------------------- GENERAL INFORMATION ------------------- Name: Johannes Gmeiner Role/Function: Data collector (main contact person) Institution: Institute for Technical and Macromolecular Chemistry, University of Hamburg Address: Bundesstrasse 45, 20146 Hamburg, Germany Email: johannes.gmeiner@uni-hamburg.de Name: Jonah Hasse Role/Function: Data collector Institution: Institute for Technical and Macromolecular Chemistry, University of Hamburg Address: Bundesstrasse 45, 20146 Hamburg, Germany Email: jonah.hasse@uni-hamburg.de Name: Gerrit A. Luinstra (ORCID: 0000-0003-4602-8319) Role/Function: Principal Investigator (alternative contact person) Institution: Institute for Technical and Macromolecular Chemistry, University of Hamburg Address: Bundesstrasse 45, 20146 Hamburg, Germany Email: gerrit.albert.luinstra@uni-hamburg.de Date of data collection: August 2025 - January 2026 Location of data collection: Institute for Technical and Macromolecular Chemistry, University of Hamburg Funding: This project is funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – SFB 1615 – 503850735. Update to Version 02: - Change of title from: Ionic Reinforced P(NiPAAm-co-AA) Beads as adjustable Smart Organogels to Iron(III) Ion reinforced P(NiPAAm-co-AA) Beads as tunable Smart Organogels - The supporting information has been added: Supporting Information_Iron(III) Ion reinforced P(NiPAAm-co-AA) Beads as tunable Smart Organogels.docx --------------------------- SHARING/ACCESS INFORMATION --------------------------- Title of data set: Ionic Reinforced P(NiPAAm-co-AA) Beads as adjustable Smart Organogels." Related publication: Yi Luo et al. Tough, Stretchable, and Thermoresponsive Smart Hydrogels. (2023) DOI of related article: https://doi.org/10.3390/gels9090695 Kathrin Marina Eckert et al. Exploring pNIPAM Lyogels: Experimental Study on Swelling Equilibria in Various Organic Solvents and Mixtures, Supported by COSMO-RS Analysis (2024) DOI of related article: https://doi.org/10.1016/j.fluid.2024.114182 Kathrin Marina Eckert et al. Enhancing Swelling Kinetics of pNIPAM Lyogels: The Role of Crosslinking, Copolymerization, and Solvent (2025) DOI of related article: https://doi.org/10.1016/j.fluid.2025.114462 Please cite the accepted version of this publication in case you use the data. Keywords: NiPAAm – acrylic acid copolymers, ionic crosslinking, organogel beads, solvent-responsive smart materials, Fe(III) coordination --------------------- DATA & FILE OVERVIEW --------------------- ### 1. Chemicals.csv (creation date: 29.01.2026, version: 01) - **Description:** List of chemicals used in the study. - **Columns:** - Chemical: Name of the chemical used - Supplier: Supplier of the chemical used - Location: Location of the Supplier - CAS-Nr.: CAS-Nr. of the chemical used ### 2. FE-HIGH_IR_DATA.csv (creation date: 29.01.2026, version: 01) - **Description:** FT-IR data for the virgin polymer OG10-10 and the iron(III) crosslinked Fe-HIGH gel. - **Columns:** - wavenumber [cm^-1] - Absorbance ### 3. FE_LOW_COMPRESSION_DATA.csv (creation date: 29.01.2026, version: 01) - **Software:** TRIOS TA INSTRUMENTS - **Description:** Raw data of the compression test of the OG10-10 bead d the iron crosslinked Fe-LOW beads. - **Columns:** - Gap [µm]: Distance between the two steel plates on the rheometer. - Force [N]: Compression force ### 4. FE_MID_COMPRESSION_DATA.csv (creation date: 29.01.2026, version: 01) - **Software:** TRIOS TA INSTRUMENTS - **Description:** Raw data of the compression test of the OG10-10 bead d the iron crosslinked Fe-MID beads. - **Columns:** - Gap [µm]: Distance between the two steel plates on the rheometer. - Force [N]: Compression force ### 5. FE_HIGH_COMPRESSION_DATA.csv (creation date: 29.01.2026, version: 01) - **Software:** TRIOS TA INSTRUMENTS - **Description:** Raw data of the compression test of the OG10-10 bead d the iron crosslinked Fe-HIGH beads. - **Columns:** - Gap [µm]: Distance between the two steel plates on the rheometer. - Force [N]: Compression force ### 6. OG10-10_COMPRESSION_DATA.csv (creation date: 29.01.2026, version: 01) - **Software:** TRIOS TA INSTRUMENTS - **Description:** Raw data of the compression test of the OG10-10 beads - **Columns:** - Gap [µm]: Distance between the two steel plates on the rheometer. - Force [N]: Compression force ### 7. CALCULATION_TAU_OG10-10_REF_RADIUS.xlsx (creation date: 29.01.2026, version: 01) - **Description:** Process data from swelling/shrinkage experiments of OG10-10_REF to determine the tau values of the swelling and shrinkage processes. - *Data* - **Columns:** - Time [s] - Diameter [pixels] - Diameter [cm] - Volume [cm^-3] - relative volume - *Calculation* - *Columns:* - Time [s] - Diameter [cm] - Simulation [cm] - *Oversight* ### 8. CALCULATION_TAU_FE-LOW_RADIUS.xlsx (creation date: 29.01.2026, version: 01) - **Description:** Process data from swelling/shrinkage experiments of Fe-LOW to determine the tau values of the swelling and shrinkage processes. - *Data* - **Columns:** - Time [s] - Diameter [pixels] - Diameter [cm] - Volume [cm^-3] - relative volume - *Calculation* - *Columns:* - Time [s] - Diameter [cm] - Simulation [cm] ### 9. CALCULATION_TAU_FE-MED_RADIUS.xlsx (creation date: 29.01.2026, version: 01) - **Description:** Process data from swelling/shrinkage experiments of Fe-LOW to determine the tau values of the swelling and shrinkage processes. - *Data* - **Columns:** - Time [s] - Diameter [pixels] - Diameter [cm] - Volume [cm^-3] - relative volume - *Calculation* - *Columns:* - Time [s] - Diameter [cm] - Simulation [cm] ### 10. OCALCULATION_TAU_FE-HIGH_RADIUS.xlsx (creation date: 29.01.2026, version: 01) - **Description:** Process data from swelling/shrinkage experiments of OG10-10_REF to determine the tau values of the swelling and shrinkage processes. - *Data* - **Columns:** - Time [s] - Diameter [pixels] - Diameter [cm] - Volume [cm^-3] - relative volume - *Calculation* - *Columns:* - Time [s] - Diameter [cm] - Simulation [cm] ### 11.PYTHON SCRIPT ORANGE IRON BEADS_BLACK BACKROUND.py (creation date: 29.01.2026, version: 01) - **Description:** A Python script that isolates orange organogel beads on a black background and computes their volumetric size/volume increase over time to quantify swelling behavior. ### 12.Supporting Information_Iron(III) Ion reinforced P(NiPAAm-co-AA) Beads as tunable Smart Organogels.docx (creation date: 29.01.2026, version: 01) - **Description:** Supporting Information belonging to Iron(III) Ion reinforced P(NiPAAm-co-AA) Beads as tunable Smart Organogels --------------------------- METHODOLOGICAL INFORMATION --------------------------- The methodological information can be found in the publication. 1. Experimental Methods The synthesis of the P(NiPAAm-co-AA) hydrogel beads is along an established procedure.21 The precursor solution was prepared from 6 g of NiPAAm and 6 g of acrylic acid (20 wt% in total) to 48 mL of water (80 wt%). Crosslinker N,N-methylene bisacrylamide (MBA; 180 mg; 0.3 wt% relative to the total monomer content) and photoinitiator TPO-Li (60 mg; 0.1 wt%) were added and dissolved with vigorous stirring. The resulting mixture was degassed under atmospheric pressure using ultrasound for 5 minutes. Hydrogel beads were prepared in 250 mL of silicone oil (ρ = 0.975 g∙cm-³) confined to a beaker placed in a reflective chamber (180 x 180 x 180 mm3) with a UV-light source (Hoenle LED Cube 100 IC; irradiation intensity up to 1100 mW/cm² at wavelength of 365 nm). The OEM chamber was modified to allow tubing to pass through the hatch door. The precursor solution was dropped into the silicone oil at a constant flow rate of 3 mL∙min-1 through PTFE tubing (1.6 mm inner diameter) using a syringe pump (LongerPump Model LSP02-1B equipped with a 20 mL HENKE-JECT Syringe). The droplets sink slowly and polymerization is essentially completed within 30 s. The hydrogel beads were collected on a Büchner funnel and were washed carefully with ethanol to remove the silicon oil (3 × 100 mL). Ionic crosslinking by Fe(III): Ethanol-equilibrated organogel beads (2.0 g wet mass) were submersed in 20 mL of ethanolic iron(III) chloride hexahydrate solutions (FeCl3·6H2O) with concentrations of 12.7 mM, 42.3 mM, and 127.0 mM (corresponding to molar feed ratios of Fe³⁺ to carboxylic acid groups of 0.1:1, 0.33:1 and 1:1, respectively). The mixtures were agitated on an orbital shaker in the dark for 48 h. The beads were collected on a frit and washed repeatedly with ethanol until the supernatant remained colorless. Colorimetric determination of Fe(III) loading : A solution of potassium thiocyanate in ethanol (5 g in 100 mL) was prepared and 300 µL of the supernatant of the iron crosslinking solutions after the 48 h of equilibration were added for the lowest and medium concentration of Fe(III), and 50 µL for the highest concentration. A UV-Vis spectrophotometer was used to record the absorbance at a wavelength of 480 nm, corresponding to the maximum of the formed iron (III) thiocyanate complex. A linear calibration curve was established using Fe(III) solutions with concentrations ranging from 0.015 to 0.100 mM. The dilution factors of 1:333 and 1:2000 of lowest/medium and highest iron concentration of the supernatant, respectively, ensured that the absorbance values fell within the linear calibration range. The calculation of the mass-specific iron loading q (mmol.g-1) uses the molar consumption of iron ions (Δc), the solution volume (V) and the dry mass of the polymer (mdry). Volumetric tracking of the swelling behavior by inline monitoring The volumetric swelling behavior of the hydrogel beads during transfer from ethanol to ethyl acetate at 25 °C was recorded using interactive image processing. The beads were fixed inside a 100 mL cuvette sealed with a 3D-printed lid. Their swelling behavior was recorded using a camera over six cycles of 60 minutes each. One image was taken every 30 seconds to ensure high-resolution tracking. The resulting image series was analyzed with a custom Python script developed for this experiment. The script identified color differences between the bead and the background, isolated the region of interest (ROI), and determined the bead diameter using contour detection. The time stamps and pixel-based diameters were used to calculate the volume changes. ----------------- RESEARCH CONTEXT ----------------- This research addresses the critical mechanical compliance of smart organogel actuators for autonomous fluid control applications. The study focuses on P(NiPAAm-co-AA) beads reinforced via post-synthetic ionic coordination with Iron(III). The investigation quantifies the correlation between stoichiometric metal uptake, the structural evolution from heterogeneous core-shell to homogeneous networks, and the resulting macroscopic stiffening . A key aspect of this work is demonstrating that the stable ionic lattice is robust enough to mechanically override thermodynamic driving forces. This is highlighted by the complete suppression of the transient cononsolvency effect in the reinforced beads, validating their potential as dimensionally stable, pressure-resistant components .