1.

1.1.

Viskositt als Materialeigenschaft

Viskositt von Schmelzen in Abhngigkeit von der Temperatur

Die Viskositts-Temperatur-Funktion (T) ist eine Schlsseleigenschaft von flssigen Systemen. Sie spielt bei der Beschreibung von Gesteinsschmelzen, Schlacken, organischen Polymerschmelzen, anorganischen Glasschmelzen sowie flssigen Metallen und Salzen eine herausragende Rolle. Die Einheit der sogenannten dynamischen Viskositt (Symbol ) ist die Pascalsekunde (1 Pas = 1 Nsm-2 = 1 kgm-1s-1). In der Glastechnologie wird meist die Einheit 1 dPas = 0.1 Pas verwandt; sie ist mit der Einheit Poise identisch: 1 dPas = 1 Poise = 1 gcm-1s-1. Dividiert man die dynamische Viskositt durch die Dichte der Schmelze, so erhlt man die sogenannte kinematische Viskositt (T) = (T) / (T); sie hat mit cm2s-1 die Einheit eines Transportkoeffizienten und spielt in der Fluiddynamik eine wichtige Rolle. Viskositten von Flssigkeiten knnen einen Wertebereich von ca. 16 Zehnerpotenzen berstreichen. Eine theoretische Untergrenze ist durch die Beziehung

0 =

h 2 3

gegeben; h = Plancksche Konstante, = mittlerer Atomabstand; 0 10-4 dPas. Die Viskosittswerte einiger Metall- und Salzschmelzen sowie des Wassers sind im folgenden Diagramm dargestellt (man trgt die Viskositt blicherweise logarithmisch auf). Man erkennt, da auch bei diesen sehr dnnflssigen Systemen die Viskositt mit fallender Temperatur stark ansteigt.
Viskositten von Metall- und Salzschmelzen; Wasser zum Vergleich
T in C fr Wasser -1.0 Fe Au log , in dPas -2.0 Na Li -1.5 Pb 0 50 Na2CO3 100

-1.5

Ag

Cu

-2.5

Sn Al -2.0

NaCl

= Schmelzpunkt -2.0 -3.0

H2O 2000 0 500 T in C 1000 500 T in C 1000

1000

1500 T in C

Daten nach: Pfeiffer (Metalle), Janz (Salze), Lange (Wasser)

Unterhalb des Schmelzpunktes (bei vielkomponentigen Systemen: unterhalb der Liquidustemperatur) kristallisiert das System. Man kann den Vorgang der Kristallisation jedoch durch hinreichend schnelles Abkhlen berlisten. Dann erhlt man anstelle eines kristallinen Festkrpers ein Glas. Bei sehr dnnflssigen Systemen sind Abkhlgeschwindigkeiten in der Grenordnung von 106 K/s erforderlich. Bei Systemen, die bereits oberhalb der Liquidustemperatur hohe Viskosittswerte erreichen, gelingt dies aber schon bei langsamen, technisch leicht realisierbaren Abkhlgeschwindigkeiten, etwa 1 K/min. Der Begriff Glas bezeichnet also nicht eine bestimmte Werkstoffklasse, sondern ganz unabhngig von der chemischen Zusammensetzung den kinetisch eingefrorenen Nichtgleichgewichtszustand einer hinreichend rasch unterkhlten Flssigkeit. 1.2. Viskositt im Fokus vieler werkstoffwissenschaftlicher Felder (englisch)

Historically, different types of empirical or science-based equations have been developed by geochemists, metallurgists, as well as by cement and glass technologists with surprisingly little interdisciplinary exchange. This is quite in contrast to the fact that the mentioned disciplines deal with chemical systems with substantial compositional overlap. (see figure 1). In glass industry, there are many products beyond the commercial float and container glass branch having compositions similar to metallurgical slags or metamorphous rocks (e.g. insulation fibres). Predicting (T) as a function of chemical composition for multicomponent systems has always been a major challenge. Since viscosity measurements are cumbersome and time consuming, several different models have been developed just for the purpose of a reliable assessment of the compositional dependence of (T). Some of these models were explicitly developed to be used for metallurgical slags [1-3; 6-7]. However, neighboring disciplines also offer such models covering similar compositional ranges [4-5; 7-8]

Compositional ranges of silicate systems commonly used in different disciplines of science and technology

Literatur zu empirischen Berechnungssystemen der Viskositt aus der chemischen Zusammensetzung [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] K.C. Mills: Viscosities of molten slags. In: Slag Atlas. M. Allibert et al. Eds. Verlag Stahleisen, Dsseldorf 1995. P.V. Riboud, Y. Roux, D. Lucas, H. Gaye: Fachber. Httenprax. Metallweiterverarb. 19 (1981), 859. G. Urbain, F. Cambier, M. Deletter, M.R. Anseau: Estimation models for molten slag and alloy viscosities. Trans. Brit. Ceram. Soc. 80 (1981), 139. L. Zagar, W. Schaefer-Rolffs: Untersuchungen von magmatischen Gesteinen im Hinblick auf ihre Verwendbarkeit fr die Herstellung von Gesteinsfasern. Sprechsaal 114 (1981), 498-511. T. Lakatos, L.G. Johansson, B. Simmingskld: Viscosity and liquidus temperature relations in the mineral wool part of the system SiO2-Al2O3-CaO-MgO-Alkalies-FeO-Fe2O3. Glastek. Tidskr. 36 (1981), 51-55. D. Mudersbach, J. Geiseler, M. Khn: Optimierung mathematischer Modelle zur Viskosittsberechnung von Schlacken. FEhS Report, Forschungsgem. Eisenhttenschlacken e.V. Duisburg 1999. M. Nakamoto, J. Lee, T. Tanaka: A model for estimation of voscosity of molten silicate slag. ISIJ Int. 45 (2005), 651-656. D. Giordano, D.B. Dingwell: Non-Arrhenian multicomponent melt viscosity: a model. Earth Planet. Sci. Letters 221 (2004), 449. SCIGLASS 6.5 Glass properties information system. ESM Software 1999-2007. W.L. McCauley, D. Apelian: Temperature dependence of the viscosity of liquids. II. Int. Symp. Metallurg. Slags and Fluxes. H.A. Fine, D.R. Gaskell, Eds. The Metallurg. Soc. of AIME 1984.

1.3.

Bedeutung der Viskositt in der Glastechnologie

Die klassische Glastechnologie beschftigt sich mit Systemen, die sich durch technisch leicht beherrschbare Abkhlgeschwindigkeiten in den Glaszustand berfhren lassen. Zu diesen Systemen gehren bekannte kommerzielle Produkte wie Flachglas, Behlterglas (silicatische Glser, die vom Grundsystem Na2O-CaO-SiO2 abgeleitet sind), aber auch optische Glser, Glser fr den Anlagen- und Apparatebau, magmatische Gesteinsschmelzen und viele metallurgische Schlacken. Bei der Formgebung und Verarbeitung technischer Glser spielt die Kenntnis der Viskositts-Temperatur-Funktion eine herausragende Rolle. In der folgenden Tabelle sind charakteristische Viskositts-Fixpunkte in der Reihenfolge steigender Viskositt, d.h., fallender Temperatur zusammengestellt. Bei jedem dieser Fixpunkte wird eine log ( in dPas) 1.5 3.0 Fixpunkt / Verhalten / technische Anwendung

Schmelzbereich Floatglasschmelze bei 1450 C; Zerfaserungspunkt Tropfentemperatur; bergabe zur Formgebung Arbeitsbereich 4.0 Arbeitspunkt; beginnendes Formgedchtnis 4.22 sogenannter Einsinkpunkt (siehe 2.1.) 6.0 Ende des maschinellen Arbeitsbereiches 7.6 Littleton-Punkt; makroskopische Formstabilitt Khlbereich 11.3 dilatometrisch Erweichungspunkt; (x) T(x) *) 13.0 oberer Khlpunkt; 1 min 13.3 dilatometrischer Glasbergang 14.5 unterer Khlpunkt; 30 min *) Feld der mechanischen Spannungen koppelt ans Temperaturfeld an

charakteristische Vernderung der Verhaltens beobachtet. Man berstreicht dabei den gesamten Bereich von vorwiegend fluidem Verhalten (bis log = 3.0) ber einen weiten Bereich viskoelastischen Verhaltens (log = 4.0 ... 14.5) bis zu sprdelastischem Verhalten (log > 14.5); bezeichnet dabei eine Relaxationszeit. Die Glastechnologen kommunizieren Viskositten stets anhand der charakteristischen Temperaturen. Man sagt also nicht: Der Viskosittswert der Schmelze bei 1200 C betrgt 103 dPas, sondern: Die Schmelze hat T(3.0) = 1200 C. Das folgende Bild zeigt die Viskositts-Temperatur-Funktion fr ein Floatglas. Einige der oben genannten Fixpunkte sind eingezeichnet. Insbesondere ist der Arbeitsbereich hervorgehoben. Die ihm zugeordnete Temperaturdifferenz heit die Lnge eines Glases.
Glasbergang: log (Tg) 13.0

16 14 12 log , in dPas 10 8 6 4 2 0 400 600 Arbeitsbereich

VFT-Gleichung: log = A + B/(T-T0), in dPas Fixpunkte T(13.0), T(7.6), T(4.22) Fixpunkte T(2.0), T(4.0), T(6.0)

Floatglas-Schmelze "Lnge" 800 1000 T in C 1200 1400 1600

Im obigen Diagramm ist auch die in der Glastechnologie gebruchlichste Formel zur Darstellung der Temperaturabhngigkeit der Viskositt dargestellt, die VogelFulcher-Tammann- oder VFT-Gleichung. Durch drei empirische Konstanten A, B, T0 lt sich der gesamte Verlauf einer Viskosittskurve mit hinreichender Genauigkeit darstellen. Man bentigt also mindestens drei unabhngige Viskosittsmessungen, um A, B, T0 zu bestimmen. Wir fhren die Abkrzung log = L ein. Dann liefern drei Viskosittsmessungen drei Wertepaare (L1, T1), (L2, T2), (L3, T3). Daraus gewinnt man die Konstanten A, B, T0 wie folgt:

T0 = T1 +

L3 L2 ; L3 L1 L2 L1 T3 T1 T2 T1

A=

L2 (T2 T0 ) L1 (T1 T0 ) ; T2 T1

B = ( L1 A) (T1 T0 ); L(T ) = log (T ) = A + B , nur bis log < 17 gltig ; in dPa s. T T0

1.4.

Weitere Theorien zur Temperaturabhngigkeit der Viskositt

Im folgenden wird weiter die Abkrzung log = L verwandt. Dann ist Lg = log (Tg) die Viskositt bei der Glasbergangstemperatur Tg (typischerweise Lg 13); L0 bezeichnet den Hochtemperatur-Grenzwert der Viskositt fr 1/T 0. Einige der wichtigsten Gleichungen, mit denen die Temperaturabhngigkeit der Viskositt beschrieben werden kann, sind unten zusammengefasst:

(1) (2) (3) (4) (5)

L = L0 + b/T L = L0 + L = Lg + B T T0 T Tg C1 ln10 C2 + T Tg

L = L0 + Lg L0 Tg L = L0 + T

/T ) 1 a Tgln(T /T)
0 g

Gleichung (1) ist die Arrhenius-Gleichung. Sie beschreibt das viskose Flieen als eine thermisch aktivierten Prozess. Dieses Konzept eignet sich nur nherungsweise zur Beschreibung sehr dnnflssiger, nicht unterkhlter Systeme. Gleichung (2) ist die bereits oben vorgestellte VFT-Gleichung. Obwohl die Entwicklung dieser Gleichung ausschlielich empirischer Natur war, stimmt sie hervorragend berein mit der Theorie des freien Volumens des viskosen Flieens. Gleichung (3) ist die Williams-Landel-Ferry (WLF) Gleichung mit den Konstanten C1 und C2; sie wurde systematisch aus der Theorie des freien Volumens entwickelt und wird zur Beschreibung organischer Polymere benutzt. Man kann zeigen, da die Gleichungen (2) und (3) vollkommen quivalent sind. Es gilt:

C1 = 2.303 B / Tg T0 = 2.303 Lg A ; C2 = Tg T0 ; B = C1 C2 / 2.303; T0 = Tg C2 .

Im Grunde ist dies eine Kuriositt der wissenschaftlichen Entwicklung in zwei nur wenig miteinander kommunizierenden Disziplinen. Hier wurde das Rad quasi zweimal erfunden. Gleichung (4) ist die so genannte Adam-Gibbs-Gleichung, welche aus dem Konzept der Konfigurations-Entropie einer Flssigkeit entwickelt wurde. Der Parameter a0 = cP/Svit ist das Verhltnis des im Glasbergang beobachteten Wrmekapazittssprunges cP und der beim Glasbergang eingefrorenen Konfigurationsentropie Svit. Die Adam-Gibbs Gleichung wird in der Technologie kaum verwandt. Sie bietet aber den groen Vorteil, die Viskositt auf thermodynamische

Daten zurckzufhren. Gleichung (5) ist die so genannte Avramov-Gleichung. Sie wurde aus der Kohlrauschschen Relaxationsfunktion entwickelt. Aus der Sichtweise des Praktikers erlauben alle oben gezeigten Gleichungen eine Inter- und Extrapolation von Viskosittsmewerten zu beliebigen Temperaturen.
Literatur zur Theorie der Viskositt: H. Vogel: Das Temperaturabhngigkeitsgesetz der Viskositt von Flssigkeiten. Physik. Zeitschrift 22 (1921), 645-646. G. Fulcher: Analysis of recent measurements of the viscosity of glasses. J. Am. Ceram. Soc. 8 (1915), 339-355. G. Tammann, W. Hesse: Die Abhngigkeit der Viskositt von der Temperatur bei unterkhlten Flssigkeiten. Z. Anorg. Chem. 156 (1926), 245-257. M.L. Williams, R.F. Landel, J.D. Ferry: The temperature dependence of relaxation mechanisms in amorphous polymers and other glass-forming liquids. J. Am. Chem Soc. 77 (1955), 3701. G. Adam, J. H. Gibbs: On the temperature dependence of cooperative relaxation properties in glassforming liquids. J Chem. Phys. 43 (1965), 139-146. C.A. Angell, K.L Ngai, G.B. McKEnna, P.F. McMillan, S.W. Martin: Relaxation in glassforming liquids and amorphous solids. J. Appl. Phys. 88 (2000), 3113-3157.

1.5.

Linearisierung der Viskosittsfunktion

Alle oben aufgefhrten Funktionen erlauben es, die Viskositts-Temperaturfunktion in einen linearen Zusammenhang zu berfhren. Das ist bei einer Versuchsauswertung von groem Vorteil, da sich die Gte eines linearen Zusammenhanges besonders einfach beurteilen und quantifizieren lt. Im Rahmen dieses Praktikums wird das nur fr die VFT-Gleichung demonstriert. Man formt wie folgt um

log = A +

B / Tg B = A+ T T0 T / Tg T0 / Tg

T0 1 Tg T0 1 Tg

Tg T Tg T

T0 1 Tg B = A+ T Tg T0 1 0 Tg Y = log , X =

Tg T (1 + a ) x = 0 + 1 Tg 1+ a x T

(1 + a ) x 1+ a x T0 = a Tg ; B = 1 (Tg T0 ); A = 0
wobei x fr das Verhltnis Tg / T und a fr das Verhltnis T0 / Tg steht. Man bestimmt nun Tg, trgt Y = log gegen X auf und variiert iterativ a so lange, bis ein linearer Zusammenhang entsteht. Auf diese Weise lt sich eine lineare Regressionsanalyse beliebig vieler Viskosittsmewerte durchfhren. Auch dieses Auswerteverfahren wird an den im Praktikum gewonnenen Mewerten erprobt. Man bentigt dazu lediglich ein EXCEL-Worksheet.

1.6

Experimentelle Verifikation (englisch)

The equations presented in the previous paragraphs are tested against viscosity data obtained for the standard float glass DGG-1 of the German Society of Glass Technology as measured by the Physikalisch-Technische Bundesanstalt, Braunschweig, Germany. The chemical composition reads SiO2 DGG 71.72 TiO2 Al2O3 0.14 1.23 B2O3 Fe2O3 FeO 0.19 MgO 4.10 CaO Na2O 6.73 14.95 K2O 0.38 F2 SO3 0.44

The left-hand graph in the following figure shows Angells plot of (T); the deviation from the straight line is a measure of the degree of depolymerization of the melt. The high-T slope for Tg/T 0 reflects the high-T Arrhenius behavior. The slope for Tg/T 1 is proportional to the quantity (1 - cP/Svit). The right-hand graph shows the straight lines as obtained from eqs. (2), (4), and (5). The equations applied represent the viscosity-temperature relation almost equally well; they differ significantly, however, in the predicted L values. From a scientific point of view, viscosity measurements at extremely high temperatures could thus be employed to decide which of the models comes closest to the physical reality of a melt.

14 12 10
log , in dPas Angells plot linearized plots

8 6 4 2 0 -2 -4 0.0 0.2 0.4 0.6 Tg/T 0.8 1.0 0.0

slope d a c b

0.2

0.4 0.6 (Tg/T)

0.8

1.0

Viscosity data of glass DGG-1, presented as a function of temper ture; left side: Angells plot; right side: numerical evaluation by linearized representations of the viscosity; a: Adam-Gibbs, eq. (4); b: modified Adam-Gibbs, no eq. given here; c: VFT/WLF, eq. (2); d: Avramov, eq. (5); data points are displayed for the case of b only

The linearization of viscosity data offers yet another advantage. This can be seen from the data for glassy anorthite and for E fibre glass (see the following figure): In the temperature range right below the liquidus temperature, viscosity measurements cannot be performed because of the rapid crystallization of these melts. Experimental data are accessible only above liquidus and in the vicinity of the glass transition (where the rearrangement processes towards an ordered structure slow down and finally freeze in). A linearized viscosity plot allows one to look behind the crystallization curtain and to perform a reliable interpolation of viscosity data to a range inaccessible to direct measurements. In the following graph, the quantity SC denotes the so-called configurational entropy. It is given (compare eq. 4) by SC = Svit (1 cP ln(Tg/T)) .
16 14 12
log , in dPas

E fibre glass

low glass

10 8 6 4 2 0 -2 0

glassy anorthite TV panel glass model glass FAL7 float glass DGG-1 model glass FAL9

10

12

14

16

18

Tg/(TSC) in (gK)/J

Different industrial and model melts, and liquid anorthite

1.7.

Angells Analyse

Trgt man die Viskositt als log gegen Tg / T auf, so erhlt man den sogenannten Angell-Plot. Aus ihm lassen sich viele interessante Details eines glasbildenden Systems ablesen, etwa der Polymerisationsgrad (Vernetzungsgrad) der Struktur oder das bereits oben erwhnte Verhltnis a0 = cP/Svit. Die Details sind im nchsten Bild gezeigt. Die Differenz Lg L0 kann durch den Wert 13 (-4) = 17 angenhert werden.

16 14 12
log , in dPas

Messpunkte: Schlackenschmelze CaOAl2O32SiO2

lze me h c S rte e i s eri ym l o gp ndi t olls ll v a f nz Gre

10 8 6 4 2 0 -2 -4 0.0

c P Steigung = Lg L0 1 vit S

0.2

0.4 Tg/T

0.6

0.8

1.0

Zusammenfassend ist zu sagen: Viskosittsmessungen sind aufwendig. Sie liefern aber sehr viel Information ber die Rheologie, Struktur und Thermodynamik eines fluiden Systems. Man sollte daher nach der Mhe einer Messung den Aufwand umfangreicher Auswertung nicht scheuen.

2.
2.1.

Die Gruppe Viskositt Dichte Oberflchenspannung

Die Rolle der Viskositt beim Impuls-, Wrme- und Stoffbergang (englisch)

TRANSPORT PROCESSES As a result of experience, transport processes can often be described as direct proportionalities between a driven flow and a driving force, with a transport coefficient as proportionality factor. The following table gives a few examples: driven flow heat flow electric current density diffusion flow volume flow through tube with radius r momentum flow = transport coefficient = thermal conductivity = electric conductivity = diffusion coefficient D = Hagen-Poisseulle coefficient r4/(8) = viscosity driving force temperature gradient voltage gradient concentration gradient pressure gradient velocity profile

So, viscosity is basically a transport coefficient related to a momentum flow. The expression momentum flow may not be as easily understood as the other types of flow. Since a momentum has the dimension kgm/s or Ns, and a flow always refers to a quantity per unit time and cross section area, a momentum flow has the

dimension N/m2. This is the dimension of a pressure. Actually, some textbooks use the name friction pressure rather than momentum flow. Both expression will help to understand the matter more deeply. Let us consider two neighbouring sheets in a fluid flowing into x direction at infinitesimally different velocities v and v + dv. At the contact boundary plane between these sheets, friction forces occur which may, when referred to the unit area of the boundary plane, be regarded as a friction pressure. This pressure tends to accelerate the slower parts, and slow down the faster parts of the flowing volume. When we think in terms of single particles (of mass m), we may observe a particle with velocity v + dv (belonging to the upper sheet) bump a slower particle with velocity v (belonging to the upper sheet) thus transferring the momentum mdv from the upper to the upper sheet. During the discussion, we made use of the term fluid. This is not a synonym to liquid. We hat to distinguish carefully between the thermodynamic categories for different phases and the mechanical categories. Thermodynamics deals with the categories gas, liquid, and solid; the latter two are often summarized by the term condensed phase *) (indicating that such a phase is restricted to a finite volume even of low pressure whereas a gas may expand without limits). For reason of clarity, we should use the expressions gaseous, liquid, and solid phase (or state). So, the reference to thermodynamics is unambiguous. In contrast to this, mechanics deal with the categories fluid and solid. For clarity, we should use the expressions fluid and solid medium, the more so since the term solid is used in this context, too.**) Fluids may be characterized by a zero shear modulus, which is equivalent to the absence of form stability. They may be either compressible or incompressible, i.e., their density may, or may not be function of the environmental pressure. Let us now contrast the thermodynamic and mechanic categories. A gas is a (compressible) fluid under all circumstances, even in the supercritical state *). Liquids usually are fluids (with a strong tendency towards incompressibility). When exposed to a sufficiently fast deformation velocity, some liquids may start to show socalled visco-elastic behaviour, i.e., they exhibit elastic form stability (non-zero shear modulus) or may even break. Solid phases are solid media as long as single pieces are considered. When accumulated to heaps of small particles (small in comparison to the dimensions of the heap) solids may start to behave like fluids. This requires a certain momentum. The resulting flow is the so-called flow of bulk solids or fluidized particles. The theory of bulk solid flow is a key to handle raw materials like sand or soda ash, to design protection measures against land slides, to understand the behavior of snow avalanches and so on. The following table briefly summarizes the relation between the thermodynamic and mechanic categories. fluid medium gaseous phase liquid phase solid phase only behavior possible usual behavior fluidized particles solid medium non-existent visco-elasticity usual behavior of single body

*) **)

the interested reader may note that above the so-called critical point of a system, gas and liquid become an indiscernible supercritical phase. Using the word rigid instead is of little help since it suggests absence of deformability; solid media, however, show elastic or plastic deformability.

CONSIDERATION OF QUANTITIES AND UNITS Let us consider a flow J = v, with = density, v = velocity, driven by a pressure difference P. Let us then take two different points of view by asking two different questions: 1. What is the resulting flow velocity v when P is known? 2. What is the resulting flow J when P is known? The first question is answered by a relation of the type

P = fgeov / L
Where fgeo is a dimensionless number depending on the geometry of the system alone; L is a characteristic length of the system (e.g., the radius of a tube). The coefficient is a material property, the so-called dynamic viscosity. It is a measure for the friction forces which the fluid sets against th applied pressure. The dynamic viscosity is given in units of 1dPas 0 0.1 kg/(ms) = 1 g/(cms) = 1 Poise. In order to answer question number 2, let us use the identity J = v and rearrange the above equation to

P = fgeo(/)J / L .
Now, the meaningful material property is /. This ratio

= /
is called cinematic viscosity. It is a measure for the ratio of friction and inertia forces in a fluid telling us how fast a stationary flow will slow down after the driving pressure difference is switched off. The cinematic viscosity is given in units of cm2/s or m2/s. The following table presents some examples for and of different fluids to provide an idea of their order of magnitude. For comparison, some typical values for molecular diffusion coefficients in the same fluids are given, too. It may be a surprise that the cinematic viscosity of water is much lower than the same quantity of a gas. Of course, water sets much more resistance towards an applied force than a gas does (which can be experienced by an improper jump into water), but is has a significantly higher ability than a gas to maintain a state of motion. Note that the viscosity of a liquid decreases with increasing temperature while, for a gas, the viscosity increases with increasing temperature. For air, and approximately for hot offgases too, the cinematic viscosity can be calculated by the polynominal

= / in cm2/s = - 0.1049 + 0.6799T + 0.6145T2, T in 1000 K.

fluid water at 20 C 90 C glass melt2) at 800 C 1000 C 1200 C 1400 C 1600 C air at 20 C 500 C 1000 C 1500 C
1) 2)

in dPas
1.00210-2 0.79810-2

in g/cm3
0.9982 0.9653

in cm2/s
1.00410-2 0.82610-2

D in cm2/s 1.3510-5 1) 2.1010-5

1.810+6 1.510+4 9.310+2 1.510+2 4.210+1 1.79810-4 3.55010-4 4.78810-4 5.46110-4

2.453) 2.43 2.41 2.39 2.37 1.18810-3 0.45010-3 0.27310-3 0.19710-3

7.410+5 6.210+3 3.910+2 6.310+1 1.810+1 0.153 0.789 1.751 2.772

8.610-10 4) 1.210-7 2.310-6 1.610-5 6.510-5 0.17 5) 0.90 2.1 3.7

D for NaCl at c = 0.01 mol/l viscosity values for DGG standard glasss 3) volume expansion coefficient above Tg approx. 110-4 K-1 4) D for NaF, approximation ; NaF reaches rather high values of D; 5) D for NaOH Diffusion coefficients for condensed phases (i.e., in liquids and in solids) cannot be calculated so far. As a general guideline, D is proportional to the reciprocal viscosity: D 1/. The diffusion coefficient Dk of a gaseous component k in a carrier gas (index 0) can be calculated from the molar masses Mk, Mo and the molecular diameters dk, do at a sufficient accuracy:
Dk = 2 T 1.7 (1 / M k + 1 / M 0 ) (d k + d 0 ) 2

Research engineers found out that a broad variety of different flow problems all follow the same pattern. They developed a set of standard solutions for flow problems in different geometry, which can now be applied to very different systems (different with respect to the size and to the matter of the fluid) with a similar geometry. From this pint of view, the convective flow of a glass melt in a 6 m x 10 m x 1 m basin, and of water in a 1 cm x 1 cm x 6 cm cuvette, respectively, can be described by the very same functional. The properties of the respective fluid and the dimensions of the respective system are summarized in dimensionless characteristic numbers. Reynolds number Re makes allowance for the ratio of the inertial to the friction forces in the fluid: Re = vL/ = vL/

Where v is the (externally enforced) velocity of the flow, and L is a characteristic length of the system (e.g., the radius of a tube). Re is used to calculate forced flow problems. Grashoffs number Gr makes allowance for a flow internally driven by buoyancy forces due to density differences in the system: Gr = (gL3/2)(/) Where g is the specific gravity. When the density differences are due to a temperature gradient in the system, the expression / may be replaced by 3T T, with T = linear expansion coefficient. Gr is used to calculate free convection problems. Among the many other characteristic numbers, finally, Schmidts number Sc and Prandelts number Pr shall be presented. Sc = /D , Pr = /T , where T is the termal diffusivity

T = /(cp) , T in cm2/s, = density in g/cm3, cP = heat capacity in J/(gK), and ? = heat conductivity in W/(mK). Sc describes the ratio between convective and diffusive mass transfer, while Pr describes the ratio between convective and diffusive heat transfer. IThe following table shows the numerical values of Re, Gr, and Sc for the fluids already referred to in the previous table. As boundary conditions, v = 1 m/s, L = 1 m, and T = 50 K are assumed. The basic data for this calculation are found in the table on the following page.
Pr = /a [1] water 20 C glass melt 1200 C 1400 C liquid Fe 1600 C air 20 C 1500 C 7 4 E4 4 E3 0.66 0.70 0.78 Sc = /D [1] 750 3 E9 6 E7 176 0.90 0.75 Le = a/D [1] 107 7.5 E4 1.5 E4 265 1.29 0.96 Re [1] 1 E4 0.3 1.7 12E4 6.5 E2 3.6 E3 Gr [1] 1 E11 8.4 E1 3.4 E3 7.5E11 4.0 E8 1.3 E6

Finally, it should be mentioned that there is an intrinsic relationship between the molecular motion in a fluid and its (macroscopic) viscosity. This must not be mixed up with Schmidts number Sc which only presents the ratio of these quantities, not their inner relation. The equation by Stokes and Einstein D = (kT)/(6r)

Relates the diffusion coefficient D in a system to its viscosity; k = Boltzmanns constant = 1.3810-23 J/K; r = radius of the diffusing molecule. The assumption of a rigid sphere moving in a continuum is very crude. Nevertheless, for metal melts, the equation holds with a surprisingly fair accuracy. For glass melts with their network or cluster structure, it is difficult to assess an appropriate value for r. Thus, the above relation cannot be applied quantitatively. Yet, the dependence D 1/ holds. This intrinsic interdependence between diffusion coefficient and viscosity has an important consequence: The crystal growth velocity in a glass melt depends on its viscosity.

[g/cm] [dPas] water 20 C glass melt 1200 C 1400 C liquid Fe 1600 C air 20 C 1500 C 1.0 2.4 2.3 7.3 0.01 950 150

a= = /(cP) / [cm/s] [m2/ 0.01 1.5 E-

D [m/ 2 E5 E-7 2 E-6

Pr = /a [1] 7 4 E4 4 E3 0.66 0.70 0.78

Sc = /D [1] 750 3 E9 6 E7 176 0.90 0.75

Le = a/D [1] 107 7.5 E4 1.5 E4 265 1.29 0.96

380 9.0 E-3 60 1.5 E-2

0.063 0.0086 0.15 2.77

1.3E-2 4.9E-5 0.22 3.55 0.17 3.70

1.2 E-3 1.8 E-4 0.2 E-3 5.5 E-4

Finally, it should be mentioned that there is an intrinsic relationship between the molecular motion in a fluid and its (macroscopic) viscosity. This must not be mixed up with Schmidts number Sc which only presents the ratio of these quantities, not their inner relation. The equation by Stokes and Einstein D = (kT)/(6r) Relates the diffusion coefficient D in a system to its viscosity; k = Boltzmanns constant = 1.3810-23 J/K; r = radius of the diffusing molecule. The assumption of a rigid sphere moving in a continuum is very crude. Nevertheless, for metal melts, the equation holds with a surprisingly fair accuracy. For glass melts with their network or cluster structure, it is difficult to assess an appropriate value for r. Thus, the above relation cannot be applied quantitatively. Yet, the dependence D 1/ holds. This intrinsic interdependence between diffusion coefficient and viscosity has an important consequence: The crystal growth velocity in a glass melt depends on its viscosity. 2.1. Viskositt Oberflchenspannung Dichte Statik und Dynamik von Fluiden im Schwerefeld (englisch)

DIMENSION ANALYSIS Like for the viscosity, a set of combined quantities involving the surface tension shall be interpreted and their dimensions shall be analyzed. Such an analysis gives much insight into the role of individual properties in complex technological processes. In the table below, a set of combined quantities involving the surface tension is compiled and explained.

name capillary velocity

definition

symbol -

unit

interpretation

[m/s] stationary velocity driven by surface forces and damped by viscosity

characteristic length

g 2 / 2 g

LA

[m]

range over which surface forces balance gravity range over which an accelerated motion becomes stationary responsible for the relaxation of local density fluctuations time by which an accelerated motion is damped down to a stationary one

retardation length

LB

[m]

capillary relaxation time

( g)
/ (g )

[s]

buoyancy relaxation time

[s]

restoring modulus in fluids

( g)

[Pa] a quantity similar to the shear modulus in solids [0] [0] a dimensionless number = (A/B)2 = (LA/LB)2 ratio of surface to bulk convective mass transfer

capillary buoyancy number g 4 / 3 Marangonis number

Ma

/ *) D / LC

*) LC is the characteristic length used in the treatment of bulk convective mass transfer The following table orders and summarizes some of the quatities given above:

equilibrium between surface and gravity forces

retardation of an accelerated motion

free buoyancy caused by a pressure gradient

L v

g
g

v cap 2 = g 2 g
2

r 4 2 g

2
r 2

r 4 g

v cap = g g

r 2 g

r2

r 2 g

= v cap

= v cap

dynamic vi scosity = / ; pressure gradient g P/h

INFLUENCE OF MELT COMPOSITION AND TEMPERATURE A few general conclusions on the influence of different oxides on the surface tension may be drawn. It is easier energetically to arrange univalent cations in the surface than higher charged ones. It is also easier to arrange highly polarizable ions than small ions with hard electron shells. Finally, for small ions with strong covalent bonds to the oxygen, it is rather the oxygen ion than the cation which brings about the surface tension effect. From these general rules, we may conclude that large alkali ions like K+ (bearing a low charge and being highly polarizable) yield a very low contribution to surface tension. The highly polarizable Pb2+ still makes a low contribution, yet due to the 2+ charge a higher one than K+. Si4+ has predominantly covalent bonds to oxygen; so the anionic character of the [SiO4] groups dominates over the effect of the cation, and the fairly well polarizable O2- ions determine its (moderately high) contribution to . By contrast, the small Mg2+ with its hard electron shell, yet its ionic bond to oxygen, increases the surface tension considerably. An especially interesting effect is observed with B3+. Similar to Si4+, the anionic character of the [BO3] groups dominates the effect on surface tension. Due to the favourable steric arrangement of the planar [BO3] triangles, boron makes a very low contribution to only. The resulting surface tension of an oxide melt at T = 900 C can be determined by the increments of j compiled in the table below. It is calculated form the oxide formula (in wt. fractions yj) by

= yj j A typical soda lime glass has = 0.32 N/m. The temperature dependence of the surface tension of glass melts is small. Its absolute value can be estimated with 0.004 N/m per 100 K. Soda lime glasses usually have positive temperature coefficients, lead crystal glasses negative ones. oxide j SiO2 TiO2 ZrO2 Al2O3 B2O3 Fe2O3 j 0.340 0.300 0.410 0.620 0.080 0.450 oxide j V2O5 CrO3 MgO CaO BaO MnO j -0.610 -0.590 0.660 0.480 0.370 0.450 oxide j CoO NiO ZnO PbO Li2O Na2O K2O j 0.450 0.450 0.470 0.120 0.460 0.150 0.010