Multi-material Printing Research Articles

Multimaterial three-dimensional printing in brachytherapy: Prototyping teaching tools for interstitial and intracavitary procedures in cervical cancers

PurposeAs the utilization of brachytherapy procedures continues to decline in clinics, a need for accessible training tools is required to help bridge the gap between resident comfort in brachytherapy training and clinical practice. To improve the quality of intracavitary and interstitial high-dose-rate brachytherapy education, a multimaterial, modular, three-dimensionally printed pelvic phantom prototype simulating normal and cervical pathological conditions has been developed. Methods and MaterialsPatient anatomy was derived from pelvic CT and MRI scans from 50 representative patients diagnosed with localized cervical cancer. Dimensions measured from patients’ uterine body and uterine canal sizes were used to construct a variety of uteri based off of the averages and standard deviations of the subjects in our study. Soft-tissue anatomy was three-dimensionally printed using Agilus blends (shore 30 and 70) and modular components using Vero (shore 85). ResultsThe kit consists of four uteri, a standard bladder, a standard rectum, two embedded gross tumor volumes, and four clip-on gross tumor volume attachments. The three anteverted uteri in the kit are based on the smallest, the average, and the largest dimensions from our patient set, whereas the retroverted uterus assumes average dimensions. ConclusionsThis educational high-dose-rate gynecological pelvic phantom is an accessible and cost-effective way to improve radiation oncology resident training in intracavitary/interstitial brachytherapy cases. Implementation of this phantom in resident education will allow for more thorough and comprehensive physician training through its ability to transform the patient scenario. It is expected that this tool will help improve confidence and efficiency when performing brachytherapy procedures in patients.

Inkjet Printing of Complex Soft Machines with Densely Integrated Electrostatic Actuators

A multimaterial inkjet printing method for integrated soft multifunctional machines is reported, combining dense arrays of electrostatic actuators, multilayer electrical routing, and complex networks of microfluidic channels in one printing process. Most additive manufacturing methods for soft robots are developed for devices driven by external fluidic pressure sources and are not suited to fabricate soft electrically driven actuators. To integrate electrostatic zipping actuators and microfluidics in stretchable soft machines without any rigid components, inks for sacrificial layers, dielectric elastomers, and compliant electrodes are developed herein, along with a unified printing process to print multilayer structures. Printed 2.5D stacks are transformed into fully functional 3D soft machines by inflating thin elastomer channels. Two demonstrators are reported, each consisting of seven printed layers: a flexible peristaltic pump and a compliant slug drive, inspired by the locomotion of slugs. The peristaltic pump has six integrated actuators, whereas the slug drive has 28 integrated actuators, generating a travelling wave used to transport objects. These soft devices demonstrate how inkjet printing produces densely packed high‐voltage actuators, including vias for electrical routing. Sensors and logic may be printed in the future to produce more complex autonomous soft machines.

A Chip-First Microwave Package Using Multimaterial Aerosol Jet Printing

We show in this article two fully additively manufactured microwave packages with integrated active and passive components. Packages were constructed using a chip-first approach where package substrates (dielectrics) and interconnects (conductors) are built up around power amplifier bare die attached to carriers. Bypass capacitor dielectrics were printed using multimaterial aerosol jet printing, where aerosols of barium titanate and polyimide inks are mixed in place to fabricate a high dielectric constant polymer matrix nanocomposite film. The material properties of the film are characterized using three printed capacitors. We present S-parameter measurements to characterize small-signal performance, as well as load-pull measurements at the saturated output power. Finally, we demonstrate package performance after power cycling and temperature cycling to show the effect of aging on the part and the robustness of this packaging strategy. We measured a maximum packaged gain of 21.7 dB and a saturated output power of 21.9 dBm for a commercial-off-the-shelf (COTS) medium power amplifier specified to have a gain of 22 dB and a saturated output power of 22 dBm. The printed package-level performance is compared with the published bare die performance and a measured COTS packaged amplifier.

Multimaterial 3D printing of a definitive silicone auricular prosthesis: An improved technique

Direct silicone printing has been reported for the manufacture of interim facial prostheses. The recent advancements in printing hardware have allowed for multimaterial simultaneous silicone printing with 4 nozzles. With this technology, an auricular prosthesis was printed with various grades of Shore hardness. A few analog steps, including polishing, sealing, coloring, and relining, resulted in an individualized prosthesis with a thin frontal margin and smooth transition into the adjacent tissue. It was considered a definitive treatment option.

3D-Printed Column with Porous Monolithic Packing for Online Solid-Phase Extraction of Multiple Trace Metals in Environmental Water Samples

In this study, we used a multimaterial three-dimensional printing (3DP) technology and porous composite filaments (Lay-Fomm, Gel-Lay, and Lay-Felt) to fabricate solid phase extraction (SPE) columns for the enhanced extraction of multiple metal ions. When employed as sample pretreatment devices in an automatic flow injection analysis/inductively coupled plasma mass spectrometry (ICP-MS) system, these 3D-printed SPE columns performed the near-complete extractions of Mn, Co, Ni, Cu, Zn, Cd, and Pb ions from natural water samples prior to ICP-MS determination. After optimizing the column fabrication, the extraction conditions, and the automatic analysis system, the column packed with the porous composite Lay-Fomm 40 was found to provide the highest extraction performance-the extraction efficiencies of the listed metal ions were all greater than 99.2%, and the detection limits of the method ranged from 0.3 to 6.7 ng L-1. The detection of these metal ions in several reference materials (CASS-4, SLEW-3, 1640a, and 1643f) validated the reliability of this method; spike analyses of collected water samples (groundwater, river water, and seawater) demonstrated the applicability of the method. The nature of the printing materials enhanced the analytical performance of 3D-printed sample pretreatment devices. Such approaches will be useful to diversify the range of sample preparation schemes and analytical methods enabled by 3DP technologies.

Mechanical Properties Tailoring of 3D Printed Photoresponsive Nanocellulose Composites

Abstract3D printing technologies allow control over the alignment of building blocks in synthetic materials, but compositional changes often require complex multimaterial printing steps. Here, 3D printable materials showing locally tunable mechanical properties are produced in a single printing step of Direct Ink Writing. These new inks consist of a polymer matrix bearing biocompatible photoreactive cinnamate derivatives and up to 30 wt% of anisotropic cellulose nanocrystals. The printed materials are mechanically versatile and can undergo further crosslinking upon illumination. When illuminating the material and controlling the irradiation doses, the Young's moduli can be adjusted between 15 and 75 MPa. Moreover, spatially controlled illumination allows patterning stiff geometries, resulting in 3D printed structures with segments of different mechanical properties tailoring the mechanical behavior under compression. The high design freedom implemented by 3D printing and photopatternability opens the venue to rapid manufacturing of devices for applications such as prosthetics or soft robotics where the 3D shapes and mechanical properties must be tailored for personalized load cases.

Chemically Coupled Interfacial Adhesion in Multimaterial Printing of Hydrogels and Elastomers.

Functional devices that use hydrogels as ionic conductors and elastomers as dielectrics have the advantage of being soft, stretchable, transparent, and biocompatible, making them ideal for biomedical applications. These devices are typically fabricated by manual assembly. Techniques for the manufacturing of soft materials have generally not looked at integrating multiple dissimilar materials. Silane coupling agents have recently shown promise for creating strong bonds between hydrogels and elastomers but have yet to be used in the extrusion printing of complex devices that integrate both hydrogels and elastomers. Here, we demonstrate the viability of silane coupling agents in a system with the rheology and functional composition necessary for three-dimensional (3D) extrusion printing of hydrogel-elastomer materials, specifically polyacrylamide (PAAm) hydrogel and poly(dimethylsiloxane) (PDMS) hydrophobic elastomer. By introducing a charge-neutral surfactant in the PDMS and adjusting silane concentrations in the PAAm, cast material samples demonstrate strong adhesion. We were also able to achieve an interfacial toughness of up to Γ = 193 ± 6.3 J/m2 for a fully extrusion printed PAAm hydrogel-on-PDMS bilayer. This result demonstrates that an integration strategy based on silane coupling agents makes it possible for extrusion printing of a wide variety of hydrogel and silicone elastomers.

Evolution of 3D Printing Methods and Materials for Electrochemical Energy Storage.

Additive manufacturing has revolutionized the building of materials, and 3D-printing has become a useful tool for complex electrode assembly for batteries and supercapacitors. The field initially grew from extrusion-based methods and quickly evolved to photopolymerization printing, while supercapacitor technologies less sensitive to solvents more often involved material jetting processes. The need to develop higher-resolution multimaterial printers is borne out in the performance data of recent 3D printed electrochemical energy storage devices. Underpinning every part of a 3D-printable battery are the printing method and the feed material. These influence material purity, printing fidelity, accuracy, complexity, and the ability to form conductive, ceramic, or solvent-stable materials. The future of 3D-printable batteries and electrochemical energy storage devices is reliant on materials and printing methods that are co-operatively informed by device design. Herein, the material and method requirements in 3D-printable batteries and supercapacitors are addressed and requirements for the future of the field are outlined by linking existing performance limitations to requirements for printable energy-storage materials, casings, and direct printing of electrodes and electrolytes. A guide to materials and printing method choice best suited for alternative-form-factor energy-storage devices to be designed and integrated into the devices they power is thus provided.

Development of a multi-material stereolithography 3D printing device.

Additive manufacturing, or nowadays more popularly entitled as 3D printing, enables a fast realization of polymer, metal, ceramic or composite devices, which often cannot be fabricated with conventional methods. One critical issue for a continuation of this success story is the generation of multi-material devices. Whilst in fused filament fabrication or 3D InkJet printing, commercial solutions have been realized, in stereolithography only very few attempts have been seen. In this work, a comprehensive approach, covering the construction, material development, software control and multi-material printing is presented for the fabrication of structural details in the micrometer range. The work concludes with a critical evaluation and possible improvements.

Concurrent Formation of Metallic Glass During Laser Forward Transfer 3D Printing

AbstractIn recent years, bulk metallic glasses (BMGs) have drawn much research attention and are shown to be of industrial interest due to their superior mechanical properties and resistance to corrosion. In spite of the interest in harnessing MG for microelectromechanical systems devices, there are limitations in manufacturing such micrometer‐scale structures. A novel approach for the fabrication of 3D MG structures using laser‐induced forward transfer (LIFT) is demonstrated. Inherent tremendous cooling rates associated with the metal LIFT process (≈1010 k s−1) make the formation of a variety of BMGs accessible, including also various binary compositions. In this work, it is demonstrated that LIFT printing of ZrPd‐based metallic glass microstructures can also be performed under ambient conditions. X‐ray diffraction analysis of the printed structures reveals > 95% of amorphous metal phase. Taking advantage of the properties of BMG, high quality printing of high aspect ratio BMG pillars, and microbridges are demonstrated. It is also shown how a composite, amorphous‐crystalline metal structure with a required configuration can be fabricated using multimaterial LIFT printing. The inherent high resolution of the method combined with the noncontact and multimaterial printing capacity makes LIFT a valuable additive manufacturing technique to produce metallic glass‐based devices.

In Situ Nanocomposite Fabrication for RF Electronics Applications With Additive Manufacturing

Using additive manufacturing (AM), in this article, we show the dynamic mixing of polymer ceramic composite materials during the 3-D printing process. Using this in situ mixing strategy, we print polyimide and barium titanate (BaTiO 3) nanocomposite films with variable levels of ceramic loading. This is accomplished with multimaterial aerosol jet printing. The relative dielectric constant and loss tangent of these composite materials are characterized using two ring resonator circuits designed for the first resonance below 12 and 110 GHz, respectively. This yields material characterization results from the X-band to the W-band. We use these results to estimate the ceramic loading by volume in the composites. In addition, we use scanning electron microscopy and energy-dispersive X-ray spectroscopy to characterize the dispersion and ceramic loading of the composite films. Using this process, we demonstrate a range of relative dielectric constants from 3.1 to 8.9. To demonstrate the capabilities of this process, a continuous gradient of material is also shown in a printed film. Finally, we demonstrate a slightly modified process in order to lower the loss characteristics of the printed films to provide insight into the loss mechanisms. By mixing composites in situ, we are able to dynamically alter the ceramic loading of the printed material without formulating multiple inks and pattern 3-D structures without the use of photosensitive materials. This allows us to manufacture material gradients and patterns that would otherwise be impractical to fabricate using conventional microfabrication. Using composite mixing in place adds a new dimension to the flexibility and capability of AM.

3D Freeform Printing of Nanocomposite Hydrogels through in situ Precipitation in Reactive Viscous Fluid

Composite hydrogels have gained great attention as three-dimensional (3D) printing biomaterials because of their enhanced intrinsic mechanical strength and bioactivity compared to pure hydrogels. In most conventional printing methods for composite hydrogels, particles are preloaded in ink before printing, which often reduces the printability of composite ink with little mechanical improvement due to poor particle-hydrogel interaction of physical mixing. In contrast, the in situ incorporation of nanoparticles into a hydrogel during 3D printing achieves uniform distribution of particles with remarkable mechanical reinforcement, while precursors dissolved in inks do not influence the printing process. Herein, we introduced a “printing in liquid” technique coupled with a hybridization process, which allows 3D freeform printing of nanoparticle-reinforced composite hydrogels. A viscoplastic matrix for this printing system provides not only support for printed hydrogel filaments but also chemical reactants to induce various reactions in printed objects for in situ modification. Nanocomposite hydrogel scaffolds were successfully fabricated through this 3D freeform printing of hyaluronic acid (HAc)-alginate (Alg) hydrogel inks through a two-step crosslinking strategy. The first ionic crosslinking of Alg provided structural stability during printing, while the secondary crosslinking of photo-curable HAc improved the mechanical and physiological stability of the nanocomposite hydrogels. For in situ precipitation during 3D printing, phosphate ions were dissolved in the hydrogel ink and calcium ions were added to the viscoplastic matrix. The composite hydrogels demonstrated a significant improvement in mechanical strength, biostability, as well as biological performance compared to pure HAc. Moreover, the multi-material printing of composites with different calcium phosphate contents was achieved by adjusting the ionic concentration of inks. Our method greatly accelerates the 3D printing of various functional or hybridized materials with complex geometries through the design and modification of printing materials coupled with in situ post-printing functionalization and hybridization in reactive viscoplastic matrices.

3D Freeform Printing of Nanocomposite Hydrogels through in situ Precipitation in Reactive Viscous Fluid

Composite hydrogels have gained great attention as three-dimensional (3D) printing biomaterials because of their enhanced intrinsic mechanical strength and bioactivity compared to pure hydrogels. In most conventional printing methods for composite hydrogels, particles are preloaded in ink before printing, which often reduces the printability of composite ink with little mechanical improvement due to poor particle-hydrogel interaction of physical mixing. In contrast, the in situ incorporation of nanoparticles into a hydrogel during 3D printing achieves uniform distribution of particles with remarkable mechanical reinforcement, while precursors dissolved in inks do not influence the printing process. Herein, we introduced a “printing in liquid” technique coupled with a hybridization process, which allows 3D freeform printing of nanoparticle-reinforced composite hydrogels. A viscoplastic matrix for this printing system provides not only support for printed hydrogel filaments but also chemical reactants to induce various reactions in printed objects for in situ modification. Nanocomposite hydrogel scaffolds were successfully fabricated through this 3D freeform printing of hyaluronic acid (HAc)-alginate (Alg) hydrogel inks through a two-step crosslinking strategy. The first ionic crosslinking of Alg provided structural stability during printing, while the secondary crosslinking of photo-curable HAc improved the mechanical and physiological stability of the nanocomposite hydrogels. For in situ precipitation during 3D printing, phosphate ions were dissolved in the hydrogel ink and calcium ions were added to the viscoplastic matrix. The composite hydrogels demonstrated a significant improvement in mechanical strength, biostability, as well as biological performance compared to pure HAc. Moreover, the multi-material printing of composites with different calcium phosphate contents was achieved by adjusting the ionic concentration of inks. Our method greatly accelerates the 3D printing of various functional or hybridized materials with complex geometries through the design and modification of printing materials coupled with in situ post-printing functionalization and hybridization in reactive viscoplastic matrices.

Multi-Material 3D Printed Shape Memory Polymer with Tunable Melting and Glass Transition Temperature Activated by Heat or Light.

Shape memory polymers are attractive smart materials that have many practical applications and academic interest. Three-dimensional (3D) printable shape memory polymers are of great importance for the fabrication of soft robotic devices due to their ability to build complex 3D structures with desired shapes. We present a 3D printable shape memory polymer, with controlled melting and transition temperature, composed of methacrylated polycaprolactone monomers and N-Vinylcaprolactam reactive diluent. Tuning the ratio between the monomers and the diluents resulted in changes in melting and transition temperatures by 20, and 6 °C, respectively. The effect of the diluent addition on the shape memory behavior and mechanical properties was studied, showing above 85% recovery ratio, and above 90% fixity, when the concentration of the diluent was up to 40 wt %. Finally, we demonstrated multi-material printing of a 3D structure that can be activated locally, at two different temperatures, by two different stimuli; direct heating and light irradiation. The remote light activation was enabled by utilizing a coating of Carbon Nano Tubes (CNTs) as an absorbing material, onto sections of the printed objects.

3D Printing in analytical sample preparation.

In the last 5 years, additive manufacturing (three-dimensional printing) has emerged as a highly valuable technology to advance the field of analytical sample preparation. Three-dimensional printing enabled the cost-effective and rapid fabrication of devices for sample preparation, especially in flow-based mode, opening new possibilities for the development of automated analytical methods. Recent advances involve membrane-based three-dimensional printed separation devices fabricated by print-pause-print and multi-material three-dimensional printing, or improved three-dimensional printed holders for solid-phase extraction containing sorbent bead packings, extraction disks, fibers, and magnetic particles. Other recent developments rely on the direct three-dimensional printing of extraction sorbents, the functionalization of commercial three-dimensional printable resins, or the coating of three-dimensional printed devices with functional micro/nanomaterials. In addition, improved devices for liquid-liquid extraction such as extraction chambers, or phase separators are opening new possibilities for analytical method development combined with high-performance liquid chromatography. The present review outlines the current state-of-the-art of three-dimensional printing in analytical sample preparation.

Preparation and Characterization of Color Photocurable Resins for Full-Color Material Jetting Additive Manufacturing.

Material jetting (MJ)-type 3D printers have been considered as one of the most versatile types of 3D printers, enabling full-color printing and multi-material printing. However, to the best of our knowledge, there are few academic studies on the development of full-color MJ technologies, and the formulation of commercial resins is confidential and proprietary. In this paper, we give an insight into the preparation of photocurable resins in the primary CMYKW (cyan, magenta, yellow, black, and white) colors that are printable with the multiple piezoelectric heads of our homemade MJ full-color 3D printer. The components comprising the resins, such as the photo-initiator, oligomers, monomers, and crosslinkers, were methodically adjusted and characterized to achieve high-performance MJ printable resins. Subsequently, the prepared resins were colored with the CMYKW colors and their ability of high-quality color appearance in full-color printing was demonstrated.

3D Printing Applications for Transcatheter Aortic Valve Replacement.

A combination of evolving 3D printing technologies, new 3D printable materials, and multi-disciplinary collaborations have made 3D printing applications for transcatheter aortic valve replacement (TAVR) a promising tool to promote innovation, increase procedural success, and provide a compelling educational tool. This review synthesizes the knowledge via publications and our group's experience in this area that exemplify uses of 3D printing for TAVR. Patient-specific 3D-printed models have been used for TAVR pre-procedural device sizing, benchtop prediction of procedural complications, planning for valve-in-valve and bicuspid aortic valve procedures, and more. Recent publications also demonstrate how 3D printing can be used to test assumptions about why certain complications occur during THV implantation. Finally, new materials and combinations of existing materials are starting to bridge the large divide between current 3D material and cardiac tissue properties. Several studies have demonstrated the utility of 3D printing in understanding challenges of TAVR. Innovative approaches to benchtop testing and multi-material printing have brought us closer to being able to predict how a THV will interact with a specific patient's aortic anatomy. This work to date is likely to open the door for advancements in other areas of structural heart disease, such as interventions involving the mitral valve, tricuspid valve, and left atrial appendage.

A Laser Written 4D Optical Microcavity for Advanced Biochemical Sensing in Aqueous Environment

The topic of 4D printing, that is based on 3D printing of structures capable to response on external disturbances over the time, has evolved enormous interest in science and engineering since its first statement in 2013. Besides multi-material printing originally intended to provide self-assembly function, the interest in use of smart materials capable for self-sensing and/or self-actuating rises. Here the necessity in precise 3D fabrication techniques and solutions for structural response control are current challenges that 4D printing faces. In this paper we report on design, fabrication and characterization of a first example of 4D optical microcavity that shows advanced sensing performance boosted by self-sensing in the form of interaction of the polymer matrix with sensed molecules in aqueous environment. Distinctive features of 4D microcavity spectral response for bulk refractive index variations and sensitivity enhancement for more than one order of magnitude have been experimentally observed and discussed. Possibility for parallel interrogation with a single coupling and detection unit for a set of 4D microresonators fabricated with two-photon polymerization out of quencher-doped SZ2080 material with quality factor of $4\times 10^4$ at 685 nm without any post-processing steps has been experimentally demonstrated. The proposed 4D microcavity-based sensor opens a new avenue for designing of a multiplexed 4D printed optical sensing platform with advanced performance compared to conventional optical detection techniques for broad variety of detection tasks.

Aerosol jet printing of biological inks by ultrasonic delivery

Printing is a promising method to reduce the cost of fabricating biomedical devices. While there have been significant advancements in direct-write printing techniques, non-contact printing of biological reagents has been almost exclusively limited to inkjet printing. Motivated by this lacuna, this work investigated aerosol jet printing (AJP) of biological reagents onto a nonfouling polymer brush to fabricate in vitro diagnostic (IVD) assays. The ultrasonication ink delivery process, which had previously been reported to damage DNA molecules, caused no degradation of printed proteins, allowing printing of a streptavidin-biotin binding assay with sub-nanogram ml−1 analytical sensitivity. Furthermore, a carcinoembryogenic antigen IVD was printed and found to have sensitivities in the clinically relevant range (limit of detection of approximately 0.5 ng ml−1 and a dynamic range of approximately three orders of magnitude). Finally, the multi-material printing capabilities of the aerosol jet printer were demonstrated by printing silver nanowires and streptavidin as interconnected patterns in the same print job without removal of the substrate from the printer, which will facilitate the fabrication of mixed-material devices. As cost, versatility, and ink usage become more prominent factors in the development of IVDs, this work has shown that AJP should become a more widely considered technique for fabrication.

Engineering crack tortuosity in printed polymer–polymer composites through ordered pores

A recently developed multimaterial printing approach, solution mask liquid lithography, is used to produce porous polymer–polymer composites inspired by hierarchical natural structures that exhibit significant crack deflection.