• Journal of the Korean Vacuum Society
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• v.15 no.5
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• pp.527-533
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• 2006

Spinel $LiNi_xMn_{2-x}O_4$ thin films were synthesized up to x = 0.9 by a sol-gel method employing spin-coating. The Ni-substituted films were found to maintain cubic structure at low x but to exhibit tetragonal structure for $x{\geq}0.6$. Such cubic-tetragonal phase transition indicates that $Ni^{3+}(d7)$ ions with low-spin $(t_{2g}^6,e_g^1)$ state occupy the octahedral sites of the compound, thus being subject to the Jahn-Teller distortion. By x-ray photoelectron spectroscopy both $Ni^{2+}$ and $Ni^{3+}$ ions were detected. Optical properties of the $LiNi_xMn_{2-x}O_4$ films were investigated by spectroscopic ellipsometry (SE) in the visible?ultraviolet range. The measured dielectric function spectra by SE mainly consist of broad absorption structures attributed to charge-transfer (CT) transitions, $O^{2-}(2p){\rightarrow}Mn^{4+}(3d)$ for 1.9 $(t_{2g})$ and $2.8{\sim}3.0$ eV $(e_g)$ structures and $O^{2-}(2p){\rightarrow}Mn^{3+}(3d)$ for 2.3 $(t_{2g})$ and $3.4{\sim}3.6$ eV $(e_g)$ structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as due to d-d crystal-field transitions within the octahedral $Mn^{3+}$ ion. The strengths of these absorption structures are reduced by the Ni substitution. Rapid reduction of the CT transition strength involving the eg states for x = 0.6 is attributed to the reduced wavefunction overlap between the $e_g$ and the $O^{2-}(2p)$ states due to the tetragonal extension of the lattice constant by the Jahn-Teller effect.

• Korean Chemical Engineering Research
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• v.49 no.1
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• pp.75-82
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• 2011

Five different composition UV-cured poly(urethane acrylate-co-acrylic acid) (PU-co-AA) films have been prepared by reacting isophorone diisocyanate(IPDI), polycaprolactone triol(PCLT), 2-hydroxyethyl acrylate(HEA), and different weight ratio trimethylolpropane triacrylate(TMPTA) and acrylic acid(AA) as diluents, and characterized using a Fourier transform infrared spectroscopy(FT-IR). The adhesion properties onto the stainless steel, morphology, mechanical hardness, and electrical property of UV-cured PU-co-AA films were investigated as a function of acrylic acid(AA) content. All the PU-co-AA films are structure-less and the molecular ordering and packing density decreased with increasing content of AA due to the flexible structure and -COOH side chains in AA. The crosscut test showed that PU-co-AA films without AA and with low content of AA showed 0% adhesion(0B) and the adhesion of PU-co-AA films in the range of 40-50% AA increased dramatically as the content of AA increases. The pull-off measurements showed that the adhesion force of PU-co-AA films to stainless steel substrate varied from 6 to 31 kgf /$cm^2$ and increased linearly with increasing AA content. The mechanical hardness also decreased as the content of AA increases. This may come from relatively linear and flexible structure in AA and low crystallinity in PU-co-AA films with higher content of AA. The higher AA-containing PU-co-AA films showed higher dielectric constant due to the increase of polarization by introducing AA monomer. In conclusion, the physical properties of UV-cured PU-co-AA films are strongly dependent upon the content of AA and the incorporation of AA in polyurethane acrylate is very useful way to increase the adhesion strength of UV-curable polymers on the stainless steel substrate.