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Influence of homologous substitutions of chemical components on the rheological properties and on isochomal workability of Silicate glass melts
Glass melts of various homologous Silicate glass series were investigated by means of the cylinder compression method with respect to their flow behaviour (Newtonian and non-Newtonian), stress generadon modulus (stiffness, brittleness) and critical deformadon rate (high-temperature tensile strength, isochomal workability). The experimental results show that decreasing CaO content and increasing basicity lead to the decrease of the brittleness of Silicate glass melts and to the increase of the critical deformadon rate, i.e. to the improvement of the isochomal workability of these melts. The mixed alkali effect of sodium potassium calcium Silicate glass melts at molar fracdon [K₂O]/[Na₂O+K₂O] = 0.5 has a favourable influence on the isochomal workability The correladon between flow behaviour and workability of glass melts is also discussed in the present paper. It could be shown that the ratio β = E2.8/E3.6 (E is the extinction of the hydroxyl band at 2.8 and 3.6 ηm, respectively) indicates the structural origin of the dependence of the mentioned rheological properties on the chemical compositions, at least within the homologous series.
Anisotropie glasses and glass melts - a survey
Α general introduction describes intentional and unintentional anisotropic phenomena resulting from chemical and thermal inhomogeneities (internal stresses) as well as anisotropies induced by external elastic stresses and strains in homogeneous glasses for special opdcal purposes. Further the paper will point out the possibilities and various phenomena of producing defmed anisotropies by means of flow stresses and strain rates in glass mehs which may be frozen-in by cooling under load. It will be distinguished between Single - and double-phase glass melts and glasses which show very different kinds and effects of anisotropies. In particular, optical anisotropies (birefringence, specific birefringence) and structural-mechanical anisotropies (densities, shrinkages and expansions during annealing) of single-phase glasses and glass melts will be investigated under defined flow condidons (in-situ measurements directly in glass melts by the classical flow birefringence) and geometries (e.g. cylindric bulk glass samples, glass fibres, glass rods). In double-phase glass Systems the following anisotropic properties will be treated: the form birefringence and the distribution birefringence of decomposed glasses, the orientation of melts with suspended anisometric crystals and birefringence effects of chemically leached microporous glasses. Finally, a new phenomenon will be reported where the frozen-in birefringence of a glass shows an other sign after deformation above Tg than the stress optical constant of the same glass at room temperature before this treatment above Tg.
stress generation modulus as a counterpart of the stress relaxation modulus
In order to measure the time dependence of the stress relaxation modulus, E, a stress-strain deformation has to precede which induces a stress within the viscoelastic sample from which the sample relaxes. The generation of stress is characterized by a strain rate-dependent and relaxation rate-dependent portion which exhibits a maximum value, E_max, which is called "stress generation modulus". E_max was called the "maximum stress relaxation modulus" in earlier papers. Meanwhile, however, it turned out that a better verbal distinction should be made in future by the new term "stress generation modulus" because E_max is about one order of magnitude larger than E.
Isothermal and isochomal workability of glass melts - Influence of melting history: Minor composition changes of redox State and hydroxyl content - Αstudy of the sensitivity of the cylinder compression method
The influence of redox State and hydroxyl concentration on the pure non-Newtonian flow behaviour, on the gross non-Newtonian viscosity, on the stress generation modulus, brittleness, high-temperature tensile strength and on the critical deformation rate of an iron oxide-containing laboratory glass melt with two different melting histories, but with the same main chemical composition, is investigated by means of the cylinder compression method. The comparison of these properties between the oxidized and the reduced glass melt is made not only at equal temperatures but also at equal viscosities in order to distinguish between isothermal and isochomal workability and to examine how sensitive the applied method is. The result is that the reduced melt with a somewhat larger Fe²⁺/F_total ratio and with a larger hydroxyl content has a smaller stiffness and brittleness and therefore, a somewhat better isothermal workability than the oxidized melt. This is valid only for the comparison at equal temperatures. When the comparison is made at equal viscosities, however, the workability - or better the isochomal workability - of the two melts is the same. The reason is that a shift of the Newtonian viscosity is produced by the redox shift and hydroxyl content of the reduced melt to lower values which diminishes with increasing temperature. It is possible to construct master curves with respect to the measured properdes at four temperatures, by which a transfer to the low viscosity range is possible, i.e., one can get the isothermal workability of the glass melts over the whole working range. The measured values of the above-mentioned properties are represented by fitting with recently developed relations which give rise to interesting practical and theoretical conclusions about industrial production optimization and about some structural aspects of stressed melts.
Anisotropic optical properties and flow behaviour of mechanically deformed single-phase glass melts
Starting from the stress-optical coefficient around and above Tg, the following effects are regarded in order to give a comprehensive picture of the structural response of various glass melts under flow conditions at various temperatures: anisotropy o f glass fibres, the flow birefringence and Maxwell constant of the melt directly and/or indirectly via frozen-in anisotropics by cooling the melt thermally stress-free under mechanical load. Some of the applied various rheological methods allow to study the Newtonian and non-Newtonian viscosity additionally to the birefringence. Four very different glass melts are investigated under these aspects: a potassium-calciumsilicate glass, a float glass, an alkali metasilicate glass and an alkali metaphosphate glass. The results show that there are significant differences in the specific birefringence and in the deviation from Newtonian flow behaviour depending on the special flow units of the glass types. The structure of these anisotropic glasses and melts extends from frozen-in deformations of the network to orientations of chain-like flow units depending on chemical composition, temperature, mechanical stress and deformation rate. Particularly, a close connection between the onset of the non-Newtonian flow behaviour and the alteration o f the specific birefringence was found at certain critical stresses.
Elastic and inelastic properties of soda lime Silicate glass melts
The influence of CaO on the elastic and inelastic behaviour of soda lime Silicate glass melts of the series (26 - x) Na₂O · x CaO * 74 SiO (composition in mol% with x = 0 to 16) is investigated. Longitudinal and transversal ultrasonic waves in the MHz frequency ränge are transmitted through the glass melt. Their velocities and damping behaviour are measured as functions of temperature. The elastic moduli, internal friction and relaxation times are calculated and their dependence on temperature and viscosity is shown. These properties describe the transition from an elastic to a viscoelastic and fmally to a pure viscous behaviour of the invesdgated glass melts by a large dispersion ränge. Enhanced values of the moduli and activation energies are determined with an increase of CaO content. Thus, the structure of the melt becomes strenger and stiffer i.e. the mean bonding strength and the linkage of the dynamic network of the Silicate melt is improved. The relaxation behaviour can be described by a Maxwell based model with a distribution function of relaxation times.
On the different descriptions of the non-Newtonian viscosity (shear-thinning effect) of glass melts with respect to heat dissipation
The range of non-Newtonian viscosity is usually connected with high strain rates or/and stresses. Therefore, the effect of heat dissipation (or viscous heating) cannot be neglected. In order to regard this effect various correlations were given in former papers, which will be analyzed and discussed in the present paper. It turns out that through the exact thermal elimination of viscous headng one can easily obtain the quantity of the pure, realistic and exclusively structurally determined non-Newtonian viscosity, ηnN, which may be normalized by the Newtonian viscosity, η0, to yield the form, ηnΝ/η0- At small amounts of strain and stress other expressions, such as η/η0,Tmax and η/η0,Tnet, may describe the non-Newtonian flow behaviour approximately where the thermal elimination is not made for the as-measured non-Newtonian viscosity, η, but for the Newtonian values, ηο. (η0,Tmax Stands for the adiabatically corrected Newtonian viscosity, due to the maximum temperature of viscous heating by the total deformation work; η0,Tnet Stands for t h e nonadiabadcally corrected Newtonian viscosity due to the gross temperature of viscous heating, regarding also the heat flow out of t he glass sample.) In contrast to these more or less pure non-Newtonian normalized viscosities the so-called normalized non-Newtonian gross viscisity, η/η0, is that viscosity which involves the viscosity decrease due to the pure non-Newtonian flow, determined by structural orientation, as well as the viscosity decrease due to the viscous heating. The various relationschips are analyzed and discussed with the help of recently developed rheological equations.
Determination of the rheological properties of high-viscous glass melts by the cylinder compression method
A detailed description of the cylinder compression method and its application on the viscoelastic behaviour of glass melts is given with the help of closed solutions and equations in contrast to algorithmic methods, like e.g. the finite element method. Special attention is paid to the system deformation and system deformation rate of the testing equipment and to the dissipation of mechanical energy within the specimen and the heat flow from the specimen. The limits of this treatment are discussed with respect to the applicability of the theoretical basis (Gent and Nadai equation) and with respect to the experimental determination of the rheological properties of glass melts. On this basis the pure non-Newtonian viscosity, ηnN, can be determined. If very small differences have to be ascertained in the rheological behaviour of glass melts due to small differences in composition or in melting history (e.g. redox condition or bad/good workability), the same conditions concerning the mechanical and thermal equipment and even the same geometry of the glass specimens have to be strictly maintained. Comparison between different glass melts should be made rather on the basis of equal (Newtonian) equilibrium viscosity, η₀, (isochomal conditions) and not on equal temperature. Owing to large thermal effects, the slope of the viscosity-temperature curve at η₀ plays a certain role, particularly for the forming process.
structure-sensitive investigations on glass fibers from the system SiO₂-Al₂O₃-GaO
Glass fibers of the system SiO₂-Al₂O₃-CaO were prepared with respect to defined drawing conditions and investigated with structure-sensitive methods (birefringence, radial and axial alterations by thermal treatment at Tg). These glass fibers, which lie in a compositional sense roughly between the disilicate and silica glasses concerning the ratio network modifiers to network formers, exhibit similar optical anisotropies. On the other hand, they show remarkably lower axial and radial alterations which are exclusively contracdons on annealing for all applied drawing conditions in contrast to the silica or the alkali disilicate glass fibers. Obviously, the filling of free volume hollows with and the reinforcement of them by the Ca²⁺ ions and the smaller polarizability of the latter as compared to alkali ions are responsible for the relatively low structural anisotropy. An increase of the optical anisotropy with increasing CaO concentration is observed at comparable viscosities. This is a consequence of the increasing incorporation of the network modifier oxide which produces a weaker network strength and a larger polarizability.
Influence of non-homologous substitutions of chemical components on rheological properties and on isochomal workability of Silicate glass melts
The glass melts of a non-homologous series were investigated with respect to flow behaviour and stress generadon behaviour as well as to workability by means of the cylinder compression method. The results show that the competition between the gross viscosity effect and the bonding strength of the dynamic glass melt structure extremely deterrnines the high-temperature tensile strength, σ_ts, the critical deformation rate hc, and by that the isochomal workability. The larger hc values are not always connected to a larger non-Newtonian flow effect or to a larger gross viscosity effect as it is usually the case for homologous series. However, the rule for homologous series that smaller Emax moduli, i.e. smaller stiffness and brittleness of a glass melt, are coupled to a better isochomal workability is also vahd for non-homologous series. The special connections between σ_ts, hc and deformation, Δh/h0, are analyzed.