Bio-based hybrid nanocomposites and ionic liquids-loaded hydrogels as new multifunctional sustainable solutions for stone conservation

(cc)2023 PABLO IRIZAR MERINO (cc by-nc-nd 4.0)
Bio-Based Hyb id Nanocomposi es and
Ionic Liquids-Loaded Hyd ogels as New
Mul i unc ional Sus ainable Solu ions o
S one Conse a ion
This Ph.D. Thesis has been de eloped in IBeA esea ch g oup, in
he Analy ical Chemis y Depa men o he Uni e si y o he Basque
Coun y (UPV/EHU), as well as in he Uni e si y o Messina in he
Chemical, Biological, Pha maceu ical and En i onmen al Sciences
Depa men , unde he supe ision o he Ph.D. di ec o s Oli ia Gómez
Lase na and I an zu Ma inez A ka azo.
Pablo I iza Me ino
Sep embe 2023
I you' e going h ough hell,
keep going.....
Wins on Chu chill

Acknowledgemen s
A
I am g a e ul o he Spanish Minis y o Economy and Compe i i eness (MINECO) o my
p edoc o al ellowship (PRE2018-085888) as well as, o he Ike kun za e a Be ikun za
Anali ikoa (IBeA) esea ch g oup o he Analy ical Chemis y Depa men o he echnical
and scien i ic suppo . Speci ically, I would like o hank P o . Ma ian Olazabal and P o .
Go ka A ana o making he unding o his PhD. hesis possible h ough he ul illmen o
he aims in ol ed in he ollowing p ojec s:
⇒ Syn hesis, cha ac e iza ion and alida ion o mul i unc ional nano- ein o ced
sus ainable hyb id p oduc s o he eco e y and p o ec ion o s one su aces
(PHETRUM, e . CTQ2017-82761-P) unded by MINECO.
⇒ De elopmen o mo a s esis an o en i onmen al con amina ion and
biode e io a ion and inno a i e sus ainable sys ems o cleaning and es o ing
Buil He i age (DEMORA, e . PID2020-113391GB-I00) unded by he Spanish
Minis y o Science and Inno a ion (MICINN).
A his espec , he Resea ch Gene al Se ices o he UPV/EHU (SGIKER) is also
acknowledged by he suppo o he Singula Coupled Mul ispec oscopy Labo a o y
(LASPEA), he Mac oconduc , Mesos uc u e and Nano echnology Uni as well as, he
Analy ical and High Resolu ion Mic oscopy in Biomedicine labo a o y and he X-Ray
Se ice o Rocks and Mine als Uni .
A e hese, I would like o especially hank he Depa men o Chemical, Biological,
Pha maceu ical and En i onmen al Sciences o he Uni e si y o Messina, speci ically o
P o . Paola Ca diano, o welcoming me in hei labo a o ies and coope a e o de elop
pa o his esea ch wo k.
Finally, I would like o exp ess my deepes g a i ude o my hesis ad iso s, D . Oli ia
Gómez and D . I an zu Ma ínez, whom I hold in e y high ega d o hei unwa e ing
suppo , and dedica ion, ha made he de elopmen o his hesis wo k and my own skills
possible. Las ly, I do no wan o o ge my iends, and my PhD. Colleagues o
accompanying me in his challenge, and especially my amily and couple ha we e always
wi h me sha ing he good and bad momen s hese las 4 yea s.
I
TABLE OF CONTENTS
CHAPTER 1: In oduc ion __________________________________________________ 1
1.1. Decay o s one ma e ials: Causes and deg ada ion pa e ns _______________________ 2
1.2. Consolida ing ma e ials o s one eco e y and p o ec ion ________________________ 7
Con en ional p oduc s __________________________________________________________ 8
1.2.1.1. Silica-based ma e ials _____________________________________________________ 8
1.2.1.2. O ganic polyme s: Epoxy esins ____________________________________________ 10
Ad anced ma e ials ___________________________________________________________ 12
1.2.2.1. Bio-based epoxy esins polyme s ___________________________________________ 13
1.2.2.2. Bio-based epoxy-silica hyb id ma e ials ______________________________________ 14
Mul i unc ional ad anced solu ions: Syn he ic s a egies _____________________________ 16
1.2.3.1. Ionic liquids ____________________________________________________________ 17
1.2.3.2. Plan ex ac s ___________________________________________________________ 19
1.2.3.3. Nano echnology ________________________________________________________ 19
1.3. Cleaning echnologies o s ained s ones _____________________________________ 20
Solid suppo and cleaning agen s _______________________________________________ 21
1.4. Re e ences _____________________________________________________________ 23
CHAPTER 2: Objec i es ___________________________________________________ 37
CHAPTER 3: Ma e ials and me hods ________________________________________ 39
3.1. Epoxy-silica hyb id ma e ial es ing _________________________________________ 39
Mic oo ganism g ow h es s ____________________________________________________ 39
S one du abili y s udies ________________________________________________________ 41
3.1.2.1. S one ma e ials _________________________________________________________ 41
3.1.2.2. S one ea men ________________________________________________________ 42
3.1.2.3. Accele a ed aging expe imen s ____________________________________________ 43
3.2. Ionic Liquids-loaded hyd ogels es ing _______________________________________ 43
Mic oo ganism g ow h inhibi ion es s ____________________________________________ 43
Me al seques e ing capabili y and cleaning es s ____________________________________ 44
3.2.2.1. S one ma e ials _________________________________________________________ 44
3.2.2.2. A i icial me allic s ains p oduc ion _________________________________________ 44
3.2.2.3. Na u al me allic s ains ___________________________________________________ 45
3.3. Ins umen s ____________________________________________________________ 45
Elemen al Analysis ____________________________________________________________ 45
Chap e 1
2
economically iable, as i se es as a c ucial pilla o main aining and enhancing long-
e m p o i abili y s a egies o sus ainable de elopmen .
As a consequence, he de elopmen o new me hods o moni o ing and conse ing s one
building ma e ials has become a majo global business. Conce ning his aspec , he
In e na ional Cha e o he Conse a ion and Res o a ion o Monumen s and Si es
emphasizes he impo ance o balancing conse a ion e o s wi h economic
de elopmen and encou ages sus ainable app oaches o manage i . Besides, hese
guidelines highligh ha any conse a ion o es o a ion ac ion mus be ca ied ou wi h
he u mos espec , aking in o accoun e e y (e en p edic able) aspec ha has his o ical
signi icance [5]. Hence, a ge ed p e en ion and emedia ion s a egies mus be sui ably
designed du ing he decision-making phase, a oiding elapsing in o inapp op ia e
p o ocols ha do no ac on he cause o do no ake in o accoun he s one ma e ial
needs and e olu ion o i s ea men along he ime [6].
This challenge equi es mul idisciplina y knowledge, which has become inc easingly
c ucial o ehabili a ion and conse a ion endea o s in ecen yea s. Among o he ields,
he in eg a ion o chemical science in o his sec o is ins umen al in os e ing he
de elopmen o cu ing-edge echnologies. The main p emise is o imp o e exis ing
ma ke s and con en ional p oduc s while also add essing eme ging needs. These e o s
hold subs an ial signi icance in na ional de elopmen and con ibu e o he s a egic
amewo k o he global economy. The esea ch and alida ion o ailo ed s one
conse a ion ea men s p esen an ambi ious ask o Resea ch and De elopmen (R+D).
The ad ancemen s achie ed in his ield can be also ex apola ed o p omo e u ban
egene a ion and enewal, con ibu ing o a sus ainable eac i a ion o he cons uc ion
sec o , as well as he chemical indus y.
To make signi ican p og ess in his line, i is impe a i e o ho oughly know he isks o
which li hic ma e ials a e subjec ed, and gain a comp ehensi e unde s anding o he
physical, chemical, and/o biological unde lying deg ada ion p ocesses.
1.1. Decay o s one ma e ials: Causes and deg ada ion pa e ns
In his espec , as a summa y ex ac ed om he diagnosis s udies ca ied ou du ing he
las decade, i has been demons a ed ha he de e io a ion o s one ma e ials is closely
ela ed o hei inhe en composi ion and hei in e ac ion wi h he en i onmen [7–10].
Speci ically, a mosphe ic pollu ion, wa e , and biode e io a ion agen s a e gene ally

In oduc ion
3
poin ed ou as he mos c i ical ac o s in hei s a e o conse a ion. Indeed, he
pollu an s exe a signi ican e ec , pa icula ly h ough he acidic a ack o combus ion
gases (CO2, SO2, and NOx), whose deg ada i e ac ion is u he ampli ied in he p esence
o wa e (humidi y, ain, and in il a ion) due o he syne gis ic e ec p oduced. The wa e
pene a es he capilla y ne wo k o he s one, ac ing as a ehicle o con aminan s,
dissol ing hem, and ac i a ing o he compounds inhe en o he subs a e composi ion.
Bo h agen s gi e ise o he p esence o soluble sal s, which a e classi ied as one o he
mos dange ous pa hologies o li hic ma e ials by he In e na ional Council on
Monumen s and Si es (ICOMOS) [9]. An ea ly s age o his pa hology is o en i s
iden i ied by he p esence o e lo escences. I le un ea ed, he chemical and physical
p ocesses o damage con inue o p og ess, esul ing in impo an losses o he
cemen i ious ma ix o he s one subs a e. The e o e, i is mani es ed on a mac o scale
h ough he o ma ion o in e nal issu es, ac u es, and he occu ence o pa hologies
such as disagg ega ion, sanding, and/o scaling (Figu e 1.1). These deg ada ion pa e ns
a e a clea signal o impo an p oblems o s uc u al in eg i y and mic omechanics. Thus,
i his pa hology is o e looked o no add essed, i can po en ially lead o he comple e
loss o he s one piece, o e en in he mos se e e cases, he collapse o he a chi ec u al
s uc u e.
Figu e 1.1. Common de e io a ion pa e ns ela ed o he soluble sal p esence in s one ma e ials.
a) E lo escence wi h whi e c us , b) al eola iza ion, c) scaling, d) sanding, and e) disagg ega ion.
Chap e 1
4
In addi ion o he a o emen ioned ac o s, he p esence o plan s and mic oo ganisms
including bac e ia, ungi, lichens, and algae, among o he s, also exe an impo an impac
on he conse a ion o s one ma e ials [11–16]. These subs a es p esen mine als,
en i onmen s wi h ligh , wa m empe a u es, and wa e , as well as ich nu ien s om
o ganic esidues, c ea ing ideal condi ions o he g ow h o li e. The gene al
mic oo ganisms, o en associa ed wi h bio ilms o a ious colo s and ex u es anging
om g een, b own, o black pa ches o slimy o c us y o ma ions, can ac indi idually o
in combina ion wi h o he en i onmen al ac o s, he eby ampli ying hei capaci y o
deg ada ion. Thus, hei impac ex ends beyond me e aes he ic changes (see Figu e 1.2).
Se e al physical and chemical damages, commonly known as biopi ing [17], include po e
size enla gemen and c acking, which can occu due o ac o s such as he opening o
pa hways o wa e ci cula ion, pene a ion o hyphae, as well as he p esence o soluble
sal s p oduced h ough he syne gis ic ac ion o wa e , colonizing bio a, and he o ganic
and ino ganic acids hey sec e e (such as hose in ol ed in he sul u cycle o ammonia
oxida ion).
Figu e 1.2. Common examples o biode e io a ion ela ed o mic oo ganisms p esence in s one
ma e ials. a) Cyanobac e ia, b) biopi ing deg ada ion, c) ungi, and d) lichens [17,18].
As a esul , hese p ocesses pose a signi ican h ea o he in eg i y and longe i y o s one
ma e ials. The e o e, p e en i e ac ions a e c ucial, pa icula ly du ing he ea ly s ages.
This in ol es selec ing sui able cleaning me hods o emo e hese damaging agen s and
subsequen ly p o ec ing he s one subs a e h ough measu es such as he applica ion o
biocidal p oduc s and coa ings o consolida ion ea men s.
In oduc ion
5
Fu he mo e, hese a ious en i onmen al ac o s can also be esponsible o s aining
pa hological mani es a ions, which a e common issues encoun e ed in he ield o s one
conse a ion. In addi ion o he o ma ion o bio ilms, he ypical discolo a ions ound can
be di ec ly a ibu ed o en i onmen al pollu ion, chemical eac ions, and aging p ocesses
[19,20] (Figu e 1.3).
Figu e 1.3. Common cases o s one de e io a ion ela ed o en i onmen al ac o s: a) Black c us s
and dissolu ion o ma e ial caused by pollu an s, b) chemical eac ions, and c) aging p ocesses.
Speci ically, me allic s ains can be poin ed ou among he mos equen deg ada ion
pa e ns. These discolo a ion a eas ypically occu ou doo s due o wea he ing p ocesses
a ec ing adjacen me allic ma e ials, which a e o en used as deco a i e o unc ional
i ems close o s one su aces. The chemical a ack on he me allic s uc u e leads o he
o ma ion o co osion p oduc s, and wi h he ac ion o wa e , ions can mig a e owa d
Chap e 1
6
he s one subs a es [9–11]. Such leaching phenomenon no only impac s he aes he ic
appea ance o he li hic ma e ials bu also has he po en ial o comp omise hei
longe i y. Addi ionally, depending on he speci ic ions in ol ed, i can e en acili a e
ce ain biological ac i i ies [21,22].
In de ail, s ains caused by i on and coppe a e o signi ican conce n due o hei
widesp ead use in oo s, sculp u es, and e en buildings cons uc ed wi h s eel and b onze
ma e ials. I is known ha leaching p ocesses gi e ise o he o ma ion o cha ac e is ic
eddish-b own and g eenish a eas, which a e composed o he ci ed oxides as well as
a ious sal s like chlo ides, sul a es, ca bona es, o ni a es [22–24]. These ch oma ic
al e a ions can be de eloped in a sho ime, e idencing ha hey a e no limi ed o
ancien cons uc ions bu can also be obse ed in ecen buildings whe e hese me allic
ma e ials a e ex ensi ely used (Figu e 1.4).
Figu e 1.4. Examples o i on and coppe me allic s ains caused by he wea he ing o he me allic
componen s o : a-b) building and c-e) s a ues
The di icul y in emo ing hese s ains depends on se e al ac o s, including he
unde lying causes, he ex en o hei sp ead, hei composi ion, and he dep h o
pene a ion in o he s one subs a e. As a esul , his seemingly s aigh o wa d pa hology
can pose signi ican challenges o con en ional cleaning me hods, which may no always
be sui able o emo ing complex s ains wi hou causing damage o al e ing he o iginal
appea ance o he s one ma ix [25,26]. The e o e, employing p ope main enance and
conse a ion echniques is c ucial o mi iga e he e ec s o his pa hology and ensu e he
long- e m p o ec ion o s one ma e ials along he ime.
In oduc ion
7
A his espec , al hough, he p ese a ion o s one ma e ials has become a signi ican
mul idisciplina y esea ch ield, he e is s ill an inc easing demand o mo e scien i ic and
espec ul app oaches, ha also p io i ize en i onmen al conside a ions [20,27].
The e o e, designing inno a i e conse a ion solu ions is a complex and c i ical pa ha
equi es he collabo a i e wo k o many p o essional p o iles (Conse a o s,
a chaeologis , chemis s, a chi ec s and his o ians). Adding o his, he explo a ion o g een
al e na i es o con en ional ea men s has no been widely implemen ed, as
consolida ing and coa ing p oduc s de i ed om ha m ul compounds a e s ill widely used
o ea ing la ge s one su aces, posing isks o bo h human heal h and he en i onmen
[28]. Addi ionally, cleaning and p e en i e p o ocols o en ely on he use o ha m ul
biocides and agg essi e chemical p oduc s ha do no con ibu e o he p inciples o
Sus ainable De elopmen Goals (SDGs) [29,30]. Hence, he e is e e -g owing social
awa eness ha calls o inno a i e e ec i e solu ions ha lea e behind decisions based
solely on cos -e ec i eness and sho - e m ou comes and p io i ize en i onmen al
conside a ions, es ablishing hem as c ucial ac o s ha equi e special esea ch
di ulga ion in he p o essional sec o and indus ial a en ion.
In acco dance wi h his necessi y, he ollowing sec ions collec an o e iew o he
p oduc s and me hodologies con en ionally employed highligh ing hei ad an ages and
limi a ions o he consolida ion, p o ec ion, and cleaning o s one ma e ials. Mo eo e ,
he oppo uni ies o e ed by ongoing chemical echnologies o design ad anced ma e ials
and me hods o e ec i ely add ess he cu en challenges in he ield a e also explo ed o
ocus a imely line o p og ess ha di ec s he objec i es o his Ph.D. Thesis, ha
speci ically deals wi h ea men s o silica e and ca bona e s ones.
1.2. Consolida ing ma e ials o s one eco e y and p o ec ion
Once wea he ing has begun, i is essen ial o ea he s ones wi h p oduc s ha can
enhance hei esis ance o decay. They should ensu e s ong adhesion and in e g anula
cohesion wi hin he s one ma ix while p o ec ing agains he u u e de imen al e ec s
o wa e , pollu an s, and biode e io a ion agen s [31,32]. Mo eo e , he new gene a ion
o ma e ials should adhe e o cu en eco-sus ainabili y c i e ia, and mee he mid- e m
ea men equi emen s o p e en issues ha may a ise om he use o un es ed
ma e ials, as seen wi h se e al p oduc s widely employed in pas es o a ion ac i i ies.
The e o e, he desi ed ange o capabili ies o a s one conse a ion p oduc necessi a es
he speci ic design o ad anced i unc ional ma e ials wi h consolida ing, hyd ophobic

Chap e 1
8
and biocidal p ope ies ha a he same ime gua an ees he use o minimal amoun s o
oxic compounds and includes s udies o hei beha io o e ime.
Con en ional p oduc s
The p oduc s i s employed o conse a ion pu poses we e selec ed acco ding o hei
a ailabili y and he scien i ic ad ances a he ime, being applied wi hou he chemical
knowledge o hei beha io in he mid- and long- e m. Howe e , al hough he scien i ic
communi y, and expe ience acqui ed om cases o s udies, ha e al eady demons a ed
hei handicaps, he eason why a e s ill cu en ly used is o en based on hei ex ended
applica ion du ing he las decades ins ead o he long- e m e ec i eness and
sus ainabili y c i e ia. Some o hem a e highligh ed by hei low cos and sho - e m
esul s a he han c ucial ea u es like chemical s abili y, pollu ing species o oxic side
p oduc s o ma ion upon UV aging, and so on. Thus, he majo i y o hese con en ional
p oduc s, ye only pa ially ma ching he abo e equi emen s, in he case o s ones o
silica e and ca bona e na u e, mainly belong o wo ca ego ies [33–36].
1.2.1.1. Silica-based ma e ials
The ino ganic consolida ing ma e ials [37,38] ha e been he mos adi ional p oduc s
used om he 19 h cen u y by hei compa ibili y wi h he li hic ma ix and hei abili y o
bind de e io a ed s one pa icles by o ming insoluble phases wi hin he oids and po es
h ough sal p ecipi a ion o chemical eac ions wi h he s one subs a e. Despi e hei
his o ical use, alkali silica es and silico luo ides ha e been widely ejec ed by cause he
o ma ion o soluble sal s o shallow c us s, and discolo a ion and ex olia ion phenomena
o he s one's su ace. In he same way, alkaline ea h hyd oxides like he highly used
calcium hyd oxide ha e been also discou aged due o i s consolidan ing capabili y is
limi ed o he su ace and hus, no each o ea he in e io o he s one subs a e and
no p o ide long- e m p o ec ion [38,39].
In con as , om he cen u y 20 h, o ganosilica-based ma e ials [40–42] ob ained by sol-
gel echnology such as alkoxysilanes and alkylalkoxysilanes (i.e. e ae hoxysilane,
ie hoxyme hylsilane, o poly(dime hylsiloxane) ha e been widely used, and in ac , hey
a e cu en ly p e e ed o consolida ing siliceous sands ones and also by hei easibili y
o eco e calca eous s ones. These amilies o monome ic molecules can eac wi h wa e
by a polyme iza ion p ocess, which s a s wi h he hyd olysis o he alkoxysilane and
con inues un il all he alkoxy g oups a e libe a ed, esul ing in he o ma ion o ei he
In oduc ion
9
alkylpolysiloxane o silica compounds in ima ely join ed o he s one subs a e (Figu e
1.5). The dilu ing alkoxysilanes wi h sol en s helps o con ol hei iscosi y and eac ion
a e, acili a ing a be e pene a ion in o he damage ma ix.
Figu e 1.5. Gene al polyme iza ion eac ion occu ed du ing he sol-gel p ocess and an example
o an in si u polyme iza ion p ocess in o a s one subs a e o silica ed na u e.
Thus, al hough hey sol e some o he abo e d awbacks, he in luence o R g oups (alkyl
g oups) and OR g oups (alkoxy g oups) on some undamen al p ope ies o he sol-gel
p ocess is he main eason why he lis o alkoxysilanes used o s one conse a ion is so
limi ed. Fo a consolidan o ul ill i s unc ion, he ma e ial mus ha e he abili y o o m
a h ee-dimensional ne wo k, and he e o e, i mus ha e a minimum o h ee eac i e
g oups. This equi emen elimina es all bi unc ional compounds, which only o m linea
polyme s. On he o he hand, some i- and e a- unc ional compounds, such as R-SiH3
and SiH4, a e oxic, ola ile, and gene a e hyd ogen gas h ough hyd olysis, so hey ha e
also been disca ded. Only i- and e a- unc ional alkoxysilanes a e ela i ely non- oxic
and non- ola ile (lowe apo p essu e), and he byp oduc s o hei hyd olysis a e
Chap e 1
10
alcohols, which a e no co osi e o s ones. Addi ionally, hey ha e low o mode a e
eac i i y wi h wa e , which can be an ad an age o a s one consolidan since an
excessi ely as eac ion can limi he dep h o pene a ion o he liquid in o he s one
ma e ial, causing i o gel be o e i can pene a e enough o ul ill i s unc ion [42].
Howe e , he mos used ma e ials o en display c acking upon d ying, hus, educing he
consolida ion e iciency and, due o hei s uc u al igidi y, show mechanical p ope ies
which a e no compa ible wi h he ones o wea he ed s ones. Mo eo e , he low
molecula weigh s a ing compounds a e also p one o e apo a ion be o e he
polyme iza ion p ocess occu s inside he s one subs a e [43,44].
1.2.1.2. O ganic polyme s: Epoxy esins
The use o syn he ic o ganic polyme s o he moplas ic and he mose na u e such as
ac ylic polyme s (me hylme hac yla e and bu ylme hac yla e), polyu e hanes, and
pe luo opolye he s ha e been implemen ed o s one consolida ion om he ea ly 1960s
due o hei po en ial o enhance he mechanical p ope ies [37,44–47]. Howe e , hei
applica ion implies he use o ha m ul sol en s (dichlo ome hane, dime hyl sul oxide, and
hexane among o he s) and, a pa om he en i onmen al issues, hei cha ac e is ic
apid e apo a ion can d aw he o ganic consolidan s back o he s one's su ace, leading
o he o ma ion o impe ious ha d su ace c us s. In addi ion, he esul s a mid- e m
also showed nega i e e ec s due o hei inhe en suscep ibili y o deg ada ion by oxygen
and ul a iole adia ion, p ima ily a ec ing he ch oma ic ea u es o he su ace o he
ea ed s one, as well as, wi h he passing o he ime hei capabili ies o main ain he
in eg i y o he s one ma ix, ypically causing p oblems.
Among he con en ionally used, epoxy esins a e s ill widely accep ed in consolida ing
asks o limes one, ma ble, and sands ones, and e en o mo a s o in eg i y highly
comp omised [37]. These polyme s a e highligh ed o exhibi excellen adhesi e and
hyd ophobic p ope ies, being also ea u ed by sui able ha dness and igidi y, wi h
he mal and chemical esis ances ha su pass he du abili y o o he polyme s. In
addi ion, hese he mose ma e ials a e capable o each deep pene a ion, gi en ha
hey a e deposi ed in solu ion, and hei in si u polyme iza ion p ocesses occu in o he
po ous s one ne wo k. These ad an ages oge he wi h hei cus omiza ion op ions make
hem he adi ional p e e ed op ion o s one consolida ion among he p oduc s o
o ganic na u e [48,49].
In oduc ion
11
Epoxy esins s and ou by hei high e sa ili y since, hanks o hei epoxide ings, single
o mul iple, can be ans o med in o he mose ing polyme s by a wide a ie y o cu ing
eac ions, which can con e he ini ially low molecula weigh p ecu so in o an in usible
c oss-linked h ee-dimensional polyme [50,51] wi h excep ional physicochemical
p ope ies. Fo his, compounds con aining ac i e hyd ogens, such as polyamines,
polyacids, polyphenols, polyme cap an, amines, and anhyd ides, among o he s, a e
commonly used as ha dening eac an s. Th ough nucleophilic a ack eac ions, hey a e
able o open he epoxy ings and lead o c osslinking by he o ma ion o co alen bonds
be ween he polyme chains o u he de elop he o ganic c oss-linked ne wo k (Figu e
1.6) [52,53]. Thus, he choice o he cu ing agen and he eac ion condi ions signi ican ly
impac s he p ope ies o he inal ma e ial, making hem c ucial ac o s in he
he mose ing design o each speci ic applica ion.
Figu e 1.6. The gene al c oss-linking eac ion o an epoxy esin polyme using a nucleophile
compound as a cu ing agen .
Gi en he capabili y o he oxi ane ing o eac h ough mul iple pa hways, oge he wi h
hei gene al excellen he mal, mechanical, and elec ical p ope ies, along wi h high
adhesi eness and esis ance o chemicals and mois u e, make hem ex ensi ely used in
nume ous sec o s (ae ospace, au omo i e, consume goods, ood packaging, elec ical
and elec onic, building and ci il enginee ing, and biomedicine) as gene al-pu pose
adhesi es, ibe - ein o ced ma e ials, high-pe o mance pain s, and coa ings o
consolidan s [51,54–57].
To mee he global demand, mo e han 75% o epoxy esin p oduc ion s ill comes om
Bisphenol A diglycidyle he (DGEBA), which is based on Bisphenol-A (BPA) as pa en
p oduc [58]. BPA is known as a con o e sial pe ochemical-based compound ha has
been ound o beha e like a syn he ic es ogen and o ac as an an agonis ic ligand o
ho mone nuclea ecep o s [59,60]. I has been shown o play an impo an ole in he
pa hogenesis o a ious endoc ine diso de s, including emale and male in e ili y,
p ecocious pube y, ho mone-dependen cance s, and se e al me abolic and neu ological
Chap e 1
18
Figu e 1.9. S uc u al ep esen a ion o commonly used cons i uen s o ionic liquids, a) ca ions
and b) anions [93].
In his espec , wo ypes o con en ional ILs ha s and ou because o hei biocidal
p ope ies a e qua e na y ammonium (QASs) and phosphonium sal s (QPSs) [106–109].
Rega ding hei s uc u es, he long lipophilic subs i uen o he QASs and QPSs alongside
he cha ged cen e allows i o become inco po a ed in o he phospholipid bilaye . As a
esul , he cell loses i s abili y o main ain a s able in e nal en i onmen , leading o he
leakage o cellula con en s and ul ima ely he dea h o he mic oo ganism. This
mechanism o ac ion is non-speci ic, meaning ha QASs and QPSs a e ac i e agains a
wide ange o mic oo ganisms, ega dless o he species; ha is, hey a e e ec i e agains
bac e ia, ungi, pa asi es, and e en lipophilic i uses. This biocidal capabili y has been
widely demons a ed in o he indus ies in which, hanks o he b oad-spec um ac i i y
o QASs and QPSs, hey ha e been employed o a a ie y o applica ions, including
disin ec ion o su aces, medical equipmen , wa e ea men sys ems, opical an isep ics,
and wound d essings and mo e ecen ly, as an imic obial ma e ial o ai disin ec ion and
s e iliza ion. This way, co alen ly inco po a ing QAS/QPS moie ies wi hin an epoxy-silica
hyb id ne wo k as mul i unc ional eco-subs i u es o he oxic indus ial biocides could
achie e a b oad-spec um an imic obial ac i i y and an imp o ed hyd ophobic beha io
gi en hei alipha ic chain leng h.

In oduc ion
19
1.2.3.2. Plan ex ac s
An e en g eene al e na i e in his esea ch line can be he inco po a ion o essen ial oils
(EOs), such as eugenol, hymol, men hol, and so on, which ha e shown ema kable
biocidal ac i i y and sui able miscibili y wi h consolida ing o mula ions [110–112]. Thei
s uc u e does no p edic a signi ica i e chemical c osslinking wi h he epoxy-silica hyb id
ne wo k, so hey could emain dispe sed in o he polyme ic ma ix wi hou modi ying he
main p ope ies, o in change, al e ing he balance o he hyb id's base cha ac e is ics.
Howe e , hei high ola ili y and deg ada ion a e a e handicaps o ha e in o accoun in
he ma e ial design phase [110,113].
1.2.3.3. Nano echnology
Nanopa icles (NPs) a e being cu en ly exploi ed in he de elopmen o ma e ials o
main aining s one subs a es, o e ing new oppo uni ies o design conse a ion p oduc s
wi h inno a i e unc ionali ies. Consequen ly, NPs a e speci ically employed o a ious
pu poses such as cleaning, consolida ion, p o ec ion, and an imic obial ea men s i.e.
me al NPs (Au, Ag, P ), oxides and hyd oxides NPs (TiO2, ZnO, SiO2, CaOH2, Mg(OH)2,
S (OH)2) o e en hyd oxyapa i e and ca bona ed de i a es [89,114–116]. In ac , i is
widely ecognized ha nanoscale ma e ials o en exhibi supe io p ope ies compa ed o
adi ional p oduc s, including enhanced mechanical and he mal cha ac e is ics,
inc eased eac i i y, and deepe pene a ion wi hin s one ma ices, among o he s. As a
esul , inno a i e s udies ha e success in inco po a ing biocidal nanopa icles in o hyb id
consolidan s and wa e epellen o mula ions o gain nanocomposi e ma e ials ha
achie e o mi iga e he deg ada ion p ocesses o s ones exposed o he en i onmen al
agen s [31,32,117–119]. In pa icula , nano-TiO2 and lan hanide-doped TiO2 (in ana ase
o m) ha e ga ne ed signi ican a en ion due o hei po en pho oca aly ic ac i i y,
making hem highly e ec i e ca alys s o he deg ada ion o a ious pollu an s.
Simul aneously, hey impa s ong sel -cleaning and an imic obial p ope ies agains
bac e ia and ungi o he ma e ials in which hey a e inco po a ed.
Fu he mo e, he ad an ages o nano echnology ha e been also ecen ly exploi ed o ac
as con aine capsules o EOs p io o he inco po a ion o biocidal o mula ions o he
ma e ials, o example, silica NPs o halloysi e nano ubes [120,121]. These kinds o
app oaches could allow he inco po a ion o biocidal p ope ies o a base ma e ial
minimizing he handicaps di ec ly ela ed o he e icacy in he long e m o EOs, as well
as he possible nega i e e ec on he inal ma e ial ea u es.
Chap e 1
20
1.3. Cleaning echnologies o s ained s ones
T adi ional physical and chemical me hods such as mechanical ab asion, sandblas ing,
sand and wa e p essu e, o acid washing ha e been widely used by hei high
e ec i eness in emo ing s ains om s one su aces (Figu e 1.10) [122]. Howe e , hey
can be ime-consuming, cos ly, and po en ially haza dous o bo h he use and he
en i onmen . In addi ion, hey a e discou aged because hey can also cause long- e m
damage o he s one subs a e, pa icula ly i used inco ec ly o on a egula basis,
causing excessi e e osion, discolo a ion phenomena, and in some cases, e en he
de e io a ion o undamaged a eas o he li hic ma e ial by acid a ack o soluble sal
p ocesses, among o he s. As a consequence, conse a o s and esea che s alike, ask o
mo e ad anced, espec ul, and en i onmen ally- iendly me hods o selec i ely
emo ing me allic s ains om s one subs a es, also claiming hei es ing a mid- and
long- e m.
Figu e 1.10. a) Examples o clean-up physical me hods using a) high-p essu e sandblas ing, b)
manual b ushing, and c) lase .
In his ega d and speci ically o me allic s ains, a ious clean-up me hods, as di e se as
lase cleaning [123–126], biological [21,127–129], o based on complexing o chela ing
agen s [130,131], a e cu en ly applied as al e na i e conse a ion solu ions. Lase
In oduc ion
21
cleaning (Figu e 1.10) is minimally in asi e and o e s a con olled and selec i e emo al
ac ion. I can be moni o ed in eal- ime and does no equi e sol en s o mechanical and
chemical con ac wi h he s one ma ix. Howe e , he me hodology equi es high cos s
when la ge a eas a e ea ed, as well as ex ensi e knowledge o he echnique and
subs a e o a oid causing damage. Biocleaning could be a sa e ea men o s ained
s ones, as i allows highly e sa ile, e ec i e, and selec i e applica ion op ions. Howe e ,
i also has some d awbacks; among hem, he adhe ence o o e ly ex u ed su aces and
he need o main ain op imal hyd o he mal condi ions o bioagen s o emain iable a e
highligh ed. Addi ionally, his me hod may no be eligible o applica ion in he case o
mixed s ains wi h biological coloniza ion, as i could po en ially be de imen al by inducing
hei expansion. On he o he hand, chemical me hods based on ligands ha (i.e. EDTA,
cys eine, L-alanine e c.) o m coo dina ion complexes wi h he me allic ion con ained in
he s ains a e conside ed one o he mos e ec i e cleaning ea men s. Howe e ,
selec ing seques e ing agen s is a complex ask, as hey should show a high speci ic a ini y
owa ds he ion o in e es and a lowe one owa ds he s one ma e ial composi ion o
a oid damage. Besides, en i onmen al and p ac ical aspec s such as non- oxici y, ease o
handling and disposal, as eac ion, and low cos mus also be conside ed. Acco dingly,
p o essionals in he ield a e con inuously seeking inno a i e and gen le cleaning
app oaches o e ec i ely emo e he s aining issues om s one su aces.
Solid suppo and cleaning agen s
In his ega d, solid ma ixes such as aga [132,133], poly inyl-based ma e ials [134–136],
ionic exchange esins [137–139], o cellulose [130,140,141] ha e been ecen ly used as
suppo ing ma e ial o seques e ing agen s. They ha e demons a ed o be capable o
ac ing as a sui able s o age suppo and enabling a liquid-liquid exchange in which he
me als di use. In addi ion, hese malleable solids allow selec i e applica ion ea men s,
and hanks o he slow elease o he cleaning agen , he applica ion can be con olled o
p ese e he ea ed subs a e co ec ly. These ad an ages a e c ucial o he ea men
o he e ogeneous deg ada ions ha could equi e di e en cleaning needs.
Among he men ioned suppo s, aga gel is a highly e sa ile and cos -e ec i e h ee-
dimensional s uc u e ha is highligh ed o being capable o holding signi ican amoun s
o wa e wi hin i s in e s ices. This cha ac e is ic allows a con olled wa e elease wi h
minimal isk on he subs a e [133,142,143]. Mo eo e , i s speci ic ad an age o e
adi ional aqueous me hods lies in i s abili y o cap u e emo ed soiling wi hin he gel
Chap e 1
22
s uc u e. Fu he mo e, se e al s udies e idenced hei capabili y o emo e he ypical
me allic s ains, hanks o he implemen a ion o he chemical agen s men ioned abo e, in
which chela an s such as EDTA and ci a es ha e been ho oughly es ed [132,143–148].
Simila ly, an inhe en ly biocidal kind o s a ch called Kuzu has ecen ly demons a ed
s uc u al cha ac e is ics and physicochemical p ope ies ha pose i as a po en ial
candida e o solid suppo o simila pu poses, in ac , i has been explo ed in he
cleaning o old pape documen s [149–151].
In he same manne , IL s a egies can be also a p omising al e na i e o classical
chela ing, hey ha e p o en o be sui able sol en s o be used as e ec i e subs i u es o
syn hesis, ca alysis, and ex ac ion p ocesses. In ac , se e al wo ks ha e p o ed he
signi ican ILs po en ial [94–99], ei he as di ec sol en ex ac ion o in eg a ed in o a
solid ma ix, o seques e me al ions in o he applica ion ields o example om solu ions
and e en dissol e a a ie y o me allic oxides, ypically he mos p e alen species in
me allic s ains. Thus, i is highly in e es ing o in es iga e i aga and/o kuzu hyd ogels
a e capable o e ain ILs o long alipha ic chains while allowing hem o ac as ion
seques e s in cleaning ea men s.
The in o ma ion he e collec ed demons a es, he e is a wide ange o ecen
echnological ad ancemen s ha can be in es iga ed along his Ph.D. hesis wo k o allow
he de elopmen o mo e e icien and speci ic ma e ials o espec ully add ess he mos
impe a i e conse a ion challenges associa ed wi h s one conse a ion. In pu suing his
goal, sus ainabili y mus be also a undamen al aspec , equi ing he sea ch o
en i onmen ally iendly solu ions ha minimize nega i e impac s on human heal h and
he na u al su oundings. Indeed, he p og ess in he design o new consolida ing and
cleaning solu ions will help us o p ese e he s one he i age, ensu ing i s legacy o u u e
gene a ions, in he same way, ha con ibu es o economic capaci y, aligning wi h he
gene al objec i es o he global SDGs.
In oduc ion
23
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36
37
CHAPTER 2: Objec i es
The aim o his PhD. hesis was o de elop ad anced bio-based ma e ials as
mul i unc ional sus ainable al e na i es o con en ional ea men p oduc s used o
he s one conse a ion. The o e a ching goal encompasses di e en conse a ion
p oblems, on he one hand, de eloping ailo -made epoxy-silica hyb id ma e ials, wi h
consolida ing, hyd ophobic, and biocidal capabili ies we e de eloped. Mo eo e , Ionic
Liquids-Loaded Hyd ogels we e also designed o clean me allic s ains and o ac as biocidal
on s one subs a es.
Acco ding o he wo g oups o ma e ials de eloped, he ollowing ope a ional objec i es
we e es ablished:
⇒ Bio-based epoxy-silica hyb ids ma e ials, wi h consolida ing, hyd ophobic, and
biocidal p ope ies, o ad anced s one conse a ion.
 To de elop ailo -made BPA- ee epoxy-silica hyb ids ha mee s he speci ic
mul i unc ional p ope ies equi ed o an ad anced s one conse a ion
ea men , as well as o he en i onmen al policies o p oduc ion and use,
h ough a sequen ial building block design s a egy composed o ou s eps.
Acco dingly, S ep, named “Epoxy p ecu so ”, consis s o he selec ion and
syn hesis o a bio-based epoxy esin p ecu so . Subsequen ly, S ep, named
“Base he mose ”, ocuses on he selec ion o he ha dening agen s o con igu e
he he mo-mechanical and hyd ophobic p ope ies o he he mose ing
Chap e 2
38
ma e ial, which ac s as he base block o he design. S ep, named as “Epoxy-Silica
hyb ida ion”, in ol es he unc ionaliza ion o he p e ious he mose ma e ial,
wi h selec ed silica p ecu so agen s, o gain an o ganic-ino ganic ne wo k o
he moplas ic na u e and, o modula e he equi ed he mo-mechanical and
hyd ophobic beha iou o i s hyb id skele on. Las ly, S ep, de ined as “Epoxy-
silica hyb id en ichmen “, ocuses on in es iga e a ious syn he ic s a egies, ionic
liquids (ILs), essen ial oils (EOs) and nanopa icles (NPs), o inely adjus he main
p ope ies, and implemen a biocidal capaci y.
 To cha ac e ize he ma e ials de eloped and o conduc he decision making
p ocess in each s ep o he design h ough he mo-mechanical, wa e epellence
and biocidal s udies. To in es iga e he ad an ages add essed by he
implemen a ion o spec oscopic me hodologies, along he di e en s eps o he
design p ocess, complemen a ily o con en ional echniques employed in he ield
o ma e ial de elopmen .
 To de e mine he e ec i eness o he mos p omising en iched epoxy-silica hyb id
o mula ions as s one conse a ion ea men s a mid- e m, h ough hei
applica ion on s one specimens, and a subsequen accele a ed aging on an acid
a mosphe e.
⇒ Bio-based ionic liquid (ILs)-loaded hyd ogels, wi h me al seques e ing and biocidal
p ope ies, as espec ul cleaning echnology o s ained s ones.
 To de elop a bio-based hyd ogels wi h loaded ILs o he espec ully emo al o
i on and coppe - ich me allic s ains om s one su aces by a sequen ial design
composed o wo s eps. S ep, named “Solid suppo selec ion”, consis s o
selec ing a bio-based hyd ogel o allow he con olled encapsula ion o speci ic ILs,
and p ese e he in eg i y o he s one su aces. Subsequen ly, S ep, named as
“IL loading adjus men ”, in ol es he selec ion o he ILs, loading le el and way o
applica ion o ob ain an e ec i e and non-agg essi e cleaning echnology.
 To e alua e he e ec i eness o he de eloped hyd ogels loaded wi h ILs o he
desc ibed pu pose, h ough labo a o y simula ed cleaning es s by using elemen al
and molecula imaging s udies.
 To es in si u he mos p omising ma e ials o alida e hei e icience o clean
na u ally s ained s ones.

Ma e ials and me hods
39
CHAPTER 3: Ma e ials and me hods
Along his chap e , he gene al ma e ials, me hods and analy ical echniques
employed o assess he de elopmen o he ma e ials, as well as o e alua e hei
e ec i eness o p ese ing and cleaning s one subs a es a e p o ided. The ela ed da a
a e add essed in he ollowing sec ions, acco ding o he wo g oups o ma e ial
de eloped.
A his espec , i should be no ed ha , aiming o enhance he comp ehension o he
complex sequen ial syn he ic app oach ollowed, he de ailed speci ica ions o he
syn hesis, cha ac e iza ion and es ing p ocesses a e p o ided in he espec i e dedica ed
chap e s. In he same manne , he in o ma ion ega ding he chemicals ha play a
signi ican ole is collec ed and ca ego ized in Appendix A.
3.1. Epoxy-silica hyb id ma e ial es ing
Mic oo ganism g ow h es s
Disk-di usion and li e-dead s aining me hods we e used o in es iga e he mic oo ganism
g ow h inhibi ion capabili y and biocidal powe , espec i ely, o he mos p omising
epoxy-silica hyb id ma e ials de eloped. Speci ically, disk-di usion was employed in
Chap e 6. Fo his pu pose, he selec ed en iched hyb id ilm samples we e cu in o
10 mm diame e disks, d ied a 60 °C in a acuum o en (< 10−2 To ) o 24 h, and
subsequen ly s e ilized by imme sion in 70% e hanol o 10 min. Then, an s ain o
Chap e 3
40
A h obac e spp. acqui ed om he Spanish Type Cul u e Collec ion (CECT) (Uni e si y o
Valencia) was subcul i a ed unde asep ic condi ions [1–3]. Acco dingly, yp one soy aga
(TSA) pla es we e inocula ed wi h 100 μL o a eshly p epa ed bac e ia suspension o
app oxima ely 1.5 × 108 CFU mL-1 and sp ead o e he en i e aga su ace using a s e ile
co on swab. A e he disks we e placed on aga su ace, he pla es we e ae obically
incuba ed a 25 °C o 48 h unde isible i adia ion. The an imic obial halo (nwhalo) was
calcula ed acco ding o he ollowing equa ion (3.1) whe e diz is he inhibi ion zone and d
he disk diame e [2,3].
𝑛𝑛𝑤𝑤ℎ𝑎𝑎𝑎𝑎𝑎𝑎 =�𝑑𝑑𝑖𝑖𝑖𝑖−𝑑𝑑
2�
𝑑𝑑 (Eq. 3.1)
The li e-dead s aining me hod [4] was employed in Chap e 8. In his case, a s ain o
Mic ococcus Lu eus [5,6] acqui ed om he CECT was subcul i a ed in a TSA pla e o 24h
a oom empe a u e. Then, a single colony was picked o he 40 mL LB (Condalab) a 37
°C and incuba ed o app oxima ely 12 h, unde shaking a 200 pm, being inally adjus ed
o an app op ia e op ical densi y o ~0.1 by dilu ion. Then, LIVE/DEAD BacLigh ki
(The mo Fishe Scien i ic Inc.) was used o s ain he incuba ed bac e ia. Acco ding o he
ki p o ocol, 25 mL o he incuba ed solu ion was aken and, he cul u e media was
emo ed by i s cen i uga ion a 4000 x g o 10 min and he emo al o he supe na an
phase. Then, he esul ing bac e ia pelle was e-suspended on 2 mL o wash bu e and,
1 mL o his suspension was subsequen ly dilu ed on 20 mL o wash bu e . A e , i was
incuba ed o 50 min a oom empe a u e and gen ly mixing e e y 15 min. The ob ained
suspension was again cen i uged, and he new pelle was e-suspended in 20 mL o clean
wash bu e . Once he washing p ocedu e was epea ed wice, he bac e ia a e inally e-
suspended on 15 mL o wash bu e . When he g ow h medium was comple ely emo ed
om he bac e ia, equal olumes o SYTO 9 and p opidium iodide compounds we e
combined in a mic o uge ube. Then, 3 μL o he dye mix u e we e added pe millili e o
he bac e ial suspension, being he la e incuba ed a oom empe a u e in da kness o
15 min. The s ained bac e ia we e placed on he p e iously s e ilized ilm hyb id ma e ials
o 10 min, and subsequen ly he bac e ia on he su ace o samples we e obse ed by
luo escence mic oscopy.
Ma e ials and me hods
41
S one du abili y s udies
The mos p omising mul i unc ional epoxy-silica hyb ids o mula ions we e selec ed o
es i he ma e ials he e designed mee he i s p emises o a mid- e m s one
conse a ion ea men .
3.1.2.1. S one ma e ials
A na u al medi e anean calca eni e s one was used o es ing he capabili y o
p o ec ion (Chap e 6) and es o a ion (Chap e 8) p o ided o he de eloped hyb id
ma e ials due o i s wide dis ibu ion ac oss he Medi e anean Basin (Spain, Po ugal,
I aly, G eece, Tunisia, e c.) since he B onze Age. Nume ous qua ies h oughou Eu ope
ex ac his ype o s one, speci ically he Albamiel a ie y used belong o he
ep esen a i e Rosales qua y (Albace e, Spain), and was pu chased om Rosal S ones
Company (Mu cia, Spain). This li ho ype is cha ac e is ic o Ibe ian cul u e and gained
popula i y du ing he Roman Empi e h ough he Ca ago No a ade ou e, eaching he
en i e Ibe ian Peninsula and no he n Eu ope and A ica. As a esul , i was u ilized by
a ious cul u es o a wide ange o pu poses, including o i ica ions, b idges, aqueduc s,
emples, esse ae p oduc ion, mosaic loo s and eligious sculp u es. No able examples o
i s use can be seen in he Lady o O e ing, Tolmo de Mina eda, he a cheological si e o
Tao mina and he Alhamb a. E en oday, i is ex ensi ely employed in i s egion o o igin
o he cons uc ion o ex e nal acades and pa emen s, and also plays a c ucial ole in
he es o a ion o he i age buildings [7–10].
Acco ding o he da a p o ided by he supplie , he s one was cha ac e ized by an
appa en densi y o 1.940 Kg.m-3, a po osi y o 28.2% and a wa e abso p ion capaci y o
14.53%. To conduc he ma e ial essays, he slab we e cu o specimens o 2 x 2 x 1.5 cm
size (Figu e 3.1). Then, he s anda d s one samples we e weighed, and colo ime ically
s udied.
Chap e 3
48
e- VISARCH [16] and e- VISART [17] s anda d da abases, he RRUFF online da abase [18]
and a da abase sel -de eloped o his pu pose.
Nuclea magne ic esonance spec ome y, 1H-NMR and 13C-NMR we e used o ca y ou
he cha ac e iza ion o he syn hesized epoxy p ecu so s (Chap e s 5 and 7) by a B uke
AVANCE 500 equipmen using CDCl3 as sol en . Da a acquisi ion and ea men was
ca ied ou by B uke Topspin 4.0.7 so wa e.
A po en iome ic sys em Me ohm 720 i ino, equipped wi h an in e changeable 20 mL
bu e e and a combined glass and Ag/AgCl(s) Ingold IL 9415 elec ode, was employed o
he de e mina ion o he polyme epoxy a io (ER) by he back i a ion me hod (Chap e
7) [19]. Da a acquisi ion was ca ied ou wi h Me ohm Tiamo 2.5 so wa e and hen
p ocessed using he G an’s me hod wi h MS Excel 2017 so wa e.
X-Ray Di ac ion (XRD) analyses o he cha ac e iza ion o he NPs syn hesized (Chap e s
6 and 8) we e ca ied ou by means o a B uke D2 Phase desk op di ac ome e , wi h a
Cu ube (λ = 1.54056 Å), eco ding he da a in he 2θ ange o 20–90°, wi h an angula
s ep size o 0.025°. The iden i ica ion was made by using he da abase PDF2 [20].
A Shimadzu Mul iSpec-1501 UV–Vis Diode A ay spec opho ome e was used o measu e
he abso bance o he calcula ion o ee amine g oups in he un ionaliza ed NPs
(Chap e 8) [21].
The momechanical and hyd ophobic beha iou analysis
The he momechanical and hyd ophobic p ope ies o he design o he mul i unc ional
epoxy-silica ma e ials, om he he mose base s ep o he en iched hyb id de elopmen
(Chap e s 5-8), we e de e mined by a combina ion o he ollowing ins umen s:
The mog a ime ic analyses (TGA) o de e mine he sui abili y o he ha dening agen s
and he silica o ming addi i es o he hyb id de elopmen we e ca ied ou using a TA
Ins umen s Q500 he mal analyze , unde ni ogen a 10 ml min-1, in he empe a u e
ange be ween 25 °C and 800 °C wi h a hea ing a e o 10 °C min-1.
To comple e he he mal da a, di e en ial scanning calo ime y (DSC) expe imen s we e
pe o med wi h a Me le Toledo DSC3+, in he empe a u e ange -60 o 220 °C, wi h a
hea ing a e o 10 °C min-1, unde a 20 ml min-1 ni ogen low.

Ma e ials and me hods
49
To in es iga e he mechanical p ope ies and de e mine he plas icizing o load oles
exe ed by he o ming silica compounds and en ichmen s used a dynamic mechanical
he mal (DMA) analyse Epexo 100 N GABO Qualime e was employed. Fo his pu pose,
ec angula hyb id ilms specimens o 9.0 mm x 13.0 mm x 2.9 mm we e p epa ed and
analysed in a empe a u e ange om -70 o 150 °C, a a hea ing a e o 2 °C min-1 in
ension mode. The es s we e ca ied ou a a s ain a e o 0.5 % and 0.2 % o S a ic and
Dynamic, espec i ely.
DSC, TGA and DMA da a we e p ocessed using Excel 2017 and O igin 2018 so wa es.
Finally, con ac angle (CA) in es iga ions we e pe o med o de e mine he wa e
epellence capabili y o he hyb id su aces by means o wo di e en con ac angle
ins umen s, Neu ek Ins umen s Da aphysics sys ems OCA 15EC and KRÜSS D op Shape
Analyze - DSA25B. Fo his, Milli-Q wa e d ops (2 μL/d op) we e deposi ed on o he ilm
su ace and he a e age o 5 eplica es was epo ed. The ma e ial beha io was classi ied
in acco dance o he es ablished le els de ined in Figu e 3.5. [22].
Figu e 3.5. Classi ica ion o he wa e epellence capabili y acco ding o he con ac angle alues.
Thus, su aces ha exhibi a CA g ea e han 150° we e classi ied as supe hyd ophobic,
indica ing ex emely high wa e epellency. Su aces wi h con ac angles be ween 90 and
150° we e conside ed hyd ophobic, meaning hey ha e a mode a e le el o wa e
epellency. Finally, su aces wi h a CA less han 90° we e classi ied as hyd ophilic, and
close o 0° supe hyd ophilic, indica ing a endency o a ac and abso b wa e .
Chap e 3
50
Mic oscopy image analysis
A RoHS X4 digi al mic oscope wi h a ocus ange o 15-40 mm was used o he op ical
mic oscopic isual inspec ion o he s ones samples, ea ed and non- ea ed, du ing he
du abili y s one es s o de e mine he e ec i eness o he ma e ials designed (Chap e 6
and 8). The images we e ob ained and p ocessed using he HiView 1.4 so wa e.
T ansmission Elec onic Mic oscopy (TEM) analyses we e pe o med o de e mine he
a e age size o he syn hesized NPs (Chap e s 6 and 8) by a TECNAI G2 20 TWIN
ins umen , ope a ed a 200 kV and equipped wi h LaB6 ilamen . The NPs samples we e
dispe sed in o me hanol sol en and kep in suspension using an ul asonic ba h o 15
min. A e , a d op o he suspension was sp ead on o a TEM coppe g id (300 Mesh)
co e ed by a ca bon ilm ollowed by d ying unde acuum.
Finally, a Zeiss LSM 880 A1 luo escence mic oscope was employed o de e mine he
biocidal capabili y o he NPs and essen ial oils (Eos) epoxy-silica doped hyb id ma e ials
(Chap e 8) by s aining assays, using a Fas Ai y scan mode wi h exci a ion a 488 and 561
nm, and a sequen ial signal e ie al o 495-550 and 570-620 nm. The ob ained images
we e p ocessed using ImageJ 1.53c so wa e.
Colo ime ic Analysis
A PCE-CSM 5 colo ime e (PCE Ins umen s), wi h he 8 mm measu ing ape u e and CIE
10°obse a ion angle and equipped wi h a silicon pho oelec ic diode senso , was
employed o moni o he ch oma ic al e a ion (colo di e ence, ∆E) (n=5) [15] caused by
he s one aging expe imen s and he applica ion o he di e en hyb id ma e ials be o e
and a e he ea men (Chap e s 6 and 8). Besides, his ype o analysis was also used o
assess he cleaning e ec i eness o he ILs-loaded hyd ogels ea men (Chap e 9). Fo
his pu pose, he ins umen was calib a ed on a s anda d whi e cap e e ence be o e
each measu emen and he L*a*b* colo space a e age alues we e collec ed ollowing
he ASTM D-1925 and CIE 2000 equi emen s [23].
S one aging expe imen s
The s one aging expe imen we e ca ied ou (Chap e s 6 and 8) using an Au onics
Kes e nich chambe (CCI, Spain). The came a was equipped wi h a TK4S High Accu acy PID
Ma e ials and me hods
51
con ol module wi h a ixable empe a u e ange, up o 50 °C, and humidi y up o
sa u a ion. Fo hese s udies, he CO2 was used as he acid a mosphe e p ecu so .
3.4. Re e ences
[1] O. Gómez-Lase na, G. Lando, L. Ko aza , I. Ma inez-A ka azo, I. Mon e ubio, E.
Se illano, P. Ca diano, M.Á. Olazabal, Eco- iendly nanocomposi e p oduc s based
on BPA- ee epoxy–silica hyb id ma e ials o s one conse a ion, A chaeol
An h opol Sci. 11 (2019) 5799–5812. h ps://doi.o g/10.1007/s12520-019-00904-6.
[2] A.W. Baue , W.M.M. Ki by, J.C. She is, M. Tu ck, An ibio ic Suscep ibili y Tes ing by
a S anda dized Single Disk Me hod, Ame ican Jou nal o Clinical Pa hology. 45 (1966)
493–496. h ps://doi.o g/10.1093/ajcp/45.4_ s.493.
[3] M. Ma í, B. F ígols, A. Se ano-A oca, An imic obial Cha ac e iza ion o Ad anced
Ma e ials o Bioenginee ing Applica ions, JoVE. (2018) 57710.
h ps://doi.o g/10.3791/57710.
[4] X. Xu, S. Ma, S. Wang, J. Wu, Q. Li, N. Lu, Y. Liu, J. Yang, J. Feng, J. Zhu, Dihyd azone-
based dynamic co alen epoxy ne wo ks wi h high c eep esis ance, con olled
deg adabili y, and in insic an ibac e ial p ope ies om bio esou ces, J. Ma e .
Chem. A. 8 (2020) 11261–11274. h ps://doi.o g/10.1039/D0TA01419B.
[5] P.J.A. Skippe , L.K. Skippe , R.A. Dixon, A me agenomic analysis o he bac e ial
mic obiome o limes one, and he ole o associa ed bio ilms in he biode e io a ion
o he i age s one su aces, Sci Rep. 12 (2022) 4877. h ps://doi.o g/10.1038/s41598-
022-08851-4.
[6] P. Descheemaeke , J. Swings, The applica ion o a y acid me hyl es e analysis
(FAME) o he iden i ica ion o he e o ophic bac e ia p esen in decaying Lede-
s one o he S . Ba o Ca hed al in Ghen , Science o The To al En i onmen . 167
(1995) 241–247. h ps://doi.o g/10.1016/0048-9697(95)04585-O.
[7] L.M. Gil-Ma ín, M.A. Fe nández-Ruiz, E. He nández-Mon es, Mechanical
Cha ac e iza ion and C eep Beha io o a S one He i age Ma e ial Used in G anada
(Spain): San a Pudia Calca eni e, Rock Mech Rock Eng. 55 (2022) 5659–5669.
h ps://doi.o g/10.1007/s00603-022-02946-0.
[8] A. Zo noza-Inda , P. Lopez-A ce, N. Leal, J. Simão, K. Zoghlami, Consolida ion o a
Tunisian bioclas ic calca eni e: F om con en ional e hyl silica e p oduc s o
nanos uc u ed and nanopa icle based consolidan s, Cons uc ion and Building
Ma e ials. 116 (2016) 188–202. h ps://doi.o g/10.1016/j.conbuildma .2016.04.114.
[9] A. Calia, A.M. Mecchi, D. Colangiuli, L. Scudele Baccelle, Conse a ion issues wi h
calca eni es used as his o ical building ma e ials in Sy acuse (Sou he n I aly), QJEGH.
46 (2013) 485–492. h ps://doi.o g/10.1144/qjegh2012-050.
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[10] C. Jimenez-Lopez, F. J oundi, C. Pascolini, C. Rod iguez-Na a o, G. Piña -La ubia, M.
Rod iguez-Gallego, M.T. González-Muñoz, Consolida ion o qua y calca eni e by
calcium ca bona e p ecipi a ion induced by bac e ia ac i a ed among he mic obio a
inhabi ing he s one, In e na ional Biode e io a ion & Biodeg ada ion. 62 (2008)
352–363. h ps://doi.o g/10.1016/j.ibiod.2008.03.002.
[11] M. To abi-Ka eh, M. Mosh e y a , S. Shi zaei, S.M.A. Moosa izadeh, B. Ménendez,
S. Maleki, Applica ion o esin-TiO2 nanopa icle hyb id coa ings on a e ine s ones
o in es iga e hei du abili y unde a i icial aging es s, Cons uc ion and Building
Ma e ials. 322 (2022) 126511. h ps://doi.o g/10.1016/j.conbuildma .2022.126511.
[12] R.J. Fla , F. Ca uso, A.M.A. Sanchez, G.W. Sche e , Chemo-mechanics o sal damage
in s one, Na Commun. 5 (2014) 4823. h ps://doi.o g/10.1038/ncomms5823.
[13] M. D dácký, J. Lesák, S. Rescic, Z. Slížko á, P. Tiano, J. Valach, S anda diza ion o
peeling es s o assessing he cohesion and consolida ion cha ac e is ics o his o ic
s one su aces, Ma e S uc . 45 (2012) 505–520. h ps://doi.o g/10.1617/s11527-
011-9778-x.
[14] L. Gianni, G. Gigan e, M. Ca allini, A. Ad iaens, Co osion o B onzes by Ex ended
We ing wi h Single e sus Mixed Acidic Pollu an s, Ma e ials. 7 (2014) 3353–3370.
h ps://doi.o g/10.3390/ma7053353.
[15] K. Bieske, C. Vandahl, A S udy abou Colou Di e ence Th esholds, in: Ilmenau,
Deu schland, 2007.
[16] M. Pe ez-Alonso, K. Cas o, J. Mada iaga, Vib a ional Spec oscopic Techniques o
he Analysis o A e ac s wi h His o ical, A is ic and A chaeological Value, CAC. 2
(2006) 89–100. h ps://doi.o g/10.2174/157341106775197385.
[17] K. Cas o, M. Pé ez-Alonso, M.D. Rod íguez-Laso, L.A. Fe nández, J.M. Mada iaga,
On-line FT-Raman and dispe si e Raman spec a da abase o a is s’ ma e ials (e-
VISART da abase), Anal Bioanal Chem. 382 (2005) 248–258.
h ps://doi.o g/10.1007/s00216-005-3072-0.
[18] D.R. T, The RRUFF p ojec  : an in eg a ed s udy o he chemis y, c ys allog aphy,
Raman and in a ed spec oscopy o mine als, P og am and Abs ac s o he 19 h
Gene al Mee ing o he In e na ional Mine alogical Associa ion in Kobe, Japan, 2006.
(2006). h ps://ci .nii.ac.jp/c id/1571417124253896704 (accessed No embe 11,
2022).
[19] H. Panda, Epoxy Resins Technology Handbook (Manu ac u ing P ocess, Syn hesis,
Epoxy Resin Adhesi es and Epoxy Coa ings), 2nd Re ise, ASIA PACIFIC BUSINESS
PRESS, 2019.
[20] S. Ga es-Rec o , T. Blan on, The Powde Di ac ion File: a quali y ma e ials
cha ac e iza ion da abase, Powde Di . 34 (2019) 352–360.
h ps://doi.o g/10.1017/S0885715619000812.
[21] L. de Oli ei a, K. Bouchmella, A. Picco, L. Capele i, K. Gonçal es, J.H. dos San os, J.
Koba g, M. Ca doso, Tailo ed Silica Nanopa icles Su ace o Inc ease D ug Load and
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Enhance Bac e icidal Response, J. B az. Chem. Soc. (2017).
h ps://doi.o g/10.21577/0103-5053.20170017.
[22] A.K. Ko a, G. Kwon, A. Tu eja, The design and applica ions o supe omniphobic
su aces, NPG Asia Ma e . 6 (2014) e109–e109.
h ps://doi.o g/10.1038/am.2014.34.
[23] NORMAL P o ocol 43/93 (NORMAL 1993), (n.d.).

54
Bio-based epoxy he mose ing polyme s
55
CHAPTER 4: Po en ial o bio-based
epoxy he mose ing polyme s o he
ad anced design o s one conse a ion
ma e ials
This chap e was ocused on a comp ehensi e esea ch e iew on epoxy
he mose ing polyme s o na u al o igin o guide S ep and S ep o he hyb id
ma e ial design. Thus, bio-based epoxy esins po en ially sui able o s one conse a ion
and he in luence o cu ing agen s on he ma e ials p ope ies a e collec ed and discussed
he e. In addi ion, aspec s such as esou ces, syn he ic ou es, and he mo-mechanical
beha io we e also add essed o gain aluable in o ma ion and de e mine he u u e
modula ion possibili ies o be designed in he ollowing chap e s o he es o a ion o
silica-based s ones.
Renewable esou ces o bio-based epoxy esins
In ecen yea s, se e al wo ks ha e ocused on syn hesizing and modi ying bio-based
polyme s o co e a wide ange o indus ial uses [1–6]. Among hem, compounds such as
ca danol, anillin, soy oil, gallic o i aconic acids, and suga de i a i es, o e en indus ial
and cooking was es ha e ecen ly gained a en ion (Figu e 4.1). Thei inc easing
impo ance as s a ing ma e ials is linked o hei a ailabili y, low p ice, and unique
Chap e 4
56
eac i e chemical s uc u e, which can easily lead o epoxy esins wi h low oxici y and
in insic biodeg adabili y [7]. In addi ion o be employed as g een al e na i es o BPA-
based epoxy esins, hey could be also e y a ac i e o he ield o s one conse a ion
i hey a e subjec ed o u he modi ica ion p ocesses.
Figu e 4.1. Renewable na u al esou ces o BPA- ee epoxy esins wi h po en ial applica ion in he
s one conse a ion ield.
In his sense, he selec ion o speci ic c oss-linking agen s could allow o ob ain
he mose ing polyme s ha gene ally ul ill ce ain well-es ablished c i e ia o be di ec ly
es ed as consolida ing s one ea men s, o o be he basis o ma e ial designs o i s
modula ion wi h simila pu poses. In ac , as was commen ed in he In oduc ion sec ion,
di e en syn he ic app oaches could achie e he adjus men o c ucial ea u es, including
he mal-mechanical beha io , UV esis ance, o e en compa ibili y wi h he s one
subs a e, among o he s. In hese cus omiza ion p ocesses, a pa o hei abili y o
es o e he in eg i y o he li hic ma ix, i is also p e e able ha hey p e en wa e
pene a ion, meanwhile main aining he aes he ic o he s one su ace unal e ed [8–12].
Bio-based epoxy he mose ing polyme s
57
Consequen ly, in he ollowing sec ions he mos p omising esins a e classi ied acco ding
o hei o igin and discussed paying special a en ion o he di e en p ope ies obse ed
wi h espec o hei DGEBA (diglycidyle he o bisphenol A) coun e pa . In addi ion, all
he molecula s uc u es and ma e ial cha ac e iza ion da a epo ed a e collec ed as a
summa y able and igu es o acili a e hei consul a ion (see Appendix B).
Ca danol
Ca danol is an oil ob ained om cashew nu shell liquid (CNSL), a non-edible ag icul u al
byp oduc ex ac ed om he shell o he cashew nu om he Anaca dium Occiden ale
ee. CNSL is a da k b own iscous liquid composed o a mix u e o phenolic compounds,
p ecisely, anaca dic acid (74-77%), ca danol (1-9%), and ca dol (15-20%). Gi en ha , i has
been ecen ly highligh ed as an appealing enewable al e na i e o pe oleum-de i ed
phenols [13–15].
Speci ically, ca danol is a long alipha ic side chain wi h mono-, di- and i-unsa u a ed
bonds, and al hough he e a e possible ways o ex ac ion, a highe yield is ob ained i he
CNSL is di ec ly hea ed and la e subjec o a dis illa ion p ocess. The ob ained p oduc
eaches an indus ial-g ade pu i y o 90 %, wi h small quan i ies o ca dol and
me hylca dol [13,16–18]. Gi en i s na u e and chemical s uc u e, se e al s udies ha e
been conduc ed on ca danol epoxida ion and ha dening eac ions o gain he mose
ma e ials [19–21].
Rocha da Sil a e al. [19] exploi ed a di ec CNSL alo iza ion o p epa e an ico osi e
coa ings o s eel pieces. The epoxida ion o he double bonds o he ca danol and ca dol
alipha ic chains, in acidic sol en - ee condi ions, esul ed in an oligome ic mix u e
ob ained as a eddish-b own iscous liquid (e-CNSL) (yield o 90 % and epoxide equi alen
weigh , EEW, o 469 g·eq-1) (Figu e 4.2).
Chap e 4
64
Xu e al. [29] exploi ed he aldehyde g oup on he anillin pe o ming a Wol -Kishne
eac ion wi h hyd azine o ob ain he 4,4'-(-hyd azine 1,2-
diylidenebis(me hanylylidene))bis(2-me hoxyphenol) (HBP). Then, i was epoxidized ia
ECH, using e abu ylammonium b omide (TBAB) as ans e ca alys , and he diepoxy-
dihyd azone (HBE) was ob ained as a whi e solid p oduc wi h a yield o 84.8%. Then, he
HBE was c oss-linked using IPDA and poly(p opylene glycol) bis(2-aminop opyl e he )
(D400), and he esul s we e compa ed wi h DGEBA (DER331) as e e ence. The HBE/IPDA
and HBE/D400 mix u es showed Tg o 146 and 76 °C, espec i ely, which a e 23 °C highe
han he DGEBA-based he mose . This ac sugges s ha he high c oss-linking o HBE-
based he mose s could be due o he igidi y o he hyd azone g oup conjuga ed
s uc u e. The same explana ion could also jus i y he highe Young's modulus alues o
HBE/D400 and HBE/IPDA and ensile s eng h da a wi h espec o he ones obse ed o
he DER331/D400 he mose . On his basis, he high po en ial o HBE o be employed as
epoxy esin o he p epa a ion o high-pe o mance he mose s is highligh ed. Howe e ,
s a ic con ac angle measu emen s e idenced a sligh ly hyd ophilic beha io ha should
be p ope ly uned o mee he i s equi emen s eques ed o s one conse a ion.
Besides, he HBE-based he mose s ha e an ex a ad an age o e DGEBA-based ma e ials
since he s udy also e ealed a bac e icidal ac i i y agains E. coli, hanks o he hyd azone
g oup, showing killing a e alues o 96 %. The e o e, i could add ess mul i unc ional
p ope ies ha a e e y compelling o he conse a ion o li hic subs a es.
Gallic acid
Gallic (GA) acid is he common name o 3,4,5- ihyd oxybenzoic acid, a na u ally
occu ing an ioxidan ound in se e al plan s, ege ables, ed ui s, nu s, and co ee. I is
known o exhibi signi ican biological ac i i y, and in addi ion o a ious pha macological
uses, GA is widely employed in he ood indus y as a p ese a i e and la o addi i e [30–
34]. Besides, he p esence o h ee phenolic -OH g oups and he ca boxylic moie y has led
o se e al epoxida ion a emp s o di e en pu poses.
Tomi a e al. [35] epo ed a pa en , in which GA-based epoxy esins we e ob ained wi h
a ious g ades o unc ionaliza ion, i.e., om mono o e a epoxy de i a i es.
Subsequen ly, o he mose s de elopmen , Pa il e al. [36] s a ed om he p epa a ion
o e adiglycidyle he o gallic acid (TGEGA) syn he ic ou e (Figu e 4.8).

Bio-based epoxy he mose ing polyme s
65
Figu e 4.8. Rou e o he syn hesis o he e adiglycidyle he o gallic acid (TGEGA) ia
epichlo ohyd in (ECH).
The e a epoxy compounds ob ained we e cu ed wi h di e en a ios o polyamide, and
he esul ing ma e ials we e compa ed o DGEBA. Then, DSC in es iga ions p o ided Tg o
54, 56, and 63 °C o he TGEGA:Polyamide a ios o 1:8, 1:12, and 1:16, espec i ely. This
ac e idenced a clea upwa d end in he c oss-linking densi y. In addi ion, hese bio-
based ma e ials displayed Tg be ween 23-42% highe han he one obse ed o he
DGEBA ma e ial. TGA es s also e ealed ha all he examined he mose s had a simila
he mal esis ance o he DGEBA-based polyme . The e o e, da a indica es ha he bio-
ma e ials displayed, a leas , he mal p ope ies ha could ma ch he ones eques ed o
an e ec i e s one conse a ion ea men . So, u he in es iga ions a e needed o assess
whe he hese polyme s could main ain hei ea u es, o ins ance, i hey a e p epa ed
wi h g een sol en s, o o check hei mechanical and hyd ophobic beha io .
Ta zia e al. [37] epo ed on he glycidyla ion o GA o gain i- and e a-glycidyl e he s
o gallic acid (TGEGA) h ough a wo-s ep syn hesis. The i s one in ol es he alkaline-
assis ed allyla ion o hyd oxylic g oups (bo h phenolic and non phenolic), and hen i was
ollowed by he epoxida ion o he esul ing e a-allyla ed GA (AGA) (Figu e 4.9),
ob ained as a yellow oil mix u e wi h a yield o 89%.
Chap e 4
66
Figu e 4.9. Rou e o he syn hesis o he e adiglycidyle he o gallic acid (TGEGA) ia allyl
b omide using alkene oxida ion.
TGEGA cu ing was hen ca ied ou a oom empe a u e using IPDA o Je amine D230
(DPG) in a s oichiome ic a io, whe eas he e ia y amine N,N-dime hylbenzylamine
(BDMA) was also used as an ini ia o . DSC scannings showed Tg o 158, 136, and 98 °C o
TGEGA/IPDA, TGEGA/BDMA, and TGEGA/DPG o mula ions, espec i ely. These alues
indica e he o ma ion o well-de eloped c oss-linked ne wo ks, gene ally also associa ed
wi h high s i ness and low lexibili y, which a e no sui able o ma e ials o be used in
s one conse a ion. Ne e heless, TGA in es iga ions indica ed excellen he mal
p ope ies, achie ing he highes esis ance upon hea ing o TGEGA/BDMA
homopolyme ized he mose (mass esidue 29%). As expec ed, mechanical analyses show
ha he he mose based on he mo e lexible amine, DPG, p o ided he highes
elonga ion a b eak and he g ea es s eng h. In addi ion, he elas ic moduli we e
ela i ely high and simila o all he in es iga ed sys ems, showing b i le ac u e.
I aconic acid
I aconic acid is a di-ca bonic unsa u a ed weak acid wi h an imic obial p ope ies
ob ained om he biological ac i i y o se e al ungi, mainly Aspe gillus e eus, ha is
al eady used as a bio-based subs i u e o ac ylic acid [38–40].
Bio-based epoxy he mose ing polyme s
67
Kuma e al. [41] ca ied ou he allyla ion o i aconic acid, ollowed by oxida ion wi h m-
chlo ope oxybenzoic acid (mCPBA) o o m he i epoxy i aconic acid (TEIA) (yield 75%,
EEW 1.02 mol/100 g) (Figu e 4.10).
Figu e 4.10. Syn he ic p ocedu e o ob ain he i epoxy i aconic acid (TEIA), ia allyl b omide
ou e, by double bond oxida ion.
The TEIA cu ed wi h MHHPA showed a Tg o 133 °C, only 11 °C lowe han he one
displayed by DGEBA/MHHPA used as e e ence. In addi ion, he TEIA he mose ea u ed
high he mal s abili y, qui e simila o ha o DGEBA/MHHPA. Bo h he mose s showed
simila ensile s eng h, al hough TEIA/MHHPA exhibi ed highe lexibili y in elonga ion
es s. These p ope ies indica e ha TEIA/MHHPA has g ea po en ial o eplacing
pe oleum-based epoxy he mose s in a wide ange o high-pe o mance applica ions.
Un o una ely, i s da k yellow colo ep esen s a limi o i s po en ial use in conse ing
li hic ma e ials.
Ma e al. [42] ollowed he same ou e shown in Figu e 4.10, and ob ained a TEIA
monome wi h a yield o 60 % and an EEW o 1.16 mol/100 g. In o de o compa e he
p ope ies exhibi ed by he bio-based he mose s wi h he ones shown by he
con en ional ones, bo h TEIA and DGEBA we e cu ed using MHHPA and DPG. The
TEIA/MHPPA he mose displayed he mal and mechanical p ope ies compa able o
hose desc ibed by Kuma e al. [41] o an analogous ma e ial. Fu he mo e, TEIA/D230
was ea u ed by a Tg o 61 °C, signi ican ly lowe han he o he ma e ials in es iga ed,
bo h bio- and pe oleum-based. This ac can be explained in e ms o a highe mobili y o
he chain segmen s in TEIA/D230, whe eas he igid MHHPA hinde ed he mo emen o
he chain segmen s o he epoxy ne wo k, esul ing in highe Tg alues. On he o he hand,
Chap e 4
68
DGEBA-based he mose s ea u ed highe he mal s abili y han bio-based ma e ials. The
mechanical in es iga ions e idenced ha he lexu al s eng h o TEIA/D230 and
DGEBA/D230 was simila , whe eas TEIA/D230 lexu al modulus and s ain a b eak we e
much highe han he ones exhibi ed by DGEBA/D230. Mo eo e , he lexu al s eng h,
lexu al modulus and s ain a b eak we e all highe o TEIA/MHHPA mix u es han o
he DGEBA/MHHPA one. F om all he abo e, i can be a i med ha TEIA sys ems had
be e p ocessabili y han he DGEBA ones, and ha , i could be conside ed as a iable
al e na i e o high pe o mance ma e ials syn hesis, e idencing once again he high
pe o mances ha can be ob ained om he bio-based ma e ials.
Isobu y ic acid
Isobu y ic acid, also known as 2-me hylp opanoic acid, is a sho -chain sa u a ed
ca boxylic acid ound in Co ea A abica [43], s awbe ies [44], and in he oo o A nica
mon ana [45], and e en as a syn he ic me abolic pa hway om E. coli ha enables he
biosyn hesis o his compound om glucose [46]. This colo less liquid is highly soluble in
wa e and o ganic sol en s and easily eac s o o m amide, es e , anhyd ide, and chlo ide
de i a i es [47]. Fo his eason, i is commonly used as an in e media e in he cosme ic
indus y and also can be ound in a wide a ie y o oods o impa di e en la o s.
Ano he in e es ing poin o his na u al compound is ha i s py olysis can be used o gain
a dime hylke ene, which spon aneously dime izes o a cyclic dike one. Then, i can be
easily hyd ogena ed o ob ain a na u al cyclodiol, 2,2,4,4- e ame hyl-1,3-
cyclobu anediol (CBDO) [48]. This cyclical s uc u e and he a angemen o bo h OH
g oups make his unexplo ed compound a e y a ac i e building block o a wide a ie y
o applica ions.
A simple syn hesis ou e was pa en ed by Daniel Schmid [48], who exploi ed he
adi ional epoxida ion app oach wi h ECH, in an alkaline medium, o ob ain a pu e
cis/ ans mix u e o 2,2,4,4- e ame hyl-1,3-cyclobu ane diglycidyle he (CBDO-DGE) wi h
a yield o 74% and an EEW o 128 g·eq-1. The s udy ob ained he mose ma e ials
employing TETA amine and di e en cu ing empe a u es, compa ing hei he mal
p ope ies o hose displayed by DGEBA/TETA. Depending on he he mal cu ing p ocess,
CBDO-DGE/TETA showed Tg occu ing be ween 68 and 82 ᵒC e sus alues o 100 and 120
ᵒC o DGEBA/TETA. TGA s udies e ealed highe he mal s abili y o DGEBA/TETA, wi h
espec o CBDO-DGE/TETA (Tonse o 326 °C), whe eas Tmax eached 381 ᵒC in he case o
he bio-based he mose and 364 ᵒC o DGEBA/TETA. The epo ed da a sugges s ha
Bio-based epoxy he mose ing polyme s
69
c oss-linking and s i ness o CBDO-DGE/TETA we e milde han hose gained o
DGEBA/TETA.
Al hough he e was no mo e da a a ailable, he esul s ob ained wi h his alipha ic amine,
and he epoxy solubili y in sus ainable sol en s, oge he wi h he low empe a u e used
o ob ain a well c oss-linked he mose ing ma e ial, poin ed o he CBDO-DGE as a
p omising candida e o being u he s udied. In ac , he s uc u al esemblance
be ween CBDO-DGE and pe oleum-de i ed epoxy p ecu so s, such as 1,4-
cyclohexanedime hanol diglycidyl e he (CHDM-DGE), which ha e al eady been
p e iously in es iga ed by ou esea ch g oup [49] as a p omising building block o he
well-con olled de elopmen o consolida ing p oduc s. In his wo k, a he mose ma e ial
de i ed om CHDM-DGE and diaminooc ane (DAO) was combined wi h 3-
glycidoxyp opylme hyldie hoxysilane (GPTMS) as a coupling agen and silica o ming
addi i e o gain epoxy-silica hyb id ma e ial wi h excellen he mal and hyd ophobic
esponses (Tg o 53°C, Tonse o 375.3 ᵒC, and CA o 105ᵒ).
Soybean oil
Soybean oil is one o he cheapes enewable sou ces a ailable and widely used in
ab ica ing se e al bio-based p oduc s [50,51] as well as in he cooking, animal eed,
biodiesel p oduc ion, and cosme ics indus ies. This e sa ili y is due o he lipidic ac ion
p esen ed, mainly composed o iglyce ides wi h p ima ily unsa u a ed a y acids ha
could be easily epoxidized by an oxida ion eac ion [51–53]. Gi en ha , epoxidized
soybean oil (ESO) also has he ad an age o being comme cially a ailable.
Kuma e al. [41] epo ed he compa ison be ween comme cial ESO (EEW 222-230 g mol-
1) and DGEBA cu ed wi h MHHPA. The bio-based he mose showed Tg o 64 °C, which
co esponds o a compa ible ange o designing a coa ing o s one conse a ion
pu poses. In addi ion, ESO/MHHPA ma e ials e idenced qui e good he mal s abili y wi h
T5% and T50% o 237 and 359 °C, espec i ely. Ne e heless, he DGEBA-based he mose
displayed highe he mal esis ance, 100 °C mo e o T5% and 45 °C mo e o T50%. Ano he
signi ican inding o de e mine he ESO sui abili y o s one applica ions is ha
heological in es iga ions highligh ed a lowe iscosi y o ESO wi h espec o DGEBA one,
which could acili a e i s pene a ion in he li hic subs a e, minimizing a common
d awback associa ed wi h con en ional epoxy-based ea men s. Mo eo e , ESO/MHHPA
mechanical p ope ies we e ea u ed by high elonga ion and impac s eng h, wi h
signi ican lexibili y a ibu ed o he long alipha ic chains in o he ne wo k, which may

Chap e 4
70
be o g ea in e es o he design o ad anced ma e ials o s one conse a ion. Howe e ,
he cu ing empe a u es needed o ob ain such success ul esul s we e impossible o
apply in ou doo in si u ea men .
Zhao e al. [54] cu ed a comme cial ESO esin wi h dihyd oxydiphenylme hane (DHM) and
a anillin-de i ed Schi base (VSB), a ha dene ob ained om he eac ion o he anillin
wi h 4,4-diaminodiphenyl me hane (DAM). The cu ing eac ions we e pe o med
employing di e en ESO/VSB a ios and a ixed ESO/DHM a io o 0.7 o compa ison
pu poses, using 1,2-dime hylimidazole (DMI) as a ca alys . The ESO/VSB Tg alues we e
g adually inc eased, anging om 30 o 66 °C o 0.5 o 1 a ios. Con e sely, he c oss-
linking densi y inc eased up o 0.7 a io, and hen i s a ed o d op. Besides, he maximum
s o age modulus was ound below he Tg o 0.9 a io and abo e he Tg o 0.7 a io. In
addi ion, ESO/DHM he mose showed Tg o 19 °C and lowe E’ alues wi h espec o he
o he in es iga ed samples, due o a lowe ne wo k s i ness impa ed by he lowe
con en o a oma ic ings, which is one-hal o he VSB one. Besides, all he he mose s
displayed excellen he mal s abili y wi h T5% a ca. 400 °C, and much highe cha esidues
a 700° han he ESO/DHM ones. These esul s a e a ibu ed o he conjuga ed a oma ic
ings and he c oss-linking o he imine a high empe a u es. The ESO/DHM he mose
displayed poo mechanical p ope ies wi h espec o he ESO/VSB ones, which showed
elonga ion b eak dec ease and ensile s eng h, and Young’s modulus inc eased wi h he
a io inc easing. F om all he collec ed da a, i appea ed ha he s udied he mose s
displayed a a ie y o uneable cha ac e is ics, being he ESO/VSB ma e ials so and wi h
no yielding s ess cu es a 0.5–0.6 a ios, whe eas a ios be ween 0.7-0.8 p oduce he
duc ile-b i le ansi ion and o a ios highe han 0.8 a b i le ac u e occu ed. Thus,
ESO/VSB he mose s could p esen he mo-mechanical p ope ies e y appealing and
highly modulable o de elop a ange o e sa ile ma e ials by simply uning he a io
eac ions, and he e o e g ea a en ion should be paid o hei po en ial applica ions.
Howe e , hei da k yellow-o ange colo is complex o sol e o he ield o s one
conse a ion.
Eugenol
4-Allyl-2-me hoxyphenol, also known as eugenol (Eu), is a na u al phenolic compound ha
can be ound in essen ial oils o clo e, basil, and peppe , among o he s. Due o i s inhe en
biocidal ac i i y, Eu has al eady been in es iga ed o assess i s sui abili y agains cul u al
he i age biocoloniza ion [55–58].
Bio-based epoxy he mose ing polyme s
71
Respec i s possibili ies as an epoxy p oduc , Wan e al. [59] de eloped a diepoxy esin by
a Williamson e he i ica ion eac ion be ween α,α’-dichlo o-p-xylene, and Eu, o ob ain a
p oduc bea ing wo allyl g oups, which was hen epoxidized wi h mCPBA o gain a
dieugenol-based diepoxide (DEu-EP) (Figu e 4.11).
Figu e 4.11. Syn he ic p ocedu e o ob ain he dieugenol epoxy (DEU-EP) using α,α’-dichlo o-p-
xylene as a binde and alkene oxida ion.
DEu-EP (yield 43%, EWW 0.380 mol/100 g,) ob ained as yellowish needle c ys als, was
cu ed wi h 4,4´-diaminodiphenyl me hane (DDM) and compa ed wi h DGEBA. DMA
s udies indica ed ha DGEBA/DDM ma e ial was ea u ed by a highe Tg han DEu-EP,
153.6 and 114.4 ᵒC, espec i ely, p obably gi en he mobili y impa ed by he xylene
agmen o he ne wo k. This e ec was also con i med by he E’ alue, which was 17%
highe han he one de ec ed o he DGEBA-based he mose . The mog a ime ic
scannings e idenced simila he mal s abili y up o 270 ᵒC, al hough he bio-based
ma e ial exhibi ed bo h lowe T5% and Tmax han DGEBA/DDM (i.e., 341 and 379 °C; 377
and 393 ᵒC, espec i ely), being he la e also ea u ed by a as e decomposi ion a e.
Fu he mo e, he cha yield a 700 °C o DEu-EP/DDM was 38%, mo e han double ha
ound o he pe oleum-based he mose , demons a ing he capaci y p esen ed by he
bio-based epoxy o o e pass he pe oleum based he mose . Howe e , hey
cha ac e is ic made i an in e es ing candida e o o he kinds o applica ions, o
example, ma e ials o lame e a dan use.
Chap e 4
72
In a wo k by Qin e al. [60], a Eu de i ed diepoxy esin (Eu-EP) was ob ained by exploi ing
a syn he ic s a egy in ol ing mCPBA and ECH as epoxida ion eac an s (Figu e 4.12). Fi s ,
he phenolic g oup was p o ec ed ia ace yla ion o sa ely oxidize he double bond wi h
mCPBA. Then, deace yla ion and glycidyla ion was pe o med in a single syn he ic s ep
using ECH in alkaline condi ions o ob ain Eu-EP as a whi e powde (yield 51.62%, EEW
129 g mol-1).
Figu e 4.12. Syn he ic p ocedu e o ob ain he eugenol epoxy (Eu-EP) ia alkene oxida ion wi h
hyd oxyl g oup p o ec ion and ia epichlo ohyd in (ECH).
Then, Eu-EP was cu ed using hexahyd oph halic anhyd ide (HHPA) and abie ic acid (MPA)
in he p esence o 1-e hyl-4-me hylimidazole (EMID) as a manda o y ca alys o ensu e
he comple e cu ing kine ics. The da a showed excellen he mo-oxida i e s abili y o
bo h he mose s, wi h a T5% alue abo e 300 °C. In addi ion, DSC scannings e idenced Tg
o 155.3 °C and 114.2 °C, whe eas DMA p o ided e y simila s o age modulus (i.e., 2.9
and 2.8 GPa) o Eu-EP/MPA and Eu-EP/HHPA, espec i ely. These da a demons a ed
once again he possibili ies o Eu-de i ed ma e ials in o he ields.
Fu ans
5-hyd oxyme hyl u u al (HMF) can be ob ained om di e en saccha ides, such as
glucose and uc ose, and biomass [61,62]. HMF is a highly e sa ile p ecu so due o i s
unc ional g oups, an aldehyde, and alcohol, as i can be con e ed in o a ious added
alue p oduc s [63]. HMF hyd ogena ion easily leads o 2,5-bis(hyd oxyme hyl) u an
(BHMF), a highly e sa ile building blocks o gain a a ie y o unc ional ma e ials [64].
Hu e al. [65] ob ained he monome ic 2,5-bis[(2-oxi anylme hoxy)me hyl]- u an (BOF) by
he epoxida ion o BHMF, wi h he ECH ou e, as a yellow liquid wi h a 99% o pu i y and
a yield o 60% (Figu e 4.13a).
Bio-based epoxy he mose ing polyme s
73
Figu e 4.13. The syn he ic p ocedu e o he a) Bis[(2-oxi anylme hoxy)me hyl]- u an (BOF) ia
epichlo ohyd in (ECH), and b) he Diels-Alde eac ion wi h N-Hexyl Maleimide (HMI) o o m he
Bis[(2-oxi anylme hoxy)me hyl]- u an (DA-BOF).
BOF was hen cu ed wi h 4,4'-Diaminodicyclohexylme hane (PACM) and die hyl oluene
diamine (Epiku e W), and he esul s ob ained we e compa ed o DGEBA ones. The Tg
alues eached 80 and 94 °C o BOF/PACM and BOF/Epiku eW mix u es, espec i ely,
signi ican ly lowe han he ones gained o he DGEBA analogous he mose s. These da a,
oge he wi h he high s o age modulus o BOF-based he mose s make i an in e es ing
candida e o be u he s udied o i s po en ial exploi a ion in he ield o conse a ion.
Meng e al. [66] wo ked wi h he a o emen ioned bio-epoxy esin o he de elopmen o
lame e a dan he mose s, using 3,3′-diamino diphenyl-sul one (33DDS) and 4,4′-
diamino diphenyl-sul one (44DDS) as ha dene s. DSC scannings e idenced Tg alues o
102 °C and 114 °C o BOF/33DDS and BOF/44DDS, espec i ely, signi ican ly lowe han
hose displayed by DGEBA-based ones. TGA analysis ca ied ou showed lowe T5% and
T30% wi h espec o he DGEBA-based ma e ials. In e es ingly, BOF/33DDS and
BOF/44DDS exhibi ed esidues highe han 40%, hus con i ming an excellen po en ial
ha can be u he in es iga ed in s one conse a ion. DMA s udies showed an enhanced
c oss-linking densi y, wi h signi ican ensile, lexu al s eng h, and ex a ha dness.
Chap e 4
80
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Design o bi unc ional epoxy-silica hyb ids de i ed om a nica oo
87
CHAPTER 5: Design o bi unc ional
epoxy-silica hyb id ma e ials based on a
na u al cycloalipha ic diol de i ed om
a nica oo
This chap e was ocused on he design o a i s line o ailo -made epoxy-silica
hyb ids ma e ials, using a building blocks sys em, which se e as base o mula ion o mee
he bi unc ional p ope ies i s ly equi ed by an ad anced s one conse a ion ma e ial.
In pa allel o his wo k, inno a i e analy ical me hodologies we e also de eloped o de ine
he ad an ages add essed by he implemen a ion o spec oscopic echniques, oge he
wi h he classical ones used in he ield, o assess he p og ess o he de eloping
p ocesses.
To achie e his, he sequen ial ma e ial de elopmen p e iously indica ed was he e
speci ically ollowed un il S ep- Epoxy-Silica hyb ida ion, and he co esponding
en ichmen o he p oduc ob ained in his chap e was app oached in Chap e 6 o
achie e he inal mul i unc ional epoxy-silica hyb id a ge ma e ial.
Conc e ely, S ep- Epoxy p ecu so was aced acco ding o he e iew esea ch ca ied
ou . Thus, he cycloalipha ic diol 2,2,4,4- e ame hyl-1,3-cyclobu anediol (CBDO) was
ixed as s a ing poin o syn hesize he bio-based epoxy p ecu so 2,2,4,4- e ame hyl-
Chap e 5
88
1,3-cyclobu anediol diglycidyle he (CBDO-DGE). Du ing he cou se o i s syn hesis and
clean-up p ocess, a me hod based on a combina ion o FT-IR and Raman analysis was
applied o sys ema ically moni o he s uc u e and pu i y o he p oduc ob ained du ing
he di e en phases. In his manne , he ad an ages o exploi ing spec oscopic analy ical
s a egies, o e he con en ional ma e ial cha ac e iza ion echniques such as in his case
1H-NMR and 13C-NMR, we e he e s udied.
A e wa ds, S ep- Base he mose was unde aken o ob ain an adequa e ma e ial
ounda ion ha make easie he implemen a ion o he he mal-mechanical and
hyd ophobic p ope ies equi ed by adding o silica- o ming addi i es. Thus, knowing ha
he selec ion o he cu ing agen plays a key ole o se up he pe o mances o he epoxy
he mose ha will ac as base laye o he hyb id ma e ial de elopmen , acco ding o
he e iew, he amines we e chosen as ha dene agen s. Bea ing in mind he da a
compiled and, wi h he in en o a oid any c acking phenomena upon c oss-linking o
ch oma ic al e a ions o he epoxy esins, as well as, o enhance hyd ophobic and duc ili y
he mose p ope ies, wo kind o amines (linea and cycloalipha ic), namely 1,8-
diaminooc ane (DAO) [1,2], ie hylene e amine (TETA) [3,4], and 5-amino-1,3,3-
ime hylcyclohexaneme hylamine (IPDA) [5,6] we e es ed o e alua e he e ec
impa ed in he o ganic ne wo k. Fu he mo e, as he ha dene a io needed o open he
epoxy ings does no co espond o an exac s oichiome ic alue, and i s excess o de ec
has a s ong in luence in he inal ma e ial pe o mance, he addi ion p ocess o he amine
was i s ollowed, and la e delimi ed, by a me hod based on ATR- FT-IR and Raman
analysis, whe eas hei sui abili y as o ganic coun e pa o he hyb ids was inally
es ablished by hei he mal cha ac e iza ion da a.
Las ly, S ep- Epoxy-Silica hyb ida ion was pe o med o de elop he he moplas ic
ma e ials acco ding o he CBDO-DGE he mose polyme cha ac e iza ion s udy. Then,
mul iple epoxy-silica hyb ids we e ob ained exploi ing he sol-gel echnology h ough he
CBDO-DGE epoxy ha dening eac ions in p esence o di e en silica- o ming p ecu so s.
Speci ically, (3-glycidyloxyp opyl) ime hoxysilane (GPTMS) and oc yl ie hoxysilane
(OcTES) we e selec ed as no haza dous ino ganic addi i es o inely une bo h he
lexibili y and hyd ophobic p ope ies o he esul ing he moplas ic ma e ials and, also
o inc ease he p oduc compa ibili y wi h he li hic subs a e [1,7–9]. In pa allel o his, a
combina ion o SEM-EDS, ATR FT-IR and Raman analysis was employed o es ablish a
sys ema ic me hod o e alua e he dis ibu ion and in e pene a ion o silica domains in o
he o ganic ma ix o med wi h each o mula ion. Las ly, he ma e ial p ope ies impa ed
Design o bi unc ional epoxy-silica hyb ids de i ed om a nica oo
89
by he di e en mix u es we e in es iga ed by he mo-mechanical analysis (DSC, TGA and
DMA) and con ac angle measu emen s. In his way, he sui abili y o each blend o be
ixed as base o mula ion o ul il he main equi emen s o an ad ance s one
conse a ion ma e ial was de e mined.
In his manne , he wo k ca ied ou and he main esul s ob ained, oge he wi h hei
co esponding discussion, a e de ailed along he ollowing sec ions acco ding o he h ee
s eps o de elopmen desc ibed.
5.1. STEP: Epoxy P ecu so
Syn hesis o CBDO-DGE
CBDO-DGE was syn hesized acco ding o he pa en (Figu e 5.1) [10]. B ie ly, in a wo-neck
ound bo om lask, CBDO (2.8 g, 0.019 mol) and epichlo ohyd in (ECH) (15.5 mL, 0.19
mol) we e added and igo ously s i ed. Then, he phase ans e ca alys e a-n-
bu ylammonium bisul a e (TBAB) (0.65 g, 0.0019 mol), sodium hyd oxide (NaOH) (7.5 g,
0.19 mol) and ew d ops o Milli-Q wa e we e added.
Figu e 5.1. Syn hesis eac ion o he epoxy p ecu so CBDO-DGE, ia epichlo ohyd in (ECH) in basic
medium, om he na u al diol CBDO.
The yellow eac ion mix u e, le unde s i ing a 40°C o 2 hou s, u ned o eddish-
o ange. Once i eached oom empe a u e, dichlo ome hane was added and he o med
suspension was il e ed (Ø 45 µm). The o ganic phase was washed wi h Mili-Q wa e un il
he aqueous phase ob ained was clea , adding a inal wash wi h an ace ic acid solu ion
(pH ≈ 4.5). Then, he o ganic phase was eco e ed and ea ed wi h anhyd ous sodium
Chap e 5
96
al hough, CT was ea u ed by highe elas ici y and enaci y han CI, which was ins ead
qui e agile. Con e sely, CD sample was lexible bu sligh ly s icky, ea u ed by isible
su ace oughness, wi h small yellowish spo s.
The FT-IR spec a aken o e i y he ex en o c oss-linking [13] showed o all he samples
he inc ease o he band a 3600-3200 cm-1 (due o he –OH g oups o ming as esul o
he epoxy ings clea age) oge he wi h he disappea ing o he oxi ane signal a 849 cm-
1. A he same ime, new peaks co esponding o p ima y amines appea ed a 1640 and
1650 cm-1, mainly, in samples CD and CI, sugges ing he p esence o signi ican un eac ed
amoun s o DAO and IPDA, espec i ely. Raman analysis showed as a common ea u e
ha he seconda y oxi ane signals a 781 cm-1 comple ely disappea ed, whe eas a weak
in ensi y o he main peak a 1260 cm-1 was obse ed as esul o he cu ing eac ion
p og ess. Hence, he opening o he epoxy g oups was double spec oscopically
con i med. Mo eo e , un eac ed p ima y amines we e again de ec ed by he bands a
a ound 1447 cm-1, bo h in CD and CI spec a [1,14].
Since o en he amoun o he amine does no co espond o he equi ed heo e ical
s oichiome ic a io, and keeping in mind ha an excess o he amine in he bulk o he
esin may cause unwan ed da kening due o i s easy oxida ion, he p ope amine amoun
o bo h DAO and IPDA ha dening agen s we e ollowed s udied.
The mose ma e ial: Op imiza ion by spec oscopic echniques
Addi ional syn he ic ials we e ca ied ou using epoxy/amine a ios o 2:0.75 and 2:0.5
o bo h amines. He ein, CBDO-DGE/DAO (CD-1 and CD-2) and CBDO-DGE/IPDA (CI-1 and
CI-2) samples we e p epa ed (Table 5.2) ollowing he p e ious syn he ic p ocess.
Un o una ely, samples CD-2 and CI-2 we e disca ded o he nex s udies a e he cu ing
p ocess due o hei semi-solid and s icky na u e which is unapp op ia ed o he de ined
ma e ial pu pose.

Design o bi unc ional epoxy-silica hyb ids de i ed om a nica oo
97
Table 5.2. Rela i e amoun s o he selec ed ha dene s employed a di e en a ios o he syn heses o he
CBDO-DGE he mose .
Sample
CBDO-DGE
DAO
IPDA
CD-1
0.30 g
1.17 mmol
0.06 g
0.43 mmol
CD-2
0.30 g
1.17 mmol
0.04 g
0.30 mmol
CI-1
0.30 g
1.17 mmol
0.07 g
0.44 mmol
CI-2
0.30 g
1.17 mmol
0.05 g
0.29 mmol
Then, he alid samples we e subjec ed o he spec oscopic s udy o de e mina e he
e ec in he c oss-linking exe ed by he modi ica ion o he epoxy/amine a io used. The
no malized abso bance in ensi y da a o he ATR-FTIR signals due o –OH and o epoxy
ings, wi h espec o he e he g oup a 1098 cm-1, is epo ed in Figu e 5.6 o hei
compa ison.
Figu e 5.6. Compa ison be ween he ATR FT-IR abso bances a 3500 (-OH), 1650 and 1640 (N-H)
cm-1 bands o CBDO-DGE cu ed samples, using 1,8-diaminooc ane (DAO) and 5-amino-1,3,3-
ime hylcyclohexaneme hylamine (IPDA) a di e en epoxy:amine a ios, 2:1 o CD and CI, and
2:0.75 o CD-1 and CI-1.
The esul s ob ained clea ly indica e ha he maximum ex en o he ing opening
oge he wi h lowe amoun o p ima y amine was accomplished o samples CD-1 and CI,
wi h an epoxy/amine a io o 2:0.75 and 2:1, espec i ely. Mo eo e , gi en he
Chap e 5
98
impo ance o he he mal ansi ions (in e ms o Tg) in he inal pu pose o hese
ma e ials, he cha ac e iza ion o he he mal beha io was also de e mined o inally
e i y i hey p esen a p ope sui abili y.
The mose ma e ial: The mal s udy
DSC in es iga ions e idenced ha all he CBDO-DGE/DAO samples display a small
exo he mic peak a app oxima ely 175 °C du ing he i s scanning and, in addi ion, he Tg
de ec ed du ing he second scan was highe , indica ing a pos -cu ing e ec due o he i s
hea ing and/o sugges ing ha he c osslinking was no o al. Mo e in de ail, Tg o 25.9
and 16.9 °C we e ound o CD-1 and CD, espec i ely, sugges ing ha CD-1 ma ix is mo e
c oss-linked (i.e. epoxy/amine a io o 2:0.75), in ag eemen wi h he indings coming
om FT-IR s udy. Simila ly, as he bibliog aphic da a indica ed, he CT eached 26.8 °C
[10]. Ye , samples CI and CI-1 showed Tg alues o 52.0 and 49.4 °C, espec i ely, indica ing
ha , he dec ease o epoxy/amine a io did no exe any signi ican a ia ion on he IPDA
he mose ne wo ks.
Mo eo e , he he mal s abili y o he mos p omising he mose (i.e. CT, CD-1, and CI)
was in es iga ed by TG-DTA. The main deg ada ion empe a u es and he ob ained % o
mass esidues om he he mog ams cu es (Figu e 5.7) a e summa ized in Table 5.3.
Figu e 5.7. The mog a ime ic aces o c oss-linked ne wo ks based on CBDO-DGE and DAO, TETA
IPDA amines.
Design o bi unc ional epoxy-silica hyb ids de i ed om a nica oo
99
Table 5.3. The mal p ope ies o CBDO-DGE c oss-linked wi h DAO, TETA and IPDA: CD-1, CT and CI samples,
espec i ely.
Samples CD-1 CT CI
Fi s e en
T
onse
[◦C]
158
154
128
T
max
[◦C]
321
356
335
% mass loss
59.9
95.9
93.9
Second e en
T
onse
[◦C]
428
T
max
[◦C]
451
% mass loss
33.3
Residual mass % * 3.3 3.9 3.4
T
g
[◦C]
25.9
26.8
50.0
*a 800 ◦C
The esul s indica ed ha he deg ada ion occu s in wo s eps o CD-1 and showed Tonse
alues o 158 and 428°C, wi h Tmax a 321 and 451 °C and a % mass loss o 60 and 33%,
espec i ely, and displaying a esidual mass o 3.3%. Howe e , samples CT and CI
displayed a single peak ea u ed by Tonse alues o 154 and 128 °C, wi h maximum
deg ada ion a es a 356 and 335 °C, de ec ing ca bonaceous esidues a 800 °C o abou
4%.
The e o e, on he basis on he esul s epo ed, in e ms o mac oscopic ex u e and
he mal ea u es, CI and CT samples we e he mos sui able and easily unable o
conse a ion pu poses, so ha u he in es iga ions we e ca ied ou o check which
silica- o ming addi i es could gene a e a hyb id ne wo k wi h he speci ic p ope ies
equi ed.
5.3. STEP: Epoxy-Silica hyb ida ion
Syn hesis o CBDO-DGE epoxy-silica hyb ids
In o de o es he capabili y o gene a e p ope o ganic-ino ganic ne wo ks o ailo ed
p ope ies, 10 di e en hyb id o mula ions we e p epa ed using sol-gel echnology. Fo
his, me hanol was selec ed as sol en o slow down o p omo e he o ma ion o mo e
Chap e 5
100
homogeneous ma e ials, aking he ad an age o i s capabili y o p o ide low eac i i y o
alkylalkoxysilanes, ensu ing a con olled sol-gel eac ions [15–17].
Then, each o mula ion s a ed wi h a 5% w/w epoxy-con aining me hanol solu ion and
included one o wo epoxy compounds. Figu e 5.8 and Table 5.4 shows he s uc u es and
speci ic amoun s o eac an s and addi i es selec ed o each sample.
Figu e 5.8. Chemical s uc u es o he alkylalkoxysilanes s udied as coupling agen s and silica
o ming addi i es, (3-glycidyloxyp opyl) ime hoxysilane (GPTMS) and oc yl ie hoxysilane
(OcTES), espec i ely.
In de ail, samples 1T and 1IP we e ob ained by dissol ing 0.5 g o CBDO-DGE in 7 mL o
me hanol and adding he ha dene (TETA o IPDA, espec i ely), p e iously dissol ed in
3 mL o MeOH. The solu ions we e s i ed o 60 min, and OcTES was added a 10% w/w
wi h espec o CBDO-DGE, hen le o s i , o 90 min. To calcula e he s oichiome ic
amine equi ed, GPTMS and OcTES we e p epa ed as well. Samples 2T and 4T we e
p epa ed using 0.3 g and 0.25 g o CDBO-DGE, espec i ely, wi h wo di e en amoun s
o GPTMS (0.2 g and 0.25 g) dissol ed in 2 mL o MeOH. A e s i ing o 60 min, TETA
amine dissol ed in 2 mL o MeOH was added and le unde s i ing o 90 min. Samples
3T and 5T we e p epa ed simila ly, bu wi h he addi ion o 0.025 g o p ehyd olyzed
OcTES. Samples 2IP and 4IP we e p epa ed using IPDA as he ha dene o he wo
di e en epoxy mix u es, and samples 3IP and 5IP we e ob ained by adding 0.025 g o
OcTES. All he samples we e le in e lon Pe i dishes capped wi h pa a ilm o 4 days,
d ied a oom empe a u e, and he mally cu ed a 60 °C o 24 hou s, eached a a
hea ing a e o 5 °C min-1.
Design o bi unc ional epoxy-silica hyb ids de i ed om a nica oo
101
Table 5.4. Rela i e amoun s o he CBDO-DGE, ha dene s and silica p ecu so s employed o he syn heses
o epoxy-silica esins.
Sample
CBDO-DGE
GPTMS
OcTES
TETA
IPDA
1T
0.50 g
0.05 g
0.095 g
1.95 mmol
0.18 mmol
0.65 mmol
2T
0.30 g
0.20 g
0.071g
1.17 mmol
0.85 mmol
0.49 mmol
3T
0.30 g
0.20 g
0.025 g
0.071g
1.17 mmol
0.85 mmol
0.09 mmol
0.49 mmol
4T
0.25 g
0.25 g
0.067 g
0.98 mmol
1.06 mmol
0.46 mmol
5T
0.25 g
0.25 g
0.025 g
0.067 g
0.98 mmol
1.06 mmol
0.09 mmol
0.46 mmol
1IP
0.50 g
0.05 g
0.17 g
1.95 mmol
0.18 mmol
1.00 mmol
2IP
0.35 g
0.15 g
0.13 g
1.37 mmol
0.63 mmol
0.76 mmol
3IP
0.35 g
0.15 g
0.025 g
0.13 g
1.37 mmol
0.63 mmol
0.09 mmol
0.76 mmol
4IP
0.30 g
0.20 g
0.12 g
1.17 mmol
0.85 mmol
0.70 mmol
5IP
0.30 g
0.20 g
0.025 g
0.12 g
1.17 mmol
0.85 mmol
0.09 mmol
0.70 mmol
The, anspa en pale yellow solid ilms we e ob ained as mac oscopically homogenous,
la and c ack- ee samples; oughly, hei elas ici y and enaci y seemed o inc ease wi h
he GPTMS con en , being hei ha dness main ained. Fo mula ions based on OcTES as
he only silica addi i e, lead o ilms ea u ing highe colo a ion (which u ned o b own
o e ime), opaci y and lexibili y, bu sligh ly s icky ex u es. On he con a y, samples
based on he combina ion o bo h alkylalkoxysilanes seemed o display a good balance o
s one conse a ion pu poses.

Chap e 5
102
Cha ac e iza ion o CBDO-DGE epoxy-silica hyb ids
5.3.2.1. Spec oscopic assessmen
To in es iga e he o ganic and ino ganic domains dis ibu ions, seconda y elec on images
(SE) and elemen al mappings we e s udied (Figu e 5.9).
Figu e 5.9. SEM-EDS images o 1T-5T and 1IP-5IP hyb id samples, whe e silicon dis ibu ion
mappings a e o e layed in ed colo on he SE images acqui ed a a magni ica ion o 1000X.
Design o bi unc ional epoxy-silica hyb ids de i ed om a nica oo
103
The esul s showed a homogeneous mo phology o all samples, excep 2IP, 4IP and 5IP,
whe e su ace emp y a eas sugges ed sligh phase sepa a ion phenomena. Thei silicon
mappings con i med a signi ican local non-uni o mi y, whe eas he homologous samples
syn hesized wi h TETA (2T and 4T) sugges ed ha GPTMS was able o p omo e he
o ma ion o a hyb id ma ix, ea u ed by di e en domains in ima ely join ed o p o ide
a homogenous ne wo k [17,18]. Howe e , acco ding o he GPMTS a io employed,
ne wo ks o di e en mic o-mo phologies we e obse ed.
On he con a y, epoxy-silica o mula ions wi h OcTES as he only silica o ming addi i e,
1T and 1IP, showed a sligh ly he e ogeneous su ace mo phology wi h de ec able
agg ega es no bigge han 15 and 65 µm, espec i ely. This ac sugges s ha OcTES may
be p one o sel -condensa ion hus o ming small hyb id clus e s; ha is, ac s as a ille
a he han in oducing join poin s be ween o ganic and ino ganic domains [19,20]. Bo h
samples cu ed wi h TETA o IPDA amines showed compa able esul s. Howe e , his kind
o beha io in he cu ing wi h diamines was no su p ising since he implemen a ion o
p e unc ionalized polysiloxanes bea ing epoxy g oups commonly p oduces he o ma ion
o single-phase sys ems ea u ed by a seg ega ion o siloxane domains in he epoxy ma ix
[21,22].
The esul s ob ained o samples 3T and 3IP indica ed ha he combina ion o bo h
alkylalkoxysilanes, ega dless o he amine used, acili a ed he in e pene a ion be ween
domains, and hus, a lowe endency owa ds he mic o-phase sepa a ion. Howe e , by
inc easing GPTMS a io, signi ican mo phologic and dis ibu ion changes we e obse ed.
In de ail, 5T and 3T hyb ids, which only di e ed in he ela i e amoun o he wo di e en
epoxy p ecu so s, i.e. CBDO-DGE and GPTMS, we e bo h ea u ed by a homogeneous
su ace, ye displaying di e en mo phologies (Figu e 5.9). In addi ion, 5T and 2T su ace
dis ibu ions we e compa able, as well as 5IP and 4IP e en hough 2T and 4IP we e only
based on GPTMS as silica o ming addi i e. In addi ion, highe GPTMS a ios in he
alkylalkoxysilanes mix u es seem o hinde he in e ac ion wi h OcTES, sugges ing ha he
wo silica o ming addi i es gi e ise o dis inc concu ing eac ions in compe i ion.
Fu he mo e, o gain a deepe insigh in o he o ganic-ino ganic c oss-linking ex en , ATR
FT-IR and Raman spec a we e s udied. In a ed spec a o samples con aining GPTMS (all
excep o 1T and 1IP) showed he disappea ing o he epoxy peaks a 849 cm-1, as a esul
o he opening by eac i e si es o amines, al hough weak signals a 1650 cm-1 e idenced
he p esence o ee p ima y amines in he case o IPDA con aining samples.
Chap e 5
104
Consequen ly, a u he amine amoun adjus men o he syn hesis is no equi ed; his
e idence also sugges ed ha he Si-OH o med du ing he sol-gel eac ions is no
signi ican ly in ol ed in he epoxy ing opening. On he con a y, hyb id samples based on
OcTES only showed he p esence o an excess o he cu ing agen ha can, e y likely,
explain he ilm da kening obse ed. I should be highligh ed ha he de ec ion o pa ially
eac ed and/o un eac ed amine in he inal hyb id composi ion is c ucial o he po en ial
easibili y o he p oduc s on his o ical li hic subs a es [23].
As a as he deg ee o c oss-linking is conce ned, only TETA hyb ids showed signi ican
signals a 1038 and 947 cm-1 due o he Si-O-Si and Si-OH bonds espec i ely, o med
du ing he hyd olysis and condensa ion s eps. In addi ion, he ci ed signals we e no
clea ly obse ed o IPDA hyb ids since hei weak in ensi y did no allow a
s aigh o wa d dis inc ion wi h he CBDO-DGE ones, i.e. bands a 1098 and 930 cm-1. Only
o 1IP and 5IP samples a li le shoulde a ibu ed o Si-OH signal was iden i ied.
Consequen ly, in o de o assess which o mula ions has p o ided he mos de eloped
silica ne wo k, he hyd olysis o alkoxysilane moie ies in TETA cu ed samples was s udied
by means o polycondensa ion a ios (PR) (see Figu e 5.10).
Figu e 5.10. ATR-FTIR spec a o he samples 3T and 4T compa ing hei polycondensa ion a io
and showcasing he polycondensa ion a io equa ion.
Design o bi unc ional epoxy-silica hyb ids de i ed om a nica oo
105
Acco ding o he a e age in ensi y a io be ween Si-O-Si and Si-OH bonds [24], 4T and 2T
samples showed he highes alues, 2.6 and 2.1 espec i ely, explaining he di e ence
obse ed by SEM-EDS and highligh ing he posi i e e ec o GPTMS as coupling agen . PR
alues o a ound 1.8 we e ob ained o 3T and 5T hyb ids, indica ing ha he combina ion
o bo h silica addi i es p omo ed he p esence o pa ially hyd olyzed -Si(OR)3 g oups o
uncondensed silanoles. As expec ed, due o he p esence o he OcTES e hoxy g oups,
sample 1T showed he lowes PR a io.
Raman spec oscopy con i med he p e ious esul s and, al hough weak signals o epoxy
ings we e iden i ied a 1260 cm-1 o all he samples, he seconda y cha ac e is ic peak
a 781 cm-1 was no de ec ed in any case. In addi ion, al hough Raman (pa ame e s: 785
nm lase , 180s lase bleaching, powe o 10 %, exposu e ime o 10 s and 20
accumula ions) signals a ibu ed o pa ially hyd olyzed -Si(OR)3 g oups a 666 cm-1 we e
o e lapped, he de elopmen o ino ganic ne wo k was obse ed only o TETA hyb id
samples by he iden i ica ion o weak Si-O-Si bond signals a 466 cm-1 as shown in Figu e
5.11.
Figu e 5.11. Raman spec um o he sample 4T indica ing he de eloped Si-O-Si bond.
Chap e 5
112
amoun o GTPMS as he unique compa ibilize be ween o ganic and ino ganic
coun e pa s (2IP and 4IP hyb ids) did no seem o a o hyd ophobici y.
5.4. Gene al ema ks
Along his chap e , he success ul syn hesis eac ion and pu i ica ion o he CBDO-DGE
epoxy esin de i ed om he a nica oo was success ully achie ed. Du ing his p ocess, a
mul ianaly ical app oach ha implemen s a a ie y o spec oscopic analysis o he
sys ema ic moni o ing o hese di e en phases was also he e de eloped and success ully
applied o con ol he quali y o he bio-epoxy p oduc ion p ocess. In his manne , he
ad an ages add essed by exploi ing he spec oscopic echniques in he ma e ial ield
e idenced a educ ion o he esou ces and ime consumed o he p ocess o quali y
assessmen , in addi ion o he minimiza ion o using po en ially ha m ul sol en s.
The po en ially o hese echniques in ma e ial design p ocesses we e u he
demons a ed in ela ion o he selec ion o he cu ing agen , and addi ion a io, o he
op imiza ion o he he mose ing ma e ial pe o mance, since i has he ole o building
up he ounda ion o he hyb id o mula ion and making easie he design based on he
building blocks sys em.
In pu sue o de eloping epoxy-silica hyb ids ma e ials, speci ically designed o being
applied on he ield o s one conse a ion, his wo k demons a ed he sui abili y o TETA
as c osslinking agen o he o ganic-ino ganic ne wo k o ma ion. Mo eo e , he
combina ion o he o ganic and ino ganic domains employing GPTMS as a coupling agen
led o di e en c oss-linked sys ems ha allow he homogenous dispe sion o OcTES,
esul ing in a p ope ies comp omise be ween igidi y and elas ici y, while p o iding he
highes hyd ophobic p ope ies, hus, ensu ing a balance o he bi unc ional
equi emen s o an ad anced s one conse a ion ma e ial.
Fo all he men ioned, wo mix u es, namely 3T (CBDO-DGE/TETA/GPTMS) and 4T (CBDO-
DGE/TETA/GPTMS/OcTES), we e es ablished as base o mula ions ha mee ing he
ecommended consolida ing and hyd ophobic capabili ies. Thus, hey enable he
explo a ion o di e en enhancemen ou es o be inely uned and implemen he also
wan ed biocidal capaci y. Fo his eason, he ob aining and alida ion o he desi ed
i unc ional p ope ies package, in a single ma e ial, is app oached in he nex phases o
he design p ocess.

Design o bi unc ional epoxy-silica hyb ids de i ed om a nica oo
113
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h ps://doi.o g/10.1016/S0032-3861(99)00525-X.
[22] S. Ananda Kuma , T.S.N. Sanka a Na ayanan, The mal p ope ies o siliconized
epoxy in e pene a ing coa ings, P og ess in O ganic Coa ings. 45 (2002) 323–330.
h ps://doi.o g/10.1016/S0300-9440(02)00062-0.
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Bioanaly ical Chemis y. 408 (2016) 5711–5722. h ps://doi.o g/10.1007/s00216-016-
9673-y.
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116
117
CHAPTER 6: Mul i unc ional epoxy-
silica hyb id ma e ials de i ed om
a nica oo o ad anced s one
conse a ion
This chap e was aimed o de elop a speci ic ailo -made bio-based s one
conse a ion ma e ial ha exhibi s a biocidal capaci y o achie e he desi ed i unc ional
ole, main aining a sui able balance o p ope ies such as elas ici y, adhesion, he mal and
chemical s abili y, and hyd ophobici y. Acco dingly, he sequen ial building block addi ion
was comple ed h ough he de elopmen o S ep- Epoxy-silica hyb id en ichmen , using
he mos p omising o mula ions accomplished in Chap e 4 as he design basis. To inely
adjus hem and achie e mic oo ganisms g ow h inhibi ion wi hou comp omising he
ea u es displayed by he base hyb ids, a ious syn he ic s a egies based on ionic liquids
(ILs), essen ial oils (EOs), and nanopa icles (NPs) we e he e in es iga ed. Fu he mo e,
he po en ial o he mul i unc ional ma e ials designed as ad anced conse a ion
ea men was de e mined a mid- e m.
In acco dance wi h he cha ac e iza ion s udy o he CBDO-DGE-based hyb id ma e ials,
3-glycidyloxyp opyl) ime hoxysilane (GPTMS) con aining o mula ion, namely
CBDO- DGE/GPTMS, was poin ed ou as a highly c oss-linked and sligh ly igid ne wo k
wi h high po en ial o be modula ed by a plas icizing e ec exe ed by he inco po a ion

Chap e 6
118
o long alipha ic ILs chains o EOs. Thus, dime hyloc adecyl[3( ime hoxysilyl)p opyl]
ammonium chlo ide (QAS), ihexyl( e adecyl)phosphonium chlo ide (TP), and hymol
we e he e in es iga ed o he i s ime wi h wo possible unc ions: o ac as ne wo k
modula ing dopings and o in oduce biocidal capabili ies [1–3]. As o NPs addi ion, he
opposi e e ec could be heo e ically p edic ed, expec ing o ac as a ein o ced load o
he epoxy-silica ne wo k [4], so he o mula ion based on GPTMS and oc yl ie hoxysilane
(OcTES), namely CBDO-DGE/GPTMS/OcTES, ha showed highe lexibili y was selec ed o
es ing his doping s a egy. Speci ically, ce ium-doped TiO2 NPs we e es ed as nano ille
as hey ha e p o en capabili ies [5–7] o imp o e coa ing hyd ophobici y, and impa
signi ican sel -cleaning and biocidal ac i i y o epoxy-silica hyb ids simila o he ones
he e de eloped. In addi ion, knowing he ola ili y handicap o EOs and he possible
de imen o he hyb id ne wo k p ope ies (caused by he di ec addi ion o EOs), as well
as he loss o biocidal p ope y, an al e na i e app oach based on he encapsula ion o
hymol in o he mesopo ous o NPs was also explo ed in pa allel. In ac , SiO2 NPs we e
selec ed no only by hei encapsula ion ad an ages bu also by he po en ial load and
hyd ophobic e ec s p o ided ha could esul in an ad an ageous inding o a balance o
ma e ial p ope ies [8–11].
A combina ion o ATR-FTIR, XRD, TEM, and µ-XRF analysis i s checked he syn hesized
NPs sui abili y. Once he en ichmen s ep was ca ied ou , dis ibu ion s udies we e
pe o med by SEM-EDS analysis. The sui abili y o each o mula ion o ma ch he main
equi emen s o a s one conse a ion ma e ial was e alua ed in e ms o he mos abili y,
hyd ophobici y, and inhibi ion o he mic obiological g ow h by a combina ion o he mo-
mechanical s udies, con ac angle and disk-di usion agains bac e ia measu emen s. The
o mula ions wi h he mos p omising esul s we e u he es ed on s one specimens by
a i icial aging expe imen s unde an acidic a mosphe e. Colo ime ic in es iga ions, mass
loss, and Sco ch ape es s e alua ed he po en ial shown by he ea men . Finally,
mic oscopic imaging analysis o ea ed s one su aces was pe o med o isual
compa ison.
Acco dingly, he wo k ca ied ou and he main esul s and discussion, we e de ailed along
he ollowing sec ions.
Mul i unc ional epoxy-silica hyb ids de i ed om a nica oo
119
6.1. STEP: Epoxy-silica hyb id en ichmen
Syn hesis and cha ac e iza ion o NPs: Thymol-SiO2
The syn hesis o SiO2 mesopo ous NPs loaded wi h hymol was ca ied ou by mixing
e ae hyl o hosilica e (TEOS) (380 μL), e hanol (12 mL), an aqueous solu ion o hymol
(60 μL, 10% m/ ) and ammonium hyd oxide (1 mL, 26% m/ ). The eac ion mix u e was
s i ed o 48 h a oom empe a u e. The esul ing NPs we e hen sepa a ed by
cen i uga ion (30 min a 10000 pm), washed wi h e hanol, and d ied a oom
empe a u e o one day [8]. The expec ed p oduc was ob ained as a ine whi e powde .
The sui abili y o he NPs ob ained was con i med by XRD di ac og ams displaying i s
cha ac e is ic signal a 23.2° 2θ, and u he co obo a ed by he p esence o he bands
a 1097, 957, and 799 cm-1 in he in a ed spec um (Figu e 6.1), which we e a ibu ed o
he Si-O-Si asymme ic s e ching, Si-OH s e ching, and Si-O-Si symme ic s e ching
ib a ions, espec i ely.
Figu e 6.1. FTIR spec um o he syn hesized hymol-SiO2 mesopo ous NPs.
The absence o he peak a 1634 cm-1, commonly a ibu ed o O-H bending ib a ion
mode o physiso bed wa e molecules inside he po es, sugges ed ha he po es, e y
likely, being wa e - ee, we e illed wi h hymol. This assump ion was u he asce ained
Chap e 6
120
by means o biocidal es s (see sec ion 6.1.4.4). Besides, he –OH g oups o he Si-OH
moie ies on SiO2 NPs su ace we e assigned o he b oad band a 3445 cm-1 [12].
TEM analysis showed an uni o m a e age NPs size o 100 nm (Figu e 6.2), wi hou NP
agg ega es o ma ion.
Figu e 6.2. T ansmission Elec onic Mic oscope (TEM) images o hymol-loaded SiO2 NPs.
Syn hesis and cha ac e iza ion o NPs: Ce-doped TiO2
Ti ania nanopa icles we e syn hesized by mixing i anium isop opoxide (TTIP, 0.5 g) wi h
isop opanol a a a io o 1:30. Once he colloidal suspension was o med, ce ium ni a e
hexahyd a e (0.023 g) was added (0.03:1 a io, wi h espec o TTIP) and s i ed o 1 h.
Then, he NPs we e washed and cen i uged h ee imes using isop opanol, ul apu e
wa e , and e hanol, espec i ely [5]. The solid was le a 80 °C o 48 h and hen he mally
cu ed a 450 °C o 3 h, wi h a hea ing a e o 2 °C min−1, o ob ain speci ically he ana ase
polymo ph o m. This way a pale-yellow solid was ob ained.
The success ul syn hesis o he Ce-doped TiO2 NPs in ana ase o m was con i med by he
Raman signals de ec ed a 145, 398, 515, and 639 cm-1. The XRD di ac og ams e ealed
peaks a 25.6, 38.2, 48.3, 54.2, 55.4, 62.8, 69.1, 70.3, and 75.3° 2θ (Figu e 6.3), e idencing
again he occu ence o ana ase as he majo phase (> 98%), i.e., he TiO2 polymo ph wi h
Mul i unc ional epoxy-silica hyb ids de i ed om a nica oo
121
biocidal p ope ies[13]. The p esence o ce ium was oughly con i med by he qui e low
spec al signal/noise a io ob ained in he di ac og am, as al eady obse ed [5,14].
Howe e , he Ce3+ inclusion was inally co obo a ed by XRF da a ha showed i s
cha ac e is ic elemen al signals a 34,719.7 eV (Ce Kα).
Figu e 6.3. XRD di ac og am o he syn hesized Ce-doped TiO2 NPs.
TEM analysis showed ha he i ania NPs a e age size achie ed was a ound 200 nm, a
double alue compa ed o he silica ones (Fig. 6.4).
Chap e 6
128
Table 6.2. The mal and mechanical da a o he en iched hyb id samples 1-5 and he base hyb ids CBDO-
DGE/GPTMS (G) and CBDO-DGE/GPTMS/OcTES (GO).
Sample
1
2
3
4
5
G
GO
Fi s s ep
T
onse
[°C]
270
259
305
253
276
273
290
T
max
[°C]
333
335
336
340
331
317
345
% mass loss
67.6
58.0
95.1
57.2
54.2
63.2
67.0
Second s ep
T
onse
[°C]
407
442
410
396
394
403
T
max
[°C]
452
463
431
435
437
410
% mass loss
17.8
20.8
21.3
25.9
14.6
14.9
% esidual mass*
14.6
21.2
4.9
21.5
19.9
22.5
18.8
T
g
[°C]
24.4
19.9
20.2
36.6
31.0
48.4
39.1
T
α
[°C]
36.3
39.7
39.1
44.0
54.0
55.4
55.8
*a 800 °C
The DSC he mog ams showed glass ansi ion empe a u es (Tg) alues (Table 6.2)
educed by mo e han a hal o samples 1, 2, and 3 o 24.4, 19.9, and 20.2 °C, espec i ely,
wi h espec o he 48.4 °C achie ed by he non-doped hyb id. These indings clea ly
indica ed ha he GPTMS capabili y o ac as a coupling agen was s ongly a ec ed by
he p esence o ILs and EO, so a signi ican dec ease in he c oss-linking deg ee in he
esul ing hyb ids may occu [16]. Al hough, in p inciple, SiOMe g oups o QAS, a e
hyd olysis, could ac i ely concu o he condensa ion o silanols coming om GPTMS, hus
p o iding addi ional ancho poin s o he hyb id de elopmen , he a he low Tg ob ained
o sample 1 sugges s ha he plas icizing e ec due o he alkyl chains o QAS ac ually
p e ailed o e he c oss-linking wi h GPTMS so ha he e icien inco po a ion o QAS in o
he hyb id ne wo k seemed unlikely. By con as , o samples 4 and 5, he de ec ed Tg
alues we e sligh ly lowe (i.e. alues o 36.6 and 31.0 °C, espec i ely) han he one
(39.1 °C) obse ed o he non-doped sample, e idencing ha he use o hymol-con aining
NPs, a he han nea hymol, could be a success ul s a egy o p o ide biocidal p ope ies
o he EO o he p oduc s wi hou a subs an ial nega i e impac on he hyb id
de elopmen .
The DMA in es iga ions (Table 6.2 and Figu e. 6.8) displayed o sample 1 a Tα alue o
36.3°C, close o he Tg, hus sugges ing ha QAS may ac i ely concu o he de elopmen

Mul i unc ional epoxy-silica hyb ids de i ed om a nica oo
129
o he o ganic-ino ganic ne wo k, al hough no o a g ea ex en . Again, i can be no iced
ha he use o TP and hymol as addi i es in samples 2 and 3 esul ed in a clea plas icizing
e ec , as he di e ence be ween Tg and Tα alues was in bo h cases a ound 20 °C, wi h
Tα o 39.7, and 39.1 °C, espec i ely. In con as , he NPs loadings, as o samples 4 and 5,
p o ided Tα o 44 and 54 °C, espec i ely, hus con i ming ha hei inco po a ion
p ese ed he c oss-linking deg ee. This was e en mo e e iden o sample 5, sugges ing
ha he e icien inco po a ion o NPs in he hyb id ma ix occu ed e y likely due o he
co-condensa ion o silica -OH g oups wi h he silanols coming om he alkylalkoxysilanes,
wi hou comp omising he in insic lexibili y o he non-doped o iginal o mula ion.
Figu e 6.8. Log s o age modulus (E′) and damping ( an δ) o hyb id samples 1-5 as a unc ion o
empe a u e.
Chap e 6
130
6.1.4.3. Wa e epellence s udies
The hyd ophobic beha io o samples 1-5 was assessed acco ding o he con ac angle
a e age da a (n=5) displayed in Figu e. 6.9, whe e wo g oups can be clea ly dis inguished.
Figu e 6.9. Con ac angle a e age alues CA (M) and s anda d de ia ions ob ained o he en iched
hyb id samples 1-5.
Samples 1, 2 and 3 showed alues lowe han 90°, hus indica ing ha he hyd ophobic
capabili y o he o iginal hyb id was no imp o ed by he inco po a ion o ILs o nea
hymol. On he con a y, he nano-en ichmen wi h hymol-SiO2 NPs managed o
p ese e he o iginal hyd ophobic capabili y, wi h a CA alue o 100°. Howe e , he mos
signi ican esul was ob ained o sample 4, whe e he en ichmen o he o mula ion
wi h Ce-doped TiO2 NPs impa ed an inc ease o 12° in he hyd ophobici y wi h espec
o he non-doped hyb id [17].
F om he whole o he collec ed da a, i clea ly appea s ha nano-en iched hyb id
samples 4 and 5 a e he ones ha displayed he mo-mechanical and hyd ophobic
p ope ies sui able o s one conse a ion pu poses. Acco dingly, u he s udies we e
ca ied ou o de e mine he biocidal capabili y and alida e hei mul i unc ional
p ope ies on s one specimens.
Mul i unc ional epoxy-silica hyb ids de i ed om a nica oo
131
6.1.4.4. An i-mic obial capaci y
The an i-mic obial es agains he bac e ia A h obac e spp. demons a ed o nano-
en iched o mula ions 4 and 5 a bac e ial inhibi ion e ec in bo h cases (Figu e 6.10). This
con i med ha he NPs embedded in o he hyb id ma ix p ese ed hei biocidal
capabili y and ha hey we e also able o p o ide addi ional p ope ies o CBDO-based
hyb ids.
Figu e 6.10. The an i-mic obial capaci y o he hyb ids samples 4 and 5 en iched wi h Ce-TiO2 and
hymol-SiO2 NPs, espec i ely, agains A h obac e spp. a e 48 h o incuba ion unde isible
ligh .
The nwhalo a e age alues o samples 4 and 5 we e 0.25 and 0.31 mm, espec i ely.
Howe e , al hough ce ium doping was employed o enhance sel -cleaning and an i-
mic obial ac i i y in he isible ligh ange, he Pe i dishes used did no allow he UV ligh
ac ion o pass, and hus, he highes biocidal e ec o Ce-doped TiO2 NPs o sample 4 is
expec ed o be ob ained in ou doo condi ions whe e UV adia ion enables a comple e
pho oca aly ic e ec [5,6,18].
6.2. S one du abili y s udy
Colo ime ic analysis
Colo ime ic measu emen s on he li hic samples e ealed ha he ea men s based on
he selec ed nano-en iched hyb id o mula ions, namely 4 and 5, did no esul in
signi ican colo changes. Conc e ely, colo di e ence alues (ΔE) o 3.27 and 2.23 we e
Chap e 6
132
ob ained, espec i ely, o he Ce-TiO2 and hymol-SiO2 NPs (GPTMS/OCTES base
o mula ions), co esponding bo h o he jus no iceable ch oma ic al e a ion le el,
acco ding o he CIE*Lab Colou -Di e ence Th esholds classi ica ion [19]. Fu he mo e,
by compa ing colo ime ic da a ob ained o non- ea ed s one samples wi h hose
collec ed on ea ed, a e aging expe imen s, i esul ed ha ΔE alues we e below 3.8,
i.e. ch oma ic al e a ions below he dis inc i ely pe cep ible le el, hus con i ming ha
exposu e o an acidic a mosphe e did no cause signi ican ch oma ic changes on he
de eloped nano-en iched ma e ials. The alues ob ained a e also below he ch oma ic
changes a ibu ed o conse a ion ea men s, which allow ΔE alues o 5 [20].
Mic oscopic image analysis
Subsequen ly, in o de o e alua e he consolida ing e ec p o ided by he hyb id
p oduc s on he s one samples, images by he magni ica ion glass and SEM analysis we e
s udied. As i is shown in Figu e 6.11, i is e iden ha he aging es unde he acidic CO2
a mosphe e modi ied he po ous ne wo k o he non- ea ed s one, enla ging he po e
size and sugges ing an al eola iza ion phenomena, which is a e y ypical deg ada ion
pa e n su e ed by hese kind o s one. Howe e , al hough bo h ea ed samples also
appea ed o be ligh ly a ec ed by he aging, he a ec ion deg ee was clea ly in e io .
Upon a close examina ion o he magni ied images, i can be in e ed ha he p oposed
T ea men 5, based on hymol-loaded SiO2 NPs en ichmen , seemed o p o ide g ea e
p o ec ion agains he deg ada i e ac ion o he ca bona e subs a e by he
en i onmen al agen a ack.
Acco dingly, hese indings we e suppo ed by SEM in es iga ions, which clea ly showed
a smoo h and uni o m su ace o non-aged sample and an e iden unde going a
deg ada ion p ocess (see Figu e 6.12). A his scale, he p o ec ion p o ided by he
ea men s we e e idenced wi hou showing signi ican di e ences be ween hei
p o ec ion capaci ies o main ain an in e nal in eg i y simila o ha o he o iginal s one
ma ix. In ac , al hough a mic o al eola iza ion a eas we e isible in he s one su aces
be o e he consolida ing essays, he esul s collec ed a e he applica ion o he
ea men s demons a ed ha he holes and supe icial impe ec ions p esen ed a mino
dep hless and hus, he ma ix was less exposed he ad e se e ec s o he en i onmen al
agen s and achie ed a p e en ion o u he decay.
Mul i unc ional epoxy-silica hyb ids de i ed om a nica oo
133
Figu e 6.11. Magni ica ion pho og aphs o he s one samples, un ea ed and ea ed wi h he
nano-en iched hyb id o mula ions 4 and 5 (ob ained om GPTMS and OCTES as silica p ecu so s
wi h Ce-TiO2 and hymol-SiO2 NPs, espec i ely) o he isual examina ion o hei abili y as
coa ing.

Chap e 6
134
Figu e 6.12. SE images o he s one samples, un ea ed and ea ed, wi h he nano-en iched hyb id
o mula ions 4 and 5 (ob ained om GPTMS and OCTES as silica p ecu so s wi h Ce-TiO2 and
hymol-SiO2 NPs, espec i ely) o he isual examina ion o hei p o ec ion capabili y.
Mass loss analysis
These esul s was inally con i med by he mass loss a e age alues collec ed a e aging
expe imen s, as non- ea ed samples displayed a weigh mass loss o 1.1 %, whe eas s one
Mul i unc ional epoxy-silica hyb ids de i ed om a nica oo
135
samples ea ed wi h 4 and 5 o mula ions showed alues be ween 0.4 and 0.3 %,
espec i ely. The Sco ch ape es e ealed he same end, wi h 87% and 92% less
disagg ega ed ma e ial obse ed on he s one su aces.
F om he whole o he discussed esul s, i is easonable o conclude ha he epoxy-silica
hyb id ma e ials en iched wi h NPs exhibi ed a signi ican capabili y o mi iga e he mid-
e m decay o he es ed s one specimens, being he SiO2 doped p oduc he one ha
displayed he mos signi ican mul i unc ionali y o e all.
6.3. Gene al ema ks
Th oughou his chap e , a sus ainable mul i unc ional bio-based epoxy-silica hyb id
nanocomposi e speci ically o s one conse a ion pu poses was success ully de eloped
using a building block design app oach by he combina ion o CBDO-DGE/GPTMS/OcTES
wi h hymol-loaded SiO2 NPs. The esul ing ma e ial exhibi ed po en ial ou s anding
p ope ies, including excellen consolida ion, lexibili y, hyd ophobici y, and ema kable
an i-mic obial inhibi ion capaci y.
This mul i unc ional balance was possible hanks o he implemen a ion o
nano echnology as a syn he ic s a egy. The oppo uni ies p esen ed by he hyd oxyl
su ace o he silica NPs a e highligh ed o he en ichmen o epoxy-silica hyb id ma e ials
ia he sol-gel p ocess, gi en ha hey acili a ed an in ima e join be ween he addi i e
doping and he o ganic-ino ganic hyb id ne wo k. In ac , 3% con en in silica NPs no only
ac s like a nano- ille capable o inely modula ing he inal ma e ial p ope ies bu also
demons a ed o be a aluable suppo o add biocidal p ope ies wi hou comp omising
consolida ing and hyd ophobic ea u es al eady displayed by he hyb id base used as a
building block. Mo eo e , his wo k e idences he ad an ages p esen ed by he EOs
adso p ion on silica NPs su ace e sus i s di ec addi ion o hyb id sys ems, achie ing a
clea minimiza ion o he handicaps in he in inal ea u es, opening an inno a i e
syn he ic app oach in he ield o he building block design wi h as ad an ages o
de eloping ad anced ma e ials o di e en applica ion pu poses.
Howe e , in con as o NPs s a egy, he di ec addi ion o ILs demons a ed no being
sui able o building block designs o epoxy-silica hyb ids ma e ials since hey induced
subs an ial changes in he base ne wo k and p oduced an excessi e plas icize e ec ,
while lowe ed he wa e epellence o he inal p oduc s below he hyd ophobici y
Chap e 6
136
h eshold. Ne e heless, he ILs po en ial in he ield should no be unde a ed since o he
syn he ic s a egies can be s udied in u u e lines o wo k.
Finally, he s one specimen ea men p o ed ha he p oduc can be easily applied
hanks o i s low densi y, due o he use o me hanol as sol en , ensu e a homogenous
and deep pene a ion in o he s one subs a e. Besides, he polyme iza ion eac ion akes
place di ec ly wi hin he s one (in si u) and allows i s sui able in eg a ion in o he s one
ma ix while dec easing he incompa ibili y handicaps p esen ed by con en ional o ganic-
based p oduc s. In ac , he du abili y s one es ca ied ou also p o ed i s po en ial as
an e ec i e ea men o ad anced s one conse a ion h ough a comp ehensi e mul i-
analy ical app oach based on simple weigh and colo ime ic measu emen s, in
combina ion o a cheap imaging s udy ca ied ou by easily a o dable magni ica ion
glasses, p o iding isual e idence o he ad an age p esen ed, by he ea men a mid-
e m. I is impo an o no e ha u he assessmen is necessa y o e alua e he inal
iabili y o he p oposed ea men ollowing UNE-EN, ASTM D, and/o RILEM egula ions.
Howe e , he p o ec ion gained, oge he i s sus ainable na u e and easy applica ion,
su pass many o he esul s ob ained by o e all ea men s wi h hei single coun e pa s,
bo h o ganic and ino ganic.
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