Commercial Photopolymer Research Articles

Towards Scarless Support Removal in Vat Photopolymerization Additive Manufacturing for Mass Manufacturing of Precision Components

This paper explores optimization techniques for support structures in Vat Photopolymerization Additive Manufacturing (VPP AM), addressing challenges posed by overhangs and inclined edges less than 45°. This research aims to overcome manufacturing optimization limitations in situations where the support structure is needed, by generating a benchmark methodology for further automated industrial mass production. Success criteria include ensuring part attachment to the support structure, minimal scarring after support removal, and high fabrication fidelity. Experiments are focused on a worst-case scenario involving a simple bar geometry positioned at 0° to the surface with support attached underneath. This setup facilitated precise control of process parameters and mask optimization per layer. Tests were conducted using the open-architecture ultra-high resolution VPP system, developed by the AM group at Technical University of Denmark (DTU), and commercial photopolymer resin. The study investigated the impact of Support-Free Factor (SFF) value, and Process Parameters (PP) for different support generation techniques. Variations in UV light intensity at the point of contact between the support tip and the part revealed correlations with final surface quality. Notably, a decrease in Z-axis dimensional error from 20% to 6.9% was observed during the study. The minimum required SFF for the VPP AM system was identified being equal to 65.19, corresponding to 1.51% of the supported area of the part. Furthermore, the study found that increased support structure and early part removal before post-processing resulted in finished part dimensions closest to the CAD model. Additionally, under-curing within the part structure improved the surface finish and achieved thicknesses closer to nominal values. These findings contribute to the advancement of VPP AM by providing insights into support structure optimization and process parameter adjustments for enhanced part quality and manufacturing efficiency.

Holographic Sensor Based on Bayfol HX200 Commercial Photopolymer for Ethanol and Acetic Acid Detection.

This paper presents a holographic sensor based on reflection holograms recorded in the commercial photopolymer Bayfol® HX 200. The recording geometry and index modulation of the hologram were optimised to improve accuracy for this specific application. The sensor was subjected to tests using various analytes, and it exhibited sensitivity to acetic acid and ethanol. The measurements revealed a correlation between the concentration of the analyte in contact with the sensor's surface and the resulting wavelength shift of the diffracted light. The minimum detectable concentrations were determined to be above 0.09 mol/dm3 for acetic acid and 5% (v/v) for ethanol. Notably, the sensors demonstrated a rapid response time. Given that ethanol serves as a base for alcoholic beverages, and acetic acid is commonly found in commercial vinegar, these sensors hold promise for applications in food quality control.

See-through display based on commercial photopolymer: Optimization and shrinkage effects

Nowadays augmented reality, 3D Image, mixed reality and see-through applications are very attractive technologies due to their great potential. Holographic optical elements can provide interesting solutions for injection and extraction of the image in the waveguides that are part of the see-through devices. We have developed a coupled waveguide system based on slanted transmission gratings recorded in manufactured photopolymers. In this work we optimize our schedule to a commercial photopolymer for this high demanded application. We demonstrate that high diffraction efficiencies can be obtained if we optimize the recording geometry, recording intensity and recording time for this material. In addition, we study the effects of shrinkage in our holographic system. In general shrinkage is an important drawback for holographic applications, nevertheless we demonstrate how shrinkage can help these systems open new possibilities. Lastly, we show how to significantly improve the quality of the guided image.

Thermal analysis and shrinkage characterization of the photopolymers for DLP additive manufacturing processes

This paper proposes an experimental investigation of a commercial photopolymer resin followed by material modelling and manufacturing system characterization. We focus on the effect of the degree of cure and temperature on the material properties of the photopolymer materials. UV curing properties of the liquid resin are assessed with the thickness measurement by optical tomography. Besides, the specific heat capacity is determined for the almost completely cured and uncured samples with DSC measurements. Photo-DSC experiments are performed to investigate the curing reaction and modelling of the evolution of the degree of cure depending on the light intensity and temperature. In addition, chemical shrinkage behaviour is captured as function of the degree of cure by the high-precision balance set-up. As a result of our experimental studies, model equations are proposed to describe the material behaviour.

3D Printing of a Graphene-Modified Photopolymer Using Stereolithography for Biomedical Applications: A Study of the Polymerization Reaction.

Additive manufacturing is gaining importance thanks to its multiple advantages. Stereolithography (SLA) shows the highest accuracy and the lowest anisotropy, which has facilitated the emergence of new applications as dentistry or tissue engineering. However, the availability of commercial photopolymers is still limited, and there is an increasing interest in developing resins with properties adapted for these new applications. The addition of graphene-based nanomaterials (GBN) may provide interesting advantages, such as improved mechanical properties and bioactivity. However, there is a lack of knowledge regarding the effect of GBNs on the polymerization reaction. A photopolymerizable acrylic resin has been used, and the effect of the addition of 0.1wt% of graphene (G); graphene oxide (GO) and graphite nanoplatelets (GoxNP) on printability and polymerization have been investigated. It was observed that the effect depended on GBN type, functionalization and structure (e.g., number of layers, size, and morphology) due to differences in the extent of dispersion and light absorbance. The obtained results showed that GO and GoxNP did not significantly affect the printability and quality of the final structure, whilst the application of G exhibited a negative effect in terms of printability due to a reduction in the polymerization degree. GO and GoxNP-loaded resins showed a great potential to be used for manufacturing structures by SLA.

Temperature- and degree of cure-dependent viscoelastic properties of photopolymer resins used in digital light processing

In the present paper, the degree of cure-dependent viscoelastic properties of a commercial photopolymer resin (Loctite^{textregistered } 3D 3830) used in digital light processing (DLP) 3D printing are investigated experimentally and described by suitable model equations. To do this, tests are carried out both on the liquid resin and printed specimens under various conditions. The experimental methods include photo-DSC, UV rheometry, and dynamic mechanical analysis. A commercial digital light processing (DLP) printer (Loctite^{textregistered } EQ PR10.1) is used for the printing of the samples. Model equations are proposed to describe the behavior of the material during and after the printing process. For the representation of the degree of cure depending on temperature and light intensity, the one-dimensional differential equation proposed in a previous paper is extended to capture a temperature-dependent threshold value. The change of the viscoelastic properties during crosslinking is captured macroscopically by time-temperature and time-cure superposition principles. The parameters of the model equations are identified using nonlinear optimization algorithms. A good representation of the experimental data is achieved by the proposed model equations. The findings of this paper help users in additive manufacturing of photopolymers to predict the material properties depending on the degree of cure and temperature of printed components.

Micro and nanoscale 3D printing using optical pickup unit from a gaming console

Conventional photopolymerization-based 3D printing still requires developing a concise and cost-effective method to improve the printing resolution at the nanoscale. Here, we propose the use of a gaming console optical drive pickup unit for 3D photopolymerization. This mass-produced optical pickup unit features a finely adjustable diode laser, allowing us to adjust the printing resolution from tens of micrometres down to hundreds of nanometres without requiring oxygen radical scavenging or costly femtosecond lasers. We evaluate the 3D printing performance using a commercial photopolymer under different laser exposure parameters. The proposed printing system achieves a resolution of 385 nm along the lateral direction and XYZ nano-resolution linear stages enable a printing volume of up to 50 × 50 × 25 mm3. Finally, we demonstrate the fabrication of 3D stereoscopic microstructures. The substantially simplified optics proposed here paves the way for affordable high-resolution micro/nanoscale 3D fabrication.

Sequential Motion of 4D Printed Photopolymers with Broad Glass Transition

AbstractThe term “4D printing” refers to the development of stimulus‐responsive structures through 3D printing of active smart materials, typically shape memory polymers. A noteworthy aim of this research field is to obtain objects able to display complex shape‐shifting motions, such as sequential transformations over time. In this work, this peculiar response is studied on a commercial photopolymer, printed by stereolithography and featuring, on the basis of its inherent broad glass transition, the so‐called “temperature‐memory effect” (TME). The TME, that is, a response in which the shape memory effect occurs on a region controlled by the deformation temperature, is studied in shape memory cycles where the deformation temperature is systematically varied, so to provide a correlation between deformation and recovery temperatures. This also allows to properly select two temperatures at which deforming a specimen along a multistep history, so as to finally separate each recovery process on the temperature and time scales. This sequential recovery is studied in double folded bars, with arms deformed at different temperatures, and on a properly designed self‐locking clamp. The obtained results are promising for the realization of smart temperature‐responsive structures printed with one single polymer and capable of multiple shape transformations.

Shape memory response and hierarchical motion capabilities of 4D printed auxetic structures

4D printing refers to a novel trend in the field of active materials, regarding the employment of additive manufacturing to obtain structures presenting inherent complex shapes and shape evolutions under the application of proper stimuli. Such a technique is a powerful tool to realize auxetic structures with customized architectures and programmable/controllable shape change. The present paper proposes 4D printed shape memory polymer-based systems with auxetic structure, capable of hierarchical motion. The systems were prepared starting from a commercial photopolymer by means of stereolithography. The mechanical behavior of the systems was characterized in uniaxial tensile tests, measuring the strains parallel/perpendicular to the load direction. Thanks to a broad glass transition region, the photopolymer displays the so-called “Temperature-Memory Effect” (TME), i.e. the possibility to tailor the thermal trigger of the Shape-Memory Effect (SME) through the deformation temperature. Thermo-mechanical histories were applied to a single unit cell to investigate both the overall shape memory response and the possibility to undergo multiple combined out-of-plane and in-plane motions on the basis of the TME. Obtained results allow discussing the effect of deformation temperatures on the thermal region triggering the SME and show the possibility to exploit the TME to achieve sequential self-deployment of auxetic structures.

Fabrication of High Permittivity Resin Composite for Vat Photopolymerization 3D Printing: Morphology, Thermal, Dynamic Mechanical and Dielectric Properties.

The formulation of a high dielectric permittivity ceramic/polymer composite feedstock for daylight vat photopolymerization 3D printing (3DP) is demonstrated, targeting 3DP of devices for microwave and THz applications. The precursor is composed of a commercial visible light photo-reactive polymer (VIS-curable photopolymer) and dispersed titanium dioxide (TiO2, TO) ceramic nano-powder or calcium copper titanate (CCT) micro-powder. To provide consistent 3DP processing from the formulated feedstocks, the carefully chosen dispersant performed the double function of adjusting the overall viscosity of the photopolymer and provided good matrix-to-filler bonding. Depending on the ceramic powder content, the optimal viscosities for reproducible 3DP with resolution better than 100 µm were η(TO) = 1.20 ± 0.02 Pa.s and η(CCT) = 0.72 ± 0.05 Pa.s for 20% w/v TO/resin and 20% w/v CCT/resin composites at 0.1 s−1 respectively, thus showing a significant dependence of the “printability” on the dispersed particle sizes. The complex dielectric properties of the as-3D printed samples from pure commercial photopolymer and the bespoke ceramic/photopolymer mixes are investigated at 2.5 GHz, 5 GHz, and in the 12–18 GHz frequency range. The results show that the addition of 20% w/v of TO and CCT ceramic powder to the initial photopolymer increased the real part of the permittivity of the 3DP composites from ε’ = 2.7 ± 0.02 to ε’(TO) = 3.88 ± 0.02 and ε’(CCT) = 3.5 ± 0.02 respectively. The present work can be used as a guideline for high-resolution 3DP of structures possessing high-ε.

Direct Wavelength-Selective Optical and Electron-Beam Lithography of Functional Inorganic Nanomaterials.

Direct optical lithography of functional inorganic nanomaterials (DOLFIN) is a photoresist-free method for high-resolution patterning of inorganic nanocrystals (NCs) that has been demonstrated using deep UV (DUV, 254 nm) photons. Here, we expand the versatility of DOLFIN by designing a series of photochemically active NC surface ligands for direct patterning using various photon energies including DUV, near-UV (i-line, 365 nm), blue (h-line, 405 nm), and visible (450 nm) light. We show that the exposure dose for DOLFIN can be ∼30 mJ/cm2, which is small compared to most commercial photopolymer resists. Patterned nanomaterials can serve as highly robust optical diffraction gratings. We also introduce a general approach for resist-free direct electron-beam lithography of functional inorganic nanomaterials (DELFIN) which enables all-inorganic NC patterns with feature size down to 30 nm, while preserving the optical and electronic properties of patterned NCs. The designed ligand chemistries and patterning techniques offer a versatile platform for nano- and micron-scale additive manufacturing, complementing the existing toolbox for device fabrication.

GO-modified flexible polymer nanocomposites fabricated via 3D stereolithography

Graphene oxide (GO) induced enhancement of elastomer properties showed a great deal of potential in recent years, but it is still limited by the barrier of the complicated synthesis processes. Stereolithography (SLA), used in fabrication of thermosets and very recently in “flexible” polymers with elastomeric properties, presents itself as simple and user-friendly method for integration of GO into elastomers. In this work, it was first time demonstrated that GO loadings can be incorporated into commercial flexible photopolymer resins to successfully fabricate GO/elastomer nanocomposites via readily accessible, consumer-oriented SLA printer. The material properties of the resulting polymer was characterized and tested. The mechanical strength, stiffness, and the elongation of the resulting polymer decreased with the addition of GO. The thermal properties were also adversely affected upon the increase in the GO content based on differential scanning calorimetry and thermogravimetric analysis results. It was proposed that the GO agglomerates within the 3D printed composites, can result in significant change in both mechanical and thermal properties of the resulting nanocomposites. This study demonstrated the possibility for the development of the GO/elastomer nanocomposites after the optimization of the GO/“flexible” photoreactive resin formulation for SLA with suitable annealing process of the composite in future.

Raman Structure of a Photopolymer for Additive Manufacturing

A commercial photopolymer used in 3D printers is studied using Raman spectroscopy. The Raman spectrum of an additive-manufactured part shows no lines at 1405 or 2992 cm–1, which are associated with the bending and stretching vibrations of C–H bonds and are present in the spectrum of the initial liquid photopolymer. That is, the vibrational spectrum changes after polymerization. This information may be of use for designing technological coatings based on the obtained samples.

Design Considerations for 3D Printed, Soft, Multimaterial Resistive Sensors for Soft Robotics.

Sensor design for soft robots is a challenging problem because of the wide range of design parameters (e.g., geometry, material, actuation type, etc.) critical to their function. While conventional rigid sensors work effectively for soft robotics in specific situations, sensors that are directly integrated into the bodies of soft robots could help improve both their exteroceptive and interoceptive capabilities. To address this challenge, we designed sensors that can be co-fabricated with soft robot bodies using commercial 3D printers, without additional modification. We describe an approach to the design and fabrication of compliant, resistive soft sensors using a Connex3 Objet350 multimaterial printer and investigated an analytical comparison to sensors of similar geometries. The sensors consist of layers of commercial photopolymers with varying conductivities. We characterized the conductivity of TangoPlus, TangoBlackPlus, VeroClear, and Support705 materials under various conditions and demonstrate applications in which we can take advantage of these embedded sensors.

Dispersion Stability and Mechanical Properties of ZrO2/High-temp Composite Resins by Nano- and Micro-particle Ratio for Stereolithography 3D Printing

This study examines the role of the nano- and micro-particle ratio in dispersion stability and mechanical properties of composite resins for SLA(stereolithography) 3D printing technology. VTES(vinyltriethoxysilane)-coated ZrO2 ceramic particles with different nano- and micro-particle ratios are prepared by a hydrolysis and condensation reaction and then dispersed in commercial photopolymer (High-temp) based on interpenetrating networks(IPNs). The coating characteristics of VTES-coated ZrO2 particles are observed by FE-TEM and FT-IR. The rheological properties of VTEScoated ZrO2/High-temp composite solution with different particle ratios are investigated by rheometer, and the dispersion properties of the composite solution are confirmed by relaxation NMR and Turbiscan. The mechanical properties of 3Dprinted objects are measured by a tensile test and nanoindenter. To investigate the aggregation and dispersion properties of VTES-coated ZrO2 ceramic particles with different particle ratios, we observe the cross-sectional images of 3D printed objects using FE-SEM. The 3D printed objects of the composite solution with nano-particles of 80 % demonstrate improved mechanical characteristics.

Three-dimensionally-printed anthropomorphic physical phantom for mammography and digital breast tomosynthesis with custom materials, lesions, and uniform quality control region.

Anthropomorphic breast phantoms mimic patient anatomy in order to evaluate clinical mammography and digital breast tomosynthesis system performance. Our goal is to create a modular phantom with an anthropomorphic region to allow for improved lesion and calcification detection as well as a uniform region to evaluate standard quality control (QC) metrics. Previous versions of this phantom used commercial photopolymer inkjet three-dimensional printers to recreate breast anatomy using four surfaces that were fabricated with commercial materials spanning only a limited breast density range of 36% to 64%. We use modified printers to create voxelized, dithered breast phantoms with continuous gradations between glandular and adipose tissues. Moreover, the new phantom replicates the low-end density (representing adipose tissue) using third party material, Jf Flexible, and increases the high-end density to the density of glandular tissue and beyond by either doping Jf Flexible with salts and nanoparticles or using a new commercial resin, VeroPureWhite. An insert design is utilized to add masses, calcifications, and iodinated objects into the phantom for increased utility. The uniform chest wall region provides a space for traditional QC objects such as line pair patterns for measuring resolution and scale bars for measuring printer linearity. Incorporating these distinct design modules enables us to create an improved, complete breast phantom to better evaluate clinical mammography systems for lesion and calcification detection and standard QC performance evaluation.

Projected UV-resin curing for self-supported 3D printing

This research introduces a new additive manufacturing process for support-free printing. This process uses an array of ultra-violet laser diodes to cure the jetted photopolymer at the laser intersection for rapid solidification. A prototype system using 405 nm laser is designed and built, and a process model is modified from conventional vat photopolymerization to find a proper range of printing speed. Using a speed of 1 mm/s for a flow rate about 0.5 mm3/s, a 60-degree overhanging structure can be repeatedly printed with commercial photopolymers. The study also discusses the challenges associated with fluid behaviors in such a dynamic condition.

Improvement of dispersion stability and 3D-printing characteristics of ceramics in photopolymers by controlling the coating thickness of silane coupling agents

For stereolithography (SLA) 3D printing applications, Al2O3 ceramic particles with a different coating thickness of silane coupling agent (VTES, vinyltriethoxysilane) were prepared by hydrolysis and condensation reactions. Then, VTES-coated Al2O3 ceramic particles were dispersed in commercial photopolymers (3DK-A83B) based on inter-penetrating network (IPN) phenomena. The morphology and average coating thickness of VTES-coated Al2O3 ceramic particles were observed by field-emission transmission electron microscopy (FE-TEM), and the particle size of VTES-coated Al2O3 ceramic particles was investigated by a laser scattering particle size distribution analyzer. The dispersion stability of the VTES-coated Al2O3/3DK-A83B composite solution with different VTES coating thicknesses and ceramic contents was investigated by Turbiscan and relaxation nuclear magnetic resonance (NMR), while the optimum coating conditions for VTES were also observed. In the case of Al2O3 ceramic particles with a similar VTES coating thickness, the dispersion stability was similar, even when the ceramic content increased. The cross-sectional images of 3D-printed objects were observed by field-emission scanning electron microscopy (FE-SEM), and about 48% of volume shrinkage of the 3D-printed objects was calculated after sintering.

A Study on the Rheological and Mechanical Properties of Photo-Curable Ceramic/Polymer Composites with Different Silane Coupling Agents for SLA 3D Printing Technology.

Silane coupling agents (SCAs) with different organofunctional groups were coated on the surfaces of Al2O3 ceramic particles through hydrolysis and condensation reactions, and the SCA-coated Al2O3 ceramic particles were dispersed in a commercial photopolymer based on interpenetrating networks (IPNs). The organofunctional groups that have high radical reactivity and are more effective in UV curing systems are usually functional groups based on acryl, such as acryloxy groups, methacrloxy groups, and acrylamide groups, and these silane coupling agents seem to improve interfacial adhesion and dispersion stability. The coating morphology and the coating thickness distribution of SCA-coated Al2O3 ceramic particles according to the different organofunctional groups were observed by FE-TEM. The initial dispersibility and dispersion stability of the SCA-coated Al2O3/High-temp composite solutions were investigated by relaxation NMR and Turbiscan. The rheological properties of the composite solutions were investigated by viscoelastic analysis and the mechanical properties of 3D-printed objects were observed with a nanoindenter.

In situ investigation of the kinetics and microstructure during photopolymerization by positron annihilation technique and NIR-photorheology.

The microstructural free volume evolution during a photopolymerization process was studied on a commercial photopolymer (SPOT LV) in situ by positron annihilation lifetime spectroscopy (PALS) and concomitant NIR-photorheology. Analysis of the positron lifetime spectra revealed a high sensitivity of the PALS technique to the different phases of photopolymerization associated with different reaction rates as well as to the evolution of microstructural free-volume shrinkage, which was described at the molecular level by the Kohlrausch–Williams–Watts equation. The in situ PALS study of microstructural changes in photopolymerization was related to the vitrification (gel point) accompanied by shrinkage stress registered via NIR-photorheology. The simultaneous NIR measurements yield information on the monomer conversion of SPOT LV, which can be correlated to the occurrence of the gel point and the evolution of the microstructural free volume. This combined study allows us to see deeper into the crosslinking process and its influence on the resulting material characteristics.