Multi-component polymer hydrogels present complex physiochemical interactions that make accurate compositional analysis challenging. This study evaluates three analytical techniques: Nuclear Magnetic Resonance (NMR), Advanced Polymer Chromatography (APC), and Thermogravimetric Analysis (TGA) to quantify polyvinyl alcohol (PVA) and polyethylene glycol (PEG) content in hybrid freeze-thaw derived PVA/PEG/PVP hydrogels. Hydrogels were synthesized using an adapted freeze–thaw method across a wide range of PVA:PEG ratios, with PVP included at 1 wt% to assess potential intermolecular effects. NMR and APC reliably quantified polymer content with low average errors of 2.77% and 2.01%, respectively, and were unaffected by phase separation or hydrogen bonding within the composite matrix. TGA enabled accurate quantification at PVA contents ≤ 62.5%, where PEG and PVA maintained distinct thermal decomposition behaviors. At higher PVA concentrations, increased hydrogen bonding and crystalline restructuring, confirmed by FTIR through shifts near 1140 cm⁻¹ and significant changes in the -OH region, altered thermal profiles and reduced TGA accuracy. Together, these findings establish APC as a high-throughput alternative to NMR for multi-component polymer analysis and outline critical thermal and structural thresholds that influence TGA-based quantification. This work provides a framework for characterizing complex polymer networks in biomedical hydrogel systems.

Multi-component polymer hydrogels present complex physiochemical interactions that make accurate compositional analysis challenging. This study evaluates three analytical techniques: Nuclear Magnetic Resonance (NMR), Advanced Polymer Chromatography (APC), and Thermogravimetric Analysis (TGA) to quantify polyvinyl alcohol (PVA) and polyethylene glycol (PEG) content in hybrid freeze-thaw derived PVA/PEG/PVP hydrogels. Hydrogels were synthesized using an adapted freeze–thaw method across a wide range of PVA:PEG ratios, with PVP included at 1 wt% to assess potential intermolecular effects. NMR and APC reliably quantified polymer content with low average errors of 2.77% and 2.01%, respectively, and were unaffected by phase separation or hydrogen bonding within the composite matrix. TGA enabled accurate quantification at PVA contents ≤62.5%, where PEG and PVA maintained distinct thermal decomposition behaviors. At higher PVA concentrations, increased hydrogen bonding and crystalline restructuring, confirmed by FTIR through shifts near 1140 cm⁻¹ and significant changes in the –OH region, altered thermal profiles and reduced TGA accuracy. Together, these findings establish APC as a high-throughput alternative to NMR for multi-component polymer analysis and outline critical thermal and structural thresholds that influence TGA-based quantification. This work provides a framework for characterizing complex polymer networks in biomedical hydrogel systems.