer. [182] In brief, LCE’s exhibit
reversible mechanical and optical properties through a transition
from the LC phase (i.e. nematic) to the isotropic phase in response
to external stimuli, such as temperature, light or electric field.
9. Additive Manufacturing Using Polymer Emulsions [183] Heating a LCE above the clearing temperature TC (transi-
tion temperature from LC phase to the isotropic phase) causes
As briefly mentioned in section 7.4, emulsions offer great the aligned mesogens to randomly distribute and the LCE expe-
potential for AM of elastomers. In emulsion polymerization, the riences a contraction along the direction of alignment. In contrast,
water-insoluble monomers (oil-phase) are dispersed in water when cooled below the TC , the mesogenic groups orient and the
using surfactants. Radical polymerization yields latex particles material expands along the direction of alignment. However, a
suspended in water, which contain high molecular weight poly- pre-orientation step of the sample and alignment of the meso-
mers. [177] Because the polymers are formed in micelles/colloidal genic segments is necessary to observe such property changes on
particles, the viscosity of the latexes are close to that of water a macroscale. [181] Highly ordered systems are usually obtained
(H2 O = 0.001 Pa·s) and do not depend on the molecular weight of via mechanical stretching of films, electrospinning, or the use of
the polymers. This offers great potential to process high molecular pre-aligned substrates. Being able to additively manufacture LCEs
weight polymers using AM techniques which require low viscosi- in three dimensions is highly attractive for creating artificial mus-
ties, e.g. inkjet printing. cles, soft actuators/robots, sensing devices, smart medical devices,
In 2016 Wells et al. investigated five different types of latex or dynamic functional architectures. [184]
inks, all commercially available. [25] Materials ranged from poly(2- While Broer et al. ink-jet printed 2D layers using LCEs
chloro-1,3-butadiene) (also known as neoprene), carboxylated in 2009, only very recently, Ware et al. harnessed the
styrene-butadiene rubber, carboxylated butadiene-acrylonitrile anisotropic nature of DIW to fabricate aligned LCEs in 3
copolymer, natural rubber, to prevulcanized natural rubber. dimensions. The authors formulated LCE inks starting from a
From this selection, only carboxylated styrene-butadiene (Litex commercially-available liquid crystalline monomer (1,4-bis-[4-(6-
T 71S20® ) was determined suitable for inkjetting, possessing a acryloyloxhexyloxy)benzoyloxy]-2- methylbenzene (RM82)) and
viscosity of 12 mPa·s, particle diameters of 0.25 ␮m and surface n-butylamine as chain-extender. [185] Both were mixed in a 1.1:1
tensions of 49 mN·m-1 . However, dilution to 35 wt.% solids and ratio, filled into the printing syringe and aza-Michael-addition at
addition of a non-ionic surfactant (Triton X-100) was needed 75 ◦ C induced chain-extension, yielding the LCE oligomers with
to avoid agglomeration and clogging of the printer nozzle. First terminal acrylate groups (Scheme 25, left). The oligomers pos-
attempts resulted in rather low printing resolution due to the for- sessed shear thinning behavior at temperatures within the nematic
mation of small secondary satellite drops and the individual printed region (85 ◦ C) and were easily extruded. The extrusion out of a
lines were visible after drying the ink. While this procedure demon- narrow nozzle (diameter = 0.31 mm) allowed for aligning the meso-
strated high potential of polymer emulsions for inkjet printing, gens parallel to the printing path and yielded controlled molecular
optimization is required to achieve better print resolution. orientation (Scheme 25, right). Afterwards, UV-light illumination
Bain et al. further investigated the concept of inkjet printing induced crosslinking of the acrylate-end groups. The crosslinking
emulsions of high molecular weight polymers. [178] The authors step enabled shape retention of the extruded structures and locked
studied the printability of dissolved polystyrene (PS) with molecu- the aligned polymer chains in place.
lar weights of Mn = 549k g·mol-1 in methyl benzoate and compared Single-layered LCE films exhibited an elastic modulus of 18 MPa
it to emulsions consisting of PS with Mn = 419k gmol-1 and SDS along the extrusion direction and a modulus of 4 MPa normal to the
(sodium dodecyl sulfate) as surfactant. These experiments revealed extrusion direction and showed maximum strains of 70-120%. The
that emulsions with 3.8 wt % PS showed Newtonian jetting dynam- LCE oligomers exhibited a nematic (LC phase) to isotropic transition
ics and enabled successful printing. In contrast, only 0.25 wt % of temperature (TC ) at 105 ◦ C. Above the TC , the material undergoes a
high-molecular weight PS, dissolved in methyl benzoate, were jet- large, reversible contraction parallel to the direction of the mesogen
table. Albeit PS is not an elastomer, oil-in-water emulsions show alignment. Upon heating to 200 ◦ C, the material reversible con-
feasibility of printing high molecular weight polymers, because tracted by 40% along the print direction and expanded normal
the low-shear viscosity is reduced and non-Newtonian dynam- to that direction. Capitalizing on the design freedom of DIW and
ics are eliminated, which is highly attractive for 3D-printing the anisotropic deformation of aligned LCEs, the authors printed
elastomers. Nevertheless, surfactants are needed to prepare oil-in- various structures, including geometries with zero, negative and
water emulsions, which might influence the overall properties of positive Gaussian curvature. The combination of positive and neg-
the printed material. Recently, Doyle et al. formulated thermore- ative Gaussian curvature in one geometry enabled the design of
sponsive nanoemulsions for selective photocuring, utilizing PDMS structures with snap-through deformation. Utilizing the same con-
as oil phase and PEG-dimethacrylate and sodium dodecyl sulfate cept, Sánchez-Somolinos et al. printed a ring-shaped LCE in a PDMS
(SDS) in deionized water as continuous phase. [179] While the Slab and demonstrated their potential as a variable focusing lens.
authors utilized this formulation to manufacture mesostructured [187] Due to the asymmetric placement of the LCE in the PDMS,
Table 3
List of commercially-available materials for AM of elastomeric structures and their detailed properties.
Trade name Supplier Polymer type Tensile Ultimate Elongation at Compression Shore Hardness Thermal AM technique
modulus [MPa] tensile strength break [%] set [%] transitions [◦ C]
[MPa]
Flexible FLGR02 Formlabs photopolymer NA 7.7-8.5a 75-85a 0.4a (23 ◦ C) 80-85Aa NA SLA
EPU 40 Carbon photopolymer (PU) NA 7.7a > 250a 23a (23 ◦ C) 68Aa 1
Tg = 8a CLIP
EPU 41 Carbon photopolymer (PU) NA 6.2a > 130a 22a (23 ◦ C) 70-73 Aa 1
Tg = -9a CLIP
FPU 50 Carbon photopolymer (PU) 860 ± 110a 29 ± 1a 280 ± 15a NA 71 Da NA CLIP
SIL 30 Carbon silicone urethane elastomer NA 3.2a > 330a 11a (23 ◦ C) 31-35 Aa 1
Tg = 8a CLIP
TangoBlackPlus FLX980 Stratasys photopolymer NA 0.8-1.5 170-220 4-5 (NA) 26-28A NA PolyJet
and TangoPlus FLX930
TangoBlack FLX973 Stratasys photopolymer NA 1.8-2.4 45-55 0.5-1.5 (NA) 60-62A NA PolyJet
TangoGray FLX950 Stratasys photopolymer NA 3-5 45-55 0.5-1.5 (NA) 73-77A NA PolyJet
Agilus30 Stratasys photopolymer NA 2.4-3.1 220-270 6-7 (NA) 30-35 Ad NA PolyJet
J. Herzberger, J.M. Sirrine, C.B. Williams et al. / Progress in Polymer Science 97 (2019) 101144
ACEO® Silicone GP Wacker UV-curable silicones (no NA > 6a > 450a < 15a (175 ◦ C) 30 Aa NA Drop on
Shore A 30 acrylates) demand,
UV-curing
ACEO® Silicone GP Wacker UV-curable silicones (no NA > 7a >200a < 20a (175 ◦ C) 60 Aa NA Drop on
Shore A 60 acrylates) demand,
UV-curing
Spot-E Spot-A materials photopolymer 12a 30a 65a NA 65 Aa NA SLA
3DSR Flexible Kudo 3D photopolymer NA NA NA NA NA NA SLA
2
NinjaFlex NinjaTek TPU 12 26 660 NA 85 A Tg = -35 2 Tm = FFF
216
2
Cheetah NinjaTek TPU 26 39 580 NA 95 A Tg = -24 2 Tm = FFF
220
2
DuraForma Flex 3D Systems TPE 7.4 1.8 110 NA 45-75 A Tm = 192 SLS
DuraForm TPU 3D Systems TPU 5.3 2.1 200 NA 59 A NA SLS
Fig. 4 ELAST-BLK 10 3D Systems photopolymer 3.6a 3.6a 83a 0.87 (NA) 65 A 1
Tg = -26 DLP
VisiJet M2 ENT and 3D Systems photopolymer 0.27-0.43 0.2-0.4 160-230 NA 28-32 A NA MultiJet
VisiJet M2 EBK
VisiJet CE-NT and 3D Systems photopolymer 0.27-0.43 0.2-0.4 160-230 NA 27-33 A NA MultiJet
VisiJet CE-BK
b b 1 2
Luvosint X92A-1 and Lehmann & Voss & Co. (LUV) ester based TPU NA 20 520 NA 88 A Tg = -14, Tm = SLS
X92A-2 160
Luvosint X97A-1 WT Lehmann & Voss & Co. (LUV) ester based TPU NA 26b 210b NA 97 A 1
Tg = 4, 2 Tm = SLS
180
PrimePart® ST PEBA Electro Optical Systems (EOS) polyether block amide 75b 8b 200b NA 35 D 2
Tm = 150 SLS
2301
TPE 210-S Advanced laser materials TPE 8 NA 110 NA 40 A NA SLS
(ALM)
TPU-70A Prodways Technologies TPU 65 ± 25 7±1 c
350 ± 25 c
NA 70 ± 5 A 105 < Tm < 122 2
SLS
Digital Series Proto labs photopolymer NA 2.4-3.1 220-270 NA 30-35 Ad NA Polyjet
ToughRubber 30.450 Adaptive3D photopolymer NA 17.3 450 NA NA NA SLA
Hytrel 3D4000FL DuPont Polyester based TPE 50 13-19e >300- 500 40 D Tm = 150 FFF
NC010
TPU dddrop TPU 150 50f 450 NA 98 A 2
Tg = -16, Tm = FFF
220
e
FlexiFil FormFutura Thermoplastic co-polyester 95 24 530 NA 45 D Tm = 180 FFF
Crystal Flex FormFutura Styrene-butadiene copolymer - 26f 230 NA 63 D NA FFF
Python Flex FormFutura TPU 150 50f 450 NA 98 A Tm = 220 FFF
1
Determined using DMA.
2
Determined using DSC.
a
Post-cured (UV-irradiation or thermal treatment).
b
x-direction.
c
Average xy.
d
Material with multiple Shore A hardness available.
e
Stress at break.
39
f
Stress at yield.
the Slab maintained flat at room temperature, but heating to 100 ◦ C an in-house designed CLIP process. [195–198] In an example syn-
induced deformation and formed a convex front (Fig. 32). thesis shown in Scheme 29, the authors combined dodecanediol
The anisotropic deformation of oriented LCEs upon heating and citric acid in the melt, in the absence of catalyst or solvent, and
above their nematic phase enables them to conduct specific work. freeze dried the polymers after isolation. A post-polymerization
Lewis et al. studied the impressive weight-specific work capacity functionalization then installed methacrylate functional groups on
of LCEs in detail. [188] The authors printed LCE strips and per- remaining hydroxyl functional groups. [197] Although no tensile
formed weight lifting experiments. Significantly, 1 mm thick AM mechanical property data is provided, the 3D printed scaffolds qual-
LCE actuators were able to lift 1̃000 times of their own body weight itatively demonstrated elastic recovery after application of 25 %
(106 mg) as illustrated in Fig. 33. Overall, DIW of LCEs is promising compressive strain. [197] Previous reports from Ameer et al. do
for the design of artificial muscles and actuators. However, regard- not discuss 3D printing but provide more extensive composition
ing biomedical applications, the development of LCE’s with phase and mechanical property analysis for non-photocurable analogs
transitions under physiological conditions, faster response times (e.g. just diols and citric acid alone), investigating the role of
and biodegradability are needed. [189] diol segment length on mechanical properties. [198] One notable
composition, poly(1,6-hexanediol-co-citric acid), obtained a stress
and strain at break of approximately 3 MPa and 375 %, though
11. Polyesters and Polycarbonates this composition is not 3D printable with CLIP due to the lack of
photocurable functionality in the polymer backbone. A viable alter-
A small number of 3D printable, polyester- or polycarbonate- native for printing this composition might be the melt extrusion
based polymers are reported, though the volume of literature does of poly(diol citrate) pre-polymer solutions, as these pre-polymers
not match that of polyurethanes or poly(dimethyl siloxane)s. In one are soluble before network formation occurs. [196] Furthermore,
example, Zhang et al. synthesized and 3D printed unsaturated, low strain at break decreased for poly(diol citrate) samples after the
Tg , random copolyester thermoplastic vulcanizates (TPVs),[190] prepolymer underwent post-polymerization network formation
shown in Scheme 26, which are based on some of their previous under vacuum, though slight increases in thermal stability and
work. [191,192] These phase-separated TPVs contain a high weight large increases in stress at break were observed, demonstrating the
fraction of elastomer and smaller thermoplastic weight fraction and tunability of this poly(diol citrate) platform [196].
undergo phase inversion upon dynamic vulcanization, resulting in
a crosslinked elastomeric phase in a thermoplastic matrix, as illus-
12. 3D Printing of Commercially Available Elastomer and
trated in Fig. 34a. Depending on composition, e.g. ratio of PLBSI to
Elastomeric-Like Materials
PLA, the authors were able to achieve 4̃40 % strain and 2̃ MPa ulti-
mate tensile strength for PLBSI alone, while a 60/40 PLA/PLBSI TPV
Table 3 provides a selective overview of commercially avail-
achieved 3̃20 % strain at break and 2̃0 MPa strain at break. 3D print-
able materials specifically distributed to additively manufacture
ing occurred via fused filament fabrication, the products of which
objects with rubbery-like and flexible characteristics. It lists the
are shown in Fig. 34b, with the 3D printed structures (up to 75 %
polymer type, resulting thermal and mechanical properties and
porous) achieving 240 – 260 % strain at break.
the respective printing technique, which are provided in the data
Burdick et al. synthesized acrylated poly(glycerol sebacate)s
sheets of the material suppliers. While chemical details on the poly-
macromonomers for direct ink write AM, shown in Scheme 27.
mer resins/powders/filaments are proprietary, the materials safety
[193] Macromonomers possessed a Mn of 6,000 g/mol relative to
data sheets (MSDS) provide some insight, e.g. type of photoinitia-
PMMA and Ð ≈ 1.7-2, while NMR spectroscopy measured 1̃5 % acry-
tor or photopolymer (e.g. oligomeric urethane acrylate). In general,
late functionalization of the available hydroxyl functional groups.
one has to keep in mind that a direct comparison of different mate-
Photorheology indicated a G’/G” modulus crossover within sec-
rials is challenging, because mechanical properties vary with part
onds for all compositions, while the uncured oligomer possessed
geometry, printing parameters/configurations, testing parameters
pre-cured viscosities between 3-9 Pa·s. UV irradiation occurred
and/or post-processing conditions.
throughout and after the DIW process, resulting in the produc-
Intriguingly, instead of providing specialized elastomers for 3D
tion of well-defined 3D scaffolds. Film-casted samples possessed
printing, Fripp Design developed a 3D printer called “PICSIMA”
a young’s modulus of 0̃.6 MPa, an ultimate tensile stress of 0̃.4 MPa,
which is designed for AM of conventional silicone elastomers.
and a strain at break of 8̃5%, with DIW created samples falling
[199] The printer utilizes commercially-available two-part room-
slightly short of these film-casted values.
temperature vulcanization silicone resins, which were developed
Grijpma et al. synthesized biodegradable poly(␧-CL-b-TMC-␧-
for molding and are FDA-approved for medical applications.
CL) triblock copolymers, shown in Scheme 28 that served as
In detail, PICSIMA uses a vat which is filled with silicone oil,
melt-processable thermoplastic elastomers for tissue scaffolding
crosslinker and thickener. A computer-operated syringe deposits
applications. [194] Triblock copolymers were printed via mate-
the curing agent into the resin bath and curing occurs only at the
rial extrusion as a 20-25 wt % solution in ethylene carbonate
deposition spots while the vat filled with liquid PDMS oil acts as
and subsequently extracted with water and dried, generating
support bath. After a post-build time of 10 minutes, the cured sili-
microporous scaffold morphologies due to ethylene carbonate
cone elastomer can be removed from the resin bath. This technique
crystallization before solvent removal and drying. Solution-cased
enables the AM of silicone elastomer objects without internal struc-
triblock copolymer films possessed a Young’s modulus, ultimate
ture and no support materials are required to create 3D geometries.
tensile strength, and elongation at break of approximately 120 MPa,
16 MPa and 620 % respectively. Though mechanical properties were
not obtained for the 3D-printed, microporous scaffolds, this effort 13. Conclusions and Outlook
represents a remarkable achievement in strain at break for non-
urethane-containing polymers. In this case, physical crosslinking The interest in additive manufacturing of elastomers is rapidly
and subsequent mechanical property improvements occur through growing because of the wide range of potential applications.
phase separation of the PCL and PTMC blocks. Elastomers play an extremely important role in the automotive
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Progress in Polymer Science 97 (2019) 101144

Contents lists available at ScienceDirect

Progress in Polymer Science

Polymer Design for 3D Printing Elastomers: Recent Advances in

Scheme 1. Shore hardness scale of everyday products.

Scheme 2. Schematic of DIW apparatus. [21] Copyright 2016. Reproduced with

used to describe such yield-stress ﬂuids, with = y + K˙ n where

3.5. Inkjet printing / material jetting

Inkjet printing is another ink-based technique and utilizes the

Scheme 5. Crosslinking of acetoxy-functional polysiloxanes via condensation reaction.

in photopolymer compositions, the afﬁne and phantom network

available PBF elastomer powders exist, which are mentioned in

5. Silicone Elastomers – Synthesis and Properties

5.1. Properties of silicone elastomers

Silicone elastomers are biocompatible, optically transparent,

Scheme 11. UV-crosslinking of methacrylate-functional PDMS oligomer yields sil-

stretchable with ultimate strains above 300%. [61]

5.2. Synthesis of silicone elastomers

Skov et al. recently provided a tutorial review on how to tailor

Scheme 16. Schematic representation of a segmented polyurethane or polyurea.

such as additional ﬁllers are completely optional. Vlassak et al. uti-

simply dissolving the Carbopol medium using phosphate buffered

Boydston et al. reinvestigated the challenge of formulat-

viated as PDMS-S) with the purpose to mimic the properties

is the case with the diisocyanate example, above. In these cases,

7.3. Traditional polyurethane printing in solution (material

The primary route towards segmented polyurethane block

PCL PUD 4.6–125 MPa 11– 35 MPa 280–778% [154]

Table 2 Magdassi et al. have designed a series of highly elastomeric

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