Raman microspectroscopy of paper ablation

products
Balakhnina I.
a
, Brandt N.
a
, Chikishev A.
a
, Rebrikova N.
b
,
and Yurchuk Yu.
a
a
Faculty of Physics and International Laser Center, Lomonosov Moscow State University, Moscow,
Russia
b
State Research Institute for Restoration, Moscow, Russia
Various physicochemical methods are used in the study of historical paper documents
!"#$. Restoration procedures must be based on comprehensive characteri%ation of
samples, &hich involves the analysis of composition 'type of cellulose, fillers, si%in(,
dyes, etc.).
Annual plants, ra(s, and &ood pulp &ere used in paper production. Calcite 'CaC*+),
aluminum trihydrate 'Al'*,)+), silica, kaolin, and titanium dio-ide are the most &ide.
spread fillers.
A(in( in the presence of atmospheric o-y(en and alternative o-idi%in( a(ents leads to
the o-idative destruction of cellulose, paper discoloration, and mechanical dama(es
/$. 0aser radiation can be used for paper cleanin( 1, 2$. It is kno&n that the
irradiation at a &avelen(th of #+3 nm leads to a decrease in discoloration in the
absence of noticeable dama(es of old paper materials 4$. 5resumably the effect of
laser irradiation is related to ablation and6or photochemical reactions that lead to the
destruction of chromophores.
In this &ork, &e analy%e the bleachin( of old paper samples usin( pulsed laser
radiation &ith a &avelen(th of #+3 nm, demonstrate that the laser ablation takes place,
and identify the ablation products. 7he ablation e-periments are performed usin( the
second.harmonic radiation of the Nd8YA9 laser &ith a pulse duration of !: ns,
repetition rate of !: ,%, and pulse ener(y of up to !2: m;. 7he diameter of the laser
spot on the sample is / mm, and the correspondin( pulse intensity is about
/: <=6cm
3
. 7he sample is shifted alon( the hori%ontal direction at :.+ mm6s to avoid
thermal dama(e. 7he total irradiation time is +/:: s. Comparative >7IR measurements
prior to and after irradiation prove the absence of dama(es of paper samples.
Raman microspectroscopy is used to study the ablation products &ith a spatial
resolution of about ! ?m, &hich is less than mean si%e of cellulose fibers '!: ?m).
Raman spectra are measured &ith the aid of a 7hermo @cientific ABR Raman
microscope '#:- obCective and e-citation &avelen(th of 12: nm). 7he identification is
based on characteristic Raman bands in the spectra of cellulose fibers, fillers, and
si%in( a(ents. =e study five paper samples of different a(es and compositions.
Cellulose fra(ments, calcite, titanium dio-ide, minerals, protein structures, and hi(hly
fluorescent species are identified as ablation products.
A statistical analysis of the ablation products sho&s dominant contribution of protein.
containin( fra(ments and hi(hly fluorescent species. Apparently, the removal of the
latter provides the bleachin( effect. 7he e-periment &ith the paper sample on &hich a
layer &ith a thickness of about +:D of the total paper thickness &as removed usin( an
erasin( rubber yields the amounts and relative contents of ablation products that are
similar to those in the e-periment &ith the ori(inal sample. 7herefore, the detected
ablation products are hardly related to surface pollutants.
Based on the e-perimental results, &e conclude that the Raman measurements of
ablation products can be helpful in the study of components of old paper materials and
monitorin( of the bleachin( effect.
ACKNOWLEDGMENT
7his &ork &as supported in part by 0omonosov <osco& @tate Eniversity 5ro(ram of
Aevelopment and Russian >oundation for Basic Research 'proCects !F.:/.::3#4.a and
!F.:/.::3FF.a).
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