Search Results (11)

The transition from conventional silica nanoparticle (SiNP) production based on purified alkoxysilanes and high-temperature flame hydrolysis of silicon tetrachloride to renewable and waste-derived silicon resources requires more than precursor substitution. It requires a mechanistic understanding of how feedstock mineralogy, silicon speciation, impurity chemistry, and processing history propagate through dissolution, nucleation, condensation, gelation, aging, drying, and pore evolution to determine material performance, environmental burden, and manufacturing feasibility. Although previous reviews have established the technical feasibility of producing silica from secondary resources, their predominant organization by feedstock, synthesis route, or application provides limited ability to explain why nominally similar processes generate materials with markedly different structural and functional properties. This review addresses these through a resource-pull, feedstock-to-function framework that links resource chemistry and process design to critical material attributes, application-specific specifications, sustainability, and scale-up requirements. Agricultural residues, industrial by-products, geothermal resources, waste glass, and fluorosilicate streams are critically compared according to silicon form and phase, reactivity, impurity profile, compositional variability, purification demand, and attainable product quality. Particular attention is given to waste-derived alkaline silicate systems, in which molecular, oligomeric, and colloidal silica coexist and therefore require characterization beyond bulk SiO₂ concentration. Established and emerging processing strategies, including controlled combustion and alkaline extraction, alkali fusion, ambient-pressure drying, microwave and mechanochemical activation, biogenic and biomimetic templating, and continuous processing, are evaluated according to their mechanistic effects, technological maturity, structural control, and demands for energy, reagents, water, solvents, effluent treatment, and capital. Across these routes, gelation and aging emerge as critical transfer stages through which feedstock composition is translated into network connectivity, pore architecture, shrinkage behavior, and ultimately functional performance. Evidence from secondary-source aerogels further shows that properly controlled waste-derived systems can attain BET surface areas of approximately 350–500 m² g⁻¹, within the textural range of many alkoxide-derived materials, indicating that feedstock variability, impurity management, and process control are more important constraints than an inherently lower performance ceiling. On this basis, this review proposes a minimum evidence framework comprising feedstock traceability, intermediate-speciation and colloidal characterization, silicon mass balance, gelation and aging metrics, application-specific qualification criteria, performance-normalized life cycle and techno-economic assessment, process analytical control, and staged pilot validation. Collectively, these principles provide a mechanistically grounded basis for moving sustainable silica synthesis beyond isolated proof-of-concept demonstrations toward reproducible, scalable, application-matched, and commercially credible manufacturing platforms. Full article

Alkaline sodium hydroxide/sodium silicate-activating high-purity metakaolin geopolymerization is described in terms of metakaolin deconstruction in tetrahedral hydrate silicate [O[Si(OH)₃]]⁻ and aluminate [Al(OH)₄]⁻ ionic precursors followed by their reassembling in linear and branched sialates monomers that randomly copolymerize into an irregular crosslinked aluminosilicate network. The novelty of the approach resides in the concurrent thermo-calorimetric (differential scanning calorimetry, DSC) and rheological (dynamic mechanical analysis, DMA) characterizations of the liquid slurry during the transformation into a gel and a structural glassy solid. Tests were run either in temperature scan (1 °C/min) or isothermal (20 °C, 30 °C, 40 °C) cure conditions. A Gaussian functions deconvolution method has been applied to the DSC multi-peak thermograms to separate the kinetic contributions of the oligomer’s concurrent reactions. DSC thermograms of all tested materials are well-fitted by a combination of three overlapping Gaussian curves that are associated with the initial linear low-molecular-weight (Mw) oligomers (P1) formation, oligomers branching into alumina-rich and silica-rich gels (P2), and inter- and intra-molecular crosslinking (P3). The loss factor has been used to define viscoelastic behavioral zones for each DMA rheo-thermogram operated in the same DSC thermal conditions. Macromolecular evolution and viscoelastic properties have been obtained by pairing the deconvoluted DSC thermograms with the viscoelastic behavioral zones of the DMA rheo-thermograms. Two main chemorheological behaviors have been identified relative to pre- and post-gelation separation of the viscoelastic liquid from the viscoelastic solid. Each comprises three behavioral zones, accounting for the concurrently occurring linear and branching oligomerization, aluminate-rich and silica-rich gel nucleations, crosslinking, and vitrification. A “rubbery plateau” in the loss factor path, observed for all the testing conditions, identifies a large behavioral transition zone dividing the incipient gelling liquid slurry from the material hard setting and vitrification. Full article

Although geopolymers, as structural materials, should have superior engineering properties than traditional cementitious materials, they often need to improve their final characteristics’ reproducibility due to the need for more control of the complex silico-aluminate decomposition and polymerisation stages. Thermosetting of a reactive geopolymeric paste involves tetrahedral Silicate and Aluminate precursor condensation into polyfunctional oligomers of progressively higher molecular weight, transforming the initial liquid into a gel and a structural solid. Viscosity and gelation control become particularly critical when the geopolymer is processed with 3D printing additive technology. Its physical state modification kinetics should match the flow and setting characteristics required by the deposition process. The reaction kinetics and the elastic and viscous characteristics preceding gelation and hardening have been investigated for an alkali-activated Metakaolin/Sodium Silicate-Sodium Hydroxide paste with a Si/Al ratio > 3. A chemoreological approach has been extended to these inorganic polymerisable systems, as already utilised for organic thermosetting polymers. Differential scanning calorimetry and Oscillatory DMA were carried out to monitor the advancement of the polymerisation reaction and the associated variations of the rheological viscoelastic properties. Dynamic thermal scans were run at 1 °C/min and a frequency of 10 Hz for the dynamic mechanical tests. The observed kinetics of polymerisation and variations of the elastic and viscous components of the complex viscosities and shear moduli are described in terms of polycondensation of linear and branched chains of oligomeric macromolecules of increasing complexity and molecular weight up to gelation (Gel1) and cross-linking of the gelled macrostructure (Gel2) and final glassy state. Geopolymerization can be allocated into two main behavioural zones: a viscoelastic liquid paste below 32.5% of reaction advancement and a viscoelastic solid above. Initial complex viscosities range from 2.3 ± 0.9  × 10⁻⁵ MPa_*s to 6.8 ± 0.9  × 10⁻² in the liquid-like state and from 1.9 ± 0.1 MPa to 9.6 ± 2.1 × 10² MPa in the solid-like state. Full article

Mesoporous zirconium-silicates have been prepared using two different methodologies, evaporation-induced self-assembly and solventless organometallic precursor dry impregnation of commercial SiO₂. The samples were characterized by elemental analysis, XRD, N₂ adsorption, TEM, DRS UV–vis and Raman spectroscopic techniques. The catalytic performance of the Zr-Si catalysts was assessed in the epoxidation of three representative alkenes, cyclohexene, cyclooctene and caryophyllene, as well as in the oxidation of methyl phenyl sulfide using aqueous hydrogen peroxide as a green oxidant, with special attention drawn to the structure/activity relationship and catalyst stability issues. The key factors which affect substrate conversion and epoxide selectivity have been defined. The catalysts with larger contents of oligomeric ZrO₂ species revealed higher activity. The nature of alkene and, in particular, its molecular hindrance is crucial, since the adsorption of the epoxide product is the main factor leading to fast catalyst deactivation. In fact, bulky epoxides do not show this effect. After optimization, the oxidation of caryophyllene gave endocyclic monoepoxide with 77% selectivity at 87% alkene conversion. Methyl phenyl sulfoxide afforded 37% of sulfoxide and 63% of sulfone at 57% sulfide conversion. The nature of catalysis was truly heterogeneous and no Zr leaching was observed. Full article

Biological hydroxyapatite (HA) contains the different minor ions which favour its bio-reactivity in vivo. In this study, the preparation of HA particles containing both silicate and carbonate ions under the presence of sodium silicate was investigated, and the physicochemical properties were evaluated according to the contents and states of silicate and carbonate ions. The increment in the silicate ion reduced the crystallinity and expanded the crystalline size along with a-axis. Solid-state ²⁹Si–NMR spectra indicated the increase in the adsorption of oligomeric silicate species on the HA particle surfaces in addition to the substitution state of silicate ions, suggesting the occurrence of the surface coating of silicates on the surfaces. The possible states of carbonate and silicate ions at the HA surfaces will provide the bioactivity. Full article

For the development of spacecraft with long-servicing life in low earth orbit (LEO), high-temperature resistant polymer films with long-term atomic oxygen (AO) resistant features are highly desired. The relatively poor AO resistance of standard polyimide (PI) films greatly limited their applications in LEO spacecraft. In this work, we successfully prepared a series of novel AO resistant PI composite films containing nanocaged polyhedral oligomeric silsesquioxane (POSS) components in both the PI matrix and the fillers. The POSS-containing PI matrix film was prepared from a POSS-substituted aromatic diamine, N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS) and a common aromatic diamine, 4,4′-oxydianline (ODA) and the aromatic dianhydride, pyromellitic dianhydride (PMDA) by a two-step thermal imidization procedure. The POSS-containing filler, trisilanolphenyl POSS (TSP-POSS) was added with the fixed proportion of 20 wt% in the final films. Incorporation of TSP-POSS additive apparently improved the thermal stability, but decreased the high-temperature dimensional stable nature of the PI composite films. The 5% weight loss temperature (T_5%) of POSS-PI-20 with 20 wt% of DABA-POSS is 564 °C, and its coefficient of linear thermal expansion (CTE) is 81.0 × 10⁻⁶/K. The former is 16 °C lower and the latter was 20.0 × 10⁻⁶/K higher than those of the POSS-PI-10 film (T_5% = 580 °C, CTE = 61.0 × 10⁻⁶/K), respectively. POSS components endowed the PI composite films excellent AO resistance and self-healing characteristics in AO environments. POSS-PI-30 exhibits the lowest AO erosion yield (E_s) of 1.64 × 10⁻²⁶ cm³/atom under AO exposure with a flux of 2.51 × 10²¹ atoms/cm², which is more than two orders of magnitude lower than the referenced PI (PMDA-ODA) film. Inert silica or silicate passivation layers were detected on the surface of the PI composite films exposed to AO. Full article

The relatively poor atomic-oxygen (AO) resistance of the standard polyimide (PI) films greatly limits the wide applications in low earth orbit (LEO) environments. The introduction of polyhedral oligomeric silsesquioxane (POSS) units into the molecular structures of the PI films has been proven to be an effective procedure for enhancing the AO resistance of the PI films. In the current work, a series of POSS-substituted poly (pyromellitic anhydride-4,4′-oxydianiline) (PMDA-ODA) films (POSS-PI) with different POSS contents were synthesized via a POSS-containing diamine, N-[(heptaisobutyl-POSS)propyl]-3,5-diaminobenzamide (DABA-POSS). Subsequently, the effects of the molecular structures on the thermal, tensile, optical, and especially the AO-erosion behaviors of the POSS-PI films were investigated. The incorporation of the latent POSS substituents decreased the thermal stability and the high-temperature dimensional stability of the pristine PI-0 (PMDA-ODA) film. For instance, the PI-30 film with the DABA-POSS content of 30 wt% in the film exhibited a 5% weight loss temperature (T_5%) of 512 °C and a coefficient of linear thermal expansion (CTE) of 54.6 × 10⁻⁶/K in the temperature range of 50–250 °C, respectively, which were all inferior to those of the PI-0 film (T_5% = 574 °C; CTE = 28.9 × 10⁻⁶/K). In addition, the tensile properties of the POSS-containing PI films were also deteriorated, to some extent, due to the incorporation of the DABA-POSS components. The tensile strength (T_S) of the POSS-PI films decreased with the order of PI-0 > PI-10 > PI-15 > PI-20 > PI-25 > PI-30, and so did the tensile modulus (T_M) and the elongations at break (E_b). PI-30 showed the T_S, T_M, and E_b values of 75.0 MPa, 1.55 GPa, and 16.1%, respectively, which were all lower than those of the PI-0 film (T_S = 131.0 MPa, T_M = 1.88 GPa, E_b = 73.2%). Nevertheless, the incorporation of POSS components obviously increased the AO resistance of the PI films. All of the POSS-PI films survived from the AO exposure with the total fluence of 2.16 × 10²¹ atoms/cm², while PI-0 was totally eroded under the same circumstance. The PI-30 film showed an AO erosion yield (E_s) of 1.1 × 10⁻²⁵ cm³/atom, which was approximately 3.67% of the PI-0 film (E_s = 3.0 × 10⁻²⁴ cm³/atom). Inert silica or silicate passivation layers were detected on the surface of the POSS-PI films after AO exposure, which efficiently prevented the further erosion of the under-layer materials. Full article

This paper introduces a new method to measure whole cycle length change non-destructively and continuously using a digital image analysis system. The macroscale length changes of mortars containing different shrinkage-reducing admixture (SRA) dosages (0%, 1%, 2% and 5% by cement weight) were first determined using a complementary metal oxide semiconductor (CMOS) image sensor under alternating dry and wet curing conditions. After that, the length change was calculated using developed digital image processing technology (DIPT) software. After that, several significant conclusions could be drawn by combining with the results of systematic tests of the macroscopic and microscale physical properties of the cement mortar using X-ray diffraction, scanning electron microscopy, mercury intrusion porosimetry (MIP) and nuclear magnetic resonance (NMR) methods. The test results indicated that SRAs exhibited significant effects on the shrinkage inhibition of cement mortars, whereas the shrinkage reduction behaviour was also affected by varying the curing conditions. The MIP and NMR analyses demonstrated that SRAs reduced the irreversible shrinkage of the cement mortars by decreasing the volume percentage of the 3–50 nm pores and promoting the conversion of calcium silicate hydrate gel from an oligomeric to a high polymerization state thereby improving the volume stability of cement mortars. Full article

Crystallite aluminosilicates are inorganic microporous materials with well-defined pore-size and pore-structures, and have important industrial applications, including gas adsorption and separation, catalysis, etc. Crystallite aluminosilicates are commonly synthesized via hydrothermal processes, where the oligomerization of silicic acids is crucial. The mechanisms for the oligomerization of poly-silicic acids in neutral aqueous solution were systematically investigated by extensive first-principles-based calculations. We showed that oligomerization of poly-silicic acid molecules proceeds through the lateral attacking and simultaneously proton transfer from the approaching molecule for the formation of a 5-coordinated Si species as the transition state, resulting in the ejection of a water molecule from the formed poly-silicic acid. The barriers for this mechanism are in general more plausible than the conventional direct attacking of poly-silicic acid with reaction barriers in the range of 150–160 kJ/mol. The formation of linear or branched poly-silicic acids by intermolecular oligomerization is only slightly more plausible than the formation of cyclic poly-silicic acids via intramolecular oligomerization according to the reaction barriers (124.2–133.0 vs. 130.6–144.9 kJ/mol). The potential contributions of oligomer structures, such as the length of the linear oligomers, ring distortions and neighboring linear branches, etc., to the oligomerization were also investigated but found negligible. According to the small differences among the reaction barriers, we proposed that kinetic selectivity of the poly-silicic acids condensation would be weak in neutral aqueous solution and the formation of zeolite-like structures would be thermodynamics driven. Full article

Mesoporous tungsten-silicates, W-MMM-E, have been prepared following evaporation-induced self-assembly methodology and characterized by elemental analysis, XRD, N₂ adsorption, STEM-HAADF (high angle annular dark field in scanning-TEM mode), DRS UV-vis, and Raman techniques. DRS UV-vis showed the presence of two types of tungsten oxo-species in W-MMM-E samples: isolated tetrahedrally and oligomeric octahedrally coordinated ones, with the ratio depending on the content of tungsten in the catalyst. Materials with lower W loading have a higher contribution from isolated species, regardless of the preparation method. W-MMM-E catalyzes selectively oxidize of a range of alkenes and organic sulfides, including bulky terpene or thianthrene molecules, using green aqueous H₂O₂. The selectivity of corresponding epoxides reached 85–99% in up to 80% alkene conversions, while sulfoxides formed with 84–90% selectivity in almost complete sulfide conversions and a 90–100% H₂O₂ utilization efficiency. The true heterogeneity of catalysis over W-MMM-E was proved by hot filtration tests. Leaching of inactive W species depended on the reaction conditions and initial W loading in the catalyst. After optimization of the catalyst system, it did not exceed 20 ppm and 3 ppm for epoxidation and sulfoxidation reactions, respectively. Elaborated catalysts could be easily retrieved by filtration and reused several times with maintenance of the catalytic behavior. Full article

We fabricated a series of mesoporous silicas and mesoporous organosilicates with hierarchical porosity through evaporation-induced self-assembly using Pluronic F127 as a template in this study. We could tailor the mesophase of each mesoporous silica sample by varying the weight ratio of its two silica sources: tetraethyl orthosilicate (TEOS) and triethoxysilane hydrosilylated octavinyl polyhedral oligomeric silsesquioxane (OV-POSS-SILY). The mesophases ranged from an ordered body-centered cubic (bcc) structure (TEOS alone) to ordered face-centered cubic (fcc) structure (10 and 20 wt.% of OV-POSS-SILY) and finally to disordered spherical pores (≥30 wt.% of OV-POSS-SILY). We used small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) to study the transformations of these mesophases, while N₂ isotherm sorption curves revealed the porosities of these mesoporous silicate samples. Moreover, ²⁹Si CP/MAS solid state nuclear magnetic resonance spectroscopy allowed us to analyze the compositions of the POSS-containing silicate frameworks. Such functional mesoporous silica samples incorporating microporous POSS building units have potential applications in various systems, including optical and electronic devices. Full article