Multimaterial Stereolithography by Crosslinking through Luminescence Excitation

Lead Research Organisation: Heriot-Watt University
Department Name: Sch of Engineering and Physical Science

Abstract

Additive manufacturing, rapid prototyping or 3D printing refer to a myriad of manufacturing techniques that build an object in a layer-by-layer approach. It represents a revolution in manufacturing because it is non-specific for an industry and many companies from different sectors benefit from being able to produce customised samples in-house at high speed and with a lower amount of residues and CO2 footprint. For this reason, the 3D printing market is in expansion, and its global value is projected to increase at a CAGR of 21.8% from 2019 to 2025
There are many 3D printing techniques, all of which present advantages and disadvantages. Only a few techniques are low-cost, which is crucial for enabling their use by a high number of users and having a higher societal impact. This is the case of FFF (Fused Filament Fabrication) and some photopolymer techniques such as Stereolithography (SLA), Digital Light Processing (DLP) and Liquid Crystal Display printing (LCD).
A second limitation is the achievable resolution that determines whether an object is "smooth-to-eye" or if the layers are visible. Thirdly, few technologies are able to print with more than one colour in the same object, or with different materials integrated in the same piece, let alone mixing conductive and non-conductive materials in a sample. Currently, there is no technique that can overcome these three limitations at the same time.
The vision underpinning this project is to develop a new 3D printing technology capable of producing multimaterial/multicolour objects for the first time, while maintaining both high resolution and low cost.
For this ambitious target, MUSCLE aims to develop a new platform for photopolymer 3D printing that will enable the sequential printing of 3D pieces with different resins. The method will be applicable to cost-efficient photopolymer printers with minor modifications. It will be based on the use of engineered optical materials and printing at different wavelengths.

Planned Impact

This project is expected to have an impact from a scientific, technological and commercial point of view.
Scientifically, new crosslinking mechanisms that relay on unexploited non-linear optical phenomena will be developed. This is an important advancement, because current photopolymer technology is limited by the short penetration depth of the exposition light beam. This is of great interest for different scientific communities working on manufacturing and optical materials.
Technologically, the knowledge developed through this project will for the first time allow the provision of a high-resolution and multimaterial 3D printing technique at a low cost. The generated knowledge on photocrosslinking with enhanced penetration depth will also be relevant to the fields of curing composites and optical adhesives.
Commercially, the link with an industrial partner from the very beginning of the research assures that market-oriented considerations will be regarded during the development of the technique, paving the way towards commercialisation potential. The industrial partner will also benefit from the interaction with the academic environment that can lead to further innovative collaborations.
The UK skills base will directly benefit from the training of the PDRA, as well as two PhD students whose PhD projects will be enhanced through interaction with the project.
The general public and society will also benefit as a whole, since this new process will allow companies to reduce their manufacturing costs, delivery time, CO2 footprint and industrial waste. As a low-cost technique, it will also allow its use by small companies and particular users.

Publications

10 25 50

 
Description The expected milestones have been achieved. This includes: 1) Most suitable resin formulations were obtained and their optical properties (UV/blue absorption, transmission at NIR, optical windows, refraction index, etc.) and performance were characterised. 2) The emission efficiency of near-infrared to ultraviolet/visible (NIR-UV/Vis) lanthanide-based upconversion (UC) phosphors was characterized via photoluminescence quantum yield (PLQY) measurements for both commercial phosphors, as well as nanoparticles (NPs) prepared by the international collaborators. The impact of scattering, inner filter effects, thickness, self absorption, and temperature on UC emission and efficiency was comprehensively investigated. 3) By matching the emission profiles of UC phosphors to the optical properties of resins, two different formulations utilizing NIR to green light and NIR to UV/blue light UC were developed. The formulation based on NIR-green light UC allowed for printing structures with curing depths of over 1 cm and high aspect ratios (20:1), compared to less than 1 mm achieved in traditional UV/blue light-based curing and 3D printing techniques. The formulation based on NIR-UV/blue light UC exhibited light penetration depths of over 5 cm and allowed for fabrication of structures with features less than 100 µm, as well as non-sequential volumetric 3D printing in a low-cost 3D printing set-up (< £350). 4) A modified resin formulation was developed and after optimisation of seed layer and plating parameters, selective copper metallization was successfully applied to 3D printed polymer objects manufactured via commercial 3D printers, as well as in a set-up based on NIR-blue/visible UC. 5) Different demonstrators have been prepared: flexible/rigid (elastomer/acrylic), 3-colour sample and metal/dielectric sample, which required the development of a plating technique for 3D printing photopolymer. 6) Most of the developments have been already published, and one of the main manuscripts is currently under review.
Exploitation Route To date, there are two routes that build up on the project developments. First, manufacturing technology with printing and plating is being investigated in the production of wearable healthcare devices with embedded electronics. Second, the non-linear behaviour of upconversion emission and its dependence on the temperature is being investigated for its use as nanothermometers in biological tissue.
Sectors Electronics,Healthcare,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology

 
Description Two aspects of the project have contributed to different work-packages in other new funded projects. The first one is a manufacturing technology that allows selective 3D printing with photopolymer [1]. This technology is being used in a work-package in a new project for the production of wearable healthcare devices with embedded electronics (Pressure Resolution by Optical Sensing Enhancement, PI: Dr. Michael Crichton, Heriot-Watt University). Second, during the project it was developed a new tool for determining the influence of temperature effects on the non-linear upconversion emission [2]. This has provided a new method for the calibration of upconversion-based nanothermometers. Such nanothermometers can be used in biological tissue in order to find anomalous metabolism (typically due to cancerogenic cells). This has triggered a new BBSRC project joining engineers from Heriot-Watt and surgeons from the University of Edinburgh (BB/X003841/1, PI: Dr. Jose Marques-Hueso, Jan.2023-Jul.2024, £181,824). [1] Ryspayeva, A., Zhakeyev, A., Desmulliez, M.P.Y. and Marques-Hueso, J. (2022), Multimaterial 3D Printing Technique for Electronic Circuitry Using Photopolymer and Selective Metallization. Adv. Eng. Mater., 24: 2201243. https://doi.org/10.1002/adem.202201243 [2] Jones, Callum MS, Nikita Panov, Eva Hemmer, and Jose Marques-Hueso. "Characterising upconversion thermometers through direct absolute photoluminescence quantum yield measurements." In Optical Sensors, pp. STh7B-7. Optica Publishing Group, 2021.
First Year Of Impact 2021
Sector Healthcare,Manufacturing, including Industrial Biotechology
Impact Types Economic

 
Description Confocal spectroscopy for cell 3D microthermometry, BB/X003841/1.
Amount £181,824 (GBP)
Funding ID BB/X003841/1 
Organisation Biotechnology and Biological Sciences Research Council (BBSRC) 
Sector Public
Country United Kingdom
Start 01/2023 
End 07/2024
 
Description Pressure Resolution by Optical Sensing Enhancement (PROSE)_PI: M. Crichton, CoI: JMH
Amount £106,013 (GBP)
Funding ID RES921408 
Organisation Heriot-Watt University 
Sector Academic/University
Country United Kingdom
Start 09/2021 
End 05/2022
 
Title Modified Fluorimeter for Photoluminescence Quantum Yield with varying temperature 
Description This tool is a modified fluorimeter with integrating sphere that enables the measurement of Photoluminescence Quantum Yield (PLQY) with varying temperature. In previous techniques the PLQY was determined from 2 measurements (emission and absorption) taken in 2 different machines. In this new configuration, both measurements are taken in the same machine, without moving the sample. While using upconverting phosphors during the project, it was noticed that their spectral emission varies with the temperature, which motivated the development of equipment in order to have accurate measurements. 
Type Of Material Improvements to research infrastructure 
Year Produced 2021 
Provided To Others? Yes  
Impact The use of the new equipment has allowed the characterization of the phosphors with the temperature (DOI: 10.1364/SENSORS.2021.STh7B.7). This is useful for determining their performance when working at different temperatures, but it also provides a method for determining the precise absolute temperature of a sample (by analyzing the spectral composition of the emission). This is a method for determining the temperature that can be used in engineering as well as in biological samples. 
URL https://www.hw.ac.uk/uk/schools/engineering-physical-sciences.htm
 
Description INRS Canada - Prof. Fiorenzo Vetrone 
Organisation National Institute of Scientific Research (INRS)
Country Canada 
Sector Academic/University 
PI Contribution Our group measured and did the optical characterisation of the nanoparticles provided by the collaborators. Remarkably, we did the photoluminescent quantum yield measurements, which provide a value for the efficiency of the optical conversion process.
Collaborator Contribution The group of Prof. Vetrone, pioneer in the thermal decomposition method for UC NPs, synthesized a new kind of upconverting nanoparticle useful for the project (these are doped LiYbF nanoparticles).
Impact Main results are reported at the manuscript with DOI: 10.1039/D0NR04357E (Nanoscale, 2020,12, 17545-17554). This collaboration is multidisciplinary, since Prof. Vetrone's group works on Inorganic Chemistry Synthesis, and where we provide the optical engineering and characterisation.
Start Year 2020
 
Description Nanjing University of Posts and Telecommunications - Prof. Xiangfu Wang 
Organisation Nanjing University of Posts and Telecommunications
Country China 
Sector Academic/University 
PI Contribution We studied the optical properties of Erbium doped Y2O3 microtubes and their behaviour as upconverting system, also in relation to their concentration and scattering characteristics.
Collaborator Contribution Prof. Xiangfu Wang synthesized the erbium doped Y2O3 microtubes.
Impact This work has been recently presented at OSA (Imaging and Applied Optics Congress), with proceedings under DOI: 10.1364/3D.2020.JW5C.4
Start Year 2020
 
Description University of Ottawa - Dr. Eva Hemmer 
Organisation University of Ottawa
Country Canada 
Sector Academic/University 
PI Contribution We performed a study about the propagation of light in scattering media. For this, we analysed the optical properties of nanoparticle suspensions provided by the collaborator. This included a wide range of concentrations, which helped to evaluate the effect of the scattering. This is important in order to evaluate how a laser beam can propagate through a turbid media with upconversion nanoparticles.
Collaborator Contribution The group of Dr. Eva Hemmer provided NaYF4:20%Yb3+, 2%Er3+ nanophosphors in the range of 30 nm size.
Impact Part of this work has been reported in the paper with DOI: 10.1364/OE.398353.
Start Year 2020
 
Description ANM2022 conference_ Contributed talk 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Contributed talk at scientific conference.
Zhakeyev, A. and Marques-Hueso, J., 'Upconversion-assisted Multi-material 3D printing', 19th International conference on Advanced Nanomaterials (ANM 2022), Aveiro, Portugal, 27-29 July 2022
Year(s) Of Engagement Activity 2022
 
Description Brightest Watts workshop aimed at high school pupils 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Schools
Results and Impact 21 pupils participated in the workshop which involved presenting the work carried out by our research group as well as demonstration of 3D printing techniques. Prior to the workshop the pupils took part in a 3D printing activity, which taught them how to design objects for 3D printing and the parts they designed were 3D printed before the workshop and demonstrated during the workshop. The certificates of participation, as well as 3D printed designs were sent to the pupils.
Year(s) Of Engagement Activity 2021
 
Description DISCOVERY TRAIL - HERIOT WATT FAMILY TRAIL 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Public/other audiences
Results and Impact The Discovery Trail was an outside activity (to comply with Covid regulations) across the campus, aimed at exploring the ongoing research across our faculty buildings. As one of the of 20 stopping points, all of which contain a post linking to web content through QR code navigation, the work of our research group, focusing on manufacturing with light was demonstrated in a video format. It also included a "take-home" activity focusing on manufacturing with light, aimed at children and whole families.
Year(s) Of Engagement Activity 2021
 
Description High School visit to campus 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Schools
Results and Impact This workshop was presented to Broughton High School students during their campus visit. The aim of the workshop was to introduce S3 students to the Electrical Engineering and give a clear message of which subjects students will need to choose in senior school years. As part of the workshop, the different 3D printing methods and applications, including the work carried out by the research group were presented and demonstrated. For the hands-on activity, students were designing 3D models during the workshop. The students' interest in 3D printing was highlighted by the request to 3D print designs of the students taking part in the STEM project.
Year(s) Of Engagement Activity 2022
 
Description OPAL2022 conference _ Contributed talk 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Contributed talk at conference.
Zhakeyev, A. and Marques-Hueso, J., 'Nonlinear Upconversion Effect for Enhancement of Curing Depths in Laser-Assisted 3D Printing of Photopolymers', 5th International Conference on Optics, Photonics and Lasers (OPAL' 2022), Tenerife, Spain, 18-20 May 2022.
Year(s) Of Engagement Activity 2022
 
Description Online workshop for two primary schools 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact An online workshop on 3D printing was held for over 80 primary school students from Carmondean Primary School and Kirkhill Primary School. The different 3D printing methods and applications, including the work carried out by the research group were presented, which sparked questions from the students and teachers. Prior to the workshop, the instructions on how to use the Tinkercad (free online 3D modeling program) were explained and distributed to the teachers, which then allowed the students to design 3D models, with the best designs 3D printed before and during the workshop and sent to the participants. This hands-on activity, has increased the interest of students in 3D design and printing.
Year(s) Of Engagement Activity 2022
 
Description SHIFT2022 conference: Organizing committee 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Organization of an international conference devoted to Spectral Conversion. More than 150 attendees.
10-14th October 2022, Tenerife, Spain.
Year(s) Of Engagement Activity 2022
URL https://shifttenerife.com/news/
 
Description SHIFT2022 conference: contributed talk 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Zhakeyev, A., Abdulrhman, M., Dunnachie A. and Marques-Hueso, J., 'Multi-material and multi-colour 3D printing enabled by upconversion and metallic catalyst', Spectral Shaping For Biomedical and Energy Applications (SHIFT 2022), Tenerife, Spain, 10-14 October 2022.
Year(s) Of Engagement Activity 2022
 
Description School of Engineering & Physical Sciences Research Seminar 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Postgraduate students
Results and Impact A seminar focused on the work and results of the MUSCLE project was given at the School of Engineering & Physical Sciences at Heriot-Watt university, which sparked questions and discussions afterwards. The audience included undergraduate and postgraduate students, as well as faculty members.
Year(s) Of Engagement Activity 2022