DIAGRAMMI DI FASE

The basis of all phase diagrams is the phase rule, P + F = C + 2, where P represents the number of coexisting phases, F
the number of degrees of freedom remaining in the system and C the number of components.

A ‘phase’ is defined as any part of the system which is physically homogeneous and bounded by a surface so that it is
mechanically separable from other parts of the system.

In terms of the phase rule, the number of ‘components’ C is defined as the smallest number of independently
variable chemical constituents necessary and sufficient to express the composition of each phase present. (For
example, although there are three elements present in calcium silicates, Ca, Si and O, all phases compositions can be
expressed in terms of CaO and SiO2. Therefore C = 2 for the ‘binary’ CaO–SiO2 system.

The number of ‘degrees of freedom’, F, is the number of intensive variables -non dipendono dalla quantità di materia-
(e.g. pressure, temperature, composition) that can be altered independently and arbitrarily without bringing about the
disappearance of a phase or the appearance of a new phase. When F = 0, the system is said to be ‘invariant’ and all
properties are fixed. For F = 1, the system is ‘unvariant’ and the specification of one variable, for example, temperature,
automatically defines all others, and so on.

Diagramma Binario.
1 Fino al primo segmento A+B
coesistono
“compatibilmente” tale
T2
segmento è la linea (curva) di
solidus.
La linea curva a V che
converge in: e, è nota come
liquidus, al di sopra non esiste
fase solida.
PUNTO e: Eutettico.

In sistemi in cui la P
(pressione) può essere trascurata come variabile intensiva:
P+F=C+1

PARTO DA 1) Ho 1 fase Liquida omogenea caratterizzata da circa 80% B e 20% A,

1 P , 2 C (diagr. Binario) quindi F = 2 (posso cambiare sia T che composizione) e non sparisce
nessuna fase.
Si raffredda fino a T2 ottengo cristalli di B e una fase Liquida omogena.
2 P, 2 C (diagr. Binario) quindi F = 1 (posso cambiare solo Composizione O Temperatura) affinché
non sparisca alcuna fase
ESTRAGGO FISICAMENTE CRISTALLI DI B E CALO ANCORA T.
Raggiungo il punto e: qui avrò cristalli solidi A e solidi B oltre che una componente Liqui.
F = 0 (punto invariante) non posso cambiare nulla o una delle fasi sparisce.
A2B fonde in modo congruente (congruently) producendo un liquidus più cristalli residui.
AB3 fonde in modo incongruente (incogruently) producento un liquidus più cristalli di B
P = PERITETTICO, si fa riferimento ad una miscela di una fase liquida (contenente due componenti
A e B) e due fasi solide α (più ricca di A) e β (più ricca di B).

QUI A DX abbiamo alp. Solidus, miscela conguente

di alp. E bet., bet. Congruente.
La miscela peritettica contiene beta e alp. Solide e
il liquid.

Tornando a sopra il peritettico ha una fase B e una

AB3 più ricca in B oltre al Liq. Che le contiene A e B.

LEGGE DELLA LEVA (Lever rule)

Vedi zona A + Liq (sopra).
2.1.1 Chemical Targets for Raw Meal
Lime saturation factor (LSF) is a measure of the ratio of limestone to other recipe components,
normally expressed as a percentage.
LSF 1⁄4 100∗CaO=ð2:8∗SiO2 + 1:18∗Al2O3 + 0:65∗Fe2O3Þ
When clinker LSF is 100, the proportion of alite, the principal strength giving calcium silicate, is
maximised. In practice clinker LSF is typically in the range 94–98. Clinker LSF depends on the raw
meal LSF and the contribution of fuel ash, which is normally low LSF.
Silica modulus (SM) and alumina modulus (AM) influence both clinker quality and burnability, the
ease with which alite forms in the hottest part of the kiln, the ‘burning zone’.

1) C2S - Belite
2) C3A Celite
3) C4AF Brownmillerite
4) C3S - Alite

A seguito del raffreddamento al

di sotto dei 1200°C si ha la
reazione:

C3S  C2S+CaO:

On cooling from elevated

temperatures, a-C2S passes
through a number of closely
related polymorphs a0, a0L and
a0H16 (the latter two formerly
were not distinguishable from a0)
before transforming to the b-form
at 630°C.

the hydraulically important polymorph in Portland cement being beta-C2S.

gamma-C2S is non-hydraulic, but fortunately b-C2S can be stabilised to low temperature by

quenching.
SISTEMA SiO2 - CaO

Pure b-C2S is not an equilibrium phase under normal atmospheric conditions,19 and therefore its
existence is not reflected in the equilibrium CaO–SiO2 diagram (Fig. 3.11).

The most abundant phase of Portland cement clinker is alite, an impure form of tricalcium silicate
(C3S).
In most clinkers, usually the MI or MII phases are present at room temperature
Sistema CaO – Al2O3
This system contains the stable phases C3A, CA, C12A7, CA2 and CA6.

All binary phases in the CaO–Al2O3 system except CA6 are hydraulically active at room
temperature.

Absorption of water into the structure is at a maximum at 900°C, giving a composition of formula
11CaO7Al2O3 Ca(OH)2.

C3A melts incongruently at 1542°C. It is cubic in the pure state; the two crystallographic
modifications often referred to in the literature, that is, orthorhombic and monoclinic, are
stabilised by about 6% Na2O.37
With the exception of C12A7, all the other phases also melt incongruently as indicated in Fig. 3.14.

Dove FL = Free Lime (CaO)

 PROCESSO DI RAFFREDDAMENTO E CRISTALLIZZAZIONE DEL FUSO

With reference to Fig. 3.16, the reactions which take place on cooling are described in detail in the
following.
----------------------------PUNTO ESTREMO DI PATENZA-(TEORICO)-2100°C-------------------------------------
For the typical bulk composition shown in Fig. 3.16 a temperature of 2100°C is needed to melt the
clinker completely. This of course never happens, but it is a useful starting point to under-
standing the reactions at lower temperature, and how historical parameters such as the ‘lime
saturation factor’ (LSF) were developed.
----------------------------------------------------------------------------------------------------------------------------------
On cooling the clinker to 2100°C lime is the first phase to crystallise (CaO(s)-Lime), and applying
the condensed phase rule (P + F 1⁄4 C + 1), the number of degrees of freedom is reduced from 3 to
2 (trivariant to divariant). The composition of the melt then follows the path ‘down’ the liquidus
surface as the melt is depleted in CaO.

When the melt reaches the boundary curve dividing the primary fields for C3S and lime, C3S(s)
begins to crystallise as lime (CaO(s)) now begins to dissolve, or is ‘resorbed’. The number of
degrees of freedom is now reduced from 2 to 1 (divariant to univariant). Since one solid phase
dissolves while another forms, this type of univariant reaction curve is called a ‘reaction’ curve.
The composition of the melt now follows the path along the C3S-lime reaction curve. At the point
where a line projected from the composition of C3S intersects the reaction curve, free lime has
been completely resorbed.

When the composition of the melt reaches the C3S–C2S boundary curve, C2S begins to crystallise
alongside C3S. The composition of the melt now follows the boundary curve until it reaches the
point on the curve where a line projected from C3S forms a tangent.

At this point the curve becomes a reaction curve and C2S is resorbed as C3S continues to
crystallise.

This continues until the invariant point at 1455°C is reached. At this point C3A begins to crystallise
and the roles are reversed for the silicates, that is, with renewed crystallisation of C2S and
resorption of C3S.

Crystallisation and melting at this point is therefore ‘incongruent’. Since the bulk composition in
this example lies within the C3S–C2S–C3A alkemade triangle, this is where the melt is finally
exhausted.

Until the melt is exhausted both temperature and composition of the melt are fixed under
equilibrium conditions. When the last of the melt has crystallised a subsolidus assemblage
consisting of C3S, C2S and C3A (relative contents indicated by where the bulk composition plots in
the alkemade triangle) will cool under univariant conditions. In theory, C3S should decompose to
form C2S and lime below 1250°C (see Fig. 3.11) but this is rarely observed in practice.
MECCANISMI DI IDRATAZIONE

The hydration of tricalcium silicate is rather complex, and is still not fully understood. As products of hydration at
ambient temperature, there are formed an amorphous calcium-silicate-hydrate phase with a CaO/SiO 2 molar ratio of less
than 3.0, called the ‘C-S-H phase’ and calcium hydroxide [Ca(OH) 2, abbreviated CH].

3CaOSiO2 + (3+m-n)H2O  nCaOSiO2 mH2O+ (3-n)CaOH2 Quindi C3S + H2O  CSH + CaOH(liq)

Il CSH è amorfo, mentre il C3S è cristallino quindi si può studiare (approssimativamente) il grado di reazione mediante
quantificazione XRD del C3S che ha reagito.

Le cinetiche di reazione sono complesse

Among them, CaCl2 and other chlorides exhibit an acceleratory effect on the process, whereas phosphates, borates and
salts of Zn2+ and Pb2+ cause a retardation. Also, some organic compounds, especially different saccharides (e.g.
sucrose), may retard the C3S hydration rate. Data on the effect of calcium hydroxide dissolved in the mixing water on
C3S hydration are conflicting. Heavy water slows down the rate of C3S hydration moderately.28

The beginning of the acceleratory period coincides roughly with the beginning of the second, main heat evolution peak.
The Ca(OH)2 concentration in the liquid phase attains a maximum at this time and begins to decline; crystalline calcium
hydroxide starts to precipitate.

Ca(OH)2 (liq.)  Ca(OH)2 (sol)

La reazione del C3S inizia per dissoluzione acida (protonolisi) congruente del cristallo ad opera
delle molecole d’acqua.
I ponti O2 del C3S entrano in acqua come OH- (quindi si comporta come base) e i gruppi SiO4-
legano H2 formando H4SiO4.
I cationi di Ca2+ reagiscono con gli OH- formando Ca(OH)2.
Dopo la saturazione in Ca(OH)2 e H4SiO4 inizia a formarsi C-S-H tale CaOxSiO2H2Oy con x e y
variabili.
Una possibile reazione con stechiometria è:

CSH = 3.28CaO 2SiO2 3.92H2O.

The equation for the reaction is:

2(3CaO SiO2) + 6.64H2 O  3.28CaO 2SiO2 3.92H2 O + 2:72CaOH2

As the C-S-H phase is a nearly amorphous material, its structure cannot be studied by XRD. Most information on the
structure of this material may be obtained by 29Si MAS NMR.

On the nanometre scale the C-S-H phase formed in the hydration of C3S at ambient temperature seems to be structurally
related to the crystalline phases 1.4 nm tobermorite and jennite and to poorly crystalline materials called C- S-H(I) and
C-S-H(II).

The idealised constitutional formula of 1.4 nm tobermorite is [Ca4(Si3O9H)2]Ca8H2O (Fig. 5.2A) and that of jennite
[Ca8(Si3O9H)2(OH)8]Ca6H2O (Fig. 5.2B). Both tobermorite and jennite contain their SiO4 tetrahedra condensed into
linear chains that are kinked so that they repeat at intervals of three tetrahedra. Such arrangement is called ‘dreierkette’
and has an empirical formula Si3O9.


Mentre la reazione del C2S porta agli stessi prodotti di quella del C3S per quanto riguarda le fasi
alluminate-idrate:

C3A + H → C-A-H

C4AF + H → C-A-H + C-F-H

 LAVORABILITA’ e PROPRIETA’ FISICHE

Le forze di dispersione (legate alla lavorabilità del prodotto – slump test) sono per lo più legate
direttamente alle forze di Van der Waals.

The effect of additives on compressive strength of concrete is generally called strength activity index. Generally, the strength activity index of cement
supplements is measured by the ratio of the compressive strength between benchmark mortars containing no supplements and mortar samples with
certain amount of cement being replaced
 MIX DESIGN
MAZZUCCO 2015) Uno degli aspetti caratteristici dei CDW è legato alla geometria dei clasti che va
considerata nel momento di realizzare la curva granulometrica.
WANG 2021) “Wall Effect” durante il
mixing del calcestruzzo gli aggregate
(coarse) vengono a contatto con il
cemento. Questo è costituito di grani di
dimensioni microscopiche ( da 1 a 100
micron) rispetto agli aggregati presenti
(sopra i 10 mm). Data la differenza di
dimensione i grani del cemento non
possono interagire attivamente come
una superficie di contatto nei confronti
degli aggregati ma come un insieme di
particelle che producono una superficie
irregolare e quindi all’interfaccia tra
l’inerte e il cemento si forma una zona
di vuoto (decine di μm) in cui si
accumulano molecole d’acqua, di aria,
e grani microscopici di cemento (ITZ).
In questo livello la forza coesiva rispetto al cemento in bulk è molto ridotta.
Dopo aver impregnato con epossidica un campione di calcestruzzo è possibile osservare tale ITZ
con il SEM dalle diverse scale di grigio (GAO et al 2013).

All’aumentare della dimensione di ITZ aumenta la porosità e l’assorbimento di acqua nel

calcestruzzo (quindi in linea generale più inerte c’è e più aumenta ITZ) ed è inoltre per questo che i
calcestruzzi fatti con RA (Avendo un doppio ITZ) hanno minore porosità e maggiore assorbimento
di acqua con conseguenti meccaniche ridotte.

L’aumento di porosità porta anche all’accumulo di specie che deteriorano sia il cemento
(espansione da solfati) che magari i ferri di armatura (ioni quali cloruri)