An investigation of the infrared (IR) spectra of polyoxymethylene (POM) mold plates was undertaken to determine the sub-micron-scale morphology and molecular orientation. The nest-structured cells concerned with the orientation were observed from scanning electron microscope (SEM) measurements with the aid of Raman spectroscopy. The intensity of the anomalous IR reflectance peak of the C–O stretching A2 mode depends on the widths of the POM layers in the SEM image along the orientation direction. The results suggest that the spectral features originate from the Berreman effect of the bulk polaritons and the radiative surface polaritons. Moreover, the IR spectra of certain treated samples suggest that enhancement of the electromagnetic fields from the gap modes and transition dipole–dipole coupling influence the spectral shapes.
TerlemezyanL.MihailovM.SchmidtP.“Conformational Changes of Poly(oxymethylene) Induced by Pressure and Mechanical Treatment”. Makromol. Chem1978; 179(3): 807–813.
2.
TerlemezyanL.MihailovM.“Dependence of the Conformation of Nascent Poly(oxymethylene) on the Conditions of Cationic Polymer: Cation of Trioxane in Solution”. Eur. Polym. J1981; 17: 1115–1120.
3.
OleinikE.F.EnikolopyanN.S.“Conformations and Molecular Structure of the Chains with (C–O)n Backbone”. J. Polym. Sci. Part C1968; 16(7): 3677–3683.
4.
ZamboniV.ZerbiG.“Vibrational Spectrum of a New Crystalline Modification of Polyoxymethylene”. J. Polym. Sci. Part C1964; 7(1): 153–161.
5.
KobayashiM.SakashitaM.HasegawaM.“Infrared and Raman Spectra of Macrocyclic Poly(oxymethylene)”. Macromolecules1991; 24(17): 4796–4800.
6.
KobayashiM.SakashitaM.“Morphology Dependent Anomalous Frequency Shifts of Infrared Absorption Bands of Polymer Crystals: Interpretation in Terms of Transition Dipole–Dipole Coupling Theory”. J. Chem. Phys1992; 96: 748–760.
7.
TanabeY.ShimomuraM.“A2 Mode Vibrations in Infrared Absorption Spectrum of Trigonal Poly(oxymethylene)”. Macromolecules1990; 23(23): 5031–5034.
8.
CarazzoloG.MammiM.“Crystal Structure of a New Form of Polyoxymethylene”. J. Polym. Sci. Part A1963; 1(5): 965–983.
9.
KobayashiM.MorishitaH.ShimomuraM.IguchiM.“Vibrational Spectroscopic Study on the Solid State Phase Transition of Poly(oxymethylene) Single Crystals from the Orthorhombic to the Trigonal Phase”. Macromolecules1987; 20(10): 2453–2456.
10.
IguchiM.“Growth of Needle-Like Crystals of Polyoxymethylene During Polymerization”. Br. Poly. J1973; 5(3): 195–198.
11.
IguchiM.MuraseM.“Polymorphosis of Poly(Oxymethylene) Crystals Grown in a Cationic Polymerization System of 1,3,5-Trioxane in Solution”. Makromol. Chem1975; 176(7): 2113–2126.
12.
UchidaT.TadokoroH.“Structural Studies of Polyethers. IV. Structure Analysis of the Polyoxymethylene Molecule by Three-Dimensional Fourier Syntheses”. J. Polym. Sci. Part A-21967; 5(1): 63–81.
13.
HexterR.M.“Intermolecular Couples of Vibrations in Molecular Crystals: A Vibrational Exciton Approach”. J. Chem. Phys1960; 33: 1833–1841.
14.
BornM.HuangK.Dynamic Theory of Crystal Lattices, New York: Oxford University Press, 1954. Sec. 8 in Chap.II.
15.
HopfieldJ.J.“Theory of the Contribution of Excitons to the Complex Dielectric Constant of Crystals”. Phys. Rev1958; 112: 1555–1567.
16.
UshiodaS.LoudonR.“Raman Scattering by Surface Polaritons”. In: AgranovichV.M.MillsD.L. (eds). Surface Polaritons, Amsterdam: North Holland, 1982, pp. 535–586.
17.
RuppinR.EnglmanR.“Optical Phonons of Small Crystals”. Rep. Prog. Phys1970; 33(1): 149–196.
18.
KliewerK.L.FuchsR.“Optical Modes of Vibration in an Ionic Crystal Slab Including Retardation. I. Nonradiative Region”. Phys. Rev1966; 144: 495–503.
19.
KliewerK.L.FuchsR.“Optical Modes of Vibration in an Ionic Crystal Slab Including Retardation. II. Radiative Region”. Phys. Rev1966; 150: 573–588.
20.
FuchsR.KliewerK.L.PardeeW.J.“Optical Properties of an Ionic Crystal Slab”. Phys. Rev1966; 150: 589–596.
21.
EnglmanR.RuppinR.“Optical Lattice Vibrations in Ionic Crystals: I”. J. Phys. C1968; 1: 614–629.
22.
EnglmanR.RuppinR.“Optical Lattice Vibrations in Finite Ionic Crystals: II”. J. Phys. C1968; 1: 630–643.
23.
EnglmanR.RuppinR.“Optical Lattice Vibrations in Finite Ionic Crystals: III”. J. Phys. C1968; 1: 1515–1531.
24.
BerremanD.W.UnterwaldF.C.“Adjusting Poles and Zeros of Dielectric Dispersion to Fit Reststrahlen of PrCl3 and LaCl3”. Phys. Rev1968; 174(3): 791–799.
25.
GervaisF.PiriouB.“Anharmonicity in Several-Polar-Mode Crystals: Adjusting Phonon Self-Energy of LO and TO Modes in Al2O3 and TiO2 to Fit Infrared Reflectivity”. J. Phys. C1974; 7(13): 2374–2386.
26.
ColeK.C.GuevremontJ.AjjiA.DumoulinM.M.“Characterization of Surface Orientation in Poly(ethylene terephthalate) by Front-Surface Reflection Infrared Spectroscopy”. Appl. Spectrosc1994; 48(12): 1513–1521.
27.
KittelC.Introduction to Solid State Physics, 8th ed. New Jersey: John Wiley &Sons, Inc., 2005. . Chap.14.
28.
BerremanD.W.“Infrared Absorption at Longitudinal Optical Frequency in Cubic Crystal Films”. Phys. Rev1963; 130: 2193–2198.
29.
NakajimaS.ToyozawaY.AbeR.The Physics of Elementary Excitations, Berlin: Springer-Verlag, 1980. Chap. 5.
30.
NagaiN.NishiyamaI.ShimadaH.ItoH.EndoK.“A New Approach to Investigate Thin Surface Layers of Polymers: Fatigue Analysis of Polycarbonate”. Appl. Spectrosc2013; 67(4): 420–432.
31.
BornM.WolfE.Principles of Optics, 7th ed. Cambridge, UK: Cambridge University Press, 1999. Chap.14.
32.
EconomouE.N.“Surface Plasmons in Thin Films”. Phys. Rev1969; 182: 539–554.
33.
OkamotoT.SimonenJ.KawataS.“Plasmonic Band Gaps of Structured Metallic Thin Films Evaluated for a Surface Plasmon Laser Using the Coupled-Wave Approach”. Phys. Rev. B2008; 77: 115425.
34.
RaetherH.Surface Plasmons on Smooth and Rough Surfaces and on Gratings, Berlin: Springer-Verlag, 1988, pp. 37–39.
35.
MieG.“Beiträge zur Optik trüber Medien, speziell kolloidaler Mettalösungen”. Ann. Phys1908; 330(3): 377–445.
36.
MeierM.WokaumA.“Enhanced Fields on Large Metal Particles: Dynamic Depolarization”. Opt. Lett1983; 8(11): 581–583.
37.
AravindP.K.MetiuH.“The Effects of the Interaction Between Resonances in the Electromagnetic Response of a Sphere-Plane Structure: Applications of Surface Enhanced Spectroscopy”. Surf. Sci1983; 124(2–3): 506–528.
38.
AravindP.K.NitzanA.MetiuH.“The Interaction Between Electromagnetic Resonances and its Role in Spectroscopic Studies Adsorbed on Colloidal Particles or Metal Spheres”. Surf. Sci1981; 110(1): 189–204.
