Chapter Four · failure evidence
What Thermogravimetric Analysis (TGA/DSC) got wrong, from 25 dissertations
Thermogravimetric analysis and differential scanning calorimetry frequently encounter analytical failures caused by overlapping thermal events, interfering reaction dynamics, and unintended sample decomposition. Methodological limitations also arise from dynamic heating ramp rates overestimating material stability and sample handling issues causing lost or distorted heat flow signals. These records come from PhD theses at 16 institutions, 2021 to 2026. Each links to its thesis. They were extracted by language models reading the full text, so treat each as a lead to read, not a verdict.
Complex degradation pathways and matrix interferences distort thermogravimetric mass loss interpretation
Thermogravimetric analysis failed to accurately quantify carbon or polymer content due to interfering chemical reactions and complex decomposition dynamics occurring at elevated temperatures. Multiple confounding parameters governing thermal stability also prevented reliable diagnosis or classification of amorphous phases from mass loss traces alone.
Tried and failed
combustion thermogravimetric analysis for polymer quantification applied to silica and fluoropolymer composite matrices. Reason: interfering reactions from co-present silicon and fluorine during combustion skewed mass loss measurements
Structured gas-solid contactors for CO2 removal from air · Georgia Tech
Considered and rejected
Considered and rejected: Rejected relying on thermal gravimetric analysis (TGA) alone to explain TiOx darkness via carbon doping due to ambiguous sample mass decomposition dynamics.
Nanomaterials and Nanostructures for Full Spectrum Solar Energy Harvesting and Conversion · DSpace at SUNY Buffalo
Considered and rejected
Considered and rejected: Abandoned TGA (Thermogravimetric Analysis) as a calibration method for carbon content because complex thermal mass loss reactions occurred at 725°C even in pure N2.
Detection of carbon using microwave excited photoacoustic spectroscopy · Iowa State
Considered and rejected
Considered and rejected: Decided against relying solely on TGA decomposition temperatures to diagnose or classify amorphous phases due to the multiple confounding parameters controlling thermal stability.
Synthetic and analytical considerations for the preparation of amorphous metal–organic frameworks · Cambridge
Dynamic temperature ramping overestimates stability and compromises degradation kinetics
Standard dynamic heating rates and non-isothermal onset temperatures substantially overestimated material thermal stability compared to isothermal conditions. Transient heating prior to reaching target temperatures triggered premature decomposition, while fixed cooling schedules in differential scanning calorimetry failed to reflect realistic isothermal crystallization behavior.
Considered and rejected
Considered and rejected: Rejected standard TGA fast ramp rates (5 °C/min) as primary metric for onset decomposition due to significant overestimation of thermal stability compared to GC-FID at 1 °C/min.
Developing novel magnetic ionic liquids and deep eutectic solvents, evaluating their solvation interactions, and utilizing them in microextractions · Iowa State University Digital Repository
Considered and rejected
Considered and rejected: Rejected non-isothermal TGA onset temperature (Tonset) as a reliable metric of thermal stability due to high variance and overestimating isothermal stability by over 100 °C.
Pressurized Mixtures of Ionic Liquids as Process Solvents for Biomass · Virginia Tech
Tried and failed
isothermal kinetic parameter fitting applied to high-temperature thermal degradation. Outcome: worse than baseline. Reason: degradation initiates during the transient heating phase before reaching the target isothermal temperature
Heat transfer modelling, optimisation and monitoring of flashlamp- assisted automated tape placement. · Cranfield
Considered and rejected
Considered and rejected: Standard DSC heat/cool sintering window criterion rejected for Tb selection; replaced with isothermal crystallization kinetics halftime analysis because standard DSC uses unrealistic fixed dynamic cooling rates.
Additive manufacturing of carbon fiber reinforced thermoplastic polymer composites · IRIS - POLITO - prod
Premature reactions and cell packing artifacts undermine calorimetric heat measurements
Calorimetric assessments failed when rapid early hydration occurred prior to sample placement inside the instrument, causing loss of the initial heat release signal. Other measurements suffered from sample vaporization and low packing density within crucibles, non-equilibrium reduction artifacts, or sample preparation shearing differences.
Considered and rejected
Considered and rejected: Rejected temperature-programmed reduction (TPR) and microcalorimetry of O2 adsorption as methods for measuring reduction energetics due to lack of thermodynamic equilibrium and irreversibility/averaging artifacts.
A Study of Red./Ox. Thermodynamic and Catalytic Properties of Metal Oxide Materials · Penn
Tried and failed
differential scanning calorimetry applied to porous refractory insulating brick. Outcome: unstable. Reason: sample vaporization and low packing density within the crucible
Thermophysical and Molten Salt Corrosion Behavior of Structural Materials for Next-Generation Clean Energy Systems · Georgia Tech
Tried and failed
isothermal solution calorimetry applied to fast-reacting calcium-rich particulate materials. Outcome: too slow. Reason: Premature flash hydration occurred prior to sample placement in the calorimeter, missing initial heat release
Assessing supplementary cementitious materials for use in concrete : long-term and rapid testing · UT Austin
Considered and rejected
Considered and rejected: Rejected hand/Hobart mixing of cement paste for calorimetry calibration because it underpredicts the shearing action and heat release rate of ready-mix concrete aggregates.
Assessment of Mass Concrete Thermal Prediction and Failure Criteria: Novel Models, Evaluation Methods, and Case Studies · Georgia Tech
Overlapping thermal transitions and indistinguishable signals obscure material characterization
Differential scanning calorimetry and thermogravimetric analysis failed when decomposition temperatures overlapped directly with melting or substrate degradation peaks. In addition, isolated calorimetric bulk measurements could not differentiate between crystallinity increases caused by thermal aging and those caused by mechanical wear.
Tried and failed
differential scanning calorimetry and thermal analysis applied to measuring melting properties of organic solids. Outcome: no signal. Reason: thermal decomposition overlapped with melting at nearly identical temperatures
Tried and failed
thermogravimetric analysis for mass loading determination applied to composite films on polymeric substrates. Outcome: no signal. Reason: overlapping thermal degradation peaks between the active composite coating and the polymer substrate
Electrochemically Tunable Reduced Graphene Oxide Membranes for Ionic and Molecular Sieving · JScholarship
Considered and rejected
Considered and rejected: Rejected using isolated single DSC/FSC bulk measurements for uranium forensics because thermal aging (e.g. 450°C), mechanical wear, and skiving gradients produce indistinguishable crystallinity increases (tens of J/g)
Left open by the authors
Problems the authors named and did not get to.
Left open
Investigate structure-activity relationships and kinetics of cyclopropenimines for CO2 adsorption and desorption in solid and solution phases via standardized TGA. Blocker: Requires a wet chemistry lab, synthesis of cyclopropenimine derivatives, and a thermogravimetric analysis (TGA) instrument
Left open
Quantify residual surfactant in extracted MSR via thermogravimetric analysis and measure silicon release during cryogel degradation. Blocker: Requires a wet laboratory, physical synthesized samples, and thermogravimetric analysis (TGA) equipment.
Biomaterials for acellular dental tissue regeneration · Imperial
Left open
Perform temperature-ramped TGA experiments using He and N2 purge gases to evaluate gas-phase diffusion and evaporation contributions. Blocker: Requires a physical thermogravimetric analysis (TGA) apparatus and laboratory access.
Thermal stability and solvent applications of protic ionic liquids · Imperial
Left open
Investigate interaction and emission control mechanisms for cadmium and mercury during mixed biomass thermal conversion. Blocker: Requires experimental validation using horizontal tube furnaces, TGA apparatus, and mixed biomass samples.
The behaviour of metal(oid)s contaminants in woody biomass during advanced thermal conversion processes. · Cranfield
Left open
Compare thermal behavior and water desorption free energy across different layered double hydroxides to correlate composition with water retention. Blocker: Requires synthesis of various layered double hydroxide materials and experimental thermal desorption characterization equipment.
Left open
Test additional characterized GAC types with varying surface areas and oxygen/silicon contents to isolate mechanisms driving HF and SiF4 generation during PFAS thermal degradation. Blocker: Requires a wet chemistry lab, high-temperature combustion apparatus, FTIR gas cell, and specific GAC materials
The impact of chain length and GAC characteristics on PFAS thermal degradation · unevada
Left open
Determine the fate and degradation products of the fourth siloxide ligand in thermal decomposition of [PrIV(OSi(OtBu)3)4]. Blocker: Requires wet lab chemical synthesis and spectroscopy/analytical equipment (e.g., NMR, GC-MS) to observe decomposition products.
Accessing homoleptic neutral and anionic five-coordinate Pr(<scp>iv</scp>) siloxide complexes · EPFL
Left open
Perform high-temperature TGA-DSC and LFA experiments from room temperature to 2,000°C to measure specific heat and thermal conductivity of char materials. Blocker: Requires specialized high-temperature physical lab equipment (TGA-DSC, LFA) and synthesized physical char material samples.
Left open
Apply frictional ignition thermal runaway criteria and tribochemical models to practical high-pressure oxygen engineering systems. Blocker: Vague scope lacking specific engineering targets and requiring physical testing or proprietary engineering design data
Tribochemistry of Frictional Ignition in High-Pressure Oxygen · MIT
Left open
Determine molecular weights of polymers lacking manufacturer specifications using DSC techniques to refine the dataset. Blocker: Requires physical polymer samples and wet lab experimental equipment (Differential Scanning Calorimetry / DSC).
Data-Driven Approaches for Predicting Polymer Solution Phase Behavior: Integrating High-Throughput Experimentation and Machine Learning · Georgia Tech
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