Langmuir 2005, 21, 8495-8501 8495

Nanoparticles of Mg(OH)2: Synthesis and Application to

Paper Conservation
Rodorico Giorgi,† Claudio Bozzi,‡ Luigi Dei,† Chiara Gabbiani,†
Barry W. Ninham,† and Piero Baglioni*,†
Department of Chemistry and CSGI, University of Florence, via della Lastruccia 3,
Sesto Fiorentino, 50019 Florence, Italy, and Stazione Sperimentale, Carta Cartoni e Paste per
Carta, SSCCP, I-20133 Milan, Italy

Received March 2, 2005. In Final Form: June 22, 2005

We report an investigation on the effects of counterions of magnesium salts on the homogeneous phase
precipitation reaction to yield nanoparticles. The results provide new parameters to guide the control of
the size, monodispersity, crystallinity, and morphology of Mg(OH)2 nanoparticles. Evidence emerged that
magnesium counterions affect the size of crystallites. The particle size increases from about 50 to 200 nm
and follows the Hofmeister anion series: sulfate < chloride < nitrate e perchlorate. All of the results show
that a proper choice of counterion and composition of reaction mixture allows one to modulate and set
conditions that predetermine production of nanoparticles with desired size. The Mg(OH)2 nanoparticles
have been applied to the successful conservation of paper. To demonstrate the efficacy of nanoparticles
as deacidifying agent and as protection against cellulose aging, some samples of paper from the 18th
century were treated with the nanoparticles and artificially aged by subjecting them to hydrothermal and
photooxidative degradation. The treatment with nanoparticles preserved the mechanical features of paper,
and the deterioration was consistently reduced. The comparison with the Wei t’O method (based on
magnesium alkoxides), one of the most common and largely used methods for paper deacidification, indicates
the following: (1) nanoparticles present a higher efficacy in the deacidification treatment since they are
much more reactive; (2) nanoparticles are less aggressive since they are easily converted into the carbonate
form; (3) they present minor disadvantages related to the chemical nature of the solvent used in the Wei
t’O (i.e., CFC); (4) papers/books can be treated with very simple procedures, and do not require any special
apparatus; (5) nanoparticle treatments have substantial economic benefits.

Introduction dependent on the first two methods.15-17 When magnesium

Several methods have been exploited for nanoparticle
synthesis. These include the reverse micelle route,1-4
microemulsions and flame spraying of microemulsions,5
precipitation from solutions at high temperature,6,7 and
hydrothermal treatment of solutions.8,9 Magnesium hy-
droxide (brucite) nanoparticles can be obtained by hydra-
tion of magnesium oxide, MgO,9-11 by precipitation of a
magnesium salt with an alkaline solution,12-14 and by the
electrolysis of an aqueous magnesium salt solution.
Industrial production of magnesium hydroxide is usually
* To whom correspondence should be addressed: Phone:
+390554573033. Fax: +390554573032. E-mail: baglioni@
csgi.unifi.it.
† University of Florence.
‡ SSCCP.
(1) Pileni, M. P. Langmuir 1997, 13, 3266.
(2) Lisiecki, I.; Pileni, M. P. Langmuir 2003, 19, 9486.
(3) Lisiecki, I.; Pileni, M. P. J. Am. Chem. Soc. 1993, 115, 3887.
(4) Sangregorio, C.; Galeotti, M.; Bardi, U.; Baglioni, P. Langmuir
1996, 12, 5800.
(5) Bonini, M.; Bardi, U.; Berti, D.; Neto, C.; Baglioni, P. J. Phys.
Chem. B 2002, 106, 6178.
(6) Ambrosi, M.; Dei, L.; Giorgi, R.; Neto, C.; Baglioni, P. Langmuir
2001, 17, 4251.
(7) Perez-Maqueda, L. A.; Wang, L.; Matijevic, E. Langmuir 1998,
14, 4397.
(8) Yu, J. C.; Xu, A.; Zhang, L.; Song, R.; Wu, L. J. Phys. Chem. B
2004, 108, 64.
(9) Ding, Y.; Zhang, G.; Wu, H.; Hai, B.; Wang, L.; Qian, Y. Chem.
Mater. 2001, 13, 435.
(10) Laska, M.; Valtyni, J.; Fellner, P. Cryst. Res. Technol. 1993, 28,
931.
(11) Feitknecht, W.; Braun, H. Helv. Chim. Acta 1967, 50, 2040.
(12) Packter, A. Cryst. Res. Technol. 1985, 20, 329.
(13) Copperthwaite, M.; Brett, N. H. Sci. Ceram. 1976, 8, 85.
(14) Baird, T.; Braterman, P. S.; Cochrane, H. D. J. Cryst. Growth
1988, 91, 610.
hydroxide powder is used as a precursor for magnesium
oxide synthesis, its particle size, shape, and agglomeration
level constitute key parameters in several applications.
An example is the sintering step in the processing of
ceramics. Inorganic hydrates are commonly used in flame-
retardant composite formulations due to their ability to
undergo endothermic dehydration in fire conditions.18,19
There is a growing interest in magnesium hydroxide as
a flame-retardant filler that does not evolve toxic and
corrosive substances upon combustion.
Magnesium-based alkaline compounds also have great
importance in the field of cultural heritage conservation.
One such area with which we are concerned is in the
preservation of old acidic papers by deacidification treat-
ment. Acid-catalyzed hydrolysis of cellulose is the main
source of paper degradation. It is well-known that the
evolution of the papermaking procedures resulted in paper
of poorer quality. At the beginning of the 18th century,
the papermaking changed production technologies and
paper was made with more reactive materials (wood pulp)
and with acid substances (rosin, used for the “sizing”).
These substances, over a long time period of environmental
conditions (i.e., temperature, moisture in the paper, light),
accelerate the chemical deterioration of paper. The overall
effect is the rapid decrease in the resistance to degradation
of paper documents, especially for modern paper.20-23
(15) US 3.787.558 to Steetley Ltd., 1974.
(16) US 5.872.169 to Flamemag International Gie, 1999.
(17) US 4.229.423 to Kaiser Aluminium & Chemical Co., 1980.
(18) Rothon, R. N. In Particulate-Filled Polymer Composites; Rothon
R. N., Ed.; Longmans: Harlow, UK, 1995; Chapter 6.
(19) Rothon, R. N.; Hornsby, P. R. Polym. Degrad. Stab. 1996, 54,
383.

10.1021/la050564m CCC: $30.25 © 2005 American Chemical Society

Published on Web 08/06/2005
8496 Langmuir, Vol. 21, No. 18, 2005
There is a general consensus that deacidification
treatment is unavoidable in the preservation of paper.
Deacidification provides a complete neutralization of paper
and, in most cases, introduces an alkaline reservoir that
opposes the incoming assault from the acidity present in
the environment (i.e., pollution). This is the reason for
the large number of studies dealing with the development
of procedures to eliminate acidity from paper.24-26 The
best methods for paper deacidification are based on the
use of nonaqueous solvents. Less polar fluids minimize
the risk of ink solubilization. Among these, the most
important are the Wei t’O25 and Bookkeeper26 methods.
Recently, we have proposed a new method based on the
use of calcium hydroxide nanoparticles in alcohols that
provided excellent results for paper deacidification.24 We
extend here the previous investigation to the synthesis
and application of nanoparticles of magnesium hydroxide
(brucite) nanoparticles since it has been recently dem-
onstrated that magnesium carbonate reduces the rate of
oxidative degradation of cellulose substrates caused by
light irradiation.27 Both the Wei t’O and Bookkeeper
methods are based on the use of magnesium compounds
that generate magnesium hydroxide in situ after hy-
drolysis. Unfortunately, some studies have demonstrated
a limited homogeneity in the distribution of the alkaline
reserve.28 Our aim was to synthesize magnesium hydrox-
ide nanoparticles, by following procedures similar to those
successfully used for calcium hydroxide.24 Differently to
the Wei t’O and Bookkeeper methods, these nanoparticles
once delivered on the paper are immediately available for
the deacidification or buffering on the paper (vide infra).
Research on new synthetic pathways for Mg(OH)2 nano-
particle production is therefore assuming a high profile
in both pure and applied research. Several papers have
reported that the precipitation of metal hydroxides from
corresponding salt solutions is strongly affected by a
variety of parameters. These include reaction temperature,
concentration of reacting species, and aging time.29-35 In
particular, it has been shown35 that temperatures above
100 °C promote the formation of nanosized particles in
nonaqueous media. Also, some studies report significant
effects of organic solvents on the shape and size of the
particles obtained by precipitation.7,36,37
(20) Barrow, W. J. Permanence/Durability of the Books VII. Physical
and Chemical Properties of the Book Papers, 1507-1949; W. J. Barrow
Research Laboratory, Inc.: Richmond, VA, 1974.
(21) Whitmore, P. M.; Bogaard, J. Restaurator 1994, 15, 26.
(22) Ryder, N. The Conservator 1986, 10, 31.
(23) Orr, R. S.; Weiss, L. C.; Humphreys, G. C.; Mares, T.; Grant, J.
N. Text. Res. J. 1954, 24, 399.
(24) Giorgi, R.; Dei, L.; Ceccato, M.; Schettino, C. V.; Baglioni, P.
Langmuir 2002, 18, 8198.
(25) Smith, R. D. Mass Deacidification at the Public Archives of
Canada. Conservation of Library and Archive Materials and the Graphic
Arts; Butterworth: London, 1987.
(26) Preservation Technologies, L.P., Bookkeper Process, U.S.; http://
www.ptlp.com.
(27) Malesic, J.; Kolar, J.; Strlic, M.; Kocar, D.; Fromageot, D.;
Lemaire, J.; Haillant, O. Polym. Degrad. Stab. 2005, 89, 64.
(28) Liénardy, A. Restaurator 1994, 15, 1.
(29) Henrist, C.; Mathieu, J.-P.; Vogels, C.; Rulmont, A.; Cloots, R.
J. Cryst. Growth 2003, 249, 321.
(30) Wilhemy, D. M.; Matijevic, E. J. Chem. Soc., Faraday Trans. 1
1984, 80, 563.
(31) Hsu, P.; Ronnquist, L.; Matijevic, E. Langmuir 1988, 4, 31.
(32) Matijevic, E.; Scheiner, P. J. Colloid Interface Sci. 1978, 63,
509.
(33) Hamada, S.; Kudo, Y.; Minagawa, K. Bull. Chem. Soc. Jpn. 1990,
63, 102.
(34) Sugimoto, T.; Matijevic, E. Colloid Interface Sci. 1980, 74, 227.
(35) Yura, K.; Fredrikson, K. C.; Matijevic, E. J. Colloids Surf. A
1990, 50, 281.
(36) Hamada, S.; Matijevic, E. J. Chem. Soc., Faraday Trans. 1 1982,
78, 2147.
(37) Matijevic, E.; Cimas, S. Colloid Polym. Sci. 1987, 265, 155.
Giorgi et al.
We report here the preparation and the characterization
of nanosized crystals of Mg(OH)2 by hydrolyzing magne-
sium salt solutions, bearing different counterions, through
the addition of aqueous solutions of sodium hydroxide at
elevated temperatures. The particles obtained were
characterized by determining the chemical nature (Fourier
transform infrared (FTIR) spectroscopy), the specific
surface area (SA) of the dry powders, the crystallinity
(X-ray diffraction (XRD)), and the shape/size character-
istics (scanning and transmission electron microscopy
(SEM and TEM)). The application to paper deacidification
and the comparison with the classical Wei t’O method are
pursued and highlighted in what follows.
Experimental Section
A. Materials. Magnesium chloride dihydrate, magnesium
nitrate, magnesium sulfate, magnesium perchlorate, sodium
hydroxide, and 2-propanol proanalysis products were obtained
from Merck (Darmstadt, Germany) and used without further
purification. Water was purified by a Millipore Organex system
(R g 18 MΩ cm).
B. Synthesis of the Particles. Nanosized Mg(OH)2 particles
were prepared by chemical precipitation in supersaturated
aqueous solutions of the reactants. Magnesium chloride (or
nitrate, or sulfate, or perchlorate) and sodium hydroxide were
first dissolved in deionized water to form 0.2, 0.4, 1, and 2 M
aqueous solutions, respectively. Equal amounts of salt solutions
were separately preheated to the synthesis temperature (25 and
90 °C in water) and then mixed under vigorous stirring. After
ripening for 1 h, the precipitates were recovered by centrifuge
and then washed with water. At least five cycles of washing and
centrifuging were required to ensure complete removal of the
sodium chloride byproduct. Philips et al.38 have showed that a
brief process of washing with distilled water caused no significant
change in particle size or shape, due to the low solubility of
magnesium hydroxide. The particles were dried under nitrogen
atmosphere and redispersed in 2-propanol or in a mixture of
fluorinated hydrocarbons.
C. Physicochemical Characterization. The chemical com-
position of the materials obtained was determined by FTIR
spectroscopy with a BioRad FTS-40 spectrometer. The spectra
were recorded from 600 to 4000 wavenumbers at 4 cm-1 resolution
averaging 64 scans. The magnesium hydroxide powders used for
FTIR measurement were dried under vacuum in an oven at 70
°C for 24 h. Small amounts of Mg(OH)2 powders were blended
with KBr under nitrogen atmosphere and pressed into disks for
the measurement. The phase composition and crystallinity of
the “as prepared” magnesium hydroxide particles were analyzed
by X-ray diffraction (XRD) using an X-ray Diffractometer Philips
PW 1830 generator equipped with a Cu KR (λ ) 1.54 Å) source.
About 1 mg of the dried Mg(OH)2 particles was deposited as
randomly oriented powder onto a Plexiglass sample container,
and the XRD patterns were recorded at a scan rate of 2°/min,
under nitrogen.
Traditionally, the broadening of peaks in the powder’s XRD
patterns of polycrystalline solids is attributed to particle size
effects. The mean crystallite size of a powder sample was
estimated from the full-width at half-maximum (fwhm) of the
diffraction peak by the Scherrer equation:
0.89λ ) L(B(2θ) × cos θ)-1
Here, B(2θ) is the width of the X-ray pattern line at half peak-
height in radians; λ is the wavelength of the X-ray (1.54 Å for
the Cu KR); θ is the angle between incident and diffracted beams
in degrees, and L is the crystallite size of the powder samples
in angstroms. The use of the Scherrer formula to estimate particle
size is widely used, especially in the study of nanoparticulate
materials.39 The morphology and size of the particles were studied
by a transmission electron microscope, TEM (Philips EM201C
(38) Phillips, V. A.; Kolbe, J. L.; Opperhauser, H. J. Cryst. Growth
1977, 41, 228.
(39) Jenkins, R.; Snyder, R. L. Introduction to X-ray Powder Dif-
fractometry; John Wiley & Sons: New York, 1996.
Nanoparticles of Mg(OH)2 for Paper Conservation Langmuir, Vol. 21, No. 18, 2005 8497

Table 1. Composition and Reaction Conditions of the

Different Samples
reaction base temperature
pathway Mg2+ source precipitant (°C) solvent
route 1 0.2 M MgCl2 0.4 M NaOH 25 water
route 2 0.2 M Mg(ClO4)2 0.4 M NaOH 90 water
route 3 1 M Mg(ClO4)2 2 M NaOH 90 water
route 4 0.2 M Mg(NO3)2 0.4 M NaOH 90 water
route 5 1 M Mg(NO3)2 2 M NaOH 90 water
route 6 0.2 M MgCl2 0.4 M NaOH 90 water
route 7 1 M MgCl2 2 M NaOH 90 water
route 8 0.2 M MgSO4 0.4 M NaOH 90 water
route 9 1 M MgSO4 2 M NaOH 90 water

apparatus operating at 80 kV). The samples were placed onto

carbon-coated copper grids supplied from Taab Chemicals &
Equipment for Microscopy Ltd., U.K. The mean size of the
particles in the dry powder was determined on a large number
of particles (>300) from the analysis of TEM micrographs. The
particle morphology was observed by scanning electron micros-
copy (SEM) on a Philips 515 microscope after coating the sample
with a very thin gold layer deposited by sputtering under vacuum.
Surface area measurements were determined from BET on a Figure 1. Surface area (SA) data obtained from N2 adsorption
Coulter SA 3100 surface area analyzer, under N2 flow. This gives on dry powders according to BET (error about 3%).
access to the value of the surface area directly with an error on
the order of 5%.
The study of the paper deacidification was performed in
collaboration with the paper conservation laboratory of the
Stazione Sperimentale Carta Cartoni e Paste per Carta, Milan.
Nanoparticles of Mg(OH)2 were used as alcohol dispersion (2-
propanol) and applied by brushing over the paper surface. To
test the efficacy of nanoparticle treatment in the deacidification
process and paper protection, we aged the paper using conven-
tional methods. In particular:
1. Photooxidation by XENOTEST was performed for 4 weeks
with a Heraeus 150s apparatus provided with a xenon arc lamp
with UV filter to simulate daylight (standard D65). Alternate
exposure to light was obtained by using a rotating platform for
the sample. Environmental temperature was kept at 45 ( 2 °C,
with air-cooling and the relative humidity (R.H.) at 65 ( 5%.
2. Samples were hydrothermally aged by keeping them for 2
weeks in an oven at 80 ( 2 °C and 65% R.H.
To quantify the state of degradation of the paper samples under
test, the degree of polymerization and tensile strength resistance
were also measured. The polymerization degree, DP, was
evaluated by intrinsic viscosity [η] measurements in cupryleth-
ylenediamine (CED) solution 0.5 M at 20 ( 0.1 °C, according to
the UNI 8282 procedure. The percentage of broken bonds (BB%)
was estimated according to the equation: BB% ) (2/DP - 2/DP0) Figure 2. Crystallite size obtained by the XRD peak broadening
× 100; where DP0 corresponds to the polymerization degree at analysis according to the Scherrer equation (error about 10%).
time zero (before the degradation process). Higher values of DP
correspond to nondegraded fibers; degradation leads to lower
DP and higher BB%. Tensile strength (TS) resistance was
to 90 °C). In addition, counterion type and concentration
obtained by a dynamometer. A set of 10 paper strips (250 × 25 also showed remarkable effects on some nanoparticle
mm size), previously aged at 25 °C and 50% R.H. for 24 h, was features, such as surface area, crystallite size, and size of
investigated. The estimated error is about 5%. The results the nanoparticles (see Figures 1-6).
obtained from papers treated with the Mg(OH)2 nanoparticles Figures 3a, 4a, and 5a show SEM pictures of magnesium
were compared with paper samples treated with the Wei t’O nanoparticles synthesized in water solution at 90 °C
method and with paper treated with calcium hydroxide nano- according to the composition reported in Table 1, routes
particles. 4, 6, and 8.
Nanoparticles are regularly shaped, and the size ranges
Results and Discussion from 200 nm (particles obtained from a magnesium
The chemical precipitation from aqueous solutions perchlorate solution) to about 50 nm (from a magnesium
provides a simple and cheap route for the synthesis of sulfate solution). TEM analysis provided evidence on the
magnesium hydroxide nanoparticles. Some reaction pa- crystal habitus of particles (hexagonally plated) and on
rameters explored in this study to control nanoparticle the size distribution of nanoparticles.
size were the temperature (see Table 1, routes 1 and 6), A precise mechanistic interpretation on the counterion’s
the counterion of the salt used as a magnesium ion source effect on the nanoparticle size is beyond the scope of this
(SO42-, Cl-, NO3-, ClO4-; see Table 1, routes 2, 4, 6, and work, but it can reasonably be inferred and postulated
8), and the concentration of salts (see Table 1, routes 3, that the surface charge of particles, the ionic adsorption
5, 7, and 9). Evidence for the effects of counterions on the on the surfaces, and the chemical nature of ions present
nucleation and growth of crystals is shown. The mean in solution all play a crucial role during crystal growth.
sizes of the resulting nanoparticles are, as expected, Surface area analysis on powders (see Figure 1) showed
strongly influenced by the temperature reaction (from 25 that perchlorate, nitrate, chloride, and sulfate ions act as
8498 Langmuir, Vol. 21, No. 18, 2005
Figure 3. SEM (a), TEM (b) pictures, and XRD pattern (c) of
Mg(OH)2 nanocrystals synthesized at 90 °C in water solution
using a nitrate magnesium source solution.
surface modifiers, so that the nucleation and growth of
crystal seeds are consistently and systematically influ-
enced. Specific surface area (SA) of particles synthesized
at 25 °C is low (33 m2/g) and significantly increases at 90
°C. In fact, the surface area of the particles prepared
following routes 2-9 (see Table 1) shows that SA ranges
from 60 to 120 m2/g, with a trend that is in accord with
the usual Hofmeister series for anions. The analysis of
Giorgi et al.
Figure 4. SEM (a) and TEM (b) pictures, and XRD pattern (c)
of Mg(OH)2 nanocrystals synthesized at 90 °C in water solution
using a chloride magnesium source solution.
the XRD patterns, according to the Scherrer method,
provided the crystallite size of particles (see Figure 2). All
the data confirmed the trend of the specific surface areas
(lower crystallite size, larger surface area). Nanoparticles
synthesized from magnesium perchlorate solution have
a mean crystallite size more than twice that from the
sulfate solution.
Nanoparticles of Mg(OH)2 for Paper Conservation
Figure 5. ESEM performed at 0.98 Torr (a), TEM (b), and
XRD pattern (c) of Mg(OH)2 nanocrystals synthesized at 90 °C
in water solution using a sulfate magnesium source solution.
The size distribution of nanoparticles was also obtained
from the analysis of TEM pictures. The size distribution
reported in Figure 6 confirms that counterions affect the
size distribution. In particular, the mean size of the
particles follows the Hofmeister series, that is, sulfate <
chloride < nitrate e perchlorate.
Langmuir, Vol. 21, No. 18, 2005 8499
The role of counterions is further evidenced by the effect
of the concentration (routes 3, 5, 7, and 9). Common sense,
by which we mean expectation based on conventional
theories, does not explain such differences. In fact, some
authors38,40 have determined the isoelectric point of
magnesium hydroxide particles in water, which is situated
at ca. pH 12. In the case of the synthesis with NaOH used
as the base, the pH reached in the reacting mixture during
synthesis is higher than 13. Therefore, the net residual
electric charge on the surface of the Mg(OH)2 nanoparticles
is expected to be negative. No effects should therefore be
expected through anion adsorption, but these counter-
intuitive effects are certainly real enough. Assuming that
high concentration salt solution promotes strong interac-
tion due to the net surface charge of particle and anions
present in solution, it turns out that the nucleation
processes, here involved, do seem to be affected by these
counterions and follow the Hofmeister series of anions.41
This means that a judicious choice of counterions and of
the solvent reaction mixture together allow modulation
of conditions for predetermining nanoparticles with desir-
able characteristics.
Finally, some tests have been carried out in order to
evaluate the efficacy of treatment for paper deacidification
based on magnesium hydroxide application of nanopar-
ticles. For this, all of the results are compared with those
provided by the traditional restorative Wei t’O (magne-
sium-methoxy methyl-carbonate, MMC) method.
Wei t’O and deacidification using nanoparticles of
magnesium (or calcium) hydroxide differ in the different
chemical pathway and kinetics. The Wei t’O method is a
two-step reaction, as highlighted in the scheme reported
below.
Wei t’O method
CH3OMgOCOOCH3 + 2H2O w Mg(OH)2 + 2CH3OH + CO2
Mg(OH)2 + 2CH3OH v + CO2 w MgCO3 (alkaline reservoir)
nanoparticles method
Mg(OH)2 + CO2 w MgCO3 (alkaline reservoir)
This method is based on magnesium-methoxy methyl-
carbonate solutions in ethyl or methyl alcohols and CFC
(chlorofluorocarbons). Magnesium-methoxy methyl-
carbonate needs to be hydrolyzed by moisture from the
paper and/or from the atmosphere before being activated.
Once activated, it induces neutralization of paper, even-
tually forming protective layers of magnesium carbonate.
By contrast, the nanoparticle treatment involves a single
step. The particles are chosen to be small enough to deeply
penetrate cellulose fibers, deacidify them, and react with
carbon dioxide to form the alkaline buffer (CaCO3).
Tables 2 and 3 summarize the results obtained for the
deacidified and aged samples, labeled according to the
deacidification method used, MMC for the Wei t’O and
Mg(OH)2 for nanoparticles. These are compared with those
of untreated materials. Table 3 also collects data referring
to the application of Ca(OH)2 nanoparticles. The degree
of polymerization and the evaluation of percentage of
broken bonds provide clear evidence on the relative efficacy
of the deacidification treatments. Data collected in Tables
2 and 3 show that deacidification treatments induce little
depolymerization effects on paper (the DP values slightly
decrease). This is probably due to the partial absence of
the sizing materials that prevent fibers from being in direct
contact with the environment. In fact, after deacidification,
the resizing of the paper with a dilute solution of cellulose-
based polymer is a commonly used procedure.
(40) Larson, T. E.; Buswell, A. M. Ind. Eng. Chem. 1940, 32, 132.
(41) Hofmeister, F. Arch. Exp. Pathol. Pharmakol. 1888, 24, 247.
8500 Langmuir, Vol. 21, No. 18, 2005 Giorgi et al.

Figure 6. Size distributions of magnesium hydroxide nanoparticles obtained from different magnesium counterions.

Table 2. Polymerization Degree (DP) and Broken Bonds Table 4. Mechanical Tests on Hydrothermally Aged
(BB%) of Hydrothermally Aged Samples (see Samples (see Experimental Section)
Experimental Section)a
samples TS (N) before ageing TS (N) after aging ∆TS (%)
Not treated MMC Mg(OH)2
not treated 15.5 6.9 -55
time (h) DP BB% DP BB% DP BB% MMC 14.4 10.9 -24
Mg(OH)2 11.00 10.9 -0.01
0 544 0 519 0 488 0
360 154 0.93 259 0.39 269 0.33
(-72%) (-50%) (-45%)
acts as a pH buffer and inhibits further degradation of
paper until present on the cellulose fiber. The improve-
a MMC refers to the paper samples treated with magnesium-
ments of the paper features provided by the deacidification
methoxy methyl-carbonate solution and Mg(OH)2 to the paper are clearly shown as a percentage variation of broken
samples treated with the nanodispersion.
bonds, which decreases from the untreated sample (0.93%)
Table 3. Polymerization Degree (DP) and Broken Bonds to the MMC and Mg(OH)2 nanoparticle treatments (0.39
(BB%) of Photodegraded Samples (see Experimental and 0.33%, respectively), for the hydrothermally aged
Section)a samples. Meaningful differences can be detected also for
Not treated MMC Mg(OH)2 Ca(OH)2 photooxidized samples. In this case, too, Mg(OH)2 nano-
dispersions and Ca(OH)2 produce better results than MMC
time (h) DP BB% DP BB% DP BB% DP BB%
solutions (0.26 vs 0.36% of MMC).
0 544 0 519 0 488 0 504 0 Mechanical tests highlight that deacidified and arti-
600 242 0.46 268 0.36 294 0.26 302 0.26 ficially aged papers retained good resistance to tensile
(-56%) (-48%) (-40%) (-40%)
strength. This is almost unchanged for the sample treated
a MMC refers to the paper samples treated with magnesium-
with a Mg(OH)2 nanodispersion, which provides better
methoxy methyl-carbonate solution, and Mg(OH)2 or Ca(OH)2 to results than MMC solution (see Table 4). On the other
the paper samples treated with the nanodispersion. hand, the nondeacidified sample showed a strong decrease
Mg(OH)2 nanodispersions in alcohol after a few days of in mechanical resistance after aging (-55%).
artificial aging (Tables 2 and 3) are the most effective, In most cases the nanoparticle method leads to better
although calcium hydroxide nanoparticles produce similar results than does the Wei t’O (MMC solution). Nanotech-
results (see Table 3). However, both nanoparticle systems nology provides an easy way to obtain hydroxide, which
seem to protect paper from degradation much better than is the intermediate product in the Wei t’O method. The
the Wei t’O method. This can be easily understood use of nanoparticles has a clear advantage in that it avoids
considering that nanoparticles are more reactive than the the first step of the whole reaction, which consists of the
chemical compounds used in conventional deacidification hydrolysis of MMC to produce hydroxide and the subse-
methods in both the processes necessary for a proper paper quent neutralization reaction.
conservation: the deacidification and the formation of Finally, we remark that nanoparticle application to
protective magnesium carbonate nanoparticles. This last paper is easier than conventional methods since nano-
Nanoparticles of Mg(OH)2 for Paper Conservation
particles can be applied by spraying, brushing, and
immersion, and their use does not require any special
safety procedures; the method is environmentally safe
and cheaper than the conventional methods for paper
deacidification.
Conclusions
Nucleation reactions in the homogeneous phase provide
several chemical pathways for obtaining magnesium
hydroxide (brucite) nanoparticles. A better control of
particle characteristics seems to be offered by judicious
choice of counterions of the magnesium salt solutions.
Evidence emerged that counterions of magnesium source
salts affect the size and the specific surface area of
crystallites with a trend that follows a Hofmeister series
of anions: (sulfate < chloride < nitrate e perchlorate).
This fact clearly opens up many possibilities for nano-
particle production.
The application of nanodispersions from organic solvents
for paper deacidification treatment was successful. Nano-
particles penetrate within the cellulose fibers of the paper
and neutralize the inherent acidity. This study reinforces
the view that natural aging of paper can be strongly
reduced. Deacidified paper seems to be more resistant
than the untreated samples to artificial aging. Probably,
the chemical reaction pathway of the degradation process
Langmuir, Vol. 21, No. 18, 2005 8501
is not changed, but the kinetics is certainly slowed
radically.
The comparison with a traditionally used method for
deacidification (Wei t’O) showed the higher efficacy of the
Mg(OH)2 and Ca(OH)2 nanoparticles in the deacidification
treatment. Some disadvantages shown by Wei t’O method,
basically related to the chemical nature of solvents and
the magnesium alkoxides employed, are completely
overcome by using nanoparticles. Mg(OH)2 and Ca(OH)2
nanoparticles show similar efficacy in protecting paper
against aging. Nanotechnologies have some economical
benefits also. These are mainly related to the very simple
nanoparticle synthetic pathway and to the application
procedure that does not require any special apparatus.
Acknowledgment. The authors acknowledge Prof.
Piergiorgio Malesani, Department of Earth Sciences at
the University of Florence, for useful comments of XRD
measurements, Dr. Massimo Ceccato for ESEM analysis
assistance, and Dr. Claudius Schettino for helpful as-
sistance in paper treatments. Financial support from
Consorzio Interuniversitario per lo Sviluppo dei Sistemi
a Grande Interfase (CSGI Florence) and MIUR (PRIN-
2003) is gratefully acknowledged.
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