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When aqueous solutions or slurries without additives are freeze cast, meaning directionally solidified, the ice crystals grow with their basal plane oriented parallel to the temperature gradient and along the crystallographic <112 ¯0> direction. Because of this orientation, the structure of the typical wine-cork-like freeze-cast sample is lamellar once quasi-steady state solidification has been reached. The first two layers in a sample are dense and cellular in structure, only a few 100 µm thick, and initially formed during the first seconds of solidification, with cooling rates so high that no phase separation occurs, but the dissolved/suspended material is trapped within the ice crystals.
In some cases, when water-based biopolymer solutions are freeze cast, the final freeze-cast materials and scaffolds exhibit features that are very unusual for directionally solidified materials; they exhibit, for example: i) highly aligned and regularly spaced ridges of uniform height, ‘jellyfish’-like caps and arrays, and ‘tentacles’-like features parallel to the direction of solidification; ii) fibrillar pillars and bridges in fiber composites; and iii) even enhanced fibrillation, a form of self-assembly and structure formation in biopolymers such as collagen.
In our study of “Structure-Property-Processing Correlations in Freeze-Cast Biomimetic Materials,” we quantify both the (to date) little studied, complex, dynamic ice crystal growth phenomena and the ice-templated hierarchical architecture of freeze-cast scaffolds, as well as the various cell wall surface features, not only because they are of interest from a fundamental science point of view but also because the ridges, pillars, bridges, and fibrillation observed in freeze-cast biopolymer scaffolds frequently result in highly desirable features for biomedical applications. In peripheral nerve repair we observe, for example, that not only the highly aligned porosity, but also cell wall surface ridges, serve as powerful structural cues to guide regenerating neurites from one end to the other of the freeze cast regenerative scaffold. While cell wall surface features, such as these regularly spaced ridges, had been observed under specific processing conditions in a range of freeze-cast biopolymers, we found that the fundamental science and underlying principles that govern their formation remain unknown and that, in fact more generally, ice crystal growth from the liquid phase and binary or ternary polymer solutions had hardly ever been studied and simulated. We therefore started to systematically study structure-property-processing correlations under well-defined conditions and complement experiments with phase-field (PF) simulations, which are essential to fully understand the observed phenomena and formulate robust and predictive structure-property-processing correlations for the design and manufacture of freeze-cast materials for a great variety of applications that range from biomedical, to energy generation and storage, to catalysis, filtration, optical and acoustical absorption, and thermal insulation.
In the first instance, we experimentally determined structure-property-processing correlations for scaffolds freeze-cast from collagen- and chitosan-based scaffolds both in the dry and the fully hydrated states. The results obtained for both ‘smooth’ and ‘fibrillar’ polymer systems contributed to a better understanding of the likely sequence of events during the solidification process and the resulting ice-templated feature formation in the polymer phase. Noteworthy are also discoveries made with respect to the dependence of the mechanical properties, such as modulus, yield strength, and toughness, on processing conditions such as applied cooling rates and mold height, and the resulting structural features such as lamellar spacing (length of the short pore axis of the rectangular pores), and cell wall thickness, and scaffold reinforcing features such as ridges, bridges, and pillars, and preferential molecular alignment with the freezing direction.
These systematic experimental studies were key first steps on the path to our long-term goal of this study: to bridge the current critical knowledge gap, which is the lack of understanding of the fundamental mechanisms of structure formation, initially in freeze-cast polymers and later also in particle-based ceramic and metal systems. Knowing how the size and shape of the pores in freeze-cast materials are defined and can be controlled by controlling the ice crystal growth, the need for a better fundamental understanding of the physics of directional solidification in aqueous systems became even more obvious. We overcame the challenge of the absence of equilibrium phase diagrams and also determined concentration- and temperature-dependent diffusion coefficients and viscosities for our ternary chitosan-acetic acid-water system, and further reduced system complexity in support of the PF simulation effort by focusing in our 2D and 3D studies on the binary systems trehalose-water and sucrose-water systems, for which the fundamental properties are known and documented.
Since crystal growth in bulk samples is difficult to observe and characterize in situ, diffusive crystal growth under terrestrial conditions is typically studied in 2D with thin samples. While we initially focused on the traditional light microscopy perpendicular to the moving freezing front primarily to observe both in aqueous and DMSO-based systems the formation of Mullins-Sekerka instabilities and their subsequent reorganization into an array of cells or dendrites as a function of polymer concentration and cooling rates, which is equal to the product of velocity and thermal gradient in directional solidification, we now apply in situ X-ray tomoscopy, which is continuous, time-resolved tomography, as the more suitable tool to analyze in 3D the dynamics of both crystal growth and structure formation phenomena. With synchrotron-based tomoscopy, we have since Year 3 been able to investigate and determine the kinetics of the ice-phase growth and the mechanisms by which the growing ice-crystals, thus ice phase, templates the polymer phase into a cellular solid with a range of cell wall surface features, while the polymer is increasingly upconcentrated and transitions from an aqueous solution to a glassy solid. Overall, our observation is that 2D thin film experiments should, whenever possible, be complemented by 3D in situ tomoscopy experiments, because it is frequently impossible to extrapolate structure formation phenomena from 2D thin film observations to bulk materials; DMSO is an excellent example.
As critical as 3D in situ X-ray tomoscopy is for our quantitative studies and the observation also of transient events during the directional solidification in freeze casting, are the 3D PF simulations, which started in Year 2 for aqueous systems. Remarkably, the PF simulations of anisotropic, faceted ice crystal growth binary aqueous systems with a dilute impurity (trehalose, sucrose), reproduced for the first time the various salient features of freeze-cast structures: from the cellular scaffold structure with their characteristic lamellar spacing to the cell wall surface features such as ridges, which are templated by secondary instabilities on the ice crystal’s basal plane. The value of the 3D phase-field simulations is immense, since they enable us to investigate little studied and not yet modeled mechanisms of hierarchical microstructure formation and cell wall material self-assembly, both of which define anisotropy, property profile, and overall performance of freeze-cast materials. Our results highlight the crucial role of both the solid-liquid interface free-energy and the interface kinetics in structure formation. They also highlight other potentially important physical effects neglected in the phase-field model, such as fluid flow generated by the expansion of ice may play a more secondary role in structure formation. The PF-modelling effort was in 2022 (Year 5) extended to DMSO-based material systems; first results were reported in 2023 (Year 6). From a practical point of view, the ability to accurately predict the detailed temporal evolution of interface structures under prescribed growth conditions is critical for optimizing processing routes and material properties. In preparation for the microgravity experiments, two Science Requirements Documents (SRDs) have been prepared for the CASTing project: one for the Pore Formation and Mobility Investigation (PFMI) Insert and a second insert-agnostic version.
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Abstracts for Journals and Proceedings
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Kamm PH, Yin K, Neu TR, Schlepütz CM, Garcia-Moreno F, Wegst UGK. "X-Ray tomoscopy reveals the dynamics of ice templating." MRS Fall Meeting 2022, Boston, MA, USA, November 27 - December 2, 2022. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2022, Boston, MA, USA, November 27 - December 2, 2022. Symposium CH01. , Nov-2022
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Abstracts for Journals and Proceedings
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Qiu K, Wegst UGK. "Excellent mechanical and electrical properties of anisotropic freeze-cast native and carbonized bacterial cellulose-alginate foams." MRS Fall Meeting 2022, Boston, MA, USA, November 27 - December 2, 2022. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2022, Boston, MA, USA, November 27 - December 2, 2022. Symposium EN09. , Nov-2022
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Abstracts for Journals and Proceedings
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Yin K, Divakar P, Wegst UGK. "Plant-derived nanocellulose as structural and mechanical reinforcement of freeze-cast chitosan scaffolds for biomedical applications." MRS Fall Meeting 2022, Boston, MA, USA, November 27 - December 2, 2022. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2022, Boston, MA, USA, November 27 - December 2, 2022. Symposium EN09. , Nov-2022
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Abstracts for Journals and Proceedings
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Wegst UGW. "Biogenic and bioinspired functional materials for sustainability." MRS Fall Meeting 2022, Boston, MA, USA, November 27 - December 2, 2022. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2022, Boston, MA, USA, November 27 - December 2, 2022. Symposium EN09. , Nov-2022
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Abstracts for Journals and Proceedings
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Yin K, Reese BA, Sullivan CR, Wegst UGK. "Magnetic nacre-superior mechanical and magnetic performance of highly anisotropic sendust-flake composites freeze cast in a uniform magnetic field." MRS Fall Meeting 2021, Boston, MA, USA, November 29 - December 2, 2021. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2021, Boston, MA, USA, November 29 - December 2, 2021. Symposium SB09. , Nov-2021
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Abstracts for Journals and Proceedings
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Yin K, Reese BA, Sullivan CR, Wegst UGK. "Mechanical and magnetic performance of highly anisotropic sendust-flake composites freeze cast in a uniform magnetic field." EuroMat 2021, Graz, Austria, September 12-16, 2021. Abstracts. EuroMat 2021, Graz, Austria, September 12-16, 2021. , Sep-2021
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Abstracts for Journals and Proceedings
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Yin K, Ji K, Strutzenberg L, Trivedi R, Karma A, Wegst UGK. "Experimental observations of mechanisms of pattern formation during freeze casting" 2021 TMS Annual Meeting & Exhibition, Virtual, March 15-18, 2021. Sponsored by The Minerals, Metals & Materials Society (TMS). Abstracts. 2021 TMS Annual Meeting & Exhibition, Virtual, March 15-18, 2021. , Mar-2021
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Abstracts for Journals and Proceedings
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Ji K, Yin K, Strutzenberg L, Trivedi R, Wegst UGK, Karma A. "Phase-field simulations of pattern formation during freeze casting." 2021 TMS Annual Meeting & Exhibition, Virtual, March 15-18, 2021. Sponsored by The Minerals, Metals & Materials Society (TMS). Abstracts. 2021 TMS Annual Meeting & Exhibition, Virtual, March 15-18, 2021. , Mar-2021
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Abstracts for Journals and Proceedings
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Wegst UGK. "Nature-inspired materials science – Challenges and opportunities." PittCon Conference & Expo, Atlanta, Georgia, USA, March 8-12, 2021. Abstracts. PittCon Conference & Expo, Atlanta, Georgia, USA, March 8-12, 2021. , Mar-2021
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Abstracts for Journals and Proceedings
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Wegst UGK, Ji K, Silva M, Strutzenberg LL, Trivedi R, Shubitidze F, Karma A, Yin K. "From fundamental science to tissue scaffolds: Mechanisms of structure formation in ice-templated materials." 8th International Conference on Mechanics of Biomaterials and Tissues (ICMOBT), Waikoloa, HI, December 15-19, 2019. Abstracts. 8th International Conference on Mechanics of Biomaterials and Tissues (ICMOBT), Waikoloa, HI, December 15-19, 2019. , Dec-2019
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Abstracts for Journals and Proceedings
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Yin K, Mylo MD, Speck T, Wegst UGK, "Bamboo-inspired porous tubes: Permeability, flow, and water purification." 8th International Conference on Mechanics of Biomaterials and Tissues (ICMOBT), Waikoloa, HI, December 15-19, 2019. Abstracts. 8th International Conference on Mechanics of Biomaterials and Tissues (ICMOBT), Waikoloa, HI, December 15-19, 2019. , Dec-2019
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Abstracts for Journals and Proceedings
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Yin K, Priemel T, Divakar P, Harrington MJ, Wegst UGK. "Fibrillation and alignment of plant-derived nanocellulose, chitosan, and collagen in freeze-cast scaffolds." 8th International Conference on Mechanics of Biomaterials and Tissues (ICMOBT), Waikoloa, HI, December 15-19, 2019. Abstracts. 8th International Conference on Mechanics of Biomaterials and Tissues (ICMOBT), Waikoloa, HI, December 15-19, 2019. , Dec-2019
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Abstracts for Journals and Proceedings
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Yin K, Divakar P, Wegst UGK. "Plant-derived nanocellulose as structural and mechanical reinforcement of freeze-cast chitosan scaffolds for biomedical applications." MRS Fall Meeting 2019, Boston, MA, December 1-6, 2019. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2019, Boston, MA, December 1-6, 2019. Symposium MS03. , Dec-2019
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Abstracts for Journals and Proceedings
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Ji K, Yin K, Strutzenberg LL, Trivedi R, Shubitidze F, Wegst UGK, Karma A. "3D phase-field simulations explain experimental observations of structure formation in ice-templated materials." MRS Fall Meeting 2019, Boston, MA, December 1-6, 2019. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2019, Boston, MA, December 1-6, 2019. Symposium MT06. , Dec-2019
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Abstracts for Journals and Proceedings
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Yin K, Ji K, Silva M, Strutzenberg LL, Trivedi R, Shubitidze F, Karma A, Wegst UGK. "Mechanisms of structure formation in ice-templated materials: Experimental observations." MRS Fall Meeting 2019, Boston, MA, December 1-6, 2019. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2019, Boston, MA, December 1-6, 2019. Symposium MT06. , Dec-2019
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Abstracts for Journals and Proceedings
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Wegst UGK. "Porous metals by freeze casting: Challenges and opportunities." TMS MetFoam 2019, Dearborn, MI, August 20-23, 2019. Sponsored by The Minerals, Metals & Materials Society (TMS). Abstracts. TMS MetFoam 2019, Dearborn, MI, August 20-23, 2019. , Aug-2019
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Abstracts for Journals and Proceedings
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Wegst UGK. "Biogenic and bioinspired functional materials for sustainability and a more circular economy." Nano-Micromaterials for Circular Economy and Sustainability, National University of Singapore, Singapore, August 29 - September 1, 2019. Abstracts. Nano-Micromaterials for Circular Economy and Sustainability, National University of Singapore, Singapore, August 29 - September 1, 2019. , Sep-2019
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Abstracts for Journals and Proceedings
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Yin K, Divakar P, Mohan S, Sundback, CA, Jowett N, Wegst UGK. "Structure-property-processing correlations and in vivo performance of freeze-cast chitosan-nanocellulose scaffolds." 9th International Plant Biomechanics Conference, Montreal, Quebec, Canada, August 9-14, 2018. Abstracts. 9th International Plant Biomechanics Conference, Montreal, Quebec, Canada, August 9-14, 2018. , Aug-2018
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Abstracts for Journals and Proceedings
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Wegst UGK. "Bioinspired materials and devices and their assessment in vitro and in vivo." 2nd Bioinspired Interfacial Materials and Devices Conference, Beihang University, Beijing, China, June 22–24, 2018. Abstracts. 2nd Bioinspired Interfacial Materials and Devices Conference, Beihang University, Beijing, China, June 22–24, 2018. , Jun-2018
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Abstracts for Journals and Proceedings
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Wegst UGK. "Architecture of natural and freeze-cast materials." Gordon Research Conference on Thin Film and Small Scale Mechanical Behavior, Micro- and Nano-Mechanics as a Tool for Materials Design, Lewiston, ME, July 15-20, 2018. Abstracts. Gordon Research Conference on Thin Film and Small Scale Mechanical Behavior, Micro- and Nano-Mechanics as a Tool for Materials Design, Lewiston, ME, July 15-20, 2018. , Jul-2018
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Abstracts for Journals and Proceedings
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Wegst UGK. "Freeze casting – The controlled solidification of water for the manufacture of new and improved materials." NUconvergence 2018: Frontiers in Aerospace Materials, Microgravity Materials Research, Northeastern University, Boston, MA, May 18-19, 2018. Abstracts. NUconvergence 2018: Frontiers in Aerospace Materials, Microgravity Materials Research, Northeastern University, Boston, MA, May 18-19, 2018. , May-2018
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Abstracts for Journals and Proceedings
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Wegst UGK, Divakar P, Yin K, Moodie KL, Hoopes PJ, Theiler R, Sundback C, Matthew M, Jowett N, Rosen J. "Biological materials, biomaterials, and biomimetics: Emulating performance-defining features in bulk with a fast and easy production process." 7th International Conference on Mechanics of Biomaterials and Tissues (ICMOBT), Big Island, HI, December 10-14, 2017. Abstracts. 7th International Conference on Mechanics of Biomaterials and Tissues (ICMOBT), Big Island, HI, December 10-14, 2017. , Dec-2017
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Abstracts for Journals and Proceedings
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Wegst UGK. "Employing the complex dynamics of ice templating to tailor performance-defining features in biomedical materials." 9th International Conference on Mechanics of Biomaterials and Tissues (ICMOBT), Waikoloa, HI, December 16 - 20, 2023. Abstracts: 9th International Conference on Mechanics of Biomaterials and Tissues (ICMOBT), Waikoloa, HI, USA, December 16 - 20, 2023. , Dec-2023
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Abstracts for Journals and Proceedings
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Wegst UGK. "Freeze casting peptide-enabled biomaterials for tissue regeneration." MRS Fall Meeting 2023, Boston, MA, November 26 - December 1, 2023. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2023, Boston, MA, November 26 - December 1, 2023. Symposium SB03. , Nov-2023
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Abstracts for Journals and Proceedings
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Kamm PH, Yin K, Neu TR, Schlepütz CM, Garcia-Moreno F, Wegst UGK. "Ice crystal growth and the dynamics of ice templating by X-ray tomoscopy." MRS Fall Meeting 2023, Boston, MA, USA, November 26 - December 1, 2023. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2023, Boston, MA, USA, November 26 - December 1, 2023. Symposium SF02. , Nov-2023
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Abstracts for Journals and Proceedings
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Ji K, Zhong M, Yin K, Littles LS, Trivedi R, Wegst UGK, Karma A. "Phase-field modeling of ice-templated hierarchical structures." MRS Fall Meeting 2023, Boston, MA, November 26 - December 1, 2023. Sponsored by the Materials Research Society (MRS). Abstracts. MRS Fall Meeting 2023, Boston, MA, November 26 - December 1, 2023. Symposium SF02. , Nov-2023
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Articles in Peer-reviewed Journals
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Kamm PH, Yin K, Neu TR, Schlepütz CM, Garcia-Moreno F, Wegst UGK. "X-ray tomoscopy reveals the dynamics of ice templating." Adv. Funct. Mater. 2023 Nov;33(48):2304738. https://doi.org/10.1002/adfm.202304738 , Nov-2023
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Articles in Peer-reviewed Journals
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Yin K, Ji K, Strutzenberg Littles L, Trivedi R, Karma A, Wegst UGK. "Hierarchical structure formation by crystal growth-front instabilities during ice templating." PNAS. 2023 Jun 6;120(23):e2210242120. https://doi.org/10.1073/pnas.2210242120 , Jun-2023
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Articles in Peer-reviewed Journals
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Caruso I, Yin K, Divakar P, Wegst UGK. "
Tensile properties of freeze-cast collagen scaffolds: How processing conditions affect structure and performance in the dry and fully hydrated states." J. Mech. Behav. Biomed. Mater. 2023 Aug 1;144:105897. https://doi.org/10.1016/j.jmbbm.2023.105897 , Aug-2023
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Dissertations and Theses
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Ji K. "Phase-field modeling of microstructural pattern dormation during ice templating and alloy solidification." Dissertation, Northeastern University, November 2021. , Nov-2021
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Dissertations and Theses
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Yin K. "Freeze casting: From the fundamentals to applications." Dissertation, Thayer School of Engineering, Dartmouth College, May 2020. , May-2020
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NASA Technical Documents
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Radlinska A, Bracker G, Collins P, Edmunson J, Edwards D, Fiske M, Phillips B, Sperl M, Sansoucie M, Shulman H, Strutzenberg L, Weber R, Wegst UGK. "Manufacturing from regolith." Huntsville, AL : Marshall Space Flight Center, 2021. NASA/20210023598. https://ntrs.nasa.gov/api/citations/20210023598/downloads/Manufacturing%20from%20Regolith%20-%20Concept%20Paper%20-%20Radlinska%20FINAL.pdf , Oct-2021
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