CHAPTER 2

Gels: properties and application in

cultural heritage conservation

2.1. Introduction

If a molecule or a monomer in a polymeric chain can form more than two

bonds, the first consequence, is that there are not limits for the size of the

aggregate that can be obtained. Let’s suppose you have a molecule and suppose

also that it can form a number of bonds equal to f (f is the functionality of the

molecule). Then if you have a molecule, like an oligomer, so that f > 2

(polyfunctional structure), it is possible to observe the formation of a three

dimensional structure called fractal. Generally a fractal mass is distinguished by

an Euclidean one because for fractals the mass m increases following the law

indicated in the equation 1:

df
m∝r (eq. 2.1)

where r is the average radius of the aggregate and df is called the mass fractal

dimension of the object. For an Euclidean object m ∝ r 3 , but for a fractal df < 3

and its density decreases as the object becomes bigger. Analogously, in the same

way, it is possible to define a surface fractal area, S, that increases following the

law indicated in equation 2:

S ∝ r ds (eq. 2.2).
Gels: properties and application in cultural heritage conservation

where ds is called the surface fractal dimension. The fractal dimensions can be

measured by SAXS or SANS [1, 2].

If the growth of one of these macromolecules occurs in a solvent and it

reaches dimensions so that it extends through all the solution, then the system

obtained is called gel [3]. For each gel it is possible to define a “gel point”, as the

coordinate reaction value at which the macromolecule is completely formed. Very

simply, a gel is a system that contains a continuous solid skeleton into a fluid

phase (a gas or a liquid). As noted by Heinsh a gel is defined “as a two component

system of a semisolid nature, rich in liquid, and no one is likely to entertain

illusions about the rigor of such a definition” [4]. In general a gel can be

considered as a continuous fluid phase. Continuity means that it is possible to

travel through the solid phase from one side to the other without having to enter

into the liquid. Analogously one can make the same trip into the liquid without

touching the solid phase.

Macroscopically, a substance is a gel if: (1) it has a continuous structure

with macroscopic dimensions that is permanent on the time scale of an

experiment, and (2) its rheological behaviour is viscoelastic (vide infra). For

screening purposes, the dictum of Jordon Lloyd: “if it looks like Jello, it must be a

gel!” is still useful. Colloidal aggregates (i.e., whose typical dimensions fall

between 20 and 2000 Å) in the gel are linked in complex, three-dimensional

networks that immobilize the liquid component to a variable extent (principally)

by surface tension.

42
 Chapter 2

2.2. Definition of gels and gelation process

Although gels have been used since the prehistoric times, the definition of

a gel is still matter of discussion. Jordon Lloyd, about 70 years ago, indicated with

a very famous comment that “....the colloid condition, the gel, is easier to

recognize than to define” [5]. This and other empirical definitions of the gelled

state, including the first by Thomas Graham in 1861 [6], were related on the

qualitative macroscopic observations available. The first attempt to link

macroscopic and microscopic properties to define a gel was made by Hermans

that indicated a gel as “a coherent system of at least two components, which

exhibits mechanical properties characteristic of a solid, where both the dispersed

component and the dispersion medium extend themselves continuously through

the whole system” [7]. A phenomenological definition of gels have been given by

Kramer in 1993 [8]: “A gel is a soft, solid or liquid-like material of two or more

components, one of which is a liquid, present in substantial quantity”. Solid-like

gels are characterized by a storage modulus G’(ω) which exhibits a pronounced

plateau and by a loss modulus G’’(ω) which is considerably smaller than the

storage modulus in the plateau region (vide infra).

The most comprehensive (and cumbersome to apply!) definition has been

advanced more than 20 years ago by Flory and Stockmayer. This theory is called

“classical theory” and it is clearly explained into the book “Principles of Polymer

Chemistry”[9, 10]. Let’s suppose you have a z-functional molecule, and indicate

with p (p ≤ m) the probability that a molecule forms a bond. To better understand

this approach, we remind that the chemical reactivity of each group is the same.

43
Gels: properties and application in cultural heritage conservation

The next assumption is that the bonds form only between polymers, but

not within them, so the polymer doesn’t contain closed loops. The structure

obtained in this case, described in Scheme 1 for z = 3, is called Cayley tree or

Bethey Lattice (see Scheme 1). Traveling along a path of completed bonds at each

node we find z-1 opportunities for constituting the journey. The probability that

one of them is a complete bond is (z – 1) p. Because the polymer is indefinitely

extended into the space, there must be at least one completed path from each

node, so we need that (z – 1) p≥ 1. so the critical condition for gel formation is

1
Pc = (eq. 2.3)
(z − 1)

Scheme 1. The Cayley tree or Bethey Lattice.

This model predict that Pc = 1 when z = 2, because such system forms

only linear chains that cannot cross-link into a network. The most interesting

aspect of the Flory’s theory is that it indicates formulas for many features of the

44
 Chapter 2

gelling solution: the critical degree of reaction at the gel point and the distribution

of the aggregates into the sol.

Figure 1. Site percolation square lattice, illustrating various cluster sizes (s) for three values of the
fraction of filled sites p. For p = 0.75 an unbounded cluster is present.

Another theory that offers a description of the gel formation process is the

percolation model. In this case the formation of closed loops is not excluded. The

main negative aspect of this model is that generally it doesn’t offer a good

matching between the theory and such properties as the percolation threshold or

45
Gels: properties and application in cultural heritage conservation

the size distribution of the clusters and of the polymers into the sol phase.

Excellent reviews of the percolation theory are the ones by Zallen [11] and

Stauffer[12]. Figure 1 illustrates the percolation in a square lattice. Each

intersection between two lines represents a site, a potentially reactive point. If two

neighboring sites are filled, they are joined by a bond. This process, called site

percolation produces clusters of size s with frequency ns. It is possible to define a

percolation threshold, pc, as the critical value of p at which there is the formation

of a cluster so that sav → ∞ where sav indicates the average cluster size, expressed

as number of sites forming the cluster itself [11].

2.3. Classification of gels and thermal behavior

It is possible to classify gels in many ways. In this paragraph the attention

will be focused only on those systems that are important for the present work. A

first classification, for example, is possible considering the nature of the

connections between the elements of the network. In this case chemical and

physical gels are the two main categories. In chemical gels the connection usually

occurs through the formation of covalent bonds. Heating this type of gels

produces, the breaking of the bonds and it is not possible to obtain back the

formation of the starting bonds (thermal irreversible systems). In the physical gels

the bonds between the gellant molecules usually occurs through van der Waals

interactions with two main consequences. The first is that being the energy

involved in van der Waals interactions in the order of kT, these gels are thermally

reversible. The second is that van der Waals interactions require cooperativity

46
 Chapter 2

between interacting groups. Then, the junction domains are not point-like, but

extended into the space.

Figure 2. Schematic structure of chemical (A) and physical (B) gels. The strands into the structure
of chemical gels are chemically interconnected, as indicated by the black and white squares
belonging at the same time to different chains.

Gels can also be classified in function of the kind of gellant substance. In

this case there are again two different categories of systems. (1) Polymer gels, in

which the gellant is a polymer (polystyrenes, polyacrylate, proteins, gelatins, etc.)

[13] and (2) the LMOG (Low Mass Organo Gelator; steroid derivatives,

organometallic compounds, surfactants of different nature, etc.) [14] based gels

called also organogels. In this last case the gellant is an organic compound usually

containing a very long alkyl chain Cn (n number of carbons between 16 and 36)

[15] characterized either by an amphiphilic behavior, or by a very high molecular

volume. Generally polymer based gels belongs to the category of chemical gels

and aren’t thermally reversible while organogels are thermally reversible [16, 17]

and belongs to the category of physical gels. Thermoreversibility is one of the

main properties of the gels usually monitored. On heating, the supramolecular

architecture is melted and individual molecules (or groups aggregated molecules)

47
Gels: properties and application in cultural heritage conservation

are re-dispersed in the bulk solution. So, the system can be heated until a critical

temperature Tg (gelation temperature) at which a solutionlike system (called sol)

is obtained and then cooled down to obtain again the starting condensed system.

This process is also called sol-gel transition. In the case of thermoreversible gels

this event occurs via first order transformation [18] due to the breaking of the

interactions between the gellant molecules and, at the same time, to the creation of

a minimum of molecular order with the formation of the sol (the opposite thing is

valid passing from a sol system to a condensed one).

All the thermal characteristics of gels are usually strictly related to the

nature of the solvent. This solvent quality effect has been studied by Flory [9]

who derived a theoretical relation between the melting point of a binary polymer

gel system to the polymer concentration and to the Flory’s interaction parameter

χ1 .

1 1 RV p
− 0 =
Tmp Tmp ∆H 0 pVs
(v s − χ 1v s2 ) (eq. 2.4)

0
where Tmp corresponds to the Tg of the gel, Tmp is the melting temperature of the

pure polymer (considered in its most stable and perfect crystal), R is the gas

constant, ∆H 0 p is the polymer melting enthalpy per mole into the crystal structure,

Vs the solvent molar volume and Vp the monomer molar volume. If the system is

diluted ( v s ≈ 1 ), the relation can be approximated to:

1 1 RV p
− 0 = (1 − χ1 ) (eq. 2.5)
Tmp Tmp ∆H 0 pVs

48
 Chapter 2

While χ1 can vary with the polymer volume fraction, Vp, and also with

temperature, Flory’s relation indicates that the higher χ1 is, the higher will be the

decrease of the melting point of the gel (Tg) with respect to the pure polymer. For

the most part of polymers χ1 is strictly related to the solvent. This is the case of

polystyrenes, poly(methyl methacrylates) and poly(alkyl acrylates) in general, but

there are also polymers like polyethylene and poly(vinyl chloride) for which the

gel formation is very little sensitive to the solvent type.

The LMOG based gels present a completely different behavior. In this case

the solvent always plays a fundamental role in determining the properties of the

condensed system (Tg values, stability of the gels, appearance) [15-17, 19, 20].

Furthermore, many LMOG based gels present a good linear relationship between

ln χ1 and Tg-1 according to the Schröder-van Laar equation, assuming (incorrectly)

that the gels form ideal solutions on heating above the Tg [15, 19, 21].

∆H fus ∆H fus
ln χ g = + (eq. 2.6)
RTg RT fus

In this equation, χ1 is the mole fraction of gelator and ∆Hfus and Tfus are the

enthalpy of melting of the gel strands and the melting temperature of the pure

gelator, respectively. Then, the calculated melting enthalpy for pure gelator can be

obtained from the intercept or from the slope. These values are usually different

[20, 21] with respect to the real ∆Hfus obtained by DSC measurements (∆Hfus

(DSC) < ∆Hfus (Schröder-van Laar)). The excess enthalpy from the gels is

probably originated by the heat of dissolution that accompanies melting of gelator

strands. Lower ∆Hfus values from DSC than from the Schröder-van Laar equation

49
Gels: properties and application in cultural heritage conservation

have been reported by Shinkai for a very different class of cholestrol derivatives

organogels [21].

One of the universally accepted classifications of gels is the one given by

Flory [10] that proposed four different categories both in function of the

aggregates structure and of the gelator nature.

1. Gelator form well ordered structures (the most part of LMOG based gels,

lamellar structures, soap gels, phospholipids and clays. In this case the driving

factor for the gelation are the electrostatic and Van der Waals forces), see Figure

2.

Figure 2. Structural model of fibrillar or ribbon-like aggregates of some C12 fatty acids
derivatives as formed in gelled organic liquids. The spheres represent the carboxylic end groups.

2. Covalent polymer networks, completely disordered (chemical networks

formed by crosslinking of high molecular weight polymers or by crosslinking

reactions in polymerization or polycondensation processes).

50
 Chapter 2

3. Partially disordered networks formed by physical aggregation (some

LMOG based gels, biopolymers and bioaggregates as helix structures etc. Usually

these gels are thermoreversible).

4. Particulate disordered structures (fibrillar protein gels and all these gels

formed by particles with large anisotropy).

2.4. Mechanical properties of gels

As previously described, the macroscopic recognition of a gel state is

somewhat ambiguous, and various classifications have been proposed based on

either morphology, consistency, or chemical and mechanistic considerations [22-

24]. Rheology properties appear to be the best way to follow the changes in

gelator aggregation during the sol-gel and gel-sol transitions [8]. They can be

described by statistical physics, and percolation models [25, 26] can simulate the

mechanical behavior near the gelation point. The sol-gel phase transition is

generally characterized by a divergence of the connection correlation length [27].

Force F0

Figure 4. Shear stress applied to idealized geometries. Force F0 is assumed to slide laterally on the
face of area A0.

51
Gels: properties and application in cultural heritage conservation

Then, from the rheological point of view two different types of 3D networks and

viscoelastic materials can be obtained in gel systems. In the first are materials

exhibiting a solidlike, viscoelastic, mechanical behavior (“strong” gel). In the

second, materials exhibiting a liquid viscoelastic behavior (“weak” gel). They

usually exhibit enhanced elasticity on short time scales. Both types of networks

are usually thermally reversible especially when the gellant is a LMOG. Before

describing the properties of the viscoelastic fluids it is important to illustrate all

the most important basis of rheology.

Figure 5. A rate u gradient produced when a fluid (green area) is sheared.

2.4.1. Fundamentals of rheology

The study of rheology is the study of the deformation of matter due to the

application of a force [28]. When the behavior of a fluid is studied in function of

the application of a stress, the result is the production of a motion. Let’s suppose

to have two surfaces separated by a fluid (Figure 4, green area) and suppose to

apply a force F0 in a direction parallel to the mobile surface. It is possible to

define the shear stress σ and shear strain γ as follows:

52
 Chapter 2

F
σ= (eq. 2.7)
A0

∆x
γ = (eq. 2.8).
z

A constant shear stress must be maintained on the mobile surface to move it at a

constant shear rate u. Suppose that there is not slip between the surface and the

liquid, there is a decrease of the fluid rate modulus moving toward the fixed

surface (see Figure 5) and the u value in function of the vertical position z is

expressed by the relationship:

du
γD = (eq. 2.9).
dz

When the plot of shear stress versus shear rate is linear the liquid behavior is

described by the Newton law (Newtonian fluid). The proportionality constant η is

the coefficient of viscosity:

σ
η= (eq. 2.10).
γD

2.4.2. Mechanical spectroscopy and linear viscoelasticity

The use of an electromagnetic field as probe to examine the molecular

properties of a compound is the basis of the spectroscopy. The application of a

range of electromagnetic frequencies to a sample is useful to induce various kinds

of transition (their nature is strictly related to the frequency range) and then to

understand what process occurs in the molecule.

53
Gels: properties and application in cultural heritage conservation

An analogous mechanical measurement can be made by applying an

oscillating strain in a wide range of frequencies. The result will be the stress of the

sample having a magnitude characteristic both of the material and of its

concentration. The main difference between the mechanical and the

electromagnetic spectroscopy is that the viscoelastic responses to a mechanical

perturbation usually arise from a wide distribution of processes occurring

simultaneously. As consequence the single structural process originating a

mechanical response is often difficult to isolate. To better understand what

viscoelasticity means, in this approach, the viscoelastic behavior of fluids will be

discussed referring to the combination of Newtonian dashpots and Hookean

springs. These two models describe schematically, from the rheological point of

view, purely viscous and purely elastic fluids respectively.

An Hookean spring is one that obeys to the Hooke’s law (the force is

linearly related to the displacement). In this case, when a stress is applied, the

deformation of the spring occurs. The entity of the displacement of the spring

from its equilibrium configuration is described by the well known relationship:

F = kx (eq. 2.11)

When the external force stops to act, the spring recovers instantaneously

its initial not stressed conformation. When any form of strain γ is applied on the

surface of a purely elastic solid or fluid, the shear stress responds proportionally to

the strain, but in this case the response of the spring can be described as a function

of the shear modulus G as follows:

σ=Gγ (eq. 2.12)

54
 Chapter 2

Where σ and γ the shear stress and the strain respectively. The shear modulus G

indicates how much elastic is the solid or fluid we are studying (it corresponds to

the strength of the spring to which our substance can be mechanically

represented).

Figure 6. Schematic representation of the Hook and Newton models for purely elastic and purely
viscous substances.

A Newtonian dashpots consists of a cup filled with an oil of viscosity η

with a piston placed in the oil. When any form of strain is placed on a purely

viscous sample, the shear stress responds instantaneously proportionally to the

strain following the Newton’s law:

σ = ηγ (eq. 2.13).

Combinations of these devices are used to understand the viscoelastic

behavior of different kinds of substances. The two simplest arrangements are the

models in parallel or in series. When they are placed in series we have the

Maxwell model and when they are in parallel the Kelvin-Voigt model is obtained.

The constitutive equations are derived from the equations 2.9 and 2.10. When a

stress is applied on the parallel elements of a Kelvin model both the elements will

respond. Then a linear addition of the stresses gives the equation:

55
Gels: properties and application in cultural heritage conservation

σ = Gγ + ηγD (eq. 2.14).

For the Maxwell model the linear addition interests the strain:

σD σ
γD = + (eq. 2.15)
G η

A graphical illustration of these models is indicated in Figure 7.

Figure 7. Maxwell and Voigt models originated by the combination of Newton and Hook
elements in series and in parallel respectively.

It is also possible to imagine situations where the piston is taken out of the

oil or the spring is permanently deformed by a too high stretching, these behaviors

are typical of the non linear viscoelastic region.

When an oscillating strain is applied on a sample at a given frequency,

after an induction period, a stress is developed as direct response to this

perturbation. The result is that the induced strain in the sample is not in phase with

the applied stress but it is delayed (see Figure 8); this phenomenon can

56
 Chapter 2

mathematically described by a shift of the strain curve with respect to the stress

curve by a phase angle δ as indicated in Figure .

phase angle
δ σ0 stress

γ0
amplitude (a.u.)

strain

time

Figure 8. An oscillating strain and the stress response for a viscoelastic material.

All the informations about the behavior of the studied sample at the given

frequency are contained in these spectra but they are not easily treatable. What is

preferably to have is a few representative terms as the relaxation time, the

elasticity or the viscosity of the sample. It is interesting to observe that at a given

frequency two different parameters are independent from the time: the first is the

ratio between the maximum stress σ0 and the maximum strain γ0 called complex

modulus G*:

σ0
G * (ω ) = (eq. 2.16)
γ0

where ω is the radial frequency equal to 2πf, f is the applied frequency in Hertz.

The second time-independent parameter is the phase difference between peak

value of the stress and the peak value of the strain δ, in radiants. For an purely

57
Gels: properties and application in cultural heritage conservation

π
elastic solid, δ is equal to zero, however for a Newtonian one, δ = (opposition
2

of phase). It follows that for a viscoelastic material some energy is stored and

some energy is dissipated.

In order to mathematically describe these properties of materials for the

Maxwell model, it is convenient to express the sinusoidal applied wave in the

exponential form:

γ * = γ 0 exp(iωt ) (eq. 2.17)

γ * = iωγ 0 exp(iωt ) = iωγ * (eq. 2.18)

as indicated above the stress response is shifted of an angle δ

σ * = σ 0 exp[i (ωt + δ )] (eq. 2.19)

σ * = iωσ 0 exp[i (ωt + δ )] = iωσ * (eq. 2.20)

substituting the complex stress in the equation 2.12:

σ * σ *
γ * = + (eq. 2.21)
G η

and using equations 2.14-2.17:

iωσ * σ *
iωγ * = + (eq. 2.22)
G η

and then

γ* G
=1+ (eq. 2.23)
Gσ *
iωη

58
 Chapter 2

σ0
From the equation 2.13 it is known that G * = , and is possible to demonstrate
γ0

η
[28] that for the Maxwell model it is true that τ m = where τm is the relaxation
G

time. Then:

G G
=1+ (eq. 2.24).
G (ω )
*
iωτ m

Equation 2.21 can be rearranged to obtain an expression for G*(ω):

 iωτ m 
G * (ω ) = G   (eq. 2.25)
 1 + iωτ m 

Separating the real and the imaginary components:

(ωτ m )2 ωτ m
G * (ω ) = G ' (ω ) + iG" (ω ) = G + iG (eq. 2.26)
1 + (ωτ m ) 1 + (ωτ m )
2 2

G’(ω) is called the storage modulus and G” (ω) the loss modulus:

G ' (ω ) = G
(ωτ m )2 (eq. 2.27)
1 + (ωτ m )
2

ωτ m
G" (ω ) = G (eq. 2.28).
1 + (ωτ m )
2

The storage modulus G’ which is related to the stress in phase with the

imposed strain, gives informations about the elastic nature of the material; for this

reason this parameter is also called elastic modulus. The loss modulus, called also

viscous modulus, on the other hand, is related to the stress component, which is

completely out of phase with the displacement and characterize the viscous nature

of the material. A purely elastic material would exhibit a non zero elastic modulus

and a viscous modulus G” = 0. In contrast a purely viscous material would show a

59
Gels: properties and application in cultural heritage conservation

zero elastic modulus (G’ = 0; the strain 90° out of phase respect to the stress). It is

possible to demonstrate [29] that both G’ and G” are related to the phase angle δ

and to the complex modulus G*by the two following relationships:

G ' = G * (ω )cos δ (eq. 2.29)

G" = G * (ω ) sin δ (eq. 2.30)

Other models can be also obtained through the combination of more than

two elements. In this case the mathematical approach is much more complex.

2.5. Determination of the gel point

As indicated above, the gel point is the one in correspondence of which the

formation of a semisolid (gelled) system is occurs starting from a liquid one. The

gel point can be determinted in a wide range of ways. Here a short review is

presented.

Solubility method. The gel point can be indicated as the minimum gelator

concentration at which a gel is obtained starting from a sol. As the gel point is the

point where at least one molecule has an infinite molecular weight and where the

system is not soluble any more.

Tilted tube test and falling ball method. From the thermal point of view the gel

point is the temperature Tg at which the transition from a gel to a sol occurs. The

For the determination of the gel point several methods are indicated in the

literature. The most simple methods are the "tilted test tube method" and the

"falling ball method" (see Figure 9). In the tilted lest tube method the solution, or

60
 Chapter 2

the gel is observed while rotating the tube during a temperature decrease or

temperature increase or during a period at constant temperature. The gel point of

the solution or the melting temperature of the gel is defined as the point where the

system stops or starts to flow respectively or at which the ball begins to fall or is

stopped into the system. The temperature range of the gel formation or of gel

melting can be monitored also by DSC experiments (thermal method). The initial

temperature of the peak, the Tg, is the one at which many properties of the gellant-

solvent mixture show a discontinuity as indicated below.

Figure 9. Description of the tilted test tube method.

Mechanical method. It is based on the determination of properties as the viscosity

and the storage modulus at given temperatures and frequencies, as a function of

the time. The instant or the temperature at which there is the growth of the storage

modulus from low values to much higher ones is a indication of the gel point. An

other way is to determine the point where the storage and the loss moduli cross

each other as a function of the temperature or the time [30].

61
Gels: properties and application in cultural heritage conservation

Storage Modulus, G' [Pa],

Viscosity, [Pa x sec]

Gel Point

Time

Figure 10. Gel point determination for a generic gel following the G’ value or the viscosity γ as a
function of the time.

The method of Winter and Chambon. Winter and Chambon [31, 32] found

experimentally that for a crosslinked system at the gel point the shear modulus

G(t) is related to the gel strength by the following power law:

G (t ) = St − n (eq. 2.31)

n is the relaxation exponent that characterize the gel at the threshold point. From

the theory of the linear viscoelasticity [29], and from equation (4) the moduli G’

and G’’ are given by:

Sπω n
G ' (t ) = (eq. 2.32)
1 
2Γ(n) sin πn 
2 

Sπω n
G ' ' (t ) = (eq. 2.33)
1 
2Γ(n) cos πn 
2 

62
 Chapter 2

From equations (5) and (6) it appears that at the gel point plotting dynamic moduli

on a double logarithmic scale in function of ω, straight lines with slopes n are

obtained.

2.6. Gels in cultural heritage conservation

As previously indicated, the use of organic solvents as cleaning agents for

easel paintings originates many problems related to the swelling of the varnish

layer and of the binding media and to their leaching. To decrease these effects a

solution had been indicated years ago by Wolbers [33]: the use of the same

solvents, but in the gel form. In this way many problems related to the traditional

cleaning procedures can be avoided and, at the same time, many further

advantages can be obtained.

1. The reduction of the penetration of the solvent (immobilized by the

gellant) into the binding media matrixes. In fact, as indicated by Michalski

in 1990 [34], many solvents commonly able in the solubilization of

coating varnishes rapidly penetrates into the paint layer, (the rate is about

10 µm/sec), causing the swelling of the most common binding media of

easel paintings (linseed oil and stand oil leached and unleached films have

been particularly studied). For example, toluene induces an increase of the

volume of linseed oil films of about 28%, the corresponding value for

acetone is 36%, xylene 29% etc. As indicated in the previous chapter the

main consequence of the swelling is the decrease of the strength of the

paint layer, due also to the drying and reforming processes of the oil film

63
Gels: properties and application in cultural heritage conservation

after the evaporation of the swelling solvent. SEM micrographs of burnt

sienna / linseed oil dried film before and after the cleaning with acetone

using the swab rolling technique are reported in Figure 11. [35] The

erosion of the binding medium surface is due to its swelling and drying

and also to the increase of the accessible amount of the medium surface in

the swelling phase. Then, reducing the penetration rate and the penetration

amount of the solvents into the paint layer for all the solvents, the main

result is the reduction of the swelling of the binding medium layer. This

target can be easily achieved by using highly viscous condensed systems

like gels, as indicated by Wolbers and many others authors [36, 37].

100 µm
A B

Figure 11. SEM micrographs of burnt sienna / linseed oil dried film before (A) and after (B)
swab-rolling with acetone for one minute. Some erosion is observed at the surface [35].

2. Possibility to better graduate the action of the solvents varying the

application times (usually for gels the contact times with the surface to be

cleaned is less than one minute). Being one of the main characteristic of

64
 Chapter 2

gels the very high retention degree for the gelled liquids, one of the

advantages given by the application of these systems is the drastic

decrease of the evaporation rate of the solvents. In this way, it is possible

to better control the action of the cleaning agent without worring about a

too aggressive action and being sure that the most part of the employed

solvent will be removed from the surface of the work of art. Figure 12

shows two micrographs of a mastic based varnish applied on the surface of

A B
50 µm

Figure 12. Micrographs of a mastic based varnish applied on the surface of a paint before
(A) and after (B) the application of an aqueous deoxycholic acid based gel system. [38].

a paint before (A) and after (B) the application of an aqueous deoxycholic

acid based gel system (buffered at pH = 8,5) [38]. The SEM images show

that after the gel application clumps of varnish (see arrow) remain on the

surface of the paint indicating that the impact of the cleaning action is

much more limited that the one typical of pure solvents. The application of

acetone or isopropanol swells the varnish layer with many negative side

effects: the rapid evaporation of acetone produces the cracking in the

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Gels: properties and application in cultural heritage conservation

remaining varnish layer at the same time the varnish that remained after

the evaporation of the isopropanol, had reformed penetrating the porosity

of the paint layer and reforming a smooth film on the surface.

3. The variegated nature of materials to be removed, especially varnishes

applied as protectives in previous restorations, implies the necessity to

obtain gels with solvents having different polarity as a function of the kind

of material to be removed. The “solvent gels” formulation satisfies this

exigency. Many gels can be obtained with different solvents characterized

by polarity varying in a wide range of values (acetone, benzene, water etc.;

vide infra) [36, 39]. From the points 2 and 3 the most important

characteristic of these systems as cleaning agents in cultural heritage

conservation is the possibility to have a very selective action limited to the

surface components to be removed.

4. The versatility of the gel based cleaning technique is large. In fact, not

only it is possible to gel different organic solvents, but also different

highly selective cleaning agents like enzymes. In this case the

environmental conditions (pH and temperature) must be highly controlled

during all the application time. Lypases have been employed in gelled

water solutions for the removal of darkened coatings mainly constituted of

degradated natural triglycerides with excellent results. [37] Analogously,

proteases and carbohydrases are commonly used for the degradation of

acid proteic coatings and carbohydrate-based polymers. [40, 41] Chelates

like EDTA or citric acid, are useful for the selective removal of salts (their

66
 Chapter 2

action is usually specific for a narrow range of ions, especially metal

cations) but also to preserve the surface to be cleaned from the possible

action of ions (both anions and cations) present into the cleaning agent.

[42]

5. Possibility to apply gels to a various range of supports. Even if these

systems have been introduced in the work of art conservation fields as

cleaning agents for easel paintings, they have successfully found

application also in the restoration of work of art made by different painted

materials as glasses [43], metals [44] and feathers too [45].

The large potentialities of this technique induced many researchers to address

their work across this new border of the applied science [46].

2.7. Formulation of gels in cultural heritage conservation

The first formulation for gels to be used as cleaning agents in cultural

heritage conservation has been given by Wolbers in the second half of the eighties

[47]. His Resins Soap, able to gel many organic solvents of different polarity, are

made by an anionic surfactant like a terpenoid or steroidal acid derivative or bile

acids. The first includes the abietic acid soap (ABA; Figure 13 a) in alkali-

buffered medium; on the other hand, an example of the second is the deoxycholic

acid soap (DCA; Figure 13 b). Usually a second, non ionic surfactant (Triton X-

100), is added to increase the surface activity and, at the same time, to maintain

the micellar dispersion. It has been verified the good efficacy of these systems in

67
Gels: properties and application in cultural heritage conservation

the removal of naturally and artificially aged natural varnishes (degraded

terpenoid varnishes) from painted surfaces [38].

HOOC

HO
COOH

HO

Figure 13. Molecular structure of abietic acid (a) and deoxycholic acid (b).

The most largely diffused cleaning agents in the gel form, are the Solvent

Gels set up by Wolbers at the beginning of the nineteen’s. in this case the gelator

is the polyacrylic acid, the structure of which is indicated in Figure 14 a. This

polymer has two different important characteristics: its molecular weight (up to 4

x 106 Dalton) and the presence of many carboxylic groups. These acidic functions

can be neutralized under the action of a base, giving the formation of

carboxylates. Then a repulsive interaction between the negative charged groups

occurs. That causes an alteration of the intermolecular configuration: before the

addition of the base the polymer chains present a spherical shape (they are folded

and the most part of the functional groups is blocked; Figure 14 b). After the

68
 Chapter 2

deprotonation of the carboxylic groups this repulsive interaction gives to the

chains an extended conformation that affords the formation of the gelling network

(Figure 14 b). The deprotonation is usually ensured by the action of a non ionic

a
n
COOH COOH COOH COOH

Figure 14. Structure of polyacrylic acid (a) and the changes of the configuration of the polymer
chains given by the repulsive interaction between the carboxylic groups (b).

CH2CH2OH
C12
R N
CH2CH2OH

(CH2CH2O)xH
R N C25
(CH2CH2O)yH

Figure 15. Structure of Ethomeen C12 (top) and C25 (bottom). R is usually between 8 and 20
carbons atoms and the sum of x and y is 15.

surfactants (Ethomeen C12 or C25 called also cocoamines) characterized by weak

basic properties; their structure is indicated in Figure 16. Both C12 and C25 have

a long alkyl chain and form a salt with the carboxylic groups of the polyacrylic

acid chains through the aminic group (Figure 16). The properties of the surfactant

are related to the alkyl chain length and to the x and y values; for C12 (HLB 10) R

69
Gels: properties and application in cultural heritage conservation

usually contains a number of carbons atoms between 8 and 20 (molecular weight

217-385 D), and is employed in the gelation of non polar solvents. C25 (HLB 19;

molecular weight 789-957 D) molecules contain more than one hydroxyl groups

HOOC COOH
O O-
R H R
N
+

Figure 16. Formation of the salt between the surfactant and the carboxylic groups of the
polyacrylic acid molecules.

and for this reason it is useful in the gelation of polar solvents. For the preparation

of gels, the polymer is usually dispersed into the solvent to be gelled (1% by

weight) and then the surfactant is added (1-2% by weight); the increase of the

viscosity occurs when a little amount of water (up to 1,5%) is added dropwise.

Other gel formulations are known especially for polar solvents and water

solutions. In this case gellant as cellulose derivative polymers [37] or agar agar

are employed: their limit is the much more lower versatility for the gelation of

media having different polarity respect to the polyacrylic acid based ones. For all

the gels previously indicated, the application can be carried out mainly in two

different ways. The first one is the application of the gel without any further

operation; the second is the use of a swab roll with which a friction can be done

on the surface of the paint itself.

70
 Chapter 2

2.8. Removal of gels from painted surfaces

The main problem connected with the use of gels as cleaning agents for

painted surfaces is related to the complete removal of both the gellant and the

surfactant when their cleaning action is finished; the effects of the residuals on the

surface of the work of art over the time are still object of the research. Burnsock

and Kieslish [48] demonstrated by chromatography mass spectrometry and SEM

analysis that residuals of the Ethomeen are present both when the gel is removed

mechanically by a swab roll and when solvents are used. The most effective

method is the one in which the removing agent is the same solvent mixture

employed into the gel. To minimise the amount of the residual surfactant on the

surface of the cleaned paint, Wolbers [49] demonstrated, by the used of

isotopically labelled compounds, that, especially for fatty acids, the amount of

residual substances is related to the critical micelle concentration (CMC). The

absorption of the surfactant molecules is minimized working below the CMC and

at pH values near to neutrality. Anyway, polymer gels have been successfully

used to remove patinas and surface varnish layers from many different kind of

supports. All these problems are the main reasons why during my PhD project of

the research has been addressed toward the development of a new family of

polymer gels completely removable from the painted surface after their

application.

2.9. Bibliography
[1] Sonwane, C. G., Bhatia, S. K., Calos, N. J., Langmuir, 1999, 15, 4603

71
Gels: properties and application in cultural heritage conservation

[2] Lin, Y., Smith, T. W., Alexandridis, P., Langmuir, 2002, 18, 6147.

[3] Brinker, C. J., Scherer, G. W. In Sol-Gel Science; Academic Press, inc.: San Diego, 1990, pp
2-11.

[4] Henish, H. K. In Crystal Growth in Gels; Pennsilvania State university press: University Park,
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[5] Jordon Lloyd, D. In Colloid Chemistry; J. Alexander, Ed.; The Chemical Cathalog Co.: New
York, 1926; Vol. 1, pp 767.

[6] Graham, T., Phil. Trans. Roy. Soc., 1861, 151, 183.

[7] Hermans, P. H. In Colloid Science; H. R. Kruyt, Ed.; Elsevier: Amsterdam, 1949; Vol. 2, pp
483-520.

[8] Almdal, K., Dyre, J., Hvidt, S., Kramer, O., Polymer Gels and Networks, 1993, 1, 5.

[9] Flory, P. J. In Principles of Polymer Chemistry; Cornell university press, Ithaca: New York,
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[10] Flory, P. J., Disc. Faraday Soc, 1974, 56, 7.

[11] Zallen, R. In The Physics of Amorphous Solids; Wiley: New York, 1983, pp Chapter 4.

[12] Stauffer, D., Coniglio, A., Adam, M., Advances in Polymer Science, 1982, 44, 105.

[13] Guenet, J. M., Thermoreversible gelation of polymers and biopolymers, Academic press, San
Diego, 1992.

[14] Terech, P., Weiss, R. G., Chemical Reviews, 1997, 97, 3133.

[15] Abdallah, D. J., Weiss, R. G., Langmuir, 2000, 16, 352.

[16] George, M., Weiss, R. G., Langmuir, 2003, 19, 1017.

[17] Abdallah, D. J. W., R. G., Chemistry of Materials, 2000, 12, 406.

[18] Guenet, J. M. In Thermoreversible gelation of polymers and biopolymers; Academic press:

San Diego, 1992, pp 2-8.

[19] Abdallah, D. J., Lu, L., G., W. R., Chemistry of Materials, 1999, 11, 2907.

[20] George, M., Weiss, R. G., Langmuir, 2002, 18, 7124.

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K., Shinkai, S., Journal of American Chemical Society, 1994, 116, 6664.

[22] Ferry, J. D., Viscoelastic Properties of Polymers, 3rd ed., Wiley, New York, 1980.

[23] Hermans, P. H. In Colloid Science; H. R. Kruyt, Ed.; Elsevier: Amsterdam, 1969; Vol. 2nd,
pp 483-651.

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 Chapter 2

[24] Russo, P. S. In Reversible Polymeric Gels and Related Systems (Acs Symposium Series 350);
P. S. Russo, Ed.; American Chemical Society: Washington, D. C., 1987, pp Chapter 9.

[25] Stauffer, D., Aharony, A., Introduction to Percolation, Taylor and Francis, London, 1985.

[26] Stanley, H. E., Family, F., Gould, H., Journal of Polymer Science: Polymer Symposium,
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[27] Adam, M., Coniglio, A., Stauffer, D., Advances in Polymer Science, 1982, 44, 103.

[28] Barnes, H. A., Hutton, J. F., Walters, K., An Introduction to Rheology, Elsevier, Amsterdam,
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[29] Goodwin, J. W., Huges, R. W. In Rheology for chemists; The Royal Society of Chemistry:
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[30] Baglioni, P., Carretti, E., Dei, L., Progress in Colloid and Polymer Science, In press.

[31] Chambon, F., Petrovic, Z. S., MacKnight, W., Winter, H. H., Macromolecules, 1986, 19,
2146.

[32] Winter, H. H., Chambon, F., Polymer Bulletin, 1985, 30, 367.

[33] Wolbers, R. C., Workshop on New Methods in the Cleaning of Paintings and other
Decorative Surfaces, Canadian Conservation Institute (CCI), 1990: Ottawa, CANADA; 1988:
Marina del Rey, California, USA, 1990, pp. 188-210.

[34] Michalski, S., Cleaning, retouching and coatings: technology and practice for easel
paintings and polychrome sculpture: preprints of the contributions to the Congress, 3-7 September
1990 (Eds.: J. S. Mills, P. Smith), International Institute for Conservation of Historic and Artistic
Works, London, United Kingdom, Brussels, 1990, pp. 85-92.

[35] Hedley, G., Odlyha, M., Burnstock, A., Tillinghast, J., Husband, C., Cleaning, retouching
and coatings: technology and practice for easel paintings and polychrome sculpture: preprints of
the contributions to the Congress, 3-7 September 1990 (Eds.: J. S. Mills, P. Smith), International
Institute for Conservation of Historic and Artistic Works, London, United Kingdom, Brussels,
1990, pp. 98-105.

[36] Cremonesi, P., Curti, A., Fallarini, L., Raio, S., Progetto restauro, 2000, 7, 25.

[37] Wolbers, R. C., Cleaning Painted Surfaces, aqueous methods, London, 2000.

[38] Burnstock, A., White, R., Cleaning, retouching and coatings: technology and practice for
easel paintings and polychrome sculpture: preprints of the contributions to the Congress, 3-7
September 1990 (Eds.: J. S. Mills, P. Smith), International Institute for Conservation of Historic
and Artistic Works, London, United Kingdom, Brussels, 1990, pp. 111-118.

[39] Dean, J. A.; Mc Graw-Hill: New York, 1985, pp 10-108.

[40] Wolbers, R. C., Workshop on New Methods in the Cleaning of Paintings, United States,
1989.

[41] Butazzoni, N., Casoli, A., Cremonesi, P., Rossi, P., Progetto restauro, 2000, 7, 11.

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Gels: properties and application in cultural heritage conservation

[42] Carretti, E., Salvadori, B., Mauro, M., Giovannoni, S., Bellé, S., De Santis, P., Dei, L.,
umpublished results.

[43] Valentin, N., Sánchez, A., Herraez, I., ICOM committee for conservation, 11th triennial
meeting in Edinburgh, Scotland, 1-6 September 1996: Preprints (Ed.: J. Bridgland), James &
James (Science Publishers) Ltd., London, United Kingdom, pp. 851-856.

[44] Tomozei, M., Balta, Z., Metal 98: proceedings of the International Conference on metals
conservation. Draguignan-Figanières, France, 27-29 May 1998, James & James, London, United
Kingdom, pp. 188-191.

[45] da Silveira, L., Studies in Conservation, 1997, 42, 11.

[46] Khandekar, N., Reviews in Conservation, 2000, 1, 10.

[47] Wolbers, R. C., Workshop on New Methods in the Cleaning of Paintings, Getty Conservation
Institute, Marina Rey, CA, United States, 1988.

[48] Burnstock, A., Kieslich, T., ICOM committee for conservation, 11th triennial meeting in
Edinburgh, Scotland, 1-6 September 1996: Preprints (Ed.: J. Bridgland), James & James (Science
Publishers) Ltd., London, united Kingdom, 1996, pp. 253-262.

[49] Wolbers, R. C. In Postprints (American Institute for Conservation of Historic and Artistic
Works. Paintings Specialty Group): London, United Kingdom, 1990, pp 60-83.

74