Thermogravimetric Measurements Research Articles

The Influence of Selected Process Parameters on the Efficiency of the Process of Gas Nitriding of AISI 1085 Steel.

The main aim of the manuscript was to investigate the impact of modifying the parameters of the gas nitriding process of samples made from AISI 1085 steel on the course and results of the process carried out in a chemical reactor allowing for thermogravimetric measurements. The tested steel was subjected in a chemical reactor to the process of gas nitriding in the temperature range of 490-580 °C, using different sample heating rates (in the range of 1-25 °C/min) and various mixtures of nitriding gases (pure NH3, or NH3 with the addition of H2 or N2). To assess the impact of the tested process parameters on its efficiency, the thickness of the nitrided layers produced, the change in sample mass, the structure of the phases produced, the phase composition and the microhardness were examined. For the research methodology used, it was found that reducing the amount of NH3 and/or using H2 or N2 admixtures adversely affects the thickness of the nitride layers produced. At the same time, the use of a lower maximum process temperature with the same gas mixture resulted in a significant difference in the thickness of the layers. It was also found that the use of pure NH3 or a gas mixture (NH3 + H2) with higher NH3 contents resulted in higher surface microhardnesses of the samples and that for these samples, the hardness increased to a greater depth.

Biopolymer-derived structured graphitic carbons as metal-free heterogeneous ozonation catalysts in water

The development of metal-free heterogeneous catalysts for advanced oxidation processes is an important area of research, advancing in sustainability, with potential practical applications in water treatment. In this work, we report the development of defective structured graphitic carbons synthesized from biomass including alginate or chitosan polysaccharides and used as metal-free ozonation catalysts in water. These solids were characterized by several techniques, including powder X-ray diffraction, several spectroscopies (i.e. X-ray photoelectron, Raman or Fourier Transform infrared), elemental combustion analyses, thermogravimetric measurements, and electron microscopic techniques. The catalytic performance of graphitic carbon was examined in the ozonation reaction and the graphitic carbon derived from alginate (G) was found to be the most active catalyst by showing complete degradation in less than 4 h under the operational conditions as oxalic acid (50 mg L−1), catalyst (100 mg L−1), 20 °C, O3 dosage (140 mg h−1) at pH 3. Importantly, this solid retains its activity mostly upon reuse for more than 20 h, an observation that compares favorably with previous reports using graphene-based materials. In addition, activity of partially deactivated catalyst can be recovered by a pyrolysis process associated to the reconstitution of graphitic active sites of the catalyst. Experimental evidence by electron spin resonance together with specific (photo)catalytic experiments is provided to support the role of 1O2 as key intermediate during the oxalic acid degradation in water in the presence of G. This study exemplifies the activity of active graphitic-based solids from biomass precursors as ozonation heterogeneous catalysts in water in the absence of any metal.

The effect of repeated washings on thermal protective performances of one most used structural firefighting turnout gear in the Gauteng Province in South Africa

Fire performance measurements of one of the most used firefighting protective ensembles (also called turnout gears), in terms of thermal and smoke hazards, were determined with the cone calorimeter, that of thermal stability were determined with thermogravimetric analyzer, the physical inspection (physical degradation) of the surface done with the scanning electron microscopy, and energy dispersive spectroscopy measurements determined the elemental compositions of the detergent used in washing and the residual elements in the turnout gears. The cone calorimeter results indicated that the values of the thermal performance parameters, namely: peak heat release rate, maximum average rate of heat emission, and fire growth rate index, all decrease with increasing number of washing cycles, while the smoke parameters: peak smoke production rate, smoke growth rate index, total smoke release, and related sustained flaming values, all increase with increasing number of washing cycles. From the thermogravimetric analyzer measurements, the thermal stability of the turnout gears decrease with increasing number of washings.

Kinetic models of HMX decomposition via chemical reaction neural network

1,3,5,7-Tetranitro-1,3,5,7-tetrazocane (HMX) is commonly used in solid propellants and explosives as energetic materials. The study of its kinetics and decomposition mechanism is of great significance to its application in the aerospace industries. This work investigates the thermal decomposition of HMX based on the combined thermogravimetric (TG) measurements and chemical reaction neural network (CRNN). Two compact kinetic models for HMX are introduced, with one consisting of four substances and a single global reaction (4–1 model) and the other consisting of four substances and four reactions (4–4 model). In the 4–1 model, the calculated activation energy is 328.44 kJ·mol−1, which agrees with the experimental value. As for the 4–4 model, the substances and reactions are assigned based on a skeleton mechanism involving reactions of N-N and C-N bond cleavage and HONO elimination. Moreover, the catalytic effects of TiO2 and Al2O3 on HMX are well simulated using the aforementioned kinetic models. The CRNN models can reproduce the peak temperature with a reduced activation energy, but the initial decomposition temperature is overestimated owing to the complex nature of catalytic impact. This work presents the application of the CRNN model to obtain a decomposition mechanism of HMX, highlighting its efficacy in accurately capturing the thermal decomposition behavior. The potential extension of CRNN to kinetic modeling of other energetic materials is anticipated in future studies.

Structural Characterisation of End-of-Life Cement–Asbestos Materials from Lithuania

Asbestos is a widely used name for natural silicate minerals with fibrous properties. Asbestos minerals were one of the most popular and cheapest raw materials used in the construction industry in the past when they was used in the form of cement–asbestos composite material. Nowadays, we know that asbestos possesses carcinogenic properties. Due to this fact, asbestos was banned in many countries including Lithuania. All asbestos-containing materials are considered waste and stored in special landfills, which causes significant environmental pollution. One of the methods proposed to solve the asbestos problem may be thermal treatment. In the present study, asbestos-containing wastes in the form of cement–asbestos materials were examined. These asbestos-containing materials were characterised via chemical analysis (XRF) connected with mineralogical phase analysis with powder X-ray diffraction (XRD) as well as scanning electron microscopy (SEM). The thermal decomposition of samples was studied via differential thermal analysis (DTA) and thermogravimetric measurements with evolved gas analysis (TG–EGA). It was found that thermal treatment is a possible way to destroy asbestos contained in cement–asbestos wastes and convert it into new mineral phases. The work also compared the obtained characteristics of asbestos waste with the characteristics of waste produced in other countries.

Exploring Deactivation Reasons of Biomass-Based Phosphorus-Doped Carbon as a Metal-Free Catalyst in the Catalytic Dehydroaromatization of n-Heptane.

Catalytic dehydroaromatization of n-alkanes into high-value aromatics has garnered extensive interest from both academia and industry. Our group has previously reported that phosphorus-doped carbon materials exhibit high selectivity for C-H bond activation in the dehydroaromatization of n-hexane. In this study, using n-heptane as a probe, we synthesized biomass-based phosphorus-doped carbon catalysts to investigate the impact of hydrogen heat treatment and carbon deposition on catalyst structure. Despite achieving an initial conversion of n-heptane at approximately 99.6%, with a toluene selectivity of 87.9%, the catalyst activity fell quickly. Moreover, longer hydrogen treatment time and higher hydrogen concentrations were found to accelerate catalyst deactivation. Thermogravimetric analysis (TGA) and N2 adsorption measurements (BET) indicated that a small amount of coke deposition was not the primary cause of catalyst deactivation. Temperature-programmed desorption of ammonia gas (NH3-TPD) revealed a significant decrease in acid-active functional groups. X-ray photoelectron spectroscopy (XPS) and solid-state 31P NMR spectroscopy confirmed the reduction of active central phosphorus species. These results suggest that catalyst deactivation primarily arises from the decrease in acidity and the partial reduction of phosphorus-containing groups, leading to a substantial loss of active sites. This work contributes new perspectives to understanding the properties and design improvements of metal-free carbon catalysts.

Pyrolysis of natural rubber–cellulose composites: isoconversional kinetic analysis based on thermogravimetric data

Despite the current growing interest in rubber composites with natural organic fillers, there is a lack of kinetic analyses that describe the decomposition of these materials during pyrolysis. For this reason, the main objective of this study was the kinetic analysis and determination of formal kinetic parameters for the pyrolytic decomposition of NR–CEL composites with different cellulose content (0, 30, 45, and 55 phr). Thermogravimetric measurements were made at heating rates of 2, 4, 6, 8, 10, and 20 °C min–1 in the temperature range of 20–600 °C. First, Friedman and KAS model-free methods were applied. Therefore, model-based methods and the model-fitting procedure were used to find the optimal multi-step kinetic model. The proposed final model consists of two parallel processes, which are kinetically independent: A → B → C and D → E → F. For each step, a kinetic triplet was calculated: the apparent activation energy, the pre-exponential factor, and the kinetic parameters of the extended empirical Prout–Tompkins model. The master plots method was used to determine the kinetic decomposition mechanism of the individual steps. It was found that step A → B has the shape of an nth-order model, step B → C mainly follows the diffusion model, the mechanism of step D → E transfers from a random scission kinetics model to an nth-order model with an increasing amount of CEL, and step E → F obeys the chain scission mechanism.

Radical scavenging and processing stability of novel biobased stabilizers in polypropylene

Bio-based molecules show great research potential to achieve alternatives to petrochemically produced products. Therefore, biogenic stabilizers (vanillates, syringates and gallates) were prepared, which were subsequently characterized by various analytical methods. Nuclear magnetic resonance spectroscopy was used for structural elucidation. Thermal stability and thus suitability for polymer processing were confirmed by thermogravimetric measurements. To assess the stabilizing effect, radical efficiency was determined using 2,2-diphenyl-1-picrylhydrazyl assays. Polymer compounds were processed in an extruder as well. In these prolonged extrusion experiments, the stabilizing effect in the melt was revealed.

Spontaneous room temperature reaction of titanium and its alloys with hydrogen during self-shearing reactive milling

Surface wear-activated spontaneous reactions of titanium and its alloys with hydrogen at room temperature are shown in this work. Titanium powder, intensively mixed under hydrogen pressure in a planetary mill, without any grinding media, reacts readily with hydrogen gas with the formation of stoichiometric titanium dihydride. The reaction, once initiated, proceeds spontaneously even without movement of the milling vial with a similar reaction rate. The moment of initiation of the reaction seems to be related to the removal of oxide impurities from the surface of the titanium particles and is strongly correlated with milling velocity. According to thermogravimetric measurements and X-ray diffraction (XRD) phase analysis, titanium is fully converted to TiH2. Titanium alloys were found to react in the same manner. Ti-5553 (β) reacts more easily than grade 5 Ti (Ti-Gd5) (α’), which is more reactive than grade 2 Ti (Ti-Gd2). The titanium alloy particles maintain their shape and coherency after hydrogenation. The method seems to be extremely cost-effective in the synthesis of titanium hydride and also allows the production of hydrogenated alloyed powders in spherical form, which can potentially be applied in the additive manufacturing of titanium foams. The results also show a significant risk of using titanium alloys in a hydrogen atmosphere at room temperature. It seems that after losing the protective oxide layer, parts made of pure titanium or its alloys may undergo catastrophic destruction after losing strength and ductility upon full conversion to hydride.

Thermodynamics of Iron Ammonia Synthesis Catalyst Sintering

The sintering of iron ammonia synthesis catalysts (nanocrystalline iron promoted with: Al2O3, CaO and K2O) was studied under a hydrogen atmosphere, in a temperature range of 773 to 973 K to obtain stationary states. The catalysts were characterized by measuring the nitriding reaction rate under an ammonia atmosphere at 748 K to obtain steady states and the measurement of specific surface area. Chemical processes were conducted in a tubular differential reactor enabling thermogravimetric measurements and the chemical composition analysis of a gas phase under conditions allowing experiments to be carried out in the kinetic region of chemical reactions. An extended model of the active surface of the iron ammonia synthesis catalyst was presented, taking into account the influence of the gas phase composition and process temperature. The surface of iron nanocrystallites was wetted using promoters in an exothermic process associated with the formation of the surface Fes-O- bond and the change in the surface energy of iron nanocrystallites. Promoters formed on the surface of iron nanocrystallites with different structures of chemisorbed dipoles, depending on the composition of the gas phase. The occupied sites stabilized the structure, and the free sites were active sites in the process of adsorption of chemical reagents and in sintering. Based on the bonding energy of the promoter oxides and the difference in surface energy between the covered and uncovered surfaces, the wetting abilities of promoters, which can be arranged according to the order K2O > Fe3O4 > Al2O3 > CaO, were estimated. By increasing the temperature in the endothermic sintering process, the degree of surface coverage with dipoles of promoters decreased, and thus the catalyst underwent sintering. The size distribution of nanocrystallites did not change with decreasing temperature. Only the equilibrium between the glass phase and the surface of iron nanocrystallites was then established.

The Performance and Reaction Mechanism of Untreated Steel Slag Used as a Microexpanding Agent in Fly Ash-Based Geopolymers

Steel slag is an industrial by-product of the steelmaking process, which is under-utilized and of low value due to its characteristics. Alkali-activated technology offers the possibility of high utilization and increased value of steel slag. A geopolymer composition was composed of steel slag, fly ash, and calcium hydroxide. Four experimental groups utilizing steel slag to substitute fly ash are established based on varying replacement levels: 35%, 40%, 45%, and 50% by mass. The final samples were characterized by compressive strength tests, and Fourier-transform infrared spectroscopy measurements, thermogravimetric measurements, scanning electron microscopy with energy dispersive spectroscopy, X-ray diffraction, and mercury intrusion porosimetry were used to investigate the chemical composition and microstructure of the final products. Higher steel slag/fly ash ratios lead to a lower bulk density and lower compressive strength. The compressive strength ranges from 3.7 MPa to 5.6 MPa, and the bulk density ranges from 0.85 g/cm3 to 1.13 g/cm3. Microstructural and energy-dispersive X-ray spectroscopy analyses show that the final geopolymer products were a type of composite consisting of both calcium aluminate silicate hydrate and sodium aluminate silicate hydrate, with the unreacted crystalline phases acting as fillers.

Optimization of the mass ratio of siloxane crosslinkers for poly(2,6-dimethyl-1,4-phenylene oxide) anion exchange membranes to improve acid enrichment by electrodialysis

Proton blocking anion exchange membranes (AEMs), which are employed in electrodialysis technology, show promise in acid recovery from industrial waste. A series of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) membranes were prepared using (3-aminopropyl)trimethoxysilane (APTMS) and weakly functionalized bases including N-butylimidazole (N-BuIm). Were networked to create AEMs with low leak rates. It was discovered that the appropriate concentration of siloxane crosslinker raised the membrane matrix's density and lowered the AEM matrix's hydrophilicity. Thermogravimetric measurements and water absorption have confirmed this, and the membranes in this series even swell up to 8.61 %. The maximum H+ concentration concentrated by the cross-linked AEM (BPPO/5Si) during the ED with a current density of 10 mA∙cm−2 was 2.35 M, which was higher than the concentration concentrated by the uncross-linked AEM (BPPO/OSi), which was 1.90 M (beginning concentration: 1.00 M). The current efficiency was 44.8 % and the energy consumption was only 1.81 kW ∙h∙kg−1. A balance between proton blocking and SO42− ions transport was achieved by the optimized AEM, which exhibited increased hydrophobicity and smaller ion clusters. The improved AEM was found to have fewer ionic clusters and greater hydrophobicity. For cross-linked AEMs, a trade-off between SO42− ions transport and proton blocking was thus accomplished. This work is thought to offer direction for developing sophisticated proton blocking AEMs.

Microstructural Evolution of Calcium Sulfoaluminate Cement during the Wet-Carbonation Process

Calcium sulfoaluminate (CSA) cement, as a type of low-carbon cement, can contribute to further reduction in carbon emissions with carbonation technologies. However, the detailed microstructure development of CSA cement during the carbonation process has been rarely analyzed. In this paper, wet carbonation was applied to CSA cement to investigate the microstructure evolution of carbonation products and carbon absorption capacity of CSA cement by means of pH measurement, X-ray diffraction (XRD) measurement, thermogravimetric (TG) measurement, Fourier-transformed infrared spectroscopy (FT-IR) measurement and scanning electron microscope measurement. During the carbonation process, the formed ettringite product and the dicalcium silicate clinker were carbonated immediately to generate calcium carbonate crystals, silica gel and aluminum hydroxide (AH3) gel. With the trend of pH increasing first and notably decreasing later, the coupling interaction between the hydration and carbonation reactions of CSA cement was revealed. From the XRD and TG results, three types of calcium carbonate crystal forms (calcite, vaterite and aragonite) were detected, and the content of calcium carbonate increased with the increase in carbonation time. FT-IR analysis further confirmed the existence of calcium carbonate, silica gel and AH3 gel with their characteristic vibrations. Moreover, the microstructure of carbonation products with different morphologies was observed. The application of wet carbonation to CSA cement provides a more comprehensive insight to the carbonation mechanism of this low-carbon cement.

Defects materials of Institut Lavoisier-125(Ti) materials enhanced photocatalytic activity for toluene and chlorobenzene mixtures degradation: Mechanism study

In this paper, the effect of three monocarboxylic acids on MIL-125 synthesis was systematically investigated and the results were discussed in detail. X-ray diffractometry (XRD) and nitrogen adsorption–desorption curves indicated that small molecule acids (acetic acid, propionic acid and butyric acid) affected the morphology of MIL-125 and induced lamellar pores and structural defects in the crystals. Thermogravimetric measurements confirmed the presence of acid-regulated defective metal–organic frameworks (MOFs). Electrochemical tests and density function theory calculations indicated that acid modulation could change the forbidden bandwidth of the material. The acid modification strategy effectively promoted the transfer of photogenerated electrons and enhanced the adsorption and activation of O2 and H2O molecules, generating reactive radicals. The modified MOFs also showed excellent performance in the removal of mixed toluene and chlorobenzene. The degradation pathways of the mixture were analyzed by in situ infrared (IR) and gas chromatography-mass spectrometry (GC–MS). The mixture was converted to chlorophenolic intermediates in the presence of reactive oxygen species, further decomposed to form ethers and ethanol, and finally formed small molecules such as carbon dioxide and water. A feasible method was provided for the preparation of photocatalysts for the treatment of mixed VOCs.

Self-healing polyacrylates based on dynamic disulfide and quadruple hydrogen bonds.

Herein, a self-healing polyacrylate system was successfully prepared by introducing crosslinking agents containing disulfide bonds and monomers capable of forming quadruple hydrogen bonds through free radical copolymerization. This polymer material exhibited good toughness and self-healing properties through chemical and physical dual dynamic networks while maintaining excellent mechanical properties, which expanded the development path of self-healing acrylate materials. Compared to uncrosslinked and single dynamically crosslinked polymers, its elongation at break was as high as 437%, and its tensile strength was 5.48 MPa. Due to the presence of dual reversible dynamic bonds in the copolymer system, good self-healing was also achieved at 60 °C. In addition, differential scanning calorimetry and thermogravimetric analysis measurements confirmed that the thermal stability and glass transition temperature of the material were improved owing to the presence of physical and chemical cross-linking networks.

Thermogravimetric study of metal–organic precursors and their suitability for hybrid molecular beam epitaxy

Although metal–organic (MO) precursors are widely used in technologically relevant deposition techniques, reports on their temperature-dependent evaporation and decomposition behaviors are scarce. Here, MO precursors of the metals Ti, V, Al, Hf, Zr, Ge, Ta, and Pt were subjected to thermogravimetric analysis to experimentally determine their vapor pressure curves and to gain insight into their temperature-dependent decomposition kinetics. Benzoic acid was used as a calibration standard and vapor pressure curves were extracted from thermogravimetric measurements using the Langmuir equation. The obtained data is used to discuss the suitability of these MO precursors in chemical vapor deposition-based thin film growth approaches in general, and hybrid molecular beam epitaxy in particular. All MOs, except for Ta- and one Ti-based MOs, were deemed suitable for gas inlet systems. The Ta-based MO demonstrated suitability for an effusion cell, while all MOs showed compatibility with cracker usage.Graphical

A New 3D Iodoargentate Hybrid: Structure, Optical/Photoelectric Performance and Theoretical Research.

The explorations of new three-dimensional (3D) microporous metal halides, especially the iodoargentate-based hybrids, and understanding of their structure-activity relationships are still quite essential but full of great challenges. Herein, with the aromatic 4,4'-dpa (4,4'-dpa = 4,4'-dipyridylamine) ligands as the structural directing agents, we solvothermal synthesized and structurally characterized a novel member of microporous iodoargentate family, namely [H2-4,4'-dpa]Ag6I8 (1). Compound 1 possesses a unique and complicated 3D [Ag6I8]n2n- anionic architecture that was built up from the unusual hexameric [Ag6I13] secondary building units (SBUs). Research on optical properties indicated that compound 1 exhibited semiconductor behavior, with an optical band gap of 2.50 eV. Under the alternate irradiation of light, prominent photoelectric switching abilities could be achieved by compound [H2-4,4'-dpa]Ag6I8, whose photocurrent densities (0.37 μA·cm-2 for visible light and 1.23 μA·cm-2 for full-spectrum) compared well with or exceeded those of some high-performance halide counterparts. Further theoretical calculations revealed that the relatively dispersed conduction bands (CBs) structures in compound 1 induced higher electron mobilities, which may be responsible for its good photoelectricity. Presented in this work also comprised the analyses of Hirshfeld surface, powder X-ray diffractometer (PXRD), thermogravimetric measurement, energy-dispersive X-ray spectrum (EDX) along with X-ray photoelectron spectroscopy (XPS).

Electrochemical analysis of thermally treated two dimensional zinc sulphide hexagonal nano-sheets with reduced band gap

Significantly reduced band gap (2.0 eV) zinc sulphide (ZnS) nanoparticles are synthesized using microwave/ultraviolet/ultrasonic assisted hydrothermal route in a two step process. Initially, ZnS nanospheres are synthesized, showing a cubic structural phase with a band gap of 3.2 eV, which is further annealed at 1000 °C to get the final product. Following annealing, the cubic ZnS undergoes a phase change to wurtzite ZnS, in the form of hexagonal nanosheets showing polymorphism phenomena, along with a reduced band gap of 2 eV. The optical analysis reveals a red shift in the absorbance region, transitioning from the absorption of UV radiations in cubic ZnS to visible radiations in wurtzite ZnS. Thermogravimetric (TGA) measurements and its analysis also revealed the phase change of ZnS (cubic) to ZnS (Wurtzite) when heated at 1000 °C. Microstructural analysis reveals the formation of sheets oriented along (100) plane, which is evidenced by the interplanar spacing and lattice fringes. The photoluminscence spectra highlights quantum energy states present between the highest occupied molecular orbital (HOMO), which is 2.36 eV for cubic phase and 1.76 eV for the hexagonal phase, and the lowest unoccupied molecular orbital (LUMO), with values of −0.84 eV for cubic while −0.24 for hexagonal ZnS. The CIE coordinates for wurtzite ZnS, at X= 0.55 and Y= 0.23, corresponds to red light emission. The suitability of wurtzite phase ZnS for solar cell applications has been demonstrated through electrochemical studies using Nyquist plot and cyclic voltrammetry (CV) techniques. CV demonstrates the presence of redox peaks and reversibility of the material during the redox process. The diffusive behaviour is also confirmed by observing the variation of peak current with scan rate, following Rendle Sevick equation. The presence of Warburg diffusion in Nyquist plot indicates the efficient charge transfer dynamics of the material, suggesting a high potential for exciton formation in energy production. Consequently, this material stands as a promising candidate for efficient solar cells.

Influence of low-grade metakaolin on creep behavior of concrete

Clay is an abundant material worldwide, but due to the high demand for pure kaolinite clay, research into the application of low-grade metakaolin (MK) is required. However, research on the effect of low-grade MK on the volume stability of concrete is lacking. In this work, concrete composed of low-grade MK, replacing 20%–60 % of Portland cement, is studied using nanoindentation, thermogravimetric, creep and strength measurement in order to demonstrate the impact of high-volume metakaolin on the long-term volume stability of concrete materials. Results show that although the incorporation of high-volume MK degrades the early-age mechanical properties of concrete (7–28 d), the addition of an appropriate amount of MK (20 %) improves the long-term compressive strength of concrete (60–180 d). Meanwhile, concrete mixed with MK (～60 %) shows lower creep stress than plain specimen, and the specimen mixed with 20 % MK has the lowest creep stress. From a nanoscale perspective, incorporating an appropriate amount of MK increases the content of high-density calcium silicate hydrate (C–S–H), which provides a positive effect on reducing the creep stress of concrete. For the 20 % MK-modified specimen, the volume fraction of C–S–H increases by 4.23 % compared to the reference sample, and the relative volume fraction of high-density C–S–H increases by 146.77 %. Meanwhile, the contents of pore and Ca(OH)2 phase, as well as the widths of interfacial transition zone (ITZ), are decreased in the 20 % MK-modified samples compared to plain concrete. The results of thermogravimetric analysis also show that the content of Ca(OH)2 decreases with the increase in MK substitution level, and the non-evaporable water content of the 20 % MK-modified paste is similar to that of plain paste. This study provides theoretical guidance for the application of low-grade clay minerals in concrete.

Structural and energetic characterization of silica-alumina gels for adsorption processes

The surface chemistry of silica-alumina gels is largely determined by number and type of silanol groups present. However, until now the influence of different silanol groups on adsorption processes is largely unknown. The aim of this study is to develop a method for an energetic characterization of silica-alumina gels by combining data measured by nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA) and adsorption calorimetry. The silica-alumina gels used for the studies are systematically modified by pretreating at temperatures between 200 °C and 1000 °C. To quantify number and distribution of silanol groups, complementary data from 29Si-NMR and 1H NMR and thermogravimetric measurements is combined. Adsorption measurements with the adsorptives cyclopentane (nonpolar) and pyrrolidine (polar molecule capable of hydrogen bonding) provide further information. Based on the adsorption isotherms and load-dependent heats of adsorption, it is shown that number and distribution of silanol groups have little effect on the adsorption of cyclopentane. In contrast, different energy levels are found for the heat of adsorption of pyrrolidine at ∼106 kJ mol−1, ∼95 kJ mol−1, ∼87 kJ mol−1, and ∼80 kJ mol−1 depending on pretreatment temperature. Based on the combination of all data, a model is proposed to assign the identified energy levels of adsorption to different silanol groups.