Understanding the relationship between geopolymer composition, microstructure and mechanical properties

Today cross-cutting approaches, where molecular engineering and clever processing are synergistically coupled, allow the chemist to tailor complex hybrid systems of various shapes with perfect mastery at different size scales, composition, functionality, and morphology. Hybrid materials with organic–inorganic or bio–inorganic character represent not only a new field of basic research but also, via their remarkable new properties and multifunctional nature, hybrids offer prospects for many new applications in extremely diverse fields. The description and discussion of the major applications of hybrid inorganic–organic (or biologic) materials are the major topic of this critical review. Indeed, today the very large set of accessible hybrid materials span a wide spectrum of properties which yield the emergence of innovative industrial applications in various domains such as optics, micro-electronics, transportation, health, energy, housing, and the environment among others (526 references).

Applications of advanced hybrid organic–inorganic nanomaterials: from laboratory to market

This article describes hybrid materials and systems in which the core integrity of inorganic nanobuilding blocks (NBBs) is preserved and reviews the main synthetic procedures presented in the literature. The relation between the NBB and the resulting hybrid networks is discussed for several striking examples:  silicon and tin oxo clusters, polyoxometalates, and transition metal−oxo-based clusters. This approach is extended to nanoparticule-based hybrids. The chemical strategies offered by the coupling of soft chemistry processes and this approach based on functional NBBs allows, through an intelligent and tuned coding, to develop a new vectorial chemistry that is able to direct the assembly of a large variety of structurally well-defined clusters or nanoparticles into complex architectures.

Designed Hybrid Organic−Inorganic Nanocomposites from Functional Nanobuilding Blocks

The hydrolysis and condensation reactions of monomeric alkoxysilanes and organylalkoxysilanes utilized in sol-gel processing are reviewed. Both reactions occur by acid or base-catalyzed bimolecular displacement reactions. The acid-catalyzed mechanisms are preceded by protonation of OH or OR substituents attached to Si, whereas under basic conditions hydroxyl or silanolate anions attack Si directly. Many of the observed structural trends are understood on the basis of the pH and [H2O] dependence of the hydrolysis, condensation, and dissolution reactions.

Hydrolysis and condensation of silicates: Effects on structure

Organic-inorganic hybrids appear as a creative alternative for obtaining new materials with unusual features. This is related to their diphasic structures, leading to multifunctional materials. The low-temperature processes which are used to synthesize such structures provide a wide versatility in the design of the compounds. The potentiality of the chemistry is to play on the structure of these mixtures and dissociate the various contributions in tailoring both phases and controlling the interfaces. In this paper, a review of some chemistry pathways to hybrid materials is presented. The nature of the bonds between organic and inorganic phases is used to divide them in two major families: class I corresponds to materials with weak interphase bonding, while class II corresponds to materials where both phases are chemically grafted. Applications of these materials in the fields of optics, iono-electronics, mechanics, biology and others are expected. Some applications are reviewed, with respect to the versatility of the synthetic procedure. Most of the properties of these new high-technology materials are dependent on their structural and chemical composition as well as on the dynamical properties inside the blends.

Hybrid organic–inorganic materials: a land of multidisciplinarity

Die 29Si-FT-NMR-Spektren von 13 Natriumsilicatlosungen mit unterschiedlichem Na:Si-Verhaltnis werden in Hinblick auf die Struktur der in den Losungen auftretenden Silicatanionen untersucht. Fur die 5 moglichen Baugruppen (Monosilicat, Endgruppen. Mittelgruppen, Verzweigungs- und Vernetzungsgruppen) lassen sich definierte Bereiche der 29Si-chemischen Verschiebung angeben, in denen durch Einflus der weiteren strukturellen Umgebung i. a. zahlreiche Signalaufspaltungen beobachtet werden. Aus den relativen Intensitaten der Signale konnen Aussagen uber die Konzentrationsverteilung und damit uber das Kondensationsgleichgewicht der Silicatanionen in Abhangigkeit vom Na:Si-Verhaltnis abgeleitet werden. Es zeigt sich, das zahlreiche Anionentypen mit unterschiedlichem Kondensationsgrad nebeneinander in einem Gleichgewicht vorliegen, das sich mit fallendem Na:Si-Verhaltnis stark auf die Seite hohermolekularer Silicatanionen mit hohem Gehalt an Verzweigungs- und Vernetzungsgruppen verschiebt.



29Si-NMR Spectroscopy of Silicate Solutions. II. On the Dependence of the Structure of Silicate Anions in Water Solutions from the Na : Si Ratio



The 29Si-FT-NMR spectra of 13 sodiumsilicate solutions with different Na:Si ratios are investigated with regard to the structure of the silicate anions in the solutions. The 5 typical building units (Monosilicate, end-, middle-, branching and crosslinking groups) show characteristic and non overlapping ranges of the 29Si chemical shift with many signals splittings caused by different neighbouring group effects. The relative intensities of the signals give informations on the concentrations and the equilibrium of condensation of the silicate anions in dependence of the Na:Si ratio. It is shown, that many types of anions with different degree of condensation coexist in an equilibrium, which is shiftet to the polymer silicate anions with high content of branching and crosslinking groups on the decrease of the Na:Si ratio.

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29Si-NMR-Spektroskopie an Silicatlösungen. - II : Zur Abhängigkeit der Struktur der Silicatanionen in wäßrigen Natriumsilicatlösungen vom Na : Si-Verhältnis

The examination of hydrolysis, homo- and hetero-condensation reactions, of the condensation degree and the extent of epoxide ring opening in the course of sol-gel process was carried out by means of liquid- and solid-state 29Si and 13C NMR in the system 3-glycidoxypropyltrimethoxysilane (GPTS)-titaniumtetraethoxide-water (molar ratio 1 : 1 : 1.5–14) which is frequently used for the synthesis of heterometal hybrid polymers. The monomeric silanol groups in the GPTS-prehydrolysate immediately co-condense with the Ti-tetraethoxide to Si–O–Ti bonds to an extent of about 50–60% which remain stable in sols and also in the corresponding gels at low amounts of free water (0.02 H2O/OR) in the sol. An increasing amount of free water in the sol (≥0.12 H2O/OR) leads to an increased hydrolytic cleavage of the heterometal bonds and to the formation of homo-condensed polysiloxanes. The condensation degree of RSiO1.5 units in the Ti-containing sols is with 30–60% relatively high in comparison to Ti-free GPTS sols (ca. 5%) whereas the condensation degree of GPTS derived gels (81%) was found to be similar to that of the Ti-containing gels (60–80%). Ti-tetraethoxide accelerates the ring opening reaction of the epoxide group in the sols in dependence on the water content. Up to 78% of the epoxide rings are opened after 24 h in the sol with the highest water content (2 H2O/OR). No epoxide rings can be detected in Ti-containing gels which derive from sols with an amount of free water of ≥0.12 H2O/OR. The results give a first insight into the different parallel reactions in this system and can contribute to more structure controlled syntheses of heterometal hybrid polymers.

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A NMR study on the hydrolysis, condensation and epoxide ring-opening reaction in sols and gels of the system glycidoxypropyltrimethoxysilane-water-titaniumtetraethoxide

Mit Hilfe papierchromatographischer, kinetischer und rontgenographischer Methoden wird gezeigt, das das Tetramethylammoniumsilicat der Zusammensetzung 1 N(CH3)4OH · 1 SiO2 · ∼8 H2O nicht – wie bisher angenommen – ein Poly- oder Phyllosilicat, sondern ein Tetra-anhydrido-bis-cyclotetrasilicat (Doppelviererringsilicat) der Formel [(CH3)4N]8[Si8O20] · ∼69 H2O ist. Durch Umsatz mit Hexamethyldisiloxan wurde daraus der entsprechende Trimethylsilylester ((CH3)3Si)8[Si8O20] in kristallisierter Form erhalten.



By means of paperchromatographic, kinetic and X-ray methods it is shown that the tetramethylammonium silicate of the composition 1 N(CH3)4OH · 1 SiO2 · ∼8 H2O has not – as hitherto supposed – the constitution of a poly- or phyllosilicate, but that of a tetra-anhydrido-bis-cyclotetrasilicate (double-fourringsilicate), [(CH3)4N]8[Si8O20] · ∼69 H2O. Its trimethylsilylation by means of hexamethyldisiloxane gives the corresponding, crystalline trimethylsilyl ester [(CH3)3Si]8[Si8O20], which has been characterised by mass spectroscopy.

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Die Konstitution des Tetramethylammoniumsilicats der Zusammensetzung 1,0 N(CH3)4OH 1,0 SiO2 · 8,0–8,3 H2O

The complexation degrees of Al-, Ti- and Zr-butoxide (M) with unsaturated and saturated β-diketones (3-allylpentane-2.4-dione-APD, acetylacetone-ACAC) and β-ketoesters (methacryloxyethyl-acetoacetate-MEAA, allylacetoacetate-AAA, ethylacetoacetate-EAA) as organic ligands (L) were examined by IR and 13 C NMR spectroscopy and were found to be L:M ≥ 1.5. The hydrolytic stability of the ligands of the metal alkoxide complexes (L:M = 1) during hydrolysis/condensation reactions at the molar ratio h (H2O : OR) = 0.5–2.0 decreases with increasing H 2O:complex ratio. Furthermore, the ligand stability depends on the type of metal in the complexes and decreases in the order Al- > Zr- > Ti-butoxide complexes at h=1. The ACAC ligand likewise shows in the Al-, Ti- and Zr-butoxide complexes a high hydrolytic stability (95–100%) at h=1 within 7 days. The Ti- and Zr-butoxide complexes with β-ketoesters as ligand show at h=1> a release to a different extent e.g., up to 60% in the case of the MEAA-ligand in the Ti-butoxide complex after 2 days. In general, the hydrolytic stability of the ligands in the Ti-butoxide complexes (L:M = 1, h=1) decreases in the order ACAC > APD > AAA > EAA ≥ MEAA. The hydrolysis/condensation reaction of complexes having a weak ligand stability leads to larger particle sizes in the sols than those with stable ACAC ligands. The results contribute to a more controlled synthesis of sols and of new inorganic-organic hybrid polymers via the sol-gel process.

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On the Hydrolytic Stability of Organic Ligands in Al-, Ti- and Zr-Alkoxide Complexes

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Dagobert Hoebbel

Papers

29Si-NMR-Spektroskopie an Silicatlösungen. - II : Zur Abhängigkeit der Struktur der Silicatanionen in wäßrigen Natriumsilicatlösungen vom Na : Si-Verhältnis

A NMR study on the hydrolysis, condensation and epoxide ring-opening reaction in sols and gels of the system glycidoxypropyltrimethoxysilane-water-titaniumtetraethoxide

Die Konstitution des Tetramethylammoniumsilicats der Zusammensetzung 1,0 N(CH3)4OH 1,0 SiO2 · 8,0–8,3 H2O

On the Hydrolytic Stability of Organic Ligands in Al-, Ti- and Zr-Alkoxide Complexes

Strukturuntersuchungen an Silikatanionen in wäßriger Lösung mit Hilfe der 29Si‐NMR‐Spektroskopie