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J. estk,

Termochimica Acta 95 (1986) 459-471

C.A. Queiros, J. estk,

Phys. Chem. Glasses: Eur. J. Glass Sci. Technol. B, June 2010, 51 (3), 165172

AND GLASSY STATES

Boivoj Hlavek, Jaroslav estk, ladislav Koudelka

Journal of Thermal Analysis and Calorimetry, Vol. 80 (2005) 271283

VIA DTA WHEN COMPARING OTHER CRITERIA IN RELATION TO

THE GLASS STABILITY AND VITRIFICATION ABILITY

Ana Kozmidis-Petrovic, Jaroslav estk,

J Therm Anal Calorim (2012) 110:9971004

CORRESPONDINGLY DEVELOPED GLASS-FORMING CRITERIA

Jaroslav estk, Ana Kozmidis-Petrovic, ivan ivkovi

J. Min. Metall. Sect. B-Metall. 47 (2) B (2011) 229 - 239

~ermochimieo Actu. 95 (1986) 459-471 459

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

3. ZESTAK

Institute of Physics of the Czechoslovak Academy of Sciences, Na Slovance 2,

180 40 Prague 8, Czechoslovakia

ABSTRACT

The classification, identificationand stability of a non-crystallinema-

terial as a glass is discussed. General thermodynamic and compositional con-

sideration are presented. Thermal characterizationof vitrification processes

are specified. A survey is given of the theoretical modelling of thermody-

namic descriptions of glass transformation. The thermodynamic functions of

undercooled liquids during vitrification are explained.

10m2 K s-I) of melts, usually silicates. If other substances are subjected to

sufficiently rapid cooling, for example water cooling of chalcogenides (102 K

s-I), melt spinning of metallic alloys (106 K s-I) or even vapour deposition

of various organic (alcohol)or inorganic (water) compounds (IOIO K s-I),

glass-like materials are similarly obtained, extending tremendously the amount

of data on the formation of glass. Previously such studies mainly have been

of academic interest but now find a wider use because of a growing number of

practical applications. Such studies were previously often related to the

field of the researcher's individual interest but they are now loosing their

original character of academic curiosity because of a grohing number of prac-

tical applications. The different kinds of glassy materials that have been

studied extensively include ionic conductor inorganic salts, semiconductor

chalcogenides,metallic alloys and various organic polymers. The study of

glassy materials focuses on the structural, kinetic and thermodyn~ic aspects,

the latter being the subject of this paper.

A GLASS

A great variety of non-crystalline solids have recently been prepared by a

number of distinct but unconventionalmethods. The methods employed include

460

disintegrations, or use of high energies. A disordered distribution of atoms

is obtained by freezing melts or as a result of other disordering processes

involved in the amorphous material formation. The latter processes usually

produce states that are poorly characterized as well as difficult to charac-

terize. That is why non-crystalline solids of an identical composition ob-

tained by various techniques, or by the same technique under different condi-

tions, can differ considerably in their physicochemical properties. A more

precise identification thus becomes difficult since certain parameters, like

local cooling rate and associated gradients, topological and compositional

short-range order, etc., cannot be specified exactly and/or directly. Thus, it

is evident that different names are currently used to describe such materials.

Eckstein (ref.1) classifies non-crystalline solids as vitroids referring to

organic and inorganic materials in the vitreous state, including glasses and

plastics. According to Roy (ref.2) the concept of non-crystallinity (meaning

structurally disordered) is considered hierarchially superior to the terms

glassy and amorphous. (The latter is currently more popular to describe the

newer types of semiconductor and metallic materials.) Many materials are con-

transformation point which, however, can be hidden in the early process of

crystallization catalyzed in such cases by excessively active sites or inter-

faces. A small number of vapour-deposited amorphous materials can even exhib-

it a pseudo glass transformation (relaxing to the state obtainable by cooling

of the corresponding liquid to the same temperature) and then immediately cry-

signify by the term glass, is understood to be preparable in a more systematic

and reproducible fashion compared to others, i.e, by cooling melts at differ-

ent quenching rates with the possibility of subsequent heating into the under-

cooled liquid state without overlapping crystallization (refs.3,4).

to Suga and Seki (ref.';) the glassy state is a thermodynamically unstable one

which can be assumed to be an undercooled metastable state at a certain in-

stant of continuous cooling by the glass transformation process which is con-

(ref.5) recommended even further classification of general glasses into glassy

liquids, glassy liquid crystals and glassy crystals formed by the glass trans-

formation of the respective metastable states of liquids (melts) and liquid

and solid crystalline phases. The state of a cooled material can be charac-

terized thermodynamically with respect to its corresponding stable phase down

to the glass transformation temperature, at which a state of internal equilib-

461

rium is lost, and even lower with some uncertainty due to the irreversible

nature of the glass transformation phenomena. Very thin sections of usually

spalt-cooled glasses are sometimes difficult to characterize precisely because

of the extreme condition of quenching and the irreversibility associated with

their formation. Some of them can even crystallize during reheating before

any glass transformation phenomena are observed. However, they are not to be

excluded from our somewhat strict classification of glasses, even though, the

dividing line between glasses and less respectable amorphous solids is vague,

particularly when compositions exhibiting or not exhibiting a glass transfor-

mation can overlap.

In recent literature, the glassy state is often called a metastable state

which, however; contradicts the common thermodynamic point of view that the

metastable state can exist in the stability region of the other neighbouring

phase and into which the extrapolation of the Gibbs energy function is pos-

sible, i.e., in the vicinity of the first-order transitions, such as melting

or crystallization, where a solid can be superheated or, more likely, a melt

undercooled, see Fig.1. The glass transformation, however, assumes second-

order-like transition, where each phase can exist only on its own stability

side because there is a break in the second derivatives of the Gibbs energy

(e.g. specific heat Cp) while its first derivative (e.g. entropy S) remains

continuous. On the other hand, however, the physical appearance of a glassy

solid looks more stable than that of an undercooled melt, the latter being

more easily transformable to the nearest state of stable crystals by a slight

action to surmount the energy barrier to nucleation. Hence, we come to the

discussion of the term solids in terms of vitroids within the framework of

rheology. This is because such a solid changes with time and observation time

is involved in detecting the extent of change. Reiner (ref.6) introduced the

Deborah number* expressing the ratio between the time of material relaxation

and that of its observation (DN). Conveniently, we can demonstrate the insta-

bility of a glassy state using the textbook case of a. variously positioned

brick, cf. Fig.1. When a brick is standing on its edge (and/or lying in an

unstable position on a very steep slope) its motion is determined by the high

viscosity of the surrounding medium (or by a large coefficient of friction of

the roughened surface, respectively). It follows that such a form of insta-

* Prophetess Deborah's famous song after the victory over the Philistines

includes the lines "The mountains flowed before the Lord". For illustration

we can consider the relaxation time for gases to be in the order of lo-12 s,

while for glasses within their region of glass transformation it is seconds,DN%

1, and approaches I010 s for stable crystals.

462

tion to the distinct state of metastability, it can be set up in different

levels (positions see Fig.l., dashed and dotted lines).

Let us thus investigate the behaviour of Gibbs energy in Fig.1. At the

melting point the liquid and crystalline phases have an equal Gibbs energy but

differ in enthalpy and entropy content. Upon cooling below the melting temp-

erature and entropy of the undercooled liquid decreases more rapidly than that

of the stable crystalline phase. Examining these different rates of the en-

tropy loss, we can determine a point where the entire entropy of melting would

be diminished, resulting in the entropy of both phases in question becoming

identical at the temperature To, which Kauzmann (ref.7.) called the pseudo-

critical temperature, still above absolute zero. Such a critical trend for

the entropy of an undercooled liquid is not always appreciated enough because

of the prior intersection by the liquid vitrification where the heat capacity

of the liquid changes abruptly to a value close to that of the corresponding

glassy state alone. However, an unsolved question remains as to what would

happen if the isoentropy temperature of the so-called ideal glass transform-

ation is nevertheless attained by infinitesimally slowing the cooling rate and

game of imagination, we have to consider the possible existence of some kind

of higher (presumably second) order transition. In this transition the heat

capacity of the undercooled liquid changes under the cond,ition of the internal

equilibrium to a value similar to that of the congruous stable crystal. The

thermodynamic properties of an ideal glass structure thus become very similar

to those of the crystalline state (ref.8). The apparent formation of such an

equilibrium glassy state can even be suggested as a "fourth state of matter",

a promising theme for theoreticians to discuss further, although some mechan-

ical instability arguments imply its occurrence (ref.9).

The viscosity of a liquid can be regarded as a reflection of the relation

between the thermal energy available at a given temperature and the strength

of forces pulling species together and restricting their positions to a given

volume within which any molecular rearrangements can Occur. The possible rate

of these rearrangements rapidly decreases with decreasing volume within which

the species are packed. The volume is determined by the strength of the at-

tractive forces and, in turn, this strength is reflected in the values of the

characteristic temperatures of the boiling, melting and Critical Points. Ac-

cording to Angel1 (ref.10) the basic reason for the "failure" Of a liquid to

463

FIG.l. Left panel: A dependence of the system Gibbs energy, G, versus the

temperature, T, indicating the characteristic regions of the existence of sta-

ble (melt, crystal - full line), metastable (undercooled liquid, superheated

crystal - dashed line) and unstable (glass - dashed and dotted line) phases.

For comparison, the second plot, the viscosity, shows typical curves represen-

ting the action of a system under the different cooling rates with the glass

transformation interval, Tg, marked while the yet lower plot shows the behav-

iour of the system entropy, S, down to the pseudocriticalpoint, To. The bot-

tom part corresponds to the derivative of the enthalpy change,AH, temperature

dependence (related to the associated phase diagram by the lever rule) whose

typical shape is similar to that of DSC (and also DTA) curves. The arrows

specify the cooling and reheating modes and the temperatureTcr indicates the

point of metastable crystallization (the dotted line in the S vs T diagram).

Right panel: A hypothetical temperature dependence of the reduced heat cap-

acityAcpr (=Ac,/ As) characteristicfor glass formation of metallic alloys

and of inorganic oxides and organic polymer (upper two curves) in comparison

with the approximationsnoted in the text: stepwise, linearly deceasing and

diffuse-lambda shaped (lower three curves) - suitable for extrapolating the

behaviour of a fictive undercooled glass-formingmelt.

464

so much in the liquid state but predominantly in the crystalline state during

ordering - the higher the crystalline symmetry of a phase to be formed the

better the glass-forming ability of its mother melt that can be anticipated.

The factors determining the probability of a given substance to freeze-in as a

glass are then related to the problems of finding a suitable solution in the

three-dimensional long-range ordering of the constituent species. The proba-

bility of glass formation increases with the formation of liquid mixtures in

which the Gibbs energy of the non-crystalline arrangement is decreased while

that for the corresponding crystalline phase to precipitate remains

unchanged. The more strongly the mixture of components interact, the more

rapidly the freezing point of the solvent is depressed and the viscosity in-

creased thus slowing the possible nucleation and the consequent growth of nu-

clei. The component interaction, however, should not be so strong as to

generate a new competing crystallizing phase which would strongly decrease the

glass-forming ability of the mother melt. Furthermore, the more stable the

crystal is, the higher the resultant melting point which simultaneously pro-

duces a less viscous melt and increases the probability of its crystalliza-

tion.It is well-known that the most easily vitrificable metallic alloys exhib-

it strong solvent-solute interactions resulting in low eutectic temperatures

but in the vicinity of which the existence of any stable binary or ternary

compound is not exhibited. On reheating such a glassy composition, a metast-

able phase is likely to be produced, but this form always decomposes later to

a combination of stable components. In this light, the theories describing

the stable glass-forming regions in multicomponent systems can be regarded as

dealing with the lowering of the Gibbs energy of a given solid phase on dis-

solution of solutes as a function of solute character (ref.10). The famous

Zachariesen rules (refs.ll,lZ), originally derived for oxide systems, may thus

be understood as rules for predicting low melting points relative to the for-

ces acting between the species, although many of the new inorganic glasses

violate these predictions. Hang et al. (ref.12) recently discussed the pre-

diction of glass formation and devitrification from the point of view of the

thermodynamics of regular solutions of complex oxide systems by examining

their immiscibility behaviour. A quasichemical model for solutions was also

used by Chen (ref.13) who evaluated the alloy formation of transition metal-

based glasses based on the binding energies of constituents in relatiOn to

changes in glass-formation temperature.

By measuring a macroscopic property of a liquid during its continuous cool-

465

te~eratures which, however, are related to the procedural para~ters of the

quenching technique employed (refs.4,15). Positioning of these points can be

specified on the basis of thermoanalytical investigations of various physical

properties, such as the heat content (by thermometric-DTA and DCC and heat

compensation-DSC-measurements), viscosity, elasticity, penetration and thermal

expansion (by thermomechancmetry and thermodilatometry), electric resistance,

coefficient of resistance and dielectricity, thermoelectric power, Hall effect

(by thermoelectrometry) and other structural studies (Midssbauer effect, X-ray

diffraction, photoemission, etc.). One of the most informative plots of

enthalpy change with temperature, resembling common recordings from DTA and/or

entropy from the plot of cp vs In T was shown by Angel1 and Rao (ref.16) ter-

med isoentropy glassy state determination.

It is evident that a correlation between the characteristic temperatures

and Tmelt has already been suggested on a theoretical basis by Kauzmann (ref.

7), assuming Tg to have a behaviour similar to To. Then a reduced glass tran-

sformation temperature Tgr was introduced so that Tgr = Tg/Tm and values of

about 213 are attained. Sakka and Mackenzie (ref.171 examined in detail its

general validity for a great variety of glasses and found it reasonable. In

addition, they reformulated Tgr on the basis of the combination of two for-

mulae relating Tmelt with the thermal expansion coefficient and Tg with the

fractional free volume of glass approaching, however, the value of l/2. The

meaning of reduced temperatures in the fast developing field of metallic glas-

ses was extensively dealt with by Davies (ref.18). Angel1 (refs.19,20) tried

to determine the extent of Tgr values on the basis of the extrapolated To data

evaluated by the Vogel-Tamman-Fulcher equation for viscosityp =po exp kp/(T-

T/J . TP, which has the unit of temperature, renders the viscosity formally

infinite when it equals the temperature of the entire measurements, which sug-

gests a certain rheological limit to the liquidus region from the the~odynam-

ic (Tp= To) and kinetic (Tp= Tg) points of view (ref.19). This showed, how-

ever, that an apparently more appropriate ratio, To/Tmelt, fails to follow the

'two-thirds' and even 'one-half' rules. Hrub$(ref.21) attempted to give a

more practical significance to glass-forming tendencies using the easily

available ratio given by Kg1 = (T,, - Tg) / (Tmelt - Tcr), see Fig.1, and

tested it on various types of chalcogenide glasses. As with Tgr the greater

the value of Kgl, the better the glass-forming ability is approached. In this

context, an interesting feature of glass transformation should be emphasised

again, viz. Tg is displaced to higher temperatures by an increase in the cool-

466

ing rate which is also reflected in the experimental variability of Tgr and

Kg1 values discussed in more details by Grest and Cohen (ref.22) and Thornburg

(ref.23), respectively. The meaning of the crystallization temperature Tcr as

a material constant is dealt with by Takayma (ref.24).

Many modelistic approaches to understand the various features of vitrifica-

tion have been described in the literature (ref.25). Free volume theory has

laid emphasis on the concomitant decrease in volume and fluidity of glass-

forming melts in the undercooled region. A recent extension of this model was

made by Cohen and Grest (refs.22,27) in conjunction with the percolation con-

cept to impute a first-order character in the glass transformation at T< Tg.

Considering a real glass as microheterogeneous, glass transformation can be

associated with the melting of clusters, recognizing thus the presence of an

intermediate range of structures between the crystalline and non-crystalline

states. Possible limitations of these models were discussed by Rao et al.

(refs.3,25,27). Some. other approaches can be briefly mentioned. Goldstein

(ref.28) has suggested that the configurational state of an undercooled liquid

can be described by an energy hypersurface of position and momentum coordi-

nates and that Tg occurs when the system of particles gets trapped upon cool-

ing into one of the many potential minima which are present on such a hyper-

surface. J'iickle(ref.29) has presented glass transformation as a transition

from ergodic to non-ergodic behaviour and discussed the meaning of the resi-

dual entropy of a glass. Ngai (ref.30) advanced a unified model of low-

argued that the concepts in the theory of viscoelasticity offer a good basis

for describing the polymeric types of glasses. The degrees of freedom can be

separated by their relaxation times into those that relax faster than the

quenching operation and those that are slower. Harris (ref.32) showed that a

simple model of glass transformation can be described by the statistical mech-

anics of a set of non-interacting particles each of them being able to assume

either of the two energy levels considered. Recognizing a parallel between

metallic, chalcogenide glasses and native solid electrolytes Phillips (ref.33)

related glass formation to directionless units and proposed possible dispro-

portionation on a molecular scale as a dominant barrier to crystallization.

Glass transformation itself is assumed to be a result of increasing cluster

size where its surface/volume ration involved means that the cluster interior

is ordered while the surface layer remains disordered.

Fundamental theoretical studies were made by DiMarzio and Gibbs (ref.34)

and Adam and Gibbs (ref.35) showing that the sluggish relaxation is under-

467

are perceived through their kinetic properties and one should be able to

arrive at a consistent description of the glassy state from the

phenomenologjcalviewpoint.

The glass transformation bears some resemblance to the second-order phase

transition, the latter, however, obeying Ehrenfest's relations dP/dT = AcplTVAa

= Act/ALU, where P,V ,cyand %I!are the pressure, volume, volume expansion and

compressibility,respectively. Due to the kinetic origin of glass

transformation,this relationship is not fulfilled during most experiments and

the degree of its irreversibilityis described by the Prigogine and Defay

factor7r (refs.32-41).

72 = Tg Vg Aa2/bcpA% 31 (1)

Some atttempts to generalize such a description were made using internal vari-

ables 5 , and corresponding affinitiesA having the role of the genertilized

forces and fluxes. The concept of internal parameters was best described in

the frequently cited study by Davies and Jones (ref.36). The essential

difficulties arise, however, when we attempt to associate 5 with physically

identificablequantities. Breuer and Rehage (ref.37) suggested that eq.(l) is

valid only ifaE/aT= 0 so that, for example,

dP

(2)

df = 6k -& (~)~~(~~~

Similarly, Staverman (ref.38) atiempted to define K on the basis of the par-

tial derivatives according to the internal parameters in question, DiMarzio

(ref.39) examined the above derivation and resolved that it leads to the equi-

librium conditions -dPfdT= asja~i~~v/dfi=asld5j/3v/c15jfor all pairs of the

order parameters i and j. Because K is always greater than one, he (ref.391

concluded that such a concept is not fully appropriate, Gupta and Moynihan

(ref.4D) proved the validity of then ratio for the systems with multiple or-

der parameters showing that eq.(2) must hold for each member of the set of or-

der parameters not including the assumption (ref.34,39) thata2G&dgj= 0 for

j# j. Therefore, the systems for which only one order parameter is required

to specify the state are trivial special cases because the order parameter, as

the extensive the~od~amic variable, can be arbitrarily subdivided into sub-

sets. If a single order parameter is sufficient to characterize the given

glass, the rate of a selected property change ii , given by dZf/dt =(~Z~~~~~TPX

cagpt)

, is proportional to another one ij. If the rates of different proper'-

ty relaxation,however,are not proportional to each other, this means that

more 5 are to be involved (ref .41). The practical aspects of the pressure ef-

fect on Tg was dealt with in refs. 42 and 43.

Following from the dissipation inequality, Christistensen (ref.44) provides

a the~odyn~i~ admissibilitycriterion for the glass transition temperature

which is characterized as the base temperature at which, for a constrained

sample with no volume change, the stress response to changes in temperature is

~nstant~neo~~,with no explicit evidence of a memory effect (creep response).

In this connection it is notable that the derivation mentioned above reveals a

transitional behaviour when internal variables have a certain relationship.

When a glass is held at a temperature below Tg its structure changes slowly

with time towards a certain equilibrium state characterizableby a fictitious

t~erature lying on the intersectionof extrapolated states of gtass and un-

dercooled liquid, respectively. The temperature difference between the fic-

titious and the actual temperatures thus gives a measure of the departure of

the material from equilibrium which, however, is true only when a single order

parameter is involved. When the description requires multiple order parame-

ters we need instead an adequate number of fictitious t~~ratures to achieve

an equally detailed picture of its actual state, The problem and usefulness

of the concept of fictitious temperatures was well developed by Moynihan et

al. (refs.4547). It should be noted, however, that the very important and

extensively studied field of processes dynamics (refs.48-51) is not dealt with

as it extends from kinetic theories on nucleation growth processes

frefs.18-52)which is a special discipline of th~r~dynamjcs. Here, it is

worth mentioning the illustrative use of hypothetical diagrams, either that of

the enthalpy change versus temperature fref,53), (cf.Fig.l),or that Of the

Gibbs energy versus the concentration frefs,48,4g)making possible the

characterizationof the type of accessible processes that occur in the given

system.

Most thermodynamic studies deal with the behaviour of heat capacity during

vitrification,e.g., Ra~achandrarao et al. (ref54) correlated the discontin-

uous change in thermal expansion and heat capacity with each other using ex-

pressions for the ideal entropy of mixing in substitutionalsolutions of the

components of different size. Similarly, Hillert (ref.50) assumed that the

abnormal heat capacity of the non-crystallinephase above Tg is due to local-

ized defects and describes its configurationalentropy by the model of inter-

stitial solutions. A very illustrativeapproach was developed by Gutzow

(refs.5557) who assumed that the difference between thermal capacities of

liquid cyq * and crystalline, ckr, phases is approximatelyconstant, co, and

that there exists a limiting temperature, To, at which this difference vanis-

hes. Using differences in the molar entropies, s, enthalpies, h, and chemical

potentials,@, well-known frm classical tber~dyn~ics, we can write (ref.%)

469

Asliqrcr j*melt

= A *melt - T

A c;iq'cr dT/T (3)

A h'iq8cr_ A $,elt - (Tmelt liq,cr dT

A cp (4)

Tr - T/Tmelt, TOr - To/Tmelt and Tgr - Tg/Tmelt we obtain

Asr- l- lST '=pr dT,/T, (7)

A h,- Ah'&, (

ASmelt Tmelt1 -l- ST '=pr dTr (8)

Tr

A% - AP~~"'~/ (AsmeLt Tmelt) - T_fTr Asr dTr 19)

can predict the behaviour of Acpr as shown in Fig.1, according to the three

gradual approaches: stepwise (Gutzow, ref.%), linearly decaying and diffuse

(Hillert, ref.50) and lambda shaped (refs.3,4) as known from the theory of

broadened phase transitions. In addition we can employ known experimental ev-

idence for the estimation of Tgr as discussed above (l/Z and Z/3). The en-

tropy difference frozen-in due to the glass formation is for a typical glass-

forming melt about l/3 (=ASr %Asg/ Asmelt) but can deviate for those glasses

that are difficult to prepare (l/4 through l/Z). For the simplest case of a

step-wise change we can calculate exploratory data by the introduction of Tgr

and Asr into the equations listed in Table 1 - using the condition of sr = 0

at Tr = Tor. The temperature dependence of the thermodynamic potential dif-

ference read from the above equations (ref.57):

Aur = T f

T9xAs, dTr + T S1(l+ '0 In Tr) dTt -AS rfTgrwTr

r gr I

not changethe limiting values in the Table. It just helps for a better fit

with reality.

470

TABLE 1

ACKNOWLEDGEMENTS

The author greatly appreciates the kind interest of Dr Gerd Olofsson of the

Chemical Center of Lund University and thanks Or Bengt Haglund of Sandvik Hard

Materials for making possible the author's participation at the 9 NSTAC.

The study has been devoted to Emeritus Professor Norbert Kreidl of the

University of Albuquerque on the occasion of his 80th birthday celebrated at

the Vienna Congress on Glass in 1984.

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Academic Press, New York, 1970, p. 281.

43 D.S. Sandinov, Zh. Fiz. Knim. 47 (1973) and 50 (1976) 1653.

44 R.M. Christistensen,

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Phys. Chem. Glasses: Eur. J. Glass Sci. Technol. B, June 2010, 51 (3), 165172

Carlos A. Queiroz*1 & Jaroslav estk2,3

1

VICARTE, Faculty of Sciences and Technology, New University of Lisbon, P-2829-516 Caparica, Portugal

2

New Technology - Research Centre in the Westbohemian Region, West Bohemian University, Universitni 8, CZ-

30114 Plze, Czech Republic

3

Institute of Physics of the Academy of Sciences R, Division of Solid-State Physics, Cukrovarnick 10, CZ-16200

Praha, Czech Republic

Manuscript received 5 March 2010

Accepted 17 April 2010

Disordered matter still presents stringent conceptual difficulties. The often confused concepts of amorphous and glassy

states (and corresponding material substances) were re-examined and previous attempts to trace a distinction are

revised and thoroughly discussed. We examine several rheological and thermodynamical aspects of glasses in the glass

transformation region as well as the dynamics of associated relaxation processes.

1. Introduction: from continuum mechanics Of course, much of the apparent success of the

to a thermodynamic based perspective continuum mechanics approach is actually elusive,

Considering the solid state we can make a distinction as the whole collection of such idealized models may

between perfect and defective crystals, as regards still be unable to perfectly translate the behaviour

metals, ceramics and polymers, when recognizing of some real materials, and intermediate cases may

their structural defects, which are understood as be particularly difficult to encompass within the

deviations from the lowest energy bonding arrange- continuum mechanics theoretical framework. On the

ments.(1) However, we still lack a widely accepted other hand, thermodynamics tries to adopt a unify-

conceptual borderline to distinguish states of matter ing perspective; has a general method that tries to

intermediating between the classic concepts of solid apply to all substances, which is less dependent on

and liquid. It is particularly noticeable that the con- particular modelling hypothesis concerning idealized

cepts of glassy and amorphous solids appear often substances.

confused, having no adjusted convention for their From a classical thermodynamic perspective a

exploitation in the published literature, while still single homogeneous substance in some definite state

lacking more widely accepted associated definitions. of matter is treated as a phase (homogeneous region

Macroscopically, and from a continuum mechan- of matter, not necessarily continuous, which is part

ics perception, which deals with a material body of the thermodynamic system) and we are mostly

response to external contact forces, a solid is a physi- concerned with the evolution of the systems macro-

cal system which resists quasi-statically to external scopic properties as a response to heat flow (heating

stresses applied at the surface, although some kind or cooling). This may be also a convenient perspective

of motion is generally expected. Such stresses are to distinguish and characterize different materials.

specified by the stress tensor and the extent of body Statistical thermodynamics, also named statistical

motion can be theoretically related with the stress mechanics, bridges classical thermodynamics, as a

tensor by constitutive equations. A number of ideal phenomenological global approach, to a particles

materials may be defined to represent particular based approach. It is concerned with the interpreta-

relations between the stress tensor and the motion. tion and prediction of the macroscopic properties

These are theoretical models used to represent and of matter in terms of properties of the microscopic

approach the behaviour of real materials. elementary subsystems that compose it, such as

Although continuum mechanics allow us to molecules, atoms, ions, electrons, etc. Here we are

theoretically treat solids and liquids under a unify- mainly concerned with equilibrium values for certain

ing perspective, comprising intermediate cases as properties (e.g. temperature, pressure, specific heat,

well (e.g. viscoelastic response), while under an viscosity, etc.) and the macroscopic system should

experimental perspective the rheological approach comprise a large number of subsystems, typically of

may be considered as pretty accomplishing the same, about the order of the magnitude of the Avogadro

we still lack a comparable satisfactory unifying ther- number, so that statistical averages can provide a

modynamic treatment. reliable description of the macroscopic system at its

most probable state (thus in equilibrium, in the sense

* Corresponding author. Email c.queiroz@fct.unl.pt that it remains unchanged with time). The statistical

Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part BVolume 51Number 3June 2010 165

C. A. Queiroz & J. estk: Aspects of the non-crystalline state

thermodynamics approach has been quite successful and pressure. Tool contoured this difficulty by intro-

working with gases (including real gases) and solids, ducing the concept of fictive temperature, Tf,(36) which

but rigorous predictions of the thermophysical prop- corresponds to the extrapolated temperature of the

erties of dense fluids derived after their canonical supercooled liquid. The concept of fictive temperature

ensemble partition function are currently difficult associates itself to the assumption that the glass struc-

to obtain. ture match up approximately to that of a frozen liquid,

Most melts can be undercooled by perhaps overcooled to Tf. The fictive temperature defines the

1020C below the temperature of melting, Tm, but actual structure of the glass and may be generally

the presence of impurities, slight disturbances, or estimated from intersection of the extrapolated su-

even the mere contact with the container, will lead to percooled liquid (equilibrium) line with the glass line,

a prompt crystallization. Low viscosity facilitates the considering a convenient property versus temperature

diffusion of constituent species, which is unavoidable plot (e.g. molar volume).(7) For a complete phenomeno-

to make possible the necessary reconstruction of the logical description of the glassy state, the parameters

fluid liquid web to that of rigid solid. The pre-nucleus necessary and sufficient to describe an equilibrium

(embryonic) sites, often existing in the melt, may state are classified as external, such as temperature

enhance straight forwarded crystallization, which (T), pressure (P) or composition; while Tf is taken as a

is also favoured by their crystallographic orienta- single internal (also called structural) parameter that

tion (e.g. lower symmetry, like monoclinic, which accounts for departure from the equilibrium state, for

can bestow easier configuration and growth of such which the Gibbs free energy is minimized.(8)

nuclei).(2) Considering a molar volume versus temperature

The melt viscosity () tends to increase rapidly plot (see Figure 1; the above plot), and herewith

along with decreasing temperature and reaches the the prolongation of the line of the supercooled liquid

traditionally expected value near Tm in order of 106 towards the equilibrium crystal line below the glass

Pa s.(1) Diffusion dies down speedily and, for that rea- transition, Tg, which, according to the thermodynam-

son, crystal formation turns out to be more and more ic theory proposed by Gibbs & DiMarzio(913) can well

intricate, but enabling, on the other hand, certain be considered as an equilibrium line between the

stability improvement toward the metastability of a supercooled liquid and the glass, it seems acceptable

supercooled liquid, until the development of viscosity that over the extrapolated segment the fictive tem-

near 1013 Pa s conducts to the constrained freeze-in perature equals the real temperature. As a melted

state that characterizes a radically constrained glass. glass under cooling enters the transformation re-

gion, a specific cooling rate may actually be selected

so that a certain fictive temperature, Tf, located over

2. Transformation temperature, fictive

the extrapolated segment range, can be reached by

temperature and Kauzmann temperature

the supercooled liquid. Tf tends to decrease as the

The supercooled liquid constitutes a metastable phase cooling rate decreases. Extrapolation for infinitely

in a state of constrained internal equilibrium, while slow cooling carries out the fictitious temperature

its free Gibbs energy is higher than that at the state towards the line of solid state and that would con-

of stable equilibrium. The free energy of the metast- duct Tf down to a specific temperature, known as

able liquid is thus kept at a local minimum, but the Kauzmann temperature, TK.(14) It is supposed that

not at an absolute minimum (which would imply Tg would then present itself as a sharp elbow, thus

crystallization). without any curvature at all.(15) This suggests that TK

In the transformation region, hereafter assumed represents a lower limit of the glass transition. The

to lie below the melting temperature (Tm) but above glass transition would then lose his dynamic charac-

the Kauzmann temperature (TK), the specific volume ter (its time dependency), thus presenting itself as a

depends on the thermal history of the material (e.g. static structural transition.(15,16) Before TK is actually

annealing time). This dependency cannot be fully reached crystal nucleation might eventually occur

understood within the framework of classic thermo- in differently noticeable manners. However, when

dynamics, were the specific volume is treated as a the crystals growing rate is sufficiently low, it still

function of state, thus depending only on temperature seems reasonable to assume the validity of a smooth

extrapolation trend for the remaining supercooled

There are some important points related to the glassy region revealing the

liquid. It should be stressed that this interpretation

allied characteristic temperatures. Most common is the Kauzmann tempera- depends conceptually on the equilibrium assump-

ture, TK, given as the intersection of extrapolated line for the equilibrium

liquid with that of equilibrium solid. The so called Vogel temperature, Tv,

tion between the supercooled liquid and the glass,

is decisive for the moment where the shear modulus terminates its increase since one needs to consider the extrapolation trend

and the viscosity becomes infinite according to the VogelFulcherTammann

model. This implies a discontinuity where viscous flow ceases (on cooling),

at a certain finite temperature (the Vogel temperature, Tv). For polymers Actually the entropy versus temperature plot should be preferred for obtain-

it customarily lays 52C below Tg but for inorganic glasses is about 100C ing a TK estimate by extrapolation, but since the lines present some curvature

lower. The Kauzmann temperature, TK, may get coincidental with Tv if in such a graph, the extrapolation procedure cannot rely in straightforward

derived from the entropy plot. linear extrapolation procedures being therefore more prone to error.

166Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part BVolume 51Number 3June 2010

C. A. Queiroz & J. estk: Aspects of the non-crystalline state

to vanish at a positive finite temperature (TK).(13,1921)

Recently, Gutzow et al(22) concluded that for glasses

one should expect Cp(T)=0 at T=0, while non zero

values of the zero point entropy (S|T0>0) cannot be

ruled out, what might be interpreted on the basis that

absolute zero cannot in fact be attained, accordingly

the most general formulation of the third principle

of thermodynamics.

Below TK the concept of fictive temperature loses

its significance and any configurationally rearrange-

ments typical of the glass transition are not expected

to occur. The theoretical model proposed by Adam

& Gibbs (AG)(2326) links the structural relaxation rate

to the configurational entropy, which is in a rather

good agreement with laboratory observations for

many orders of magnitude of the structural relaxa-

tion time.(27) Taking it in consideration, while provid-

ing that TK may stand as the transition temperature

of the supercooled liquid for the hypothetical case of an

ideal glass with null-approaching configurational

entropy (Sc=0),(2830) such a transition would corre-

spond to an infinite relaxation time.(9,26,31) However, it

may be admitted that, in these idealized conditions,

glass transition would correspond to a discontinuity

in the first derivative of the molar volume (transi-

tion of second order) while true crystallization

Figure 1. Schematic typical plots for glass transition. Above: occurs with discontinuity of the specific volume

molar volume versus temperature; glasses, A and B, with (transition of the first order). Since one cannot carry

decreasing fictive temperature (TfA and TfB) can be derived by out experiments under such a limiting condition

decreasing the cooling rate; a TK estimate may be obtained as (while taking into account a theoretical point of

the extrapolation limit at null cooling rate; hysteresis effect view), and the glass transition is, in reality, still

is shown for glass B, only. Below: isobaric heat capacity (Cp) not fully understood,(32,33) we must face extrapola-

showing a step-like nonlinear variation with some hysteresis tions with some reservation. Even if not realizable

at the calorimetric Tg (depicted for glass B, on cooling) experimentally, since in practice is expectable that

the usual (kinetic) glass transition always preempts

as coexistence curve, so that a hypothetical ideal such an ideal thermodynamic glass transition, the

glass transition might be assumed.(17) associated limiting notion has provided a stimulat-

Slower cooling rates lead to glasses of lower ing debate and has been included as a key idea in a

enthalpy contents, and providing that crystalliza- number of models of disordered glassy systems that

tion does not occur, the isobaric heat capacity (Cp) is significantly contributed to our current understand-

expected to present a step-like nonlinear variation ing of the glassy state.

with some hysteresis, within a temperature range Accordingly the AG approach, it is worth noting

centred at the calorimetric Tg, decreasing from values that at TK only liberational motion frequencies (often

close to that of the equilibrium liquid to values close associated with angular displacements) are expected

to that of the equilibrium crystal, although a positive to freeze-in. These can be associated to the liquids

but relatively small gap is still expected (Figure 1; configurational heat capacity. The higher frequencies

the plot below). Excess values for entropy and Cp are are still expected to hold at lower temperatures, as

expectable for glasses below Tg, as compared to the they are associated with the vibrational frequency

corresponding crystallized substance. Such excess modes of the amorphous solid. However, the struc-

values are even expected to be retained below TK, tural relaxation of the supercooled liquid is expected

although the observed gaps can somehow decrease

as the temperature drops until they eventually van- It may be possibly argued that point defects can still be expected at T<TK,

ish (at absolute zero or above), as long as Nernsts either for amorphous and/or crystalline structures, and this precludes the

associated entropic contribution to vanish above absolute zero, and hence

heat theorem is obeyed, what is still a question of at TK. This contribution is not strictly accounted for by the original AG

debate for glasses in general [e.g. Ref. 18]. Those model. Noticing that at TK the configurational entropies of supercooled

liquid (extrapolated to the ideal glass hypothetical state) and that of the

gaps are thought to become smaller and smaller for crystal are equal, it seems preferable to identify Sc with the excess entropy

lower cooling rates, and eventually, for a sufficient of the non-equilibrium glassy state with regards to crystal.

Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part BVolume 51Number 3June 2010 167

C. A. Queiroz & J. estk: Aspects of the non-crystalline state

to be completed at TK. Below TK the glass-like matter dercooled liquid is indistinguishable to that of the

still shows higher specific volume and entropy than congruous stable crystal, it comes to pass defend-

the corresponding the crystalline solid, but, in either able, instead, that the glass transition may be best

case, the contributions for the specific heat are mainly thought as a first-order-like transition, although of

vibrational. a disordered type. Such an approach leaded to the

An ideal glass transition can be interpreted as, random first-order transition (RFOT) theory developed

more or less, resembling a second order phase transi- by Wolynes et al, as a mean-field model approach

tion, according to the Ehrenfest classification.(3436) governed by the assumption of localized excita-

The corresponding theory makes certain that at the tions (entropic droplets).(3945) The thermodynamic

fictive temperature, the two coexisting phases (a properties of such an undercooled highly vitreous

gluey supercooled liquid and an extremely viscous glass) melt possesses novel properties of an ideal glass

should then possess matching entropy, holding, how- structure, becoming therefore very similar to those

ever, distinct specific heat [e.g. Ref. 36]. This implies of the crystalline state, as first noticed by Cohen &

that the two phases should then become isentropic. Turnbull.(46) The meaning of TK for chalcogenide

Besides, the molar volume of these two phases must glasses was studied in more details by ernoek et

also tend to reach a common value. The jump verified al(47) and other statistical, structural, and frequentional

in the specific heat suggests a certain congealment of details of Kauzmann (and other temperatures) are

some kind of structural movements at the Kauzmann given by Hlavek et al.(48)

temperature, which are expected to cease their contri- The Vogel temperature, Tv, taken from the Vogel

bution toward the specific heat. One may interpret the FulcherTammannHesse (VFTH) empirical equa-

rise in the glass transition temperature above TK for a tion(4951) has first been identified with TK under the

real glass transition as related with the period of time framework of the classical AG entropy model,(9,23)

available for the observation of such freezing move- and since then by other theoretical models. The same

ments during typical laboratory experimentation. confluence between Tv, were a kinetic divergence is

So far, the most stringent criticism toward the expected, and the entropy crisis at TK, was found

ideal glass concept (and hence the AG model) seems justifiable within the framework of the RFOT theory.(43)

to be that of Stillinger, who pointed the apparent need This conclusion also was corroborated by the fluctua-

for configurational excitations at such an ideal glass tion theory proposed by Donth,(52,53) by calculations

state to require an unbounded energy.(32) However, based in a ionic potential model presented by Hunt

we should bear in mind that such excitations are as- (for ionic glasses),(54) by a thermodynamic approach

sociated with activation kinetic barriers on the free developed for the model of spin-glasses,(55,56) and

energy surface and with the associated probability of also by means of a stochastic model suggested by

escaping from a particular structural configuration. Odagaki et al.(57) Experimental results obtained by the

The AG assumption of a underlying (kinetically technique of specific heat spectroscopy seem to support

obscured) second order phase transition with an this identification as well.(58)

associated infinite relaxation time seems, at least Taking Tv>0 K, B and ho (a pre-exponential factor)

as a theoretical limiting notion based on simplified as fitting parameters, the equation of VFTH expresses

continuous approach, not consistently invalidated by the glass viscosity as

the argument. For a recent critique of the AG model

B

the reader is directed to the work of Dyre et al(37) which h(T ) = h0 exp (1)

T - Tv

also questioned,(38) based on dielectric relaxation

data for organic liquids obtained just above Tg, the In the limiting case of Tv0 K, the VFTH equation re-

VogelFulcherTammann prediction for divergence duces to a familiar dependence of the Arrhenius type,

of the relaxation time at a finite temperature, Tv>0 K. where Tv is habitually determined from adjusted

It is also worth noting that a number of authors experimental viscosity data, most often reported for

took into account that the inspired existence of some T>Tg>Tv . For this reason, attempts for the attribution

higher (presumably second order) transition should of physical meaning to the parameter of adjusting Tv

be regarded as somewhat speculative. Accordingly, can be questioned outside the range were the experi-

bearing in mind that at the matching conditions of mental data can be obtained. Viscosity measurements

internal equilibrium, the heat capacity of the un- at T<Tg were seldom reported, and they must be in-

terpreted carefully, owing to the structural relaxation

If the thermodynamic equilibrium may be assumed for the phases, the effect and the possible occurrence of shear thinning

Ehrenfest classification affirm, for a first order transition, that the first

derivatives of de Gibbs free energy with regards to the temperature and

(as reported for silicate melts(26)), since elastic work

pressure present a discontinuity at the phase transition temperature. If the done by a shear stress may generate configurational

first derivatives are continuous but the second ones are discontinuous, the

phase transition is said of second order. For low cooling rates, and when

entropy. The usefulness of the AG model to interpret

considering glass as obtained by undercooling melt, the glass transition may and correlate the temperature dependence of sub-Tg

be seen approximately as a second order phase transition, being however

continuous (doesnt occurs at a definite temperature) and cooling rate

viscosities seems however well established for silicate

dependent, what marks a difference toward a genuine phase transition. melts.(26,59)

168Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part BVolume 51Number 3June 2010

C. A. Queiroz & J. estk: Aspects of the non-crystalline state

3. Dynamics of the glassy state: non- remains fairly insensitive to the variation of tem-

crystallinity, vitroids and Deborah number perature.(26,59,68,69)

Eckstein(60) classified non-crystalline solids as vitroids, The glass transition occurs when the time of

referring to organic and inorganic materials in the structural relaxation considered reaches the order

vitreous state, including inorganic glasses and or- of magnitude of a reasonable time period needed for

ganic plastics. Vitroid structures are interpreted as the observation of the phenomena with the available

paracrystalline networks (topologically disordered), laboratory equipment (usually ~1103 s), and, as a

thought as intermediary arrangements between melts consequence, for subsequent cooling experimenters

and the corresponding crystals. Such structures can cease to observe structural rearrangements in the

be quantitatively characterized by temperature-like glass network.(70) Pointing in the same direction,

parameters, named configurational temperatures. Nieuwenhuizen(71,72) refers that a system is glassy

Interesting is the use of a terminology that combines when the observation time is much smaller than the

the term solids with the term vitroids, seen within equilibration time. As a glassy system cools through

the framework of rheology. This is because such a the transformation region, the relaxation time of

vitroid changes with time, thus being dependent on slow dissipative phenomena (named -process)

the existent observation time involved in detecting becomes much larger than the time of observation;

the extent of the change (as with viscous flow). while the fast processes (-process) are still observ-

Reiner (61) introduced the so-called Deborah able at equilibrium. There is, apparently, no obvious

number expressing the ratio between the time of the structural signature associated with the steepest

materials relaxation and that of its actual observation increase displayed by the time constant associated

time, i.e. the experimental time scale (De=/). The with the a relaxation process, which is followed by a

name comes from the bible, where the prophetess correspondent viscosity increase. Nevertheless, such

Deborahs song after the victory over Philistines in- a dramatic increase of the relaxation time associated

cludes: the mountains flowed before the Lord. For to the a-process is seemingly connected to a rapid

gases it reaches ~1012; for crystals we have De~1010; fall-off of entropy, as it was first pointed by Gibbs &

and, for glasses close to the transition temperature, DiMarzio.(9)

it lays in an order of units. For an ordinary, as- The distinction between relaxation processes

quenched glass, the experimental relaxation time of and (classification after JohariGoldstein(7375)) is as

a given frozen structure, represented by Tg , is said follows. The leading relaxation process () is charac-

to be proportional to the shear stress relaxation time terized by a time constant that increases from ~1012 s

related to a shear viscosity expediently laying in (~1012 Hz) to ~100 s (~102 Hz) in the glass transition

order of 1012 Pa s. The Deborah number may be used region, accompanying (in an approximately propor-

as a criterion to distinguish solid from liquid-like tional form) the steepest increase of the viscosity,

behaviour.(62) At the glass transition temperature we and deviating from Arrhenius law. A kinetic glass

expect De~1. Thus, when Tg is accessed by dynamic transition temperature Tg,kin is therefore identifiable

mechanical thermal analysis (DMTA), which identi- from dielectric relaxations measurements, ascribed

fies itself with a pronounced peak in the loss tangent to the temperature at which the average (structural)

(tan), the corresponding average relaxation time () relaxation time for the a process approaches 100 s.(76)

may be considered tuned with the angular frequency, Tg,kin often agrees with the temperature at which the

=1/.(63) shear viscosity reaches 1012 Pa s,(77) which is widely

Suga & Seki(64) stressed out that the glassy state is identified with the glass transition temperature,

thermodynamically unstable and can be assumed to e.g. Ref. 78, being also, generally comparable with

subsist as an undercooled metastable state obtained the calorimetric Tg, ascribed to the onset of the heat

at a certain instant of continuous cooling through the capacity jump observed in the transition region. One

glass transformation process, which is considered to may also be able to observe a secondary process of

be a general property of all such metastable phases. relaxation (), in the kHz region (~103 s), which

As Wong & Angell(65) indicated, the distinction obeys to an Arrhenius temperature dependence

between supercooled liquid and glass assumes that and is not significantly altered within the glass

experimental essays are carried out in a time scale of transition region. One may thus consider this last

seconds or minutes, that is, in the usual range of the process as fast in the transition region with respect

Maxwell relaxation time(66) for a glass within the Tg to the alternative process.(55) The process can be

region. This is the relaxation time for tensions when a attributed to reorientation movements in the glass

constant shear is applied, and can be obtained as the network.(79) At higher temperatures (above ~12Tg to

ratio between the viscosity (h) and the shear modulus 14Tg ) the process and amalgamate in a unique

at infinite frequency (G)(67) process.(27,8083) The merging occurs at a temperature

that seems coincidental with the dynamical glass

=G (2)

transition (at Tc, known as crossover temperature)

Remarkably enough is that the shear modulus predicted by mode coupling theory,(84,85) while such

Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part BVolume 51Number 3June 2010 169

C. A. Queiroz & J. estk: Aspects of the non-crystalline state

a temperature may even be regarded as an upper the nondeterministic chaos theories is thus conse-

bound for the glass transition region, although the quently reflected into the structure of the amorphous

actual melting temperature also seems a reasonable body in glassy state,(48,88,89) which depends on the way

limit to be considered. A deeper connection between of cooling and will have this irregular character.

and relaxation processes seems to exist, as it was Microscale inhomogeneities linked to the glass

recently discussed by Prevosto et al.(86) transition process were also found in frozen aqueous

solutions of organic solutes. Sikora et al(90) found that

as a result of a phase separation processes accompa-

4. Structural features of the glassy state:

nying the freezing process of aqueous solutions of

nanoscale or microscale heterogeneities

sucrose from 120C to 30C, at least two crystalline

The role of the heterogeneities developed within the phases and two amorphous glasses could generally

liquid phase, now a true experimentally sustained fact be clearly identified, while solutions of composition

(largely recognized as a main characteristic feature of close to the eutectic were usually found to freeze

the transition region), was first treated trough the as- directly into glass.

sumption of a semi-crystalline phase by Kauzmann,(14) A feasible intervention of heterogeneity within the

as well as by an assumption of coexistence of gasliquid range of a so called mediumrange order (or modu-

(semi-evaporated) structural units related to numer- lated structures) becomes particularly common

ous works, e.g. Cohen & Turnbull.(46,48) The nonlinear in resolving the liquid and glassy states of various

oscillators contribute also to an abnormal coefficient non-crystalline semiconductors, where the concept

of thermal expansion and the amorphous-like liquid of inhomogeneous random network was most exten-

is thus structurally different from the amorphous-like sively studied.(1) This is also connected with the limits

solids, which casts some light into the explanations where the ordered and disordered states transpire its

regarding the Kauzmann paradox.(14,87) Below Tg factual distinguishing (delimitability). The standard

thermodynamic properties, as the specific heat and way for such observations, based on measuring the

the coefficient of expansion, decrease noticeably and crystallographic characteristics and the amount of

simple extrapolations towards lower temperatures crystalline phases (typically by XRD), is able to detect

lead to the expectancy that the supercooled liquid the amount of crystalline phase down to about 2%

would ultimately decrease to lower energy, entropy, within the glassy matrix (certainly under the restrain

and molar volume, as compared to the crystal, which of a minimum crystal-size detectability).(2,91)

seems unreasonable, hence the paradox. The Kauz- Since we are not concerned here with the capability

mann paradox is based on extrapolation and does to distinguish a minimum of crystallite magnitude

not take into account the fact that the liquid is a (which can be accessed by traditional XRD peak

mechanically heterogeneous substance in which the broadening), neither we account for a specialized

heterogeneity is partially removed as the tempera- diffraction measurement at low diffraction angles

ture goes down below Tg, and the highly nonlinear (to obtain the radial distribution function), we can

oscillators disappear. The liquid phase is structurally direct our attention towards the critical amount of

different from the solid in mechanical sense, viz. by crystalline phase that subsists in the glassy sample.

the appearance and disappearance of highly mobile, This issue is yet befitting the crucial question of how

diffusive, nonlinear oscillators. relevant is to define the limit of yet true glassiness

The blocks (inter-molecular clusters displaying and already nanocrystallinity. There are a few

correlated displacements), and their inter-blocks proposals but the generally accepted figure is, for

(adjacent rearranging clusters)(48) bonding structure, long, the value of 106 vol% (or a less common 103 %)

form the main contributing factor responsible for of crystallites existing within the glass matrix(2) as

dynamical parameters, such as the viscosity or bulk not yet disturbing its non-crystalline categorization

elasticity of the liquid phase. The blocks are also and consequent definition of glassiness. The appro-

responsible for complex relaxation effects, because priateness of this value is difficult to authorize, but,

the interconnected linear oscillators forming their however, keeps its continuance on basis of severe

structures interact. On the other hand, the semi- convenience.

evaporated particles acting as the nonlinear oscilla-

tors can perform their oscillations on several different

5. Concluding remark: on the distinction

amplitudes,(88) and their motions carry with them

between amorphous and glassy materials

elements of uncertainty that can be described, in most

cases, by the nonlinear, non-deterministic theories of According to Roy(92) the concept of non-crystallinity

chaos. Because the initial positional coordinates of (meaning structurally disordered) should be con-

such nonlinear oscillator for its subsequent position sidered as hierarchically superior to the glassy and

and momentum cannot be determined in advance, amorphous concepts, the latter being more popular

the differential changes in initial conditions will bring to describe certain types of semiconductors and met-

completely different trajectories. The general rule for als. These are, however, two related but misleading

170Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part BVolume 51Number 3June 2010

C. A. Queiroz & J. estk: Aspects of the non-crystalline state

controversial concepts as it was noticed by Gupta,(93) the kinetics of glasses, J. Res. Nat. Inst. Stand. Tech., 1997, 102, 135157.

as he demonstrated that non-crystalline solids could 13. Baschnagel, J., Wolfgardt, M., Paul, W. & Binder, K. Entropy theory

and glass transition: A test by Monte Carlo simulation, J. Res. Nat. Inst.

be divided into two distinct classes, amorphous

Stand. Tech., 1997, 102 (2), 159170.

and glassy solids, because they behave differently 14. Kauzmann, W. The nature of the glassy state and the behaviour of

upon heating, and he proposed a structure-based liquids at low temperatures, Chem. Rev., 1948, 43, 219256.

15. Nieuwenhuizen, Th. M. Ehrenfest relations at the glass transition:

definition for distinctions. Accordingly Gupta, a

solution to an old paradox, Phys. Rev. Lett., 1997, 79 (7), 13171320.

non-crystalline solid is a glass if the short range order 16. Nieuwenhuizen, Th. M. Thermodynamic description of a dynamical

of the freeze-in solid below glass transition and that glassy transition, J. Phys. A, 1998, 31, L201L207.

17. Stillinger, F. H. & Debenedetti, P. G. Phase transitions, Kauzmann

of the delivering melt are the same. Glasses are also

curves, and inverse melting, Biophys. Chem., 2003, 105, 211220.

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19. Angell, C. A. Entropy and fragility in supercooling liquids, J. Res. Nat.

satisfied for any non-crystalline solids, which are

Inst. Stand. Tech., 1997, 102, 171185.

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must undergo a glass transition to vitrify (if earlier state: Configurational energy as a modest source of energy, J. Chem.

Phys., 2001, 115 (17), 80838088.

crystallization is prevented). On the other hand, a

21. Pinal, R. Entropy of mixing and the glass transition of amorphous

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Acknowledgement Technol., 71C, 1988, 198203.

29. Shell, M. S., Debenedetti, P. G., La Nave, E. & Sciortino, F. Energy

This work has been supported by the Portuguese landscapes, ideal glasses, and their equation of state, J. Chem. Phys.,

Foundation for Science and Technology (FCT) and by 2003, 118, 88218830.

30. Matsuoka, S. Entropy, free volume, and cooperative relaxation, J. Res.

the Czech Science Foundation (GAR: P204/10/02112,

Nat. Inst. Stand. Tech., 1997, 102 (2), 213228.

MMT: 1M 06031 and MPO: FR-T11/335). 31. Franz, S. & Parisi, G. Effective potential in glassy systems: theory and

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172Physics and Chemistry of Glasses: European Journal of Glass Science and Technology Part BVolume 51Number 3June 2010

Journal of Thermal Analysis and Calorimetry, Vol. 80 (2005) 271283

STATE

1

Department of Polymers, University of Pardubice, s. Legi 565, 532 10 Pardubice, Czech Republic

2

Institute of Physics, Academy of Sciences, Cukrovarnick 10, 162 53 Prague 6, Czech Republic

3

Department of General and Inorganic Chemistry, University of Pardubice, s. Legi 565, 532 10 Pardubice, Czech Republic

The forms of vibrations and displacements of particles in amorphous structures have been investigated. The particles, moving on

highly non-linear amplitude, are responsible for the creation of disordered structures of amorphous bodies. The non-linear oscilla-

tors, even if few in concentration, are characterized by unpredictable trajectories in phase space. The non-linear oscillators are

fully developed in the liquid state above the crossover temperature Tcr and between Tcr and Tg their number decreases. Under Tg

they completely disappear. The interconnection between the linear oscillators in blocks plays the most important role in the charac-

teristic time spectra in liquid state. Using the additive properties of elements polarizibilities, the number of acoustical units in indi-

vidual blocks at Tcr is estimated to be about 600 units. The diameter of blocks at Tcr was estimated to be about 1.8 nm. Even if the

non-linear high amplitude motions disappear at solidification, the remnants of structural irregularity remain and the disordered

structure of glass is formed.

Keywords: crossover temperature, deterministic chaos, glass transition, non-linear oscillators, solidliquid transition

Introduction ter of their motions and are taken, in the present study,

as simple individual units about a monomer size [12].

Substantial fluctuations of liquid density in the area of On the other hand, the blocks are assumed to possess

critical temperature Tc appear as observable phenomena interconnected microstructure and are composed of

visible to naked eye [1]. The facts that liquid phase un- identical elastically bonded particles packed to the

der critical temperature is divided into solid-like struc- high (density) level reaching the density of van der

tures and voids filled up with gas-like molecules (the so Waals liquid phase (Fig. 1).

called wanderers), has been well known for a long The blocks are characterized by a module, which

time [2]. Some of the modern structural theories reaches the level of glassy state and keeps the swarm

(so-called mode coupling theory, MCT) describing the of particles in one block together. A dynamical equi-

structural phenomena of liquid state at lower tempera- librium exists between the block particles and the

tures are also based on a similar idea of local density semi-evaporated particles, as well as between the

fluctuation as well [3]. The assumption of heterogeneity semi-evaporated particles and the gas phase. The ex-

in liquid phase goes back to assumption of semi-crystal- istence of randomly distributed, random size molecu-

line phase by Kauzman [4], as well as to the assump- lar clusters in a viscous liquid has been discussed

tions of coexistence of gas liquid semi-structures related since 1959 till present days [511, 13]. Loosely

to numerous works of Cohen et al. [511]. packed regions separate these clusters. Here we con-

sider that the inter-clusters regions contain molecules

whose vibrations are strongly anharmonic, giving rise

Model structure to non-deterministic vibration movements.

The blocks and their inter-blocks bonding struc-

In this study we take also the liquid structure as a me- ture form the main contributing factor responsible for

chanically divided structure formed by blocks (do- dynamical parameters, such as the viscosity or bulk

mains, or clusters) on one side, and the individual elasticity of liquid sample. The blocks are also re-

semi-evaporated units, which are subjected to sponsible for complex relaxation effects, because the

non-linear anharmonic motions of high amplitudes, interconnected linear oscillators forming their struc-

on the other side. It is assumed that the highly tures interact. On the other hand, the semi-evapo-

non-linear oscillators maintain the individual charac- rated particles acting as the non-linear oscillators are

2005 Akadmiai Kiad, Budapest Springer, Dordrecht, The Netherlands

HLAVEK et al.

plitudes [15, 16], and their motions carry with them

elements of uncertainty described most cases by the

non-linear, non-deterministic theories [1725] of

chaos. Because the initial positional coordinates of

such non-linear oscillator for its subsequent position

and momentum cannot be determined in advance, the

differential changes in initial conditions will bring

completely different trajectories. The general rule for

the non-deterministic chaos theories [1725] is

consequently reflected into the structure of amorp-

hous body in glassy state, which depends on the way

of cooling and will have the irregular character.

For the displacement of block as a whole, the

maximum retardation time will show the level of in-

terconnections inside of block structure, characteris-

tic of a given block size, which changes with tempera-

ture (Fig. 3). It is assumed that the block size, together

with maximum block retardation time max, decreases

with increasing temperature. The block disintegrates

as the critical temperature is approached [15, 16]. In

the opposite case, the blocks bind themselves to a

rigid structure as the temperature decreases below Tcr.

below the critical temperature

Fig. 1 Schematic model for solid-like structure just above the lowing most important marking points, as the charac-

Tg temperature, when the first particle starts to act as teristic temperatures for amorphous body, regarding

non-linear oscillator and causes irregularity in structure the vibration amplitudes size:

of linear elements. The separation of blocks causes in-

terference with process, which forms the infinite

the boiling point temperature Tb,

structural network

the crossover temperature Tcr,

the transition temperature of glassy state Tg,

responsible for erratic character of Brownian motion Vogels temperature Tv.

displacements in liquids [14]. The semi-evaporated It can be stated: Tc Tb Tcr Tg Tv (the model

particles are acting against the external pressure and proposed has the following distinct characteristics of

exercise a push aside effect on the individual blocks vibration modes at different temperatures or tempera-

in their vicinity. The opening thus created (Fig. 2) ture areas, which should be mentioned and pinpointed

through straightforward amplitude jump, can be di- beforehand for the text to be clearer).

rected to any direction in amorphous phase. The

non-linear oscillators of semi-evaporated particles

Fig. 2 Sudden amplitude jump of non-linear particle (a), (b) can be performed in any direction (case c) in the sample space

FORMS OF VIBRATIONS AND STRUCTURAL CHANGES IN LIQUID STATE

the liquid point Tb, without the destruction of the sample

through the creation of a gas phase in the sample bulk.

The level of bottom of van der Waals curve for iso-

thermal case can be found easily for small volumes by

looking for the intercept of spinodal curve [26] with the

low volume of van der Waals dependence. The intercept

point is at volume fraction of 0.385 of critical volume.

At boiling point Tb, the non-linear movement stops for

some semi-evaporated particles, as the bond of particle

to a strange attractor of Lorenz type [23, 24] enlarges

its basin of attraction and is eventually interrupted as the

particle leaves the oscillatory movement for a gas phase.

Between the crossover temperature and the boiling

point, the high amplitudes of vibration are able to me-

chanically perturb the original bonding of blocks to such

a level, that shear module disappears. In contrast to be-

havior of material at this higher temperature zone, be-

low the crossover temperature, the substantial rise in

shear module G contributes (as a new element) to limita-

tion in vacancy enlargement, as the sample is able to

store the elastic energy W connected to shear module

[27], inside of the vacancy space:

W = 8Gr0 ( r1 r0 ) 2 (1)

The radius r0 represents the radius of a rigid sphere

approximating the particle, and r1 is approximating

the size of radius of the cavity. For example the cavity

of size r1=2r0 formed in solid with modulus G of

about G=1010 N m2 needs about 125 kJ mol1 [27],

while in liquids of van der WaalsEyrings type, such

level of internal void expansion inside of bulk of liq-

uid sample, leads to Troutons rule [2].

The non-zero shear module below the Tcr has

drastic impact on vacancy size and on the sizes of

maximal diffusion jumps, which are depressed or elimi-

nated as the temperature decreases. The presence of

Fig. 3 Schematic picture for a liquid-like structure where the inter-block bonding will bring the shear module to the

linear elements represented in blocks by Voigt series non-zero level and the elastic network will be formed.

are not connected through the elastic network and are The fact of different ways of inter-block bonding has

mobile, being restricted in their mobility by balance of basic influence also on the fragility phenomenas

saturation pressure Psat and by the external pressure Pext [28, 29]. Above the crossover temperature the diffusion

only (Fig. 1). The blocks are a source of cooperative

phenomena of sample time response

process, is driven mainly by few particles, out of the

block areas, which are undergoing the amplitudes

The bottom part of van der Waals curve on the switch. Thus the relation formed by product of viscosity,

liquid side plays the important role for the evaluation size of the diffusing particle and diffusion coefficient,

of non-linear amplitude size. divided by absolute temperature and Boltzmanns

The onset of the spinodal part of van der Waals constant [30, 31] cannot retain its form below Tcr. The

curve seems to pose a sensible restrain on the upper most apparent impact of shear module can be demons-

amplitude of vibration motion. This limit, if exceeded trated on the temperature dependence of the alpha and

has to lead to vacancy enlargement in which the parti- beta relaxation processes. (Also this topic will be

cles in vicinity of high-amplitude oscillator have to treated more closely in the following text). In Tg vicinity

take away the vibration energy of particle, by their own the changes in vibration amplitudes of average vibra-

avalanche like displacement. This type of energy with- tions can be also demonstrated by the experimental

drawal from high amplitude vibrating particle can only measurements of DebyeWaller factor [32].

HLAVEK et al.

Earliest experimental justification of the plated as well [15, 16]. For the temperatures T Tg the

structural heterogeneity of liquids entropy S main contributions can be explained as:

X-ray diffraction S k B [ln Wth + ln Wconf ] (2)

The X-ray diffraction studies are the oldest methods and for T Tg

supporting the existence of dual structure in bulk of liq- S k B [ln Wth + ln Wconf + ln Wsemievap ] (3)

uids [33]. These studies have shown that for a liquid,

even above its boiling point, the coordination number

(characterizing the number of particles in the closest vi-

cinity) falls drastically in the area of temperatures be-

tween boiling point and Tc, but the distance characteris-

tic of the first peak of radial distribution g r of particles

in vicinity hardly changes as the temperature ap-

proaches the critical temperature region. On the other

hand, the experimental proof of compact structure, ex-

pressed through unchanged radial distribution g(r), im-

plies the existence of voids and cavities filled with

semi-evaporated particles, to make up for the overall

volume of the sample characterized by average density.

positron annihilation spectroscopy

The volumes of vacancies are exactly determined and

are reported in numerous papers on positron annihila-

tion spectroscopy PASCA [3438] (Fig. 4). The ex-

periments of PASCA provide the unusually high co-

efficients of thermal expansion in the vacancy area.

The volumes of vacancies are very sensitive to tem-

perature changes above the glassy transition and to

the external pressure changes in the boiling point

area. In the present study, the vacancies in liquid state

contain the semi-evaporated particles without which

the transition from bulk of sample to gas phase at

boiling point would not be possible. As can be seen

from the data of Fig. 4 the coefficient of thermal ex-

pansion in vacancies areas is about ten to a hundred

times as high as that in the block areas. At tempera-

tures T Tg (for the amorphous bodies and the whole

piece of sample) the coefficient of thermal expansion

is 11104 K1. At temperatures T Tg the coeffi-

cient of thermal expansion is 2=4.1104 K1. The

PASCA readings at crossover temperature are higher

than V,14103 K1. The discontinuity in properties

for liquid structure is apparent. It could be contem-

plated that the liquid contains locally expanding

spots, which bear a responsibility for the high coeffi-

cient of thermal expansion of liquids in general.

Three types of entropy contributions of Tg=168 K for polybutadiene; the data provided by

Barto et al. [19] are gratefully acknowledged, b The

The entropy contribution connected with the semi-evap- coefficient of volumetric thermal expansion calculated

orated state (Fig. 2), which is created inside the liquid from Fig. 4a, for the vacancies, and the data of ap-

proximately taken from literature [43, 60] quoted for

system in vacancies areas, can potentially be contem-

the sample at glassy state

FORMS OF VIBRATIONS AND STRUCTURAL CHANGES IN LIQUID STATE

This type of entropy changes composed of three term U0n stands for the basic level of internal energy,

distinct contributions, viz. thermal, conformational f n , gn are characteristic parameters of local potential

and highly non-linear, has been experimentally con- valley, which depend on positions of particles in the

firmed in recent works of Johari [39, 40]. Because the closest vicinity. The equation of motion for particles

vacancies areas, thanks to the reports on PASCA ex- in the form of Eq. (4) is the same for block particles as

periments, have well defined size (which is larger for the semi-evaporated particles. However, if Eq. (5)

than the van der Waals volume, but smaller than is the is substituted into Eq. (4), great differences will ap-

0.385 fraction of critical volume of the particles in- pear in the solutions obtained between the individual

volved), we can estimate the change in enthalpy con- cases for gn0, r0,n(t)=const. (the case of ideal solids)

nected with the semi-evaporated state. As has been or for gn0 (the case of real solids or liquids) or when

shown by Hirschfelder et al. [2], the whole amount of gn(t), f n (t), U0n(t) vary with time. The last example

evaporation enthalpy is needed to produce an expan-

sion of cavity to level of twice as high as is the parti- represents the structural changes in solids and the dif-

cle diameter. So to produce a cavity of size about fusion or flow onset for liquids.

0.385 of fraction of critical volume, a proportionally Beside Eq. (4) in variables and t an additional

smaller part of evaporation enthalpy Hevap can be equation for description of r0,n(t) development in time

used, as the first estimate for the energy of void cre- (for the bottom well displacements) would be needed.

ation. The assumption of the Hsemievap=Hevap/n,

where n is about 24 or even higher, will be in agree- The mathematical treatment of strong non-linearity

ment with the PASCA experiments as well as with the for one oscillator above T g transition

estimate on viscosity by Eyring et al. [41, 42].

To find fast solution to Eq. (4) and provide illustrative

examples that can be easily visualized, the second-or-

The basic phase space behavior of semi- der differential Eq. (4) is usually turned into two sepa-

evaporated particles highly non-linear rate first-order differential equations. This procedure is

oscillator performed in the deterministic chaos theories [1725]

as well as in studies of organized structures or in

studies of non-equilibrium thermodynamics [21, 22].

The equation of motion for particle vibrations By choosing the variables A1 and A2d/dt we

The equation of vibration motion for non-linear oscil- can rewrite Eq. (4) into (two first order differential

lations of nth particle is: equations) the following forms [15, 16]:

2 U n dA1

mn + = Fext, n (4) = 11 A1 + 12 A2 (6)

t 2 dt

dA2

where the oscillator external force Fext,n(t) is created = 21 A1 + 22 A2 (7)

through action of many particles in the vicinity, and mn dt

is the particle mass, comparable in size with dimen- Equations (6) and (7) can be analyzed further in the

sions of acoustical unit [12] of about monomer size. Un vicinity of vibration stationary point. The system of

is the potential energy characteristic of the potential Eqs (6) and (7) will have non-zero solution only if

valley in which the nth vibration acoustical unit is per- 11 12

forming its oscillations. The term =rr0,n is the devia- det = 0 = 2 + a 1 + a 2 = 0 (8)

21 22

tion from the bottom of local potential valley.

The vibrations of particle take place inside of the where a1=11+11, 2=11221221.

potential valley Un(t) of the nth oscillator: The changes from a solid to a liquid state, as well

as the other higher temperature transitions, can be in-

U n ( t ) = U 0n ( r0,n ( t ) ) +

vestigated through the change of parameters a1 and a2

(5) within a certain range as shown in our previous com-

+ f n ( r0,n ( t ) ) 2 g n ( r0. n ( t ) ) 3

1 1

2 3 munication [15, 16].

The mathematical reasoning gives the basis to

where in the first approximation the individual pa- the existence of vacancies, which stems from the con-

rameters U0n, f n , gn, r0,n for the blocks particles are siderations of high non-linearity of Eqs (48), sug-

constant and time-independent and vary smoothly gesting the particle trajectories have a non-determin-

with temperature only; r0,n is a vector pointing to the istic character. At solidification process, the end

bottom of potential valley of the nth oscillator. The points of the trajectories in phase space are aiming at

HLAVEK et al.

different spots, which forms the irregular structure of The estimate on the size of blocks from the shear

the glassy state. The scheme for the amplitude devel- viscosity data

opment for two coordinates n, dn/dt for different

Numerous predictions regarding the size of the blocks

temperatures in phase space is shown in [15, 16].

are reported in literature by many authors

Following such line of perception, the higher transi-

[13, 5056]. These predictions are based upon differ-

tions such as the boiling or critical point can be con-

ent experimental techniques. Focusing the attention

sidered too. The fraction of vacancies can roughly be

now in a direction not yet used for the block size esti-

estimated through the density changes for the liquid

mate, it will be tried in this study to provide the block

sample [15]. While only few vacancies exist at lower

size approximation, using the techniques of rheology.

temperatures (according to Bueche [43] the ratio of

The answer is searched for two unknown parameters.

vacancies to vibrating particles is equal to 1:40 at Tg),

The first represents the number of linear elements in

at the critical temperature the amount of vacancies

block at which the blocks start to be interconnected in

reaches the level at which the condensed phase disin-

shear flow and start to interfere mutually producing a

tegrates completely [15, 16] and all oscillating parti-

contribution to the elastic shear module response. A

cles are able to reach the upper vibration amplitude

useful source of data, for the domains (blocks) inter-

with addition of very tiny amount of energy.

actions, is the measurements of shear viscosity data

obtained at zero velocity gradients, which have been

known for about forty years for different structures of

The linear cooperative phenomena in blocks

polymer melts with a variety of molecular mass val-

ues [5759]. These data show one common feature in

As a result of separation of the non-linear effects from

the dependence of shear viscosity on the number of

the linear blocks areas, some more than half-century-old

monomer (acoustical [12]) units in chain X sequence.

experimental results and mathematical techniques can

As is considered, as the first example, that the number

successfully be used for the investigation of very topical

X is small and remains below a certain limit, XXc,

time phenomena in liquidsolid transitions (following

where Xc500625, and that the polymer melt is char-

the temperature interval between TV and Tcr). The new

acterized by a constant and gradient-independent vis-

physical explanations about certain phenomena, nowa-

cosity. In this particular case the module of shear elas-

days intensively studied [13, 4456], connected with

ticity is zero, as well as the first normal stress difference

and processes, about the crossover temperature, and

remains zero too. The macromolecules are smaller than

also about the Kauzman paradox [4] can thus be re-

the block size (XXc), and the blocks, if subjected to

vealed, as the system changes its structure as it cools

shear flow, do not exhibit any mutual interference. A

down below the crossover temperature and under Tg, as

different level of viscosity, which rises in linear de-

the particles generating the voids and associated with

pendence on X, characterizes each polymer at this

the higher amplitudes of motion disappear.

particular case. However, at the point when the criti-

cal value Xc is reached in the polymer chains, there

The limiting values of block time characteristic occur changes in the rheological properties. The

block interconnections start to interfere through the

For the time dependence limits for the fastest time in-

overgrown size of macromolecules. For polymers

terval of retardation we use the time interval calcu-

with XXc the melt viscosity in dependence on shear

lated from the sound velocity, which for solid blocks

gradient starts to have the non-Newtonian character

is about 105106 cm s1, and from the minimal length

as the gradient grows and the first normal stress dif-

of acoustic waves, which are determined by the mesh

ference starts to be an important flow characteristic as

size r0,n

. Thus we get: 1/maxmin and vsound=

well. This effect is usually explained in connection

=minmax, where min 2r0,n .

with the chain entanglements. The concept of entan-

Substituting from the estimate of values outlined

glements was introduced originally base upon

above we get max1013 s1for the maximum fre- sketchy pictures [43, 60, 61] and as an evident phe-

quency in sample body and for the fastest time of ma- nomenon while the nature of couplings [60] was left

terial response in block min max1=1013 s. (The esti- as open, with the alternative to cooperative motions

mate on the fastest bottom well displacement based of molecular areas, which is also suited for the low

upon the experiment is quoted by Rossler [47], viz. molecular structures. The later case corresponds more

13

min=310 s.) For the longest time characteristic for closely to scheme presented in this study, which is

the material we take the characteristic time connected also supported by findings of Achibat et al. [80, 81],

with permanent displacement in series of elements in- reporting a relationship between the domains and the

side of block space and bonded together through elas- entanglements. The model presented attributes the

tic force (Eqs (14), (15)). property of inter-blocks bonding either to the entan-

FORMS OF VIBRATIONS AND STRUCTURAL CHANGES IN LIQUID STATE

glements (as the individual blocks start to be interwo- as the temperature is increased above Tcr. The inflexi-

ven by polymer network) or to inflexible bonds of van ble blocks interconnection reflects itself into the in-

der Waals type, or to the bonds of chemical nature. ternal energy related shear module contribution under

The inter-block bonding has a consequence in devel- the Tcr. (This is valid for the blocks contacts for the

opment of non-zero shear module. Although different polymers under Tcr temperature too).

polymers have different levels of viscosity or chain The parameter left to be determined is the cross-

flexibility, different molecular mass, or exhibit differ- over temperature itself. For these purposes the mea-

ent levels of normal stresses, the numerical value of surements of the dependence of shear relaxation mod-

Xc for blocks mechanical interference in shear flow ule on temperature in area of main phase transition

has a universal character. Just quoting [59], for poly- can provide this information [62, 63] (Fig. 5). For the

styrene Xc=600, for poly(vinyl acetate) Xc=600, for reasons of clarity of explanations in text, some data of

polyisobutylene Xc=500, for polydimethylsiloxane Schultz [59], Alkonis [63] and Tobolsky [62] were

Xc=625. If the level of critical interconnection is presented to show the idea behind the text more

reached in linear sequence for polymers, the blocks clearly. The crossover temperature Tcr (Fig. 5) is de-

are inter-bonded and exhibit the shear elasticity repre- termined on the basis of the shear elasticity of internal

sented by shear modulus or by the first normal stress energy related relaxation module. The value Xc is de-

difference. Such elasticity created by flexible termined on the basis of the zero gradient viscosity

macromolecules is entropy related. (This type of in- curves. At this level of internal connection the blocks

terconnection has a long distance character rela- start to interfere in flow.

tively to the block size, and one macromolecule can At the temperature Tcr the characteristic domain

over-bridge several blocks too). In contrast to size can be estimated and for the lower temperatures

blocks connected by flexible macromolecules, the TTcr, the part of force responding to external deforma-

blocks can also be interconnected by inflexible chem- tion has internal energy related component (fINT0).

ical bonds. This is the case for the low molecular mass Taking the size of one oscillator unit in interconnection

substances under the crossover temperature. The sequence from the polarizability values [64, 65], for the

blocks connected by inflexible bonds cannot be interconnection number of Xc=600, the characteristic

stretched to higher deformations and have to break up size of a domain of about 6 nm3 (for the molecules of

most typical size of pentane) can be obtained. For the

linear dimension of a domain 61/3=1.81 nm can be ob-

tained. This seems to be in good agreement with the

published values [13, 5056] obtained by different ex-

perimental techniques. As the polarizability of mole-

cules is simple additive properties of individual atomic

polarizabilities, the domain size can be easily estimated,

from the polarizabilities values of individual monomer

unit and from the Xc values, as the Table 1 hints.

For the particles forming the block structures, in addi-

tion to the motion in coordinate, which does not lead

to linear particles diffusive displacements, an addi-

tional motion connected with r0,n displacements can be

superimposed on the movements of particles. Besides

the potential valley deformation the additional degree of

freedom, if added to the particle movements, will bring

by itself the increment in specific heat capacity cp.

For the differentially small changes in bottom

Fig. 5 The typical picture of relaxation module behavior of position r0,n (Eq. 5), the coordinated changes of par-

polymer. The sample is undergoing the temperature and

molecular mass change. (According to Tobolsky [62]

ticles positions, ...r0,(n1)r0,(n+1), r0,(n+2)r0,(n+k) in

and Alkonis [63].) The elongation relaxation modulus the vicinity of semi-evaporated participle are needed

of polystyrene, for two different molecular masses as the precondition for permanent displacement of the

Mw =M1M2 as a function of temperature. The relax- nth particle.

ation experiment is performed for a time of 10 s. The

area a stands for glassy zone and b is the rubber-like

zone [60, 61]

HLAVEK et al.

acoustical units

Estimate on Domain

The type of

polarizability of size/nm

polymer

acoustical segment /3 for Xc=600

polystyrene 11.6 1.90

polyisobutylene 7.2 1.62

polybutadiene 6.4 1.55

polyvinyl

8.0 1.68

acetate

polymethyl

9.8 1.95

methacrylate

SiO2 6.7 1.59

GeO2 7.6 1.65

B2O3 4.4 2.05

As2S3 17.3 2.18

glycerol 8.6 1.72

pentane 10.0 1.81

(9)

r0,(n + 2) ( t ), ...... r0,(n + k) ( t )

taken as an unknown function of time t associated

with material characteristic series of discrete retarda-

tion times. The actual positions of r0,n, r0,(n+1) etc. does Fig. 6 A detail of Fig. 1. The individual particles in necklace

not enter into the mathematical formulation. The indi- are numbered according to their positions separating

vidual oscillators can be placed consecutively, in the them from the non-linear particle stress perturbation

space of sample, touching each other in form of neck- shown schematically above of particle '0'

lace (Fig. 6). The mathematical formula will involve

the particle consecutive order in chain time response r0,n

acting on each element f 0nFr expressed sepa-

and also the direction and size of deviations from t

equilibrium positions r0,n, r0,(n+1), etc. rately as shown in Eq. (11). The term Fext represents

In simplistic view of interconnections for one the interaction of non-linear oscillator (the

line of particles connected in the form of an elastic semi-evaporated particle), acting on the ends of chain

necklace such as shown in Fig. 6 we get: (point 0 in Fig. 6), by which the individual blocks

segments are displaced in time. The non-linear oscil-

d 2 r0,n

mn = (10)

lator of semi-evaporated particle acts as the local

dt 2 stress perturbation source on the necklace of elasti-

= k e ( rn, +1 r0,n ) k e ( r0,n r0,n -1 ) + Fext cally connected masses. The blocks play the role of

the sidewalls, and from mathematical point of view,

Through extension of Eq. (10) inside of block we get: they act as the source of exact time response of mate-

d 2 r0,n rial. For the case of Fext=0 we get a homogeneous

mn = equation as a source for the calculation of vibration

dt 2 (11) modes. These modes give the evidence about the ac-

r0,n

= k e ( r0,n + 1 + r0,n 1 2r0,n ) + f 0nFr + Fext tual distribution of resonance frequencies and time re-

t sponses of material. The shifts in r0,n can be consid-

where Fext represents the external force acting on the ered in any direction inside of sample.

particle through the particles localized in its vicinity. d 2 r0,n

The simplest form of interconnections of elements, mn = k e ( r0,n + 1 + r0,n 1 2r0,n ) (12)

dt 2

without branching or bridging is considered. The term

Fext can involve the effects of local friction force f 0nFr

FORMS OF VIBRATIONS AND STRUCTURAL CHANGES IN LIQUID STATE

Equations (1012) have many classical solutions The individual retardation times covering the

for many options of Fext and are solved in connection motions inside of blocks, are mutually interdependent

with many different topics of engineering or scientific through Eq. (15) (Figs 7, 8). The time for total block

applications [18, 27, 43]. The typical solution to ho- displacement is thus proportional to N 2 while the fric-

mogeneous Eq. (12) of relaxing block consists of se- tion force for the block movement, which character-

ries of resonance frequencies n, izes the shear viscosity of sample, remains propor-

tional to N only if the total block friction is defined as

4k n dr0,n

2n = e sin 2

N

mn 2( N + 1) (13)

i =1

f 0n

dt

. It can be assumed that the friction coef-

and leads to the time response of blocks characterized only mildly with temperature changes. However, it is

by series of relaxation or retardation times (for creep re- expected that the number N increase smoothly with

lated experiments) of interconnected elements [18, 43]. decreasing temperature. At the crossover temperature

(The solutions of Eqs (11)(13) are given in Ap- the inter-chain branching start to appear. The knots

pendix A and B. Please note also that for and bridges between the chains characterizing the

n structure, affect the relaxation times in different way

N

sin 2 and n the argument of from the viscosity, making the chain sequences

2( N + 1) 2 shorter. For example if two necklaces are connected

n n2 together, then the viscosity rises by factor of two. The

sin 2 const. is valid.)

2N 4N 2 rise in maximal relaxation time will depend on the

Solving Eq. (13) means finding the resonance way how the interconnection is made, leaving the

frequencies n, which determine the mechanical char- maximum increase only for the head-tail interconnec-

acteristics of the block. The block is invariably a lin- tion type. (The last reports on relaxation time and vis-

ear system, and the times of block response are given cosity measurements [13] state that while the viscos-

through simple arithmetic multiplication if constant ity increases with slope of 3.4 with average molecular

local friction is considered. mass M w3.4 , the increase in maximal relaxation time is

less dramatic (M w3 ) [66].

f 0,Frn

n = (14)

2n mn

The alpha and beta slow processes the

and for the constant frictions and masses of each os- mechanical shelters for shear elasticity components

cillator inside of block f 0Fr,n / mn = const' = 1 , we get:

The retardation time 1 is thus the starting point in a

n sequence through which the longer retardation time n

1 (15)

n2 can be created. The longest retardation time N should

grow with decreasing temperature and reflect the ap-

For the sequence of resonance modes in the proximation for the level of interconnections in linear

1 2 1 elements of block size.

sense of Eq. (12) the matrix = 1 2 1

The term N stands for the time necessary for dis-

...... etc...... placement of a block as a whole. The shortest retarda-

of Eq. (12) plays the crucial role in the separations of tion time will reflect the fastest response of bottom of

retardation times and in the separation of resonant fre- potential valley by differentially small displacements

quencies of n. From Eq. (11) for the case of the nth of r0,n. The fastest displacement will involve only

k f Fr the acoustical units in shortest vicinity of the particle

element we get 2n = e = 0,n . considered. Because the acoustical units usually con-

mn mn n tain few atoms and are approximately of monomer

Taking the ratio between the elasticity and size [12], the shortest relaxation time is expected to

friction for each oscillator in block as the same represent connection of about 20100 atoms and to be

k e / f 0Fr,n = const = 1

1 , Eq. (12) gives very simplified in the vicinity of the so-called fast relaxation process

spectra distribution n= 1n2. It can be seen that the [49]. One bead in necklace pictured in Fig. 6 will be

higher retardation times are formed in blocks spaces involved in the friction force of many molecules

through growing sequence of interconnected ele- forming the first level of coordinated motion in the

ments and not through variation of local friction or closest neighborhood of the particle displaced. (This

local elasticity. The friction force f 0,nFr or the external will provide the relaxation time in the vicinity of the

forces F'ext, Fext do not influence the separation of so-called fast relaxation process, which is reported

individual material time responses either. [49, 67] to be about 3.01013 s). It can be seen in Figs

HLAVEK et al.

7 and 8 that for the so-called (line A) relaxation the sample elasticity is mainly connected to the parti-

process the interconnection level reaches infinity as cles associated with process as the elastically

soon as the temperature decrease starts to approach interconnected network covering the space of a whole

the Tg temperature and the infinite elastic network is sample is formed. On the other hand, the particles

developed. The so-called slow process (lines connected with slow process are apparently anchored

B, C, D) is different because the parameter N for in space differently, being ultimately bound with very

these processes cannot reach the infinite interconnec- high viscosity coefficient rather than with purely elas-

tion level as the temperature decreases. Searching the tic response to external shear deformation. It can be

N at the crossover temperature for 600 elements we stated that the slow processes are connected with the

get N(T =Tcr)= 16002=3.0101360021.08107 s. loosely anchored or floating parts of a network

Rossler [49] experimentally confirmed such charac- structure.

teristic time level at the crossover temperature. Below Because the area between the Tcr and Tg is con-

the Tcr temperature the term , which means, that nected with sharp increase in shear modulus, it can be

said that the slow processes are shear-module-insensi-

tive. Therefore, the slow processes appear to be local-

ized in sample in different, mechanically sheltered ar-

eas, which certainly transport the shear component of

stress in a way different from what the process does.

Because the number of interconnected elements form-

ing the slow process does not reach infinity (which is

the precondition for the formation of elastic solid

phase with the infinite relaxation time), the elastic

solid phase formation seems to be determined by the

process.

The views presented in this paper are more

closely approaching the description of process pre-

sented in early theories [7176] of Eisenberg [77, 78],

Heijboer [7476] and Bueche [43] which has been

taken as well proofed by experiment and which con-

Fig. 7 The logarithms of characteristic relaxation times determined tradict the recent theories which are involving all par-

by Rossler [49] for variety of organic and inorganic materi- ticles of the system participating in the slow mo-

als. The graphs are testing the sequence shown in

tions [69]. The theories of plasticizers [79] suggest

Eqs (14, 15). Rosslers relaxation times are taken for

also the structural heterogeneity and give example of

the limiting variable interconnection number N. In our

model, 1=31013 s and 600=107 s according to Rossler

materials for which the islands of mobility can be

[49] and according to Eq. (15). At T =Tcr we take the N hardly excluded. (On the other hand, in the case of

value equal to 600 glycerol, the slow process is not present). The other

explanation for the slow processes is connecting them

with changes in coordinates displacements not di-

rectly connected with external shear deformation (the

perpendicular rotation of two different parts of poly-

mer chains around two perpendicular axes has been

described already by Bueche [43] in his discussion of

substance of and slow processes.)

These studies are the subject of our various inter-

disciplinary projects and are the continuation of our

previous and recent interrelated discussions pub-

lished in different sources such as papers [16, 8283]

or books [84, 85].

Conclusions

Fig. 8 The numbers of linear interconnections N for variable The estimate on the size of domain at crossover tem-

relative temperatures obtained from Eq. (15). The lim- perature has been provided based upon the rheologi-

ited interconnection level for slow processes (curves B, cal data of viscosity at zero gradients.

C, D), below Tg are clearly visible

FORMS OF VIBRATIONS AND STRUCTURAL CHANGES IN LIQUID STATE

The crossover temperature has been estimated the equally distributed masses mn per length

from the relaxation module data. The crossover tem- l=(N +1)=(N +1)x where is a distance between subse-

perature is connected to first appearance of internal en- quently connected masses mn1=mn= =mn+1=mx etc.

Except for the variability of shape of irregular block, the

ergy related shear module.

elastic rod seems to be the geometrically nearest object resem-

The irregular structure of amorphous phase has bling the block structure. If choosing the following substitu-

been explained through the existence of non-deter- tion in Eqs (1012) for the ke=Te/; dx=mn where is a bar

ministic oscillators, which exist in liquid phase. The (spring) density, then Eqs (1214) take the form of wave equa-

disappearance of these particles under the Tg and the tion for F ext=0.

non-predictability of end points of their positions in

mn d r0 ,n =k e (r0 ,n+1 + r0 ,n1 2r0 ,n )

2

phase space coordinates gives rise to the existence of (16)

irregular structure of amorphous phase. dt 2

The non-linear oscillators have also an abnormal d 2 r0 ,n =Te r0 ,n+1 2r0 ,n + r0 ,n1 =

coefficient of thermal expansion and the amorphous

dt 2 m x

liquid is thus structurally different from the amor-

phous solids, which casts some light into the explana- =Te r0 ,n+1 r0 ,n r0,n r0 ,n1 = (17)

m x x

tions regarding the Kauzman paradox [4]. The

Kauzman paradox is based on extrapolation and does =Te r0 r0

not take into account the fact, that the liquid is a me- m x n +1 x n

chanically heterogeneous substance in which the het-

d 2 r0 =Te d 2 r0 (18)

erogeneity is partially removed as the temperature

dt 2 dx 2

goes down below Tg, and the highly non-linear oscil-

lators disappear. The liquid phase is structurally dif- The connection of difference equation to the wave equa-

ferent from the solid in mechanical sense, viz. by the tion opens further possibilities connected to elasticity and

appearance and disappearance of highly mobile, dif- fracture theories.

fusive, non-linear oscillators.

The and slow processes seem to have a common

origin in the fast process. The process differs from Appendix B: Solution of difference equation

the slow process in numbers of interconnected ele- in form of Eqs (12)

ments, which increase for the process to infinity as

the sample solidifies. The slow process does not pos- The solution of Eqs (12) can be searched in form:r0 e j( t kx )

sess this property and apparently is not fully contrib- where k is a wave vector.

uting to the shear elasticity level. Being localized in- 1

2

(19)

inter-blocks bridging which gives rise to shear module Te

and as such, the slow process need not to be present in

In discrete form for the nth particle we get:

some materials, at the point of formation of glassy

r0,n =An e j( t kx ) =An e j( t kan ) since x=na.

state. The characteristic vibration frequencies of linear

Substituting these expressions into Eq. (14) provides:

domains localized outside the non-linear areas provide

the source for discrete characteristic time spectra. The 2n mn =Te (ejka + ejka 2) =

experimental data supporting the double character of a (20)

vibration and double values for amplitude sizes have jk a jk a

e ) = 4Te sin 2 ka

2 2

a a 2

and by previous work of Rossler et al. [6870].

Substituting from boundary conditions, i.e. that the os-

cillators out of sample with index n=0 and index n=N+1 can

be associated with zero amplitudes An=0, we get the conve-

Appendix A: Differential displacements of nient substitution:

particles in block ruled by wave equation

ka = n (21)

The solution of Eqs (10, 11) in the form of Eqs (1315) has 2 2(N + 1)

many interesting features, and some of them should be men-

tioned. The first interesting feature seems to be the fact that 2n =2Te 1 cos n =4Te sin 2 n (22)

Eqs (1012), relating the individual bottom well displacements mn a N + 1 ma 2(N + 1)

r0,n for many (n) particles do not have to depend on the actual

bottom wells positions of r0,n of interconnected particles. As a

special solution, Eqs (1012) can represent the wave equation

for vibration modes of elastic rod, or the motion of spring with

HLAVEK et al.

New Jersey 1955, p.12.

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J Therm Anal Calorim (2012) 110:9971004

DOI 10.1007/s10973-011-1926-6

when comparing other criteria in relation to the glass stability

and vitrification ability

Ana Kozmidis-Petrovic Jaroslav Sestak

Received: 13 July 2011 / Accepted: 16 September 2011 / Published online: 7 October 2011

Akademiai Kiado, Budapest, Hungary 2011

Hruby glass-forming coefficient (as well as of other anal-

ogous coefficients by, e.g., Weinberg and LuLiu) reveals In the 1960s, the former Institute of Solid-State Physics of

some generalized correlations between glass-forming the Academy of Sciences was one of the leading institu-

ability (GFA) and glass stability. The relative change of the tions in solid state physics within the so called Eastern

Hruby parameter is supreme in almost all cases. The Hruby socialist block then dominated by the former Soviet Union.

parameter is more sensitive in relation to the change of They knew how to prepare super-pure single-crystalline as

both the super-cooled region and the reduced glass-transi- well as glassy Si and Ge, were capable of their various

tion temperature. The only exception is the restricted sen- doping and even tackled the secrecy of transistor but did

sitivity respecting the reciprocal reduced glass-transition not realized its technical usefulness yet. The research

temperature in some cases of the bulk metallic glasses. The turned then to the field of amorphous (mostly chalcogen-

correlation of the Hruby coefficient with GFA is agreeable ide) semiconductors recognizing that the band gap does

for oxide glasses and thus can be commonly employed as a exists in spite of the absence of atomic long-range order

reliable and precise glass-forming criterion. Associated and is not empty containing an appreciable amount of

problems are the experimental determination of relevant localized states but having its edges no more sharp.

temperatures, most pertinent that for glass transition which Transport band edges coincide with so called mobility

is dependent to preparative condition of glass formation. edges where the mobility of carriers dramatically changes

while the optical band gap is determined by the extrapo-

Keywords Glass transition Reduced quantities lated absorption curve. It was discovered by Jan Tauc

Hruby criterion Sensitivity Glass-forming ability (19222010) [1, 2] who later immigrated to the US (Brown

DTA/DSC determination Temperatures University, Rhode Island). His coworker Arnost Hruby

(1919) was technologist who synthesized and analyzed

thousands of chalcogenide compounds and glasses and

investigated their thermal behaviors [3, 4]. He proposed the

A. Kozmidis-Petrovic

evaluation of glass-forming tendency by means of DTA

University of Novi Sad, Faculty of Technical Sciences,

Trg D. Obradovica 6, 21000 Novi Sad, Serbia (lately known as the renowned Hruby glass-forming cri-

e-mail: analeto@yahoo.com terion), which was published in a less known Czech journal

of physics [4] even though having received up to now

J. Sestak (&)

several hundreds of citations becoming the best cited paper

New Technology, Research Centre in the Westbohemian Region,

West Bohemian University, Universitn 8, Pilsen 30114, in the journal history. Besides giving a tribute to the

Czech Republic masterwork of Arnost Hruby, the purpose of this article is

e-mail: sestak@fzu.cz to revise the meaning and usefulness of Hruby criterion in

comparison with the other analogous coefficients and

J. Sestak

Division of Solid-State Physics, Institute of Physics, uncover some generalized correlations between glass-

Cukrovarnicka 10, 16200 Praha, Czech Republic forming ability (GFA) and glass stability (GS).

123

998 A. Kozmidis-Petrovic, J. Sestak

nucleation theory for condensed systems, Tammann [19,

Glass is a specific matter reflecting its original liquid makeup 20] called attention to a tendency revealing that the higher

and can be prepared by a suitable freeze-in of various, even the melt viscosity at the melting temperature (Tm), the

non-stoichiometric, combinations of elements/compounds. lower its crystallizability. Qualitatively, this tendency can

Such a disordered matter still presents stringent conceptual be explained by an increased inhibition of motion or

difficulties [59]. The often confused concepts of amorphous molecular rearrangement of the basic units of any melt with

and glassy states have recently been re-examined and pre- increasing viscosity. Mentioned by Kauzman [21] but

vious attempts to trace the distinction revised [5, 6]. Cur- particularly stated by Turnbull [22], who early indicated

rently, Queiroz et al. [7] considered thermodynamic aspects that when Trg is larger than 2/3, the homogenous crystal

of glasses focusing to their behavior in glass-transition nucleation will be essentially suppressed due to the slug-

region (GTR). Sunol et al. [8] examined phenomenological gishness of the crystallization kinetics. Therefore, Trg

and atomic methods by which glass transition can be became the earliest criterion to evaluate GFA of a liquid.

described. This new generic and phenomenological However, experimental observations indicated that Trg may

approach describes the kinetics and thermodynamics of fail to truthfully predict GFA in various cases, often doc-

vitrification as a real non-equilibrium process. Volume and umented by conventional relationships between Rc and

enthalpy relaxation in the GTR was analyzed by Svoboda Trg for different sort of glasses, where some good glass

et al. [9]. The finding that the activation energy of viscous formers show a low Trg and vise versa. Referring to a large

flow in the glass-transition range was identical with the set of available experimental data obtained for nucleation

effective activation energy for relaxation process. This of several silicate glasses, Zanotto [14] concluded that

subject received abundant number of citation responses [10]. glasses having Trg higher than *0.580.60 display only

Parameters predicting the GFA and consequent GS of its surface (mostly heterogeneous) crystallization, while

constrained state (of freeze-in glass) are of a substantial glasses showing volume (homogeneous) nucleation have

meaning to all those interested in various applications to Trg \ 0.580.60. The reduced glass-transition temperature

which glassy materials lend themselves. A timetempera- was examined in more details by Sakka and Mackenzie

turetransformation diagram for material annealing can [23], Uhlmann [24], and for metallic glasses also by Davis

provide all necessary data, but such data are rarely available [25]. Determination of theoretical values of reduced tem-

and moreover are often predicted on the assumption of peratures were approached by Angell [26] based on

homogeneous nucleation, which is a rather unlikely event in extension and extrapolation by means of application of the

practice. When a glassy matter turn out to be experimentally VogelFulcherTamman (VFT) viscosity equation. Sestak

accessible upon a suitably fulfilled melt quenching (critical [27] dealt with a greater augmentation of reduced quanti-

cooling rate, Rc) from its melting point (Tm) through the ties, such as a difference between liquid and crystalline

GTR [11, 12] (defined by the mean glass-transition tem- heat capacities DCpr, and tried to estimate approximate

perature, Tg), certain data became accessible for such a changes of entropy DSr, enthalpy DHr and chemical

material identification. A liquid with good GFA exhibits a potential Dlr assuming the values Tor and Trg. (Tor is the

low value of Rc for the glass formation which, however, has reduced Kauzman temperature).

remained a long-standing question as to why one liquid In order to unify notations, which use to vary in the cited

exhibits better GFA than another and how we can portray it. papers, the following text will employ Tx to denote the

According to the standard nucleation theory, a liquid onset crystallization temperature and Tc to indicate the

with a high viscosity between Tg and Tm typically exhibits peak crystallization temperature, which is convenient

a high GFA with a low Rc. Since the viscosity of oxide today. Let us also remind that GFA is noticeably related to

glasses at Tg is nearly constant (%1012 Pa s) [13], it was the ease of the reverse process of devitrification related to

postulated that a high value of the reduced glass-transition the difference between temperatures of re-crystallization

temperature, Trg (=Tg/Tm), would result in a high viscosity and glass transition.

in the undercooled liquid state, and, consequently, lead to a However, other parameters can be included, which can

low Rc. Zanotto [14, 15] showed that glass tendency to be comfortably monitored by DTA/DSC upon certain

homogeneous and heterogeneous nucleation can be dis- precautions (glass heating, etc.). It can provide a choice of

tinguished on bases of Trg. Cabrall et al. [16] pointed out data about the non-equilibrium glass crystallization tem-

that the maximum homogeneous nucleation rates, Imax, of perature laying customary below that for an analogous

silicate glasses strongly diminish with Trg and that Rc for melt. Then the interval between Tm and Tc (and Tx) is

metallic glass formation also drops with rising Trg. Corre- inversely proportional to GFA and the interval between the

lation between maximum growth rates and Trg for silicate onset of crystallization Tx and Tg is directly entitled to

glasses was shown by Fokin et al. [17, 18]. display GFA. A range of examples revealed that this

123

Forty years of the Hruby glass-forming coefficient 999

difference vary habitually with composition changes and calculated these data and found that the stability of glasses

tends to reach its maximum value in a composition range having parallel viscosity curves g(T) could be qualitatively

which appears to provide best/optimum glasses. evaluated according to the two above expressions, but they

Even a more sensitive interrelation to the glass forma- were not quantitatively reliable and none of them appears

tion peculiarities can be found on a basis of the widespread to be superior. Moreover, the paper also discloses that for

Hruby parameter [4], developed mostly for chalcogenide glasses for which g(T) significantly differs from each other

systems [28], which are typically available only upon in the region of Tg the stability criteria can become

physical preparation of a given type of glass.This criterion delusive.

[3, 29, 30] has an almost matching implication as the dif-

ference (Tx - Tg ) alone varying, however, more rapidly

when crystallization peak is shifted and taking also into Determinability of glass-transition temperature

account ease of melting. This factor may not be of a par-

ticular significance as the values of Tg and Tm are usually Glasses as an important domain of a generalized disordered

correlated [2931]. A wider applicability of KH was dis- matter still present experimentally stringent conceptual and

cussed by Thornburg [31]. thermodynamic difficulties. It was recently reexamined by

In the recent years, various GS parameters related to the Wunderlich [44] who revealed that in a continuous random

three characteristic temperatures have been investigated. web of a macromolecular system (which can properly

Table 1 contains some popular GS parameters. model a glass); the network can be a single amorphous

Aware that the potential correlation between GS and phase, mesophase, molecularly coupled multiphases of

GFA is of a great importance, this issue became the subject different degrees of order and metastability or even a

of various theoretical studies as well as of assorted modulated crystal-like structure (liquid or plastic crystals)

experimentation. [45].

For example, Weinberg [43] made use of the standard Different state of a similar network (such as silicate

theoretical expressions for crystal nucleation and growth quenched melts and/or solution prepared polysialates) may

rates considering homogeneous nucleation and screw dis- show a range of glass-transitions processes observable even

location growth in stoichiometric glasses. In his paper [43], at a simultaneous manner. Perceptible values needed for a

the trends in GFA and GS were compared with systematic correct recognition of the phase transitions lies in the fact

changes in the melting entropy, DSm, and the viscosity that materials must be pliable for being prepared into its

parameters. The resulting conclusion was that GFA and final shape and then experimentally measurable (often by

GS, defined by (Tc - Tg)/Tm, were poorly related [43]. In a means of DTA/DSC), which involves lot of experimental

subsequent work, Weinberg [33] derived the time neces- variability and associated uncertainty. Therefore, the

sary for crystallization of a minimum detectable fraction determination of glass-forming criteria requires sustaining

based again on a classical homogeneous nucleation and certain precautions and data standardizations. There are

screw dislocation growth. Worth mentioning are time cri- numerous publications discussing the theme, e.g., [4649].

teria used to assess GFA and test the reliability for two However, the best analysis was shown by studies of

particular GS parameters, given by the expressions: (Tx - Illekova [5054] who separated various influences in

Tg)/Tm and (Tx - Tg)(Tc - Tx)/Tm. Weinberg [43] alienated areas emphasizing that in metallic glasses the

measured Tg is habitually lower than the true thermody-

Table 1 Some GS parameters based on the characteristic tempera- namic Tg while for other oxide or chalcogenide glasses, the

tures specified in the text true Tg depends also on the inherent fragility of sample

GS parameter Envisaged by glass. Moreover, Tg of metallic glasses is often affected by

aging of glass even at room temperature. There is also a

KH = (Tx - Tg)/(Tm - Tx) Hruby [4] obvious difference for Tg obtained for either during cooling

KSP = (Tc - Tx)(Tx - Tg)/Tg Saad and Poulain [32] and heating, moreover for some cases is sketched by mere

KW = (Tc - Tg)/Tm Weinberg [33] estimation.

KLL = Tc/(Tg ? Tm) Lu and Liu [34, 35] There is a common correlation of both kinetic processes

cm = (2Tx - Tg)/Tm Du [36] of structural relaxation and crystallization. Nevertheless,

/ = Trg(DTxg/Tg)a Fan [37] the crystallization kinetics is of two major types (JMAYK

x = Tg/Tc - 2Tg/(Tg ? Tm) Long [38] and NGG) and may contradictory affect the peak position,

b = TxTg/(Tm - Tx)2 Yuan [39] namely any thermal annealing may shift the exothermic

Some unusual criteria you can find in [4042] involving extra kinetic crystallization peak opposite, i.e., to higher temperatures

factors [40, 41] or a contrary interpretation in terms of glass state for the classical nucleation-growth (JMAYK) and contrary

safeguarding [43] to, lower temperatures for NGG. Therefore, any thermal

123

1000 A. Kozmidis-Petrovic, J. Sestak

treatment must be avoided during the determination of This is the reason why we shall analyze the individual

glass-forming coefficients unless the study is aimed to the criteria in more detail respecting the three characteristic

resolution of nucleation/growth rates [5560]. temperatures and mentioning assessment in the paper [39],

Staying power of individual criteria evidently depends which stresses that GS parameters (estimating GFA) should

on a correct determination of characteristic temperatures be enough sensitive. The larger the values of the KH, KW,

and further more detailed analysis falls beyond the subject and KLL the higher is stability of a glass against devitrifi-

of this communication. cation [4, 62]. Also, when comparing one glass to another,

it is essential to know how large the relative changes of the

given parameters are and how they can be compared with

Expressing the Hruby parameter using temperature the relative change of other GS. In other words, it is nec-

relations normalized to Tg essary to distinguish which of the GS parameters shows the

fastest change.

After Weinbergs paper [43], Cabral et al. [61] brought into Our starting point is the fact that all the criteria, KH, KW,

play experimental values and found a correlation between and KLL, include the same characteristic temperatures. For

the Hruby parameter of GS and GFA. However, these this reason, we can express them in a somewhat different

results [61] were somehow contradictory in relation to the way based on the intact ratios of the temperatures, namely

theoretical calculations of Weinberg [43]. Extending these m = Tm/Tg and r = Tc/Tg. In doing so, we assume that in

calculations, Avramov et al. [62] decided to test out these defining both KH and KLL it is possible to replace onset

two approaches upon examining different assumptions, crystallization temperature Tx with maximum crystalliza-

which were supported by experimental data. The paper [62] tion peak temperature Tc as was shown in the paper by

demonstrated that GFA and GS follow the same trend and Nascimento [64]. After simple mathematical transforma-

are directly related to each other. tions [70], one obtains relations KH = (r - 1)/(m - r) and

Several other considerable studies have appeared, which KW = (r - 1)/m and KLL = r/(m ? 1).

inveterated correlation between the GS parameters and By using the substitutions of r and m, the GS parameters

critical cooling rate Rc, or between the GS parameters and can be expressed indirectly by means of both the reduced

maximum section thickness, i.e., the diameter Dmax, by glass-transition temperature Trg and the super-cooled

which the GFA are also estimated [34, 3639, 6365]. In region DTxg. It is because the parameter m factually rep-

the papers [34, 62, 64, 66], a rather good correlation is resents the reciprocal value of Trg, and the parameter

shown between GFA and GS parameters, which are based r correlates to DTxg, as was shown in the work of Lu and

on the three characteristic temperatures such as the Hruby Liu [34], Mondal [71], or in a recent work by Zhang et al.

(KH), Weinberg (KW), and LuLiu (KLL) criteria. Nasci- [72]. Namely, in order to enable the comparison for dif-

mento et al. [64] proved that for the oxide glasses a very ferent glasses, the value of the super-cooled region is

good correlation between the Hruby parameter and GFA divided by Tg [34], which gives (Tx - Tg)/Tg = r - 1.

exists. Also, very good correlation between KLL and GFA Mondal et al. [71] used the same normalization and pro-

has been found for the oxide glasses from [64] and for posed that Tx/Tg (in our cases r) can also be considered as a

those from [67]. However, the parameters Rc and Dmax are measure of the thermal stability of glass. In [72], Zhang

hard to measure a in a sufficiently precise way [35, 38, 39, et al. introduced the factor of crystallization resistance Tg/

6669] so that of essential importance become the corre- (2Tx - Tg), which can be auxiliary expressed as 1/(2r -

lations between GFA and GS expressed via characteristic 1). From a mathematical point of view, the introduction of

temperatures [6169]. These temperatures are usually the ratios r and m allows the reduction of the number of

determined by DTA/DSC [3, 30, 37]. A satisfactory degree independent variables by which the parameters KH, KW,

of correlation between the determined GS parameter and Rc and KLL are defined. Instead of the three characteristic

(or Dmax) would allow one to use the given GS parameter temperatures, we use their two ratios (r and m) acting as

to assess GFA. independent variables.

In spite of the criteria discussed above approachable

through the three characteristic temperatures, the entire

reduced glass-transition temperature shows a weaker cor- Relative changes of GS parameters

relation with GFA. The work of Nascimento [64] proves

that Trg has a reduced correlation with GFA for oxide In order to derive expressions for the relative changes of

glasses than KH, KW, and/or KLL. Furthermore Lu and Liu these parameters, as shown in our previous paper [70], we

[34, 35] showed that Trg had the weaker correlation with first employ logarithms of the expressions for KH, KW, and

GFA than their criterion KLL for glasses analyzed in [34]. KLL and then make differentiation

123

Forty years of the Hruby glass-forming coefficient 1001

KH r1 mr mr KW r1 m to the changes of temperature ratios

dKLL dr dm 1

KLL r m1 The next objective was to find out how these GS parame-

ters are sensitive to the changes of r and m, and whether

It is necessary to point out that we assume the following

this is reflected on the correlation of the given parameter

relations hold for m [ 1, r C 1, m [ r.

with the GFA. Besides the KH and KLL, the newly defined

By comparing the right hand side expressions in Eq. 1

parameters / [37], and x [38], showed also a rather good

[70], it holds that if the condition dr [ dm is fulfilled, i.e.,

correlation with GFA for a variety of glasses [3739].

if d(Tc/Tg) [ d(Tm/Tg) is satisfied, then the following

Thus, it is necessary to include them in our analysis.

relation keeps continuously valid dKH/KH [ dKW/KW [

Simple transformations of the expressions by which they

dKLL/KLL.

have been introduced allow us to express the parameters /

Such a relation of the relative changes of the GS

and x, using ratios r and m, instead of using the charac-

parameters will also hold when a less stringent condition is

teristic temperatures [70]. Thus, / = (r - 1)a/m and

satisfied, i.e., when dr/r [ dm/m. If the condition dr/

x = 1/r - 2/(m ? 1). In order to determine the change

r [ dm/m is not fulfilled, then the following relation of the

of the investigated GS in relation to r and m, we take the

relative changes of the GS parameters will maintain: dKW/

derivatives of expressions for KH, KLL, /, and x with

KW [ dKH/KH [ dKLL/KLL. As it can be seen, the relative

respect to both values of r and m. On this way, for KH is

change of the LuLiu parameter will always have the

obtained dKH/dr = (m - 1)/(m - r)2 and dKH/dm = -

smallest value, and will never become greater than the

(r - 1)/(m - r)2. The analogous expressions for changing

relative change of the Hruby parameter. The above theo-

KLL, /, and x in relation to r and m can be found in [76].

retical derivations were successfully tested on two series of

The individual partial sensitivity of the GS parameter to

oxide glasses and one series of chalcogenide glasses [70]

r and m is, however, not related to the R2 coefficient for the

showing a good agreement with the theoretical results.

correlation of the GS parameter and GFA [76]. The balance

The next step was to establish a relation between the

of sensitivity of the GS parameter to r and m, (i.e., the ratio

maximal value of relative changes of the Hruby, Weinberg,

dGS/dr:dGS/dm) implies the magnitude of the R2 coeffi-

and LuLiu parameters. In order to obtain the maximal

cient. At the same time, the degree of correlation of values

value of relative changes notice that the minus signs in

r and m with the GFA is significant.

expressions (1) should be replaced by the plus ones,

Results of the above theoretical derivation were tested on

because for maximal change we should assume that all

series of oxide glasses. The characteristic temperatures Tg,

changes have the same direction. Thus, we obtain

Tc, and Tm were taken from the work of Cabral et al. [65] for

dKH dr dm dr dKW the following seven oxide glasses: Li2O2SiO2 (LS2);

KH max r 1 m r m r KW max Na2O2CaO3SiO2 (NC2S3); 2Na2OCaO3SiO2 (N2CS3);

BaO2SiO2 (BS2); LiO22SiO2 with 0.2% mol OH (LS2OH);

dr dm dKLL dr dm

2BaOTiO22SiO2 (B2TS2), and 0.44Na2O0.56SiO2

r1 m KLL max r m1

(44NS).

After comparing right hand side of expressions in Eq. 2, Figure 1 shows the ratios dGS/dr:dGS/dm that we cal-

the following relation between the maximal values of culated for these oxide glasses.

relative changes keeps up [73] As it can be seen from Fig. 1, the values of the ratios

dKH/dr:dKH/dm, dKLL/dr:dKLL/dm and dx/dr:dx/dm are

dKH dKW dKLL

[ [ 3 always greater than one. This means that KH, KLL, and x

KH max KW max KLL max

are more sensitive to the change in relation to r than to the

The relation between maximal relative changes of GS change in relation to m. For KH, this is easy to predict by

parameters (cf. Eq. 3) has been tested on several series of comparing the appropriate expressions above. We take the

oxide glasses from [64] and chalcogenide glasses from characteristic temperatures and values for critical cooling

[74, 75]. rate from [65] and calculate the values of GS parameters as

The glass having the largest value of r, that is the largest Tc/ well as the values of R2 factors in correlation with critical

Tg ratio, was selected as reference one, with respect to which cooling rate for mentioned oxide glasses. The higher the R2

we calculated the differences. From these results, it follows value, the better the correlation between GS parameter with

that for the considered glasses the relation between the max- critical cooling rate. With the analyzed oxide glasses,

imal relative changes of GS is in accordance with Eq. 3. It is r correlates well (R2 = 0.900), whereas m does not corre-

worth accentuating that the maximal relative change of the late with GFA. Since only r (and not m) correlates satis-

Hruby parameter KH subsist the greatest upshot. factorily, it can be supposed that for KH, KLL, and x the R2

123

1002 A. Kozmidis-Petrovic, J. Sestak

9 0.8

dKH/dr:dKH/dm

8

0.7

dKLL/dr:dKLL/dm

7

0.6

dGS/dr:dGS/dm

6 d /dr:d /dm

KH

0.4

3

0.3

2

1 0.2

0 0.1

3

NS

2

3

H

CS

LS

TS

2S

BS

O

44

0

2-

B2

NC

N2

LS

Glasses KLL

Fig. 1 Ratios dGS/dr:dGS/dm (GS = KH, KLL, /, x) for oxide Fig. 2 Correlation between the Hruby parameter KH and parameter

glasses using abbreviation for 0.44Na2O0.56SiO2 (44NS); KLL for BMG bulk metallic glasses, adjusted from [38]

Li2O2SiO2 (LS2); LiO22SiO2 with 0.2% mol OH (LS2OH);

BaO2SiO2 (BS2); Na2O2CaO3SiO2 (NC2S3); 2Na2OCaO3SiO2

(N2CS3); and 2BaOTiO22SiO2 (B2TS2) significantly different from those of the linear connected G-

criteria for tested glasses. This does not mean that KH do

coefficient of correlation with GFA will be larger, because not show good correlation with GFA, in cases for example,

the value of r has a greater influence than m. But for /, the for oxide glasses.

influence of m, which does not correlate with GFA, is

significant. Hence, one can expect that R2 for / is smaller Summary

than for KLL, KH, and x. This was confirmed by our cal-

culation of R2 obtaining the following values: KH = 0.829, All the results discussed above show that the initially

KLL = 0.759, x = 0.784, and / = 0.649. These R2 factors proposed Hruby criterion [4] is one of the best parameters

are smaller from the ones obtained for oxide glasses which at all. As can be seen from the theoretical derivations, the

we investigated in [76], but the tendency of changes of relative change of the Hruby parameter KH is the greatest in

correlation of GS parameters in relation to critical cooling almost all cases, and the maximal value of the change of

rate is similar. The difference between oxide glasses in [76] the Hruby parameter occur the greatest too. Also, the

and in this analysis is that KH has the best correlation with correlation of the Hruby parameter with GFA is very

Rc. Also, in this analysis (as a difference from [76]), values apposite considering oxide glasses.

of dGS/dr:dGS/dm are always the biggest for KH if we

compare these relations for KH, KLL, and x. Acknowledgements This study has been carried out with the partial

In this article, we will look (only from the mathematical support of the Serbian Ministry of Science and Technological

point of view), what occurs when the r \ 1 (Tg [ Tx in the Development, within the projects Nos. III 45021 and 172059 and the

grant support in the field of geopolymers No. FR-TI 1/335 provided

ribbon form of metallic glasses). From above expressions, by the Ministry of Industry and Business of the Czech Republic.

it easily follows that in this case dKH/di [ dKH/dm too.

When comparing the values of dGS/dr and dGS/dm for

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123

Journal of

J. Min. Metall. Sect. B-Metall. 47 (2) B (2011) 229 - 239 Mining and

Metallurgy

CorrespondIngly developed glAss-formIng CrIterIA

A personAl reColleCtIon At the forty yeArs

AnnIversArIes

University, Universitn 8, CZ-30114 Pilsen, Czech Republic

**University of Novi Sad, Faculty of Technical Sciences,

Trg D. Obradovia 6, 21000 Novi Sad, Serbia

***University of Belgrade, Technical Faculty, VJ 12, 19210 Bor, Serbia

Abstract

Hruby glass forming criterion. Despite various analysed modifications it reveals that the sensitivity

of original criterion is unsurpassable. The applicability of Sestak-Berggren empirical equation for

the description of crystallisation kinetics is comparable with the classical modelling based on

Johnson-Mehl-Avrami equation. Their employment is certainly dependent to the purpose of

evaluation showing their substitution ability and limits.

constrained metastable phases (metallurgy);

There are numerous important personalities in extreme providing the unusual freeze-in

who paved the scientific road toward a better state of glasses. Associated processes

understanding of new phase formation, which remained in the center of research until today,

is the core of most crystallization processes. It but rich figures have got lost in the extended

became especially important during the past of extensive scientific research. Some

application of fast temperature changes often important scientist are shown in the raw of

# Corresponding author: sestak@fzu.cz

DOI:10.2298/JMMB110612014S

230 J. estk / JMM 47 (2) B (2011) 229 - 239

photos below, just to keep in mind illustrious emphasizing their great protagonists, see Fig.

history of exploration of solid-state reactions 1., read from the left.

Fig 1. Gustav H.J. Tammann (1861-1938) called earliest attention to a tendency, which revealed observation

that the higher the melt viscosity at the melting temperature, the lower is its crystallizability [1]. He also invented

the term thermal analysis[2]. Frederik F.H. Zachariasen (1906-1979) considered the principles how the

bonding requirements are met and the nearest neighbor coordination maintained without imposing an exact long

range order [3]. Walter Kauzman (1916-2009) analyzed the behavior of liquids at lower temperatures, pointing

out that the entropy of undercooled liquid decreases rapidly on cooling towards the kinetic glass transition

temperature [4] and extrapolates to the entropy of the crystal at so called Kauzman temperature. Jakov I. Frenkel

(1894-1952), became famous for his fundamental book [5] factually introducing the concept of disorder. David

Turnbull (1915-2007) brilliant material scientists who in 1946 joined the famous General Electric laboratory

performing research into nucleation of structural transformations [6], introducing reduced temperatures and

demonstrating that such complex glass-forming processes could be quantitatively better understood [7]. Below

raw, Robert F. Mehl (1898-1976) was famous with the American Institute of Mining and Metallurgical concerned

with areas of solid-state reactions, diffusion, precipitation, plastic deformation, preferred orientations, and

oxidation. He separated the role of nucleation from that of growth of new phases in solid-state transformations

and developed generalized theories applicable to re-crystallization describing the volume fraction of a solid

transformed in terms of the formation rate and spatial distribution of nuclei and the subsequent growth of the

nuclei [8]. Arnot Hrub (1919-) was an accomplished technologist who synthesized and analyzed thousands of

chalcogenide compounds and glasses identifying and describing their properties and proposing so called Hruby

glass forming criterion [9]. Donald R. Uhlmann (1936-) former director of the Arizona Research Laboratory,

fellow and awarder of the American Ceramic Society, the coauthor of both the recognized nucleation-growth

theory [10] and the famous Kingerys and Kreidls fundamental book on ceramics [11]. Michael C. Weinberg

(1942-2003), architect of various alternative theories on nucleation and glass-formation, [12,13]. Edgard D.

Zanotto (1954-) another representative of emerging generation of new theoretical kineticists responsible for the

advanced nucleation and crystallization theories mostly applied to silicate glasses [14,15], the chair of the ICG

(TC7) committee on glass crystallization and the editor of J Non-cryst. Sol.

J. estk / JMM 47 (2) B (2011) 229 - 239 231

A special attention should be paid to the its opposite hindrance, i.e., contradictory

Institute of Physics of the former obstruction of glass-forming ability and

Czechoslovak Academy of Sciences, which associated glass stability. The classical

in the turn of 1970s was one of the leading nucleation-growth description became thus

institutions in solid state physics and important and is analyzed in terms of the

chemistry [16-19] within the so called estk-Berggren empirical equation [18] all

Eastern socialist block then dominated by the hints instigated at the occasion of the forty

former Soviet Union. Its employee Arnot years anniversary of the earliest papers

Hrub [9] was a gifted technologist who publication [9,18].

investigating thermal behaviors of

chalcogenides mainly by means of DTA. His hruby glass-forming coefficient and

famous glass-forming criterion published in related criteria

a less known Czech Journal of Physics [9]

nevertheless received abundant citations Disordered matter still presents stringent

responses [19]. His coworker J. estk conceptual difficulties being prepared under

contributed kinetic study of crystallization extreme conditions of either the self-cooling

processes by various means of thermal of compositionally adjusted mixtures [22]

analysis [16,17] showing the way how to (silicates, alloys even in metallurgy) or by

formulate a generalized model of logistic attuned quenching [23] (usually applied to

(autocatalytic) equation [18] effectively the ribbon preparation of metallic glasses).

analogous to nucleation-growth kinetics. All Coupled and repeatedly confusing concepts

these topics got a prospect to be extensively of amorphous and glassy states were re-

cited in the literature, for example, Hruby [9] examined recently by Queiroz and estk

gained as many as 372 and Sestak Berggren [24-26] considering thermodynamic aspects

equation [18,19] 566 responses becoming of glasses in the glass transition region.

thus the best cited papers in the respective Associated parameters endeavoring the

journal [19], which are comparable with the prediction the glass forming ability (GFA)

Jander equation on diffusion [20] with and/or the consequent glass stability (GS) of

551citations. It is still below Mehl paper [8] the constrained states of freeze-in glasses are

on general kinetics of phase changes with of substantial terminology meaning [22,26].

2172 or Kissinger paper [21] on DTA It is often related to the time-temperature-

determined kinetics with 4461 but analogous transformation (T-T-T) diagram [22]

to similar Uhlmann paper [10] on common for the description of material

crystallization kinetic 417 or Zanotto paper annealing creditable for the subsequent

[14] on generalized nucleation theory with occurrence of nucleation-growth kinetics.

190 citations. The soaring output of the However, T-T-T is rarely available and

kinetic papers published during 1970s is thus moreover needs to be predicted on the

worth of attention revising their meaning and assumption of homogeneous nucleation,

uncovering some generalized correlations which is an unlikely event in practice. When

between the easiness of crystallization and a glassy matter does happen to be

232 J. estk / JMM 47 (2) B (2011) 229 - 239

experimentally accessible upon a suitable formation was assumed by Saad and Poulain

melt quenching (critical cooling rate, Rc) [34] which took into their consideration the

down from its melting point (Tm) through the width of a DTA/DSC peak, i.e., the difference

glass transition region (GTR), defined by the between the onset of crystallization Tc and its

mean glass transition temperature (Tg) maximal value Tx [34, 35]. Such a new

certain data became accessible for such a criterion (Tx Tc)(Tc - Tg)/ Tg comprises the

material identification [27-33]. unit of Kelvin, but is capable to become

Consequently a range of following criteria dimensionless if weighted by squared Tg.

was proposed. The other popular glass-forming parameters

was proposed by Weinberg [36] KW = (Tc

Tg)/Tm and in the recent years, various

other parameters have been investigated,

such as the parameter envisaged by Lu and

Liu [37, 38] as KLL = Tc/(Tg + Tm). There are

additional parameters proposed in the papers

[39-42] mostly related to the previously

mentioned characteristic temperatures dealt

in details with allied papers [31-57].

In the paper by Weinberg [43] the trends

in GFA and GS were compared with

systematic changes in the melting entropy,

DSm and the viscosity h concluding that GFA

and GS (defined by (Tc-Tg)/Tm ) are poorly

related. Weinberg [36] also derived the time

necessary to crystallize a minimum

detectable fraction based again on a classical

Fig. 2. Original proposal of reading the

characteristic temperatures in the Hruby glass- homogeneous nucleation and screw

forming criterion dislocation growth in stoichiometric glasses.

Time criteria were used to assess GFA and

A rather sensitive interrelation to the glass test the reliability of two particular GS

formation (GF) particularity can be found on parameters (given by the previously

basis of the widespread Hrub parameter mentioned expressions [34, 43]) observing

[9,31]. It is typically available upon a that the stability of glasses with the parallel

physical preparation of a given type of glass viscosity curves h(T) could be qualitatively

and can be calculated as KH = (Tc - Tg)/(Tm - weighed up. Zanotto et al [44] used

Tc) on basis of experimentally detectable experimental values and found a correlation

quantizes (usually figured out by DTA [9, 31, between the Hrub parameter [9] of GS and

32], such as Tc , which is the onset of GFA being, however, contradictory in

crystallization temperature). A more relation to the theoretical calculations of

receptive parameter toward the glass Weinberg. Avramov et al. [45] extended the

J. estk / JMM 47 (2) B (2011) 229 - 239 233

calculations of Weinberg [43] but tested a that all the coefficients KH, KW and KLL,

different assumption, which is supported by include the identical three characteristic

experimental data demonstrating that GFA temperatures possible to express them in a

and GS follow the same trend and are jointly somewhat distinctive way by mere ratios of

interrelated. Recently, several other respective temperatures, such as m = Tm/Tg

important studies have appeared [46-55], and r = Tc/Tg. where that the following

which demonstrate correlation between the relations always sustain, i.e. : m>1, r1, m>r.

GS parameters and critical cooling rate Rc, or Thus the both KH and KLL is possible to

between the GS parameters and the incept the crystallization temperature Tx with

maximum sample thickness, i.e. the section the maximum crystallization peak

diameter Dmax, by which the glass forming temperature Tc as was shown by Zanotto et al

ability are estimated [37, 39-42, 46, 47]. It [46]. After simple mathematical

again reveals a rather good correlation transformations we obtain KH = (r-1)/(m-r),

between GFA and GS, based on the above KW = (r-1)/m and KLL = r/(m+1). Using the

three characteristics given by the Hrub substituted r and m, the GS parameters can

(KH), Weinberg (KW) and Lu-Liu (KLL). be expressed indirectly via the reduced glass

Zanotto et al [46] proved that for the oxide transition temperature Trg and super cooled

glasses a very good correlation between the region Txg. It is because the parameter m

Hrub parameter and GFA can exists and represents the reciprocal value of Trg, and the

another good correlation between KLL and parameter r can be correlated to Txg, as was

GFA was also established [46, 49]. Another shown in the work of Lu and Liu [37] and

exploit was found even for metallic glasses Mondal [53] or in a recent work by Zhang et

[50, 51]. al [54]. In order to enable the comparison for

The work of Zanotto et al [46] different glasses [55], the value of the super

proves that Trg has the weaker correlation cooled region is divided by Tg [37], which

with GFA for oxide glasses than KH, KW and gives (Tc-Tg)/Tg = r-1. Mondal et al [53]

KLL,. Similarly, Lu and Liu showed that Trg used the same normalization and proposed

has the weaker correlation with GFA than that Tx/Tg (= r) can also be considered as a

their parameter KLL for glasses analyzed in measure of the thermal stability of glass.

[37]. Larger values of the coefficients KH, Zhang et al [54] introduced the factor of

KW and KLL imply higher stability of the crystallization resistance Tg/(2Tx-Tg)

glass in respect to devitrification [45] Also, (=1/(2r-1)).

when comparing one glass to another, it is In order to derive expressions for the

essential to know how large the relative coefficients relative changes, Kozmidis-

change of the given parameter is and how it Petrovic [31, 52, 57] first took logarithms of

can be compared with the relative change of KH, KW and KLL and then differentiated the

other GS parameters. In other words, it is obtained values achieving inequality

necessary to know which of the GS dKH/ KH > dKW/ KW > dKLL/ KLL, which is

parameters shows the fastest change. valid when d(Tc/Tg) > d(Tm/Tg) i.e. if the

Kozmidis-Petrovic [52] pointed the fact condition dr>dm is satisfied. Resulting

234 J. estk / JMM 47 (2) B (2011) 229 - 239

relative changes of the GS parameters will Prout-Tompkin equation (turning thus into its

also hold under a less stringent condition dr/r limiting case [61]). The increasing value of

> dm/m. The relative change of KLL will m often indicates a more important role of

always have the smallest value being never the precipitated phase on the overall kinetics

greater than the relative change of the consequently showing that this two

original Hrub parameter [9, 31, 57], which parameter model preserve its physical

satisfactorily the best sensitivity KH. The meaning for m 1 [61, 62]. It also appears

ensuing relation between the maximal values that a higher value of the second kinetic

of relative changes of the individual K- exponent (n > 1) signifies increasing reaction

parameters approves thus the priority of complexity. Besides the S-B equation

Hruby coefficient [4,57] by (dKH/ KH)max > subsists as a generalized operate based on the

(dKW/ KW)max > (dKLL/ KLL)max. logistic function [59, 61], a{a(1 a)}, which

is customarily exploited to depict the case of

estk-berggren (sb) kinetic equation population growth where a is the

for a generalized crystallization proportional factor of so called attractivity.

It consists of two essential but counteracting

At the anniversary [19] of estk- parts, the first one responsible for mortality @

Berggren (S-B) equation [18], it reads as am (i.e., reactant disappearance and the

da/dt @ am(1a)n, (where a is the product formation) and the other for fertility

dimensionless degree of crystallization, t is @ (1a)n (i.e., a kind of products hindrance

time, da/dt is the crystallization rate and the generally accepted as an counter-parting

omitted proportional Arrhenius constant autocatalytic effect [61]). The non-integral

exp(-E/RT) incorporates temperature, T). S- exponents, m and n, play thus the similar role

B was proposed in a particular association as a broadly assumed non-integral

with a well established kinetic model dimensions common in the natural world of

introduced jointly by Johnson-Mehl-Avrami fractals [62].

(JMA) [8, 18, 58-62] as da/dt @ {-ln (1- The S-B equation can be found credulous

a)}p(1-a). Since 1971, S-B received for serviceability as an alternative to the

abundant citation responses and even classical JMA equation [61-66] and thus

became a part in the titles of various kinetic exploitable for an assortment of model

papers [62-66]. It is worth noting that upon descriptions of both the interface-controlled

the Taylors expansion the function {-ln (1- and the diffusion-limited crystallization.

a)}p can display a certain mathematical Such a modeling starts from an original

inter-convertibility upon the expansion and comprehensive form of ln ( 1- a ) = - kTtr,

recombination to the matching am [58-61]). where the general exponent, r, can be seen as

The two appropriately paired exponents a multipart number of a robust (so called

of the S-B equation (m and n) are suitable for overall) analysis. In terms of DTA

a wide-ranging kinetic assessment, which measurements it reveals that the overall

includes the classical model of autocatalytic apparent values of activation energies Eapp

reaction (where m=1 and n=1) often called [67] can be commonly correlated to the

J. estk / JMM 47 (2) B (2011) 229 - 239 235

partial activation energies of nucleation, EN, enabling, however, certain but limited

growth, EG and/or diffusion, ED by a simple conversion to the traditional geometrical

relation Eapp = (aEN + bdEG)/(a + bd) where models [60-70]. There is a certain correlation

a and b are characteristic multiplying between the S-B exponents m-n and JMA

constants providing that the denominator (a exponents r (and p) [60, 62, 69, 70] see Fig 3.

+ b d) equals to the power exponent, r, of the Another agreeably workable alternative to

original JMA equation, and the value b the JMA crystallization is the mechanism of so

corresponds to 1 or related to the called normal-grain-growth (NGG)

movement of growth front controlled by resembling mode close to the mathematical

either chemical reaction (1) or diffusion () modeling of phase-boundary reactions [59-

[16, 61, 67]. Moreover, the coefficients d and 61], i.e., am(1a)n where m0. This case is

b are associated with the nucleation velocity abbreviated as the Atkinsons NGG model

and the growth dimension, respectively. [72], which has been effectively applied by

However, it endowed with a rather complex Illekova [73, 74]. NGG factually reflects the

pattern so far mathematically soluble but process of coarsening of the nano-crystalline

experimentally problematic in order to reach phase, when grain size falls below 10 nm,

reliable association with (desirable) which is common in some metastable

microscopic observations [58]. metallurgical alloys and constrained glasses.

In 1990 this S-B equation was completed In this instance the DSC/DTA exothermic

[68] by the conjecture of the so called crystallization peaks is converted into different

accommodation function, h(a) which is a shape possessing atypical symmetry, which is

effortless empirical function containing the the result of rationale arising from the

smallest possible number of constant and differences in JMA and NGG mechanisms

enabling certain flexibility in order to [72-74].

sufficiently match mathematically the real

course of a process under study. In such case,

the kinetic model of a heterogeneous reaction

is factually assumed to be a distorted case of a

simpler (ideal) instance of homogeneous

kinetic prototype, i.e., h(a)f(a) h(a) (1-a)n

[68]. It thus gives a credit to the recognition of

a certain defect state (imperfection, non-

ideality, heterogeneity such as the controlling

role of interfaces). The function h(a) can be

equally am and/or [-ln (1-a)]p displaying in a

way, above mentioned inter-convertibility with

the JMA model function, which brought to

kinetics an additional sphere of a more

widespread applicability approaching thus the Fig. 3. Portrayal correlation between JMA

model-free domain of kinetic evaluations (r) and SB (m-n) exponents.

236 J. estk / JMM 47 (2) B (2011) 229 - 239

we assume, however, that the goal of most

The determination of characteristic studies is a more and less pragmatic [59-61,

temperatures is an ordinary task in thermal 71, 76, 77], i.e., the reportable

analysis [59-61, 75] (and likewise derived determination of an unspecific data on

SB-equation) possibly providing a rather reaction mechanism the SB-equation

good mathematical match toward the trial subsist satisfactory. However, if we are

modeling of crystallization, see Fig.4. It seeking a correlation to one of the

should be reminded that somehow confidential physical-geometric models we

inconsequential information is involved have to look for an alternative

representation based on otherwise

observable morphology between the true

reaction image and the theoretical portrait

symbolized by the model assumed.

However, a more in-depth seeking may

correspond with an innovative so called

model-free kinetics (e.g. imon [78]) and/or

congruent dissociative vaporization kinetics

(e.g. Lvov [79]). In the first case [78] the

kinetics for an analogous crystallization of two brands of similarly vitrified alloys [74] melt-quenched by

a single roll technique to form ribbons (10-20mm thick and 10mm wide). Right is the tangible glass of

composition of Fe75Si15B10 while left is the nano-crystallized finemetal with a comparable stoichiometry

Fe74Si13B9Cu1Nb3 [80, 81] (just with a small doping of Cu and Nb). Both flat samples were treated

correspondingly, freeze-in ribbons were cut in several pieces and pressed into a Pt-cell with the in-weight

of 15mg; heating rate was 40 K/min (applied under nitrogen inert atmosphere to avoid oxidation). The

ribbons were pre-annealed at the fixed temperature of 500oC and annealing time was progressively

prolonged, for the sake of simplicity the particular curves fall within the shaded areas.

Right: the classical JMA nucleation-growth mechanism [8, 58-62], which display the non-integral

values of S-B exponents [16-18, 70], i.e., m<1 and dimension dependent 1<n<3 (in conjunction with a

nucleation short-rage diffusion plausibly involving their radii relation r/ro = (1 a)1/n , where r and ro

are the radii at t = t and t = 0. The resulting sharp peak apexes are typically shifted along with the

increased heating to commonly follow the kinetic evaluation method by Kissinger [21], widely employed

in the literature [59-69].

Left: a more distinctive Atkinson [72-74] normal-grain-growth (NGG) of nano-particles coarsening,

which show signs of phase boundary reactions (controlled by interface propagation). Such a process is

reliant on a longer range diffusion and nano-particles initial and actual size ro and r. For m approaching

zero (am~1) the scheming exponent n holds for the reaction rate in the form of (1 a)n+1/(n ron). In

consequence the experimentally measured DTA peaks (DT vs. T) reveal different symmetry with an

atypical behavior of broadened apexes and their shifting under increased heating rate [74,80], which

may cause certain intricacy in traditional kinetic appraisals.

J. estk / JMM 47 (2) B (2011) 229 - 239 237

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