Re se ar c h and applic ations of nanomate r ials in Cultur al - - PDF document

01/02/2017 1

Re se ar c h and applic ations of nanomate r ials in Cultur al He r itage

SIL VE ST RO ANT ONIO RUF F OL O

UNI VE RSIT À DE L L A CAL ABRI A

Unive rsity o f Ca la b ria -Co se nza -

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Unive rsity o f Ca la b ria Ca mpus

 14 De pa rtme nts  34500 Stude nts  836 Pro fe sso rs & Re se a rc he rs  200 he c ta re s o f surfa c e  3000 sle e ping a c c o mmo da tio ns  Ca nte e ns: 3500 me a ls e a c h da y  2 the a tre s

Unive rsity o f Ca la b ria Ca mpus

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Re se a rc h g ro up o n Sc ie nc e a pplie d to Cultura l He rita g e

 Gino M. Crisc i (F

ull pro fe sso r)

 Do na te lla Ba rc a (Asso c ia te pro fe sso r)  Ma uro F

. L a Russa (Re se a rc he r)

 Do me nic o Mirie llo (Re se a rc he r)  Silve stro A. Ruffo lo (Re se a rc h fe llo w)  Mic he la Ric c a (Re se a rc h fe llo w)  Na talia Ro ve lla (Co ntra c to r)  Ra ffa e lla De L

uc a (Co ntra c to r)

 Va le ria Co mite (Co ntra c to r)

T

• pic s o f o ur re se a rc h

(sto ne ma te ria ls)

Arc he o me tric Ana lysis Arc he o me tric Ana lysis

K no wle dg e

• f ma te ria ls

Pro ve na nc e a na lysis

Sc ie ntific Suppo rt to Re sto ra tio n a nd Co nse rva tio n Sc ie ntific Suppo rt to Re sto ra tio n a nd Co nse rva tio n

De g ra da tio n Co nse rva tio n stra te g ie s

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Ove rvie w o f the le c ture

Wha t is na no te c hno lo g y Why we sho uld a pply na no te c hno lo g y

to re sto ra tio n o f Cultura l He rita g e

Sta te o f a rt o f re se a rc h Co nso lida tio n with na no pa rtic le s Pro te c tio n with na no pa rtic le s

https:/ / ka ho o t.it

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Wha t is Na no te c hno lo g y

T he study o f the c o ntro lling o f ma tte r

• n a n a to mic a nd mo le c ula r sc a le .

Ge ne ra lly na no te c hno lo g y de a ls with struc ture s size d b e twe e n 1 to 100 na no me tre s in a t le a st o ne dime nsio n, a nd invo lve s de ve lo ping o r mo difying ma te ria ls o r de vic e s within tha t size .

So urc e : http:/ / sinte fi.b lo g spo t.it/ 2013/ 05/ na no fib ra .html

A Huma n Ha ir is a b o ut 100 µm wide

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Applic a tio ns o f na no te c hno lo g y

Nanote c hnology

Infor ma tion T e c hnolog y Me c ha nic a l E ngine e r ing Biote c hnology T r a nspor ta tion National Se c ur ity & De fe nse F

• od a nd

Agr ic ultur e Me dic ine / He a lth Ae r

• spa c e

E ne r g y & E nvir

• nme nt

Adva nc e Ma te r ia ls & T e xtile s R e stor a tion of Cultur a l He r ita g e

Applic ations of nanote c hnology in Cultur al He r itage

Why we sho uld use na no pa rtic le s in re sto ra tio n? E xa mple : fo r c o nso lida tio n o f sto ne ma te ria ls, the re is the ne e d

• f sma ll pa rtic le s in o rde r to

a c hie ve a de e pe r pe ne tra tio n

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L ime wa te r a nd milk o f lime

Ca (OH)2 + CO 2  CaCO 3 + H2O

Solubility of Ca (OH)2 = 1.7 g/ l (0.17% ) A satur e d solution of Ca (OH)2 is c alle d lime wate r

L ime wa te r a nd milk o f lime

If I add mor e lime I will obtain a milky suspe nsion c alle d milk of lime T he main pr

• ble m is r

e late d the dime nsion of the par tic le s (sc ar c e pe ne tr ation)

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na no lime

Ba g lio ni & Gio rg i 2006

Na no silic a

SiO 2 SiO 2

30 nm Unb o nb e d pa rtic le s

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Re a c tive Na no silic a

SiO 2 SiO 2

30 nm b o nb e d pa rtic le s

Str e nghts

• Wa te r b a se d
• L

e ss se nsitive to mic ro c lima tic c o nditio ns

• Quic k c uring

Str e nghts

• Wa te r b a se d
• L

e ss se nsitive to mic ro c lima tic c o nditio ns

• Quic k c uring

We akne sse s

• Pe ne tra tio n de pht

We akne sse s

• Pe ne tra tio n de pht

Oppor tunitie s

• Use a s b inde r fo r

mo rta rs

Oppor tunitie s

• Use a s b inde r fo r

mo rta rs

T hr e ats

• F

lo c c ula tio n with sa lts

• Be st pra c tic e

issue s T hr e ats

• F

lo c c ula tio n with sa lts

• Be st pra c tic e

issue s

SWOT SWOT

Na no silic a a s c o nso lida nt fo r sto ne

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T e sting na no silic a

Cappadoc ia

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T e sting na no silic a

Na no te c hno lo g y a nd Cultura l He rita g e

A surve y in SCOPUS da ta b a se

20000 40000 60000 80000 100000 120000 140000 160000 180000 200000

2016 2015 2014 2013 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2002 2001 2000 1999 1998 1997 1996

Pape r s

Nanopar tic le s Gr aphe ne Cultur al He r itage T itanium dioxide

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Na no te c hno lo g y a nd Cultura l He rita g e

A surve y in SCOPUS da ta b a se

10000 20000 30000 40000 50000 60000 70000 80000

2016 2015 2014 2013 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2002 2001 2000 1999 1998 1997 1996

Pape r s

Nanopar tic le s Gr aphe ne Cultur al He r itage T itanium dioxide

Pa pe rs b y c o untry:

Nanote c hnology

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Pa pe rs b y c o untry:

Cultur al He r itage

Que ry: Nanote c hnology +

Cultural He ritage

50 100 150 200 250 300 350

2016 2015 2014 2013 2012 2011 2010 2009 2008 2007 2006 2005 2004 2003 2002 2001 2000 1999 1998 1997 1996

Pape r s

Cultur al He r itage + Nanopar tic le s

T

• ta l numb e r o f pa pe rs (1996-2016): 1942

Ra tio (Na no te c hno lo g y + Cultura l He rita g e )/ Cultura l He rita g e : 1.5%

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Que ry: Nanote c hnology +

Cultur al He r itage

Pa pe rs b y c o untry

So me e xa mple s

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Stone de gr adation

Biologic al fac tor s Che mic al fac tor s Physic a l fac tor s

SAL T CRYST AL L ISAT ION

Whe n a salt-ric h so lutio n pe ne trate s into the po re struc ture , in spe c ific supe rsaturating and the rmo dynamic c o nditio ns, the salt c rystallizatio n take s plac e and nuc le atio n and gro wth o f salt c rystals within the po re spac e s c an induc e alte ratio n and de gradatio n o f the sto ne

SAL

T SOL UT ION

POROUS

MAT E RIAL

PRE

CIPIT AT ION

G ROWT

H OF SAL T CRYST AL S WIT HIN T HE PORE

WE

AT HE RING

Efflo r e sc e nc e Cr ac ks (Sub-e fflo r e sc e nc e )

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T he c rystallizatio n pre ssure o f salt c rystals, gro wing in c o nfine d po re s, is fo und to be the main c ause fo r damage T he pre ssure e xe rte d by salt c rystals o n the c apillary wall, is dire c tly pro po rtio nal to salt c o nc e ntratio n and c rystal size , and inve rse ly pro po rtio nal to the radius o f the po re

Afte r c rystalgro wth T he po re struc ture is c o mpro mise d due to pre ssure e xe rte d by the c rystal

Ne w Mic ro c rac ks

SAL T CRYST AL L ISAT ION

Salt crystallisation process

The crystal growth generates pressure

• n the pore walls.

Crystal

Due to the pressures, the pore increases its size

E fflor e sc e nc e Cr ac ks

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Salt c r ystallization + wind = Alve olization

Alve olization?

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Ne w insig hts o n the CONS OL I DAT I ON

• f sa lt we a the re d lime sto ne : the

c a se study o f Mo dic a Sto ne

Ruffo lo e t al 2015, Bulle tin o f E ngine e ring Ge o lo gy and the E nviro nme nt



Pe tro g ra phic o b se rva tio ns (Be lfio re e t a l. 2010) re ve a le d a g ra in-suppo rte d te xture with a b o ut 30% o f mic ritic ma trix. Allo c he mic a l c o mpo ne nts, with pe rc e nta g e s b e twe e n 40 a nd 45%, c o nsist o f se ve ra l b io c la sts.

Mo dic a sto ne

T he po ro sity (a b o ut 27%) is ma inly inte rg ra nula r. Ac c o rding to Dunha m (1962), the Mo dic a sto ne c a n b e c la ssifie d a s a pa c ksto ne , a c c o rding F

• lk (1962) a s a

b io mic rite .

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Ruffo lo e t al 2015, Bulle tin o f E ngine e ring Ge o lo gy and the E nviro nme nt

01/02/2017 20

We ig ht lo ss Po int lo a d te st

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Crysta lliza tio n pre ssure

Ruffolo e t al.

Sub mitte d to I nte rna tio na l Bio de te rio ra tio n & Bio de g ra da tio n

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Biologic al de gr adation of stone sur fac e s Use of bioc ide s in r e stor ation

• f stone sur

fac e s

 I

n the e a rly sta g e s o f c le a ning o f a n a re a a ffe c te d b y b io lo g ic a l de g ra da tio n, a funda me nta l o pe ra tio n is re pre se nte d b y the re mo va l o f b io lo g ic a l pa tina s

 T

he re mo va l o f b io lo g ic a l pa tina s re q uire s the use o f b io c ide s (o rg a nic c o mpo unds in a q ue o us o r o rg a nic so lve nt)

 T

he re mo va l o f b io lo g ic a l pa tina s do e s no t e nsure a n inhib iting e ffe c t o ve r time

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Re mo va l o f b io lo g ic a l pa tina s

Be fo re During Afte r

Conse r vation “philosophy”

A pro duc t tha t c a n a ssure a n inhib itio n e ffe c t c a n pro duc e b e ne fits:

 E

c o no mic : le ss c le a ning inte rve ntio ns

• ve r time fo r the re mo va l o f b io lo g ic a l

pa tina

 E

nviro nme nta l: linke d to re duc e d use o f b io c ide s a nd so lve nts

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T itanium dioxide

Color ing age nt E 171 T itanium dioxide

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Crystalline phase s of T iO 2

Photo- c atalytic e ffe c t

UV light < 390 nm

Se lf c le aning e ffe c t and bioc idal e ffe c t

• c c ur

s on titania sur fac e

01/02/2017 26 1 g T iO 2 2.3 c m 2 0.0023 m 2 0.23 c m

Par tic le size 0.01 c m

141 c m 2 0.0141 m 2

Nanopar tic le s

01/02/2017 27 1g T iO 2 Par tic le size 25 nm:

300 m 2

40 g T iO 2 12000 m 2

By doping the T iO 2 it is possible to e nhanc e the e ffic ie nc y In lite r atur e ma ny doping me tals have be e n use d for this pur pose

M- Dope d T iO 2

Za le ska , 2008

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Ag- Dope d T iO 2

Ag-dope d titania e nhanc e s the photoc atalitic e ffe c t F r e e silve r c an ac t itse lf as antimic r

• bic s

T he c olour be c ome dar ke r

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E xpe r ime ntal

Synthe sis and physic al/ c he mic al c har ac te r ization of T iO 2, and dope d T iO 2 E ffic ie nc y asse ssme nt In vitr

• biologic al e xpe r

ime ntation Me thyle ne Blue de gr adation Choic e of the most suitable binde r

In Situ applic ation

ID mate r ial

Pr e c ur sor Ac id (1 ml)

T

• tal

volume (ml) Re ac tion r ate

1 T iO 2 T BT HCl 0,01M 25 F a st 2 T iO 2 T PT HCl 0,01M 25 F a st 3 5% Ag -T iO 2 T BT HCl 0,01M 25 F a st 4 1% Ag -T iO 2 T BT HCl 0,01M 25 F a st 5 5% Sr-T iO 2 T BT HCl 0,01M 25 F a st 6 1% Sr-T iO 2 T BT HCl 0,01M 25 F a st 7 T iO 2 T PT HCl 1M 25 Slo w 8 T iO 2 T PT HCl 1M 25 Slo w 9 T iO 2 T PT Ac e tic Ac id 1M 25 F a st 10 T iO 2 T PT Ac e tic Ac id 1M 25 F a st 11 T iO 2 T PT Ac e tic Ac id Gla c ia l 3 Ve ry Slo w 12 1% Ag -T iO 2 T PT Ac e tic Ac id Gla c ia l 3 Ve ry Slo w

01/02/2017 30

MB de gr adation te sts Do ping e ffe c t

With UV Radiation Without UV r adiation

01/02/2017 31

• 0,030

0,170 0,370 0,570 0,770 0,970 1,170 1,370 1,570

1 2 3 4 5 6 OD

T ime [hour s] T iO 2

0,5 mg/ ml 0,25 mg/ ml 0,1 mg/ ml 0,05 mg/ ml 0,01 mg/ ml c ontrol wate r

Growth inhibition assay of E sc he ric hia c oli and mic robial viability te st

• 0,030

0,170 0,370 0,570 0,770 0,970 1,170 1,370 1,570

1 2 3 4 5 6 OD

T ime [hours]

Ag- T iO 2 1%

0,5 mg/ ml 0,25 mg/ ml 0,1 mg/ ml 0,05 mg/ ml 0,01 mg/ ml c ontrol wate r

01/02/2017 32

SE M o b se rva tio n o f b a c te ria l a ) witho ut c o nta c t with na no b io c ide s (c o ntro l) a nd b ) a fte r 30 min o f c o nta c t with Ag T

• iO2. Ba c te ria re sult

e mb e dde d into the Ag do pe d tita nia pa rtic le s. Arro ws indic a te the b a c te ria

01/02/2017 33

Applic ation

I ta lia n pa vilio n a t E xpo 2015 Mila n

01/02/2017 34

Color ime tr ic var iations

Binde r nPs Stone

01/02/2017 35

Choosing the binde r :

I

no rg a nic

Minima l inte rfe re nc e with the

e ffic a c y o f tita nia 3 binde r s have be e n te ste d

Ammo nium pho spha te Ammo nium o xa la te Na no Silic a

Blue me thyle ne te st

nanoSilic a Phosphate Oxalate

01/02/2017 36

Blue me thyle ne te st

na no Silic a ha s sho w the b e st b e ha vio r, pro b a b ly due to the hig he r pH whic h e nha nc e s the pho to c a ta lytic e ffe c t

I n situ a pplic a tio n

UNDE RST ANDI NG T HE BE HAVI OR OF T HE COAT I NGS I N RE AL SI T UAT I ONS

01/02/2017 37

Case studie s

F

• ntana di T

r e vi Roman the r mae Re ggio Calabr ia E r c olano, Villa de i Papir i

Cho o sing o f the a re a s fo r e xpe rime nta tio n

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E xpe rime nt wo rk flo w

Sampling be for e c le aning

Sa mple s ha ve b e e n ta ke n b y using a no n-de struc tive sa mpling me tho d o f a dhe sive ta pe strips (F ung ita pe Did, Mila n, I ta ly) a s de sc rib e d b y Urzì a nd De L e o , 2001)

Cle aning phase

T he surfa c e s wa s first tre a te d with a so lutio n o f Bio tin R (CT S, I ta ly). T he a pplic a tio n ha s b e e n c a rrie d o ut b y b rush. T he tre a tme nt ha s b e e n re pe a te d thre e time s (e ve ry 15 da ys),a nd the n the surfa c e s ha ve b e e n rinse d with de io nise d wa te r.

E xpe rime nt wo rk flo w 2

Sampling afte r c le aning

Sa mple s ha ve b e e n c o lle c te d to c he c k the re sidua l b io c o lo niza tio n

T itania tr e atme nt

Dispe rsio ns o f na no silic a a nd tita nia ha ve b e e n a pplie d o n sto ne surfa c e s b y b rush a t a mo unt o f a b o ut 400 ml/ m2

01/02/2017 39

E xpe rime nt wo rk flo w 3

Monitoring after TiO2 treatment

9 samples. Check the bio inhibition feature

E xpe rime nta tio n time line

01/02/2017 40

L a b o ra to ry a na lyse s

Ba c te ria l, F ung i a nd Pho to tro phs I de ntific a tio n a nd q ua ntific a tio n

 Mic ro sc o pic o b se rva tio ns  SE

M a na lysis

 Cultura l a na lyse s  I

T S-PCR fo r b a c te ria

 16SrDNA pa rtia l se q ue nc ing fo r Ba c te ria  DNA e xtra c tio n a nd PCR a mplific a tio n fo r fung i

Re sults –b e fo re c le a ning -

Table 2. Amount of chemoorganotrophic microorganisms determined as cfu/g or as different degree

• f abundance for phototrophic ones.

Sample Bacteria (cfu/g) Fungi (cfu/g) Phototrophs (Presence/absence) ERB1 3.2·105 2.0·104 ++++++ ERB2 6.5·104 4.4·106 ++++++ ERB3 7.2,·105

• ccasional

++ ERB4 2.9·106 3.0·106

• ERB5

8.0·107

• ccasional

++++ ERB6 1.1·108

• +

ERB7 4.4·107 1.0·104

• ERB8

2.1·107

• ccasional

++++ ++++++ (very abundant growth); ++++ (abundant growth), ++ (discrete growth), + (scarce growth).

01/02/2017 41

Re sults –b e fo re c le a ning -

F re q ue nc y o f fung i iso la te d fro m the diffe re nt E RB sa mple s prio r a ny tre a tme nt a nd the ir ta xo no mic a ttrib utio n. F re q ue nc ie s o f b a c te ria l iso la te s fro m sa mple s E RB ta ke n prio r a ny tre a tme nt a nd the ir ta xo no mic a ttrib utio n

Re sults - a fte r c le a ning -

. Summary of cultural analysis carried out after 1 months of biocide treatments Sample Bacteria cfu/cm2 Fungi cfu/cm2 Phototrophs Presence/absence ERBD1 145 ERBD2 75 ERBD3 65 6 + ERBD4 15 ERBD5 50

01/02/2017 42

Re sults - a fte r tita nia c o a ting a pplic a tio n -

Bacteria, fungi and phototrophs growing in BRII, DRBC e BG11 respectively after streaking on the surface 1 cm2 of adhesive tape. Samples are divided on the basis of the treatment as shown in Plate Ic. Samples Treatment* Bacteria Fungi Algae ERBN1 B5%+Ag-TiO2

• +

++ ERBN2

• +
• ERBN3

++ + +/- ERBN8 + +

• ERBN4

B ++ + +++ ERBN9 + +

• /+

ERBN5 B10%+TiO2 ++ +

• /+

ERBN6 B5%+TiO2 + +

• ERBN7

TiO2 +/- + + * = Binder; - = no growth; +/-= scarce growth; +=occasional growth; ++= discrete growth; +++= abundant growth.

T itanium dioxide : whic h futur e ?

I n Ma y 2016 the

• Ag e nc e

na tio na le de sé c urité sa nita ire de l'a lime nta tio n, de l'e nviro nne me nt e t du tra va il – ha s sub mitte d a CL H pro po sa l to E CHA to c la ssify tita nium dio xide a s 1B with ha za rd sta te me nt H350i (Ma y c a use c a nc e r b y inha la tio n)

01/02/2017 43

ANNE X 2 - COMME NT S AND RE SPONSE T O COMME NT S ON CL H PROPOSAL ON T IT ANIUM DIOXIDE

Co nc lusio ns

 I

n o ur c a se study, Na no size d tita nium dio xide se e ms to ha ve a b io -inhibitio n e ffe c t (mitig a tio n)

 A lo ng e r pe rio d o f mo nito ring is ne e de d to

unde rsta nd the lo ng -te rm b e ha vio r

 T

he use o f the se ma te ria ls c o uld b e thre a te ne d b y its c la ssific a tio n b y E CHA

01/02/2017 44

Ac knowle dgme nts

POR Calabr ia F E SR pr

• je c t

‘‘NANOPROT E CH’’ (NANO PROte c tion T e c hnology for Cultur al He r itage )