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UV-Curable Nanocomposites Containing Zirconium

Vinylphosphonate or Zirconia
Lavinia Macarie,1 Nicoleta Plesu,1 Smaranda Iliescu,1 Adriana Popa,1 Gheorghe Ilia1,2
1
Institute
2

of Chemistry Timisoara, Timisoara 300223, Romania
Faculty of Chemistry-Biology and Geography, West University, Timisoara 300115, Romania

Received 28 July 2009; accepted 31 May 2010
DOI 10.1002/app.32881
Published online 23 August 2010 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: UV-cured nanocomposite films were prepared from acrylic monomer and two types of nanomaterial: zirconium vinylphosphonate and zirconia, in the
presence of a photoinitiator. The films were characterized
by FTIR, SEM, and AFM. FTIR spectra showed the disappearance of band assigned to the C¼
¼C group both of
monomer and zirconium vinylphosphonate by polymerization and the presence of the phosphonate group in
polymer. The influence of zirconium vinylphosphonate

and zirconia content on thermooxidative degradation of
polymeric films was studied by thermogravimetry. SEM
and AFM images showed that nanomaterials are dispersed in polymer matrix with no macroscopic phase
C 2010 Wiley Periodicals, Inc. J Appl Polym Sci
separation. V

INTRODUCTION

The nanosized inorganic components are usually
incorporated into monomer or polymeric matrices
by physically blending. A major problem with nanosized particles is their homogeneous dispersion
within the organic matrix avoiding macroscopic
phase separation. To obtain a better compatibility
between the filler and the host polymeric material
and achieve coatings with high content of inorganic
particles, the use of coupling agents such as low molecular weight trialcoxysilanes as the precursor for
sol–gel reactions is recommended.24–28
The organic–inorganic polymer nanocomposites
have been prepared by various methods depending on the type of monomers and nanomaterials:
bulk polymerization,29,30 photoinitiated polymerization,6,10,14,16,17,24,28 emulsion polymerization,31
in situ thermal polymerization,11,32 or copolymerization in solution,6,33 by blending the polymer
with nanoparticles.34
Among these methods, the use of ultraviolet light
and photoinitiators to produce polymeric films is one
of the most rapid and advantageous method.35,36
UV curing technology is attractive from environmental point of view because the photopolymerizable systems are free of organic solvents. Technical
advantages are also significant: e.g., low energy consumption and low temperature operation (room
temperature) as well as the possibility of curing
coatings on sensitive substrates such as wood, paper,
and plastics.37
In this article, the obtaining and characterization
of UV-curable epoxy acrylate polymers as nanocomposite films containing zirconium vinylphosphonate

Organic–inorganic polymer nanocomposites have
been developed in recent years1 as new materials
with enhanced mechanical properties including
hardness, resistance to scratching and abrasion, and
high chemical resistance.
Polymer nanocomposite are two phase materials
consisting of organic polymeric matrix and inorganic
nanosized materials, combining the organic and
inorganic characteristics at the molecular level.
Therefore, a blending of singular physical properties
can be achieved. Nanocomposite materials have successfully been applied in many fields such as protective coatings, plastic processing, optics, electronics,
textiles, medicine, etc.
Different metal oxides nanoparticles, such as SiO2,
TiO2, ZnO, CeO2,2–9 ZrO2,10–13 Al2O314 can be
employed as fillers, to obtain nanostructured materials. Also, composite materials were reinforced
with clays such as montmorillonites, modified, or
unmodified.15–18
The morphology and properties of polymer composites depend on the type of incorporated nanoparticles, their size and shape, their concentration, and
interactions with the polymer matrix.19–23

Correspondence to: G. Ilia (ilia@acad-icht.tm.edu.ro
gheilia@yahoo.com).

or

Journal of Applied Polymer Science, Vol. 119, 1820–1826 (2011)

C 2010 Wiley Periodicals, Inc.
V

119: 1820–1826, 2011

Key words: nanocomposite; zirconium vinylphosphonate;
zirconia; UV-curable resins

Thus. to investigate the homogeneity of the coatings. RESULTS AND DISCUSSION The photoinitiator Darocure 4265 produced after UV-irradiation radicals able to react with C¼ ¼C group. Zirconium vinylphosphonate (ZrVP) hybrid material was obtained by hydrothermal method according to Ref. Photoinitiator Darocure 4265 containing 50% 2hydroxy-2-methyl-1-phenyl-propan-1-one and 50% 2. the ZrVP is incorporated into the network by chemical bonding. commercial product as Photomer 3016F (PHA) (Cognis. Curing procedure The various photopolymerizable formulations were obtained from monomer. The wet films were exposed to medium-pressure mercury vapour lamp (maximum power 120 W cm1. Journal of Applied Polymer Science DOI 10.versus monomer mass. 10. and 15% content. Romania).74 94. Characterization Fourier transform infrared spectra (FTIR) of the monomer and polymers were recorded. following the band attributable to the phosphonic groups and decrease of the band attributable to the C¼ ¼C group. with high viscosity.UV-CURABLE NANOCOMPOSITES hybrid material (ZrVP) and zirconia (ZrO2) nanoparticles are reported. using Model Jasco FT/IR-4200 apparatus.51 96. The nanomaterials are dispersed in monomer. Figure 1 FTIR spectra of monomer PHA. belt speed 3 m min1). ZrO2 (doped with 4% mol Y2O3) nanoparticles with size lower than 100 nm.46 93. and polymer ZrVP-PHA 10%.50 94. at room temperature. The nanocomposite films were characterized by FTIR spectroscopy. in KBr pellet. both of the monomers and ZrVP.48 The gel content was determined on cured films by measuring the mass loss after 24 h extraction with dichloromethane.4. The pendulum hardness was evaluated on photocured films with Koenig pendulum according with ASTM D4366-95. Switzerland) was used at 4 wt % versus monomer. without covalent bonds38 in the case of zirconia and with covalent bonds between components in the case of zirconium vinylphosphonate hybrid material. For adjusting proper viscosity of this resin. The nanomaterial was dispersed in the dispersing agent and added to the liquid monomer at 5. Basel. SEM analyses were performed using Inspectes apparatus. synthesized by hydrothermal method.1002/app .83 91. 39 and 40 at nanosized scale. with a heating rate 108/min from ambient temperature to 7508C. to yield an insoluble network. using TGA/SDTA 851-LF 1100Mettler aparatus. As a dispersing agent was used the commercial product Dispersant 182 (Azur SA. using ultrasonic bath at 358C. in the presence of air. The formulation was laid on glass panel and PTFE plates using a film applicator to obtain film of about 100 lm. The photocured films are characterized by a high gel content values (Table I) indicating the formation of almost completely insoluble network and therefore confirming the efficiency of UV-initiated polymerization. photoinitiator. polyglycolether. Monheim. 5 wt % of monomeric diluter trimethylolpropane tryacrylate as Photomer 4006 F (Cognis) was added. 1821 TABLE I Polymer Content of Nanocomposite Films Film Gel content (%) PHA ZrVP-PHA 5% ZrVP-PHA 10% ZrVP-PHA 15% ZrO2-PHA 5% ZrO2-PHA 10% ZrO2-PHA 15% 98.6-trimethylbenzoyl-diphenyl-phosphine oxide (Ciba Specialty Chemicals. Timisoara. due to the polymerization. by bonding monomer and vinylphosphonate. and thermogravimetric analysis.10 96. Germany). EXPERIMENTAL Materials The starting monomer was an epoxyacrylate oligomer. was provided by National Research Institute for Nonferrous and Rare Metals Bucharest. and nanomaterial. ZrVP. and AFM images were performed by Nanosurf easy Scan 2 Advanced Research AFM. AFM. SEM. The cured nanocomposite films were analyzed by TGA to record their thermal stability at different content of nanomaterial.

and 981. and 15% content. because the polmerization occured.7 cm1 are assigned to C¼ ¼C group in ZrVP. 10.6 cm1 and 1407.42 The absorption at 1626.5 cm1 assigned to the C¼ group and at 1720. ZrVP.1822 MACARIE ET AL. .41 The absorption at 1047. Thermal properties of the films Figure 2 shows TG-DTA curves of the pure PHA polymer film and films containing ZrVP of 5. and polymer ZrVP-PHA 10% are shown.1 cm1 is attributed to the phosphonate group of ZrVP. the spectra of the monomer PHA.8 cm1 are also identified. from room temperature to 7508C. IR spectra of the films In Figure 1.1 cm1 to C¼ ¼O of acrylate. The presence of absorption band assigned ¼O to phosphonate group at 1052. The FTIR spectrum of the polymeric film ZrVPPHA 10% showed the decrease of the absorption Journal of Applied Polymer Science DOI 10. The possible chemistry43 related in the polymeric films can be revealed by Scheme 1.3 cm1.9 cm1 and to C¼ group at 1730.1002/app bands attributed to C¼ ¼C. Scheme 1 Copolymerization of acrylic monomers with zirconium vinylphosphonate. in dry air.7 cm1. The monomer presents absorption bands at 1609. ¼C 1407.

when a small mass loss of around 8.28C.9 300.38C and 710.2 309.2 440. removal of unreacted monomers. the first region of thermograms shows the low mass loss in the range of 6.02 7.44 The second region is in the temperature domain between 308. The thermal behavior of PHA.4 60. especially in the case of ZrO2-PHA when Tg were significantly enhanced (Table II). it can be assumed that the polymer PHA is stable till 308.0 313. when a major mass loss of 39. and the decomposition occurs above this temperature.1 228.4 46.5 39. The third region is between 441.1 38.2 448.6 78. For PHA film.5 62.38C.9 232. we assume that the enhanced glass transition temperatures resulted from the restricted motion of the polymer chains that was caused by the random polymerization of the ZrVP units in the polymer chain.0 37. although the polymerization of ZrVP in polymer chain was occured. Practically.2 63.38C with another major mass loss of 52% attributed to the degradation of the polymeric chain by a complex oxidative processes. This can be attributed to the desorption of humidity. due to the decomposition of polymer.7 39. the glass transition temperatures of the nanocomposites increased.3 246.5 47.1 52 48.5 33.3 5.8 48.3 37.28C. In the case of ZrVP-PHA nanocomposites.57 11.7 445. attributed to the removal of dispersant.UV-CURABLE NANOCOMPOSITES 1823 Figure 2 TG-DTA curves of thermal analysis of films containing ZrVP at 5.7 197.5% is observed.3 309. ZrVP-PHA and ZrO2-PHA at different nanomaterial content can be divided in three regions.3 446.8 49. In the case of films with ZrVP and ZrO2 content. This Tg depression is in accordance with literature data46 and could be attributed to the influence of the increased content of the low molecular weight species. and 15% content in comparison with PHA polymer. 10. The results of thermal behavior of nanocomposites are presented in Table II.3 Journal of Applied Polymer Science DOI 10.9 310.28C and 441.45 In the case of ZrO2-PHA nanocomposites. only a slight increase of decomposition temperatures Tdec1 and Tdec2 was noticed.4 0. we selected the temperature when the 5% mass is lost (Td-5%) as a comparison point. Also. it can be observed that the first region is from room temperature to 308.2 10.5–8%.2% occured.3 44. and structural decomposition of the epoxy groups from monomer.7 Mass loss (%) Tdec2 ( C) Mass loss (%) Reziduu (%) 39. In comparison with PHA polymer.9 62.3 57.3 234. This may be TABLE II TGA Data for the UV-Cured Nanocomposites Sample Tg ( C) Td-5% ( C) PHA ZrVP-PHA 5% ZrVP-PHA 10% ZrVP-PHA 15% ZrO2-PHA 5% ZrO2-PHA 10% ZrO2-PHA 15% 56.9 5.8 271.6 Tdec 1 ( C) 308.5 184. it can be observed the unexpected decrease of the Tg as loading is more.4 436. unreacted monomers.3 439. or humidity.8 441.2 8.1002/app .5 310. In the case of ZrVP-PHA polymer.

and ZrO2-PHA films are relatively opalescent. the thermal behavior of the obtained nanocomposites showed an increase of temperature when Journal of Applied Polymer Science DOI 10. 5% mass loss occured in comparison with neat polymer. When the resin has a lower reactivity. . but not on the PTFE plates from which they can be peeled and analyzed.1824 MACARIE ET AL. because in this case. Also. which presents a homogeneous texture. respectively. The uneven variation of decomposition temperatures Tdec1 and Tdec2 of nanocomposites containing ZrO2 can be explained by the influence of two factors which have opposite influences on the thermal behavior. The film were very adhesive on the glass plates. The second factor reffers to the fact that the decomposition temperature increases with the increase of inorganic material content. the decomposition temperature decreases to 300. For 15% ZrO2 content.74% for 10% ZrO2. that means the formation of the homogeneous phase between organic and inorganic components. it is known that a longer polymer chain is less stable thermally than a shorter chain. Figure 3 shows the SEM images of ZrVP. for 5% content of ZrO2. (b) SEM image of the film containing ZrO2-PHA 5%. the higher content of inorganic material overcomes the influence of the decrease of the crosslinking density. The film containing ZrVP. Appearance of the films Figure 3 SEM image of the ZrVP. This is also supported by the solubility results (Table I). the decomposition temperature increases to 310. and. the addition of inorganic material like zirconium oxide decreases the curing reactivity of epoxy resin.1002/app By visual investigation. First. Figure 4 (a) SEM image of the film containing ZrVP-PHA 5%. Figure 4(a.21 so the nanocomposites are easier to degrade than the neat epoxyacrylate resin. The gel content decrease from 96. as a result.98C is close to the polymer PHA decomposition temperature of 308.b) shows the SEM images of the polymeric film of PHA containing 5% ZrVP (a) and 5% ZrO2 (b). the decomposition temperature of 309. the ZrVP-PHA films are colourless and transparent. In the case of 10% content. due to the presence of organic functional group in the ZrVP molecule that has low decomposition temperature (<3108C). The decomposition temperatures of the epoxyacrylate nanocomposites are slightly influenced by addition of nanomaterials at different content. Hence. it results a lower crosslinking density of the cured resin and the longer polymer chains among the crosslinking points.28C.58C. the influence of the decrease of crosslinking density could not be overcome by the influence of the increase of ZrO2 content.78C.46% for 5% to 93. Therefore. by adding ZrVP and ZrO2 to epoxyacrylate resin. because the influence of the inorganic amount predominates the influence of the decrease crosslinking density.

1002/app . which is chemical bonded to polymer. however. (b) AFM images at 2. 6).b) shows the AFM images of ZrVPPHA 5% (a) and ZrO2-PHA 5% (b) films.3 lm2 surface of the films ZrVP-PHA 5%. has a dense and more homogeneous structure in comparison with the film containing ZrO2. Mechanical film properties The Koenig pendulum hardness test measured the surface hardness of the films laid on glass panel (Fig.3  2. the film hardness increased in comparison with PHA film. CONCLUSIONS Transparent ZrVP-PHA and opalescent ZrO2-PHA nanocomposite films were prepared by photoinitiated polymerization (photoinitiator Darocure 4265) of formulations containing epoxyacrylate oligomer and Zr-vinylphosphonate or ZrO2 nanomaterials at different content. in the latter case.UV-CURABLE NANOCOMPOSITES 1825 Figure 5 (a) AFM images at 2. where the inorganic nanoparticles are physically included in polymer matrix. with no macroscopic phase separation. The images show that the organic and inorganic phases are dispersed. the values of the pendulum hardness are higher than ZrVP-PHA films due to the intrinsic hardness of ZrO2.3 lm2 surface of the films ZrO2-PHA 5%. The film containing ZrVP is more homogeneous than film containing ZrO2. The FTIR spectra suggested that zirconium vinylphosphonate was covalent bonded to monomer to form a cross-linked network polymer (by disappearance of the band assigned to C¼ ¼C around 1400 cm1). By adding ZrVP and ZrO2. The film containing 15% ZrVP presents a moderately lower hardness in comparison with 5% and 10% content. Figure 5(a. Although the thermal analysis showed that the ZrO2-PHA polymeric films have lower thermal stability. SEM and AFM images showed that zirconium phosphonate hybrid and inorganic Journal of Applied Polymer Science DOI 10. the inorganic material is uniformly embedded in the polymer matrix on nanometric scale.3  2.

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