Thermal Analysis of the Poly(Siloxane)–Poly(Tetrafluoroethylene) Coating System

Thermal properties of poly(siloxane)–poly(tetrafluoroethylene) (SIL–PTFE) system were investigated, using Perkin Elmer DSC-7 differential scanning calorimeter and TGA-7 thermogravimetric analyzer. For SIL–PTFE compositions, one glass transition temperature T _g has been found, in accordance with the reciprocal rule up to about 40 mass% of PTFE. However, for higher PTFE contents, T _g values about –118 to –112°C were observed that can be ascribed to motions of cross-linked SIL structures. Endo- and exothermic transitions, found in the range from 70 to 290°C, not observed for pure SIL and PTFE components, are considered as specific ones for the SIL–PTFE semi-IPN structures. The SIL–PTFE system, as well as its components, is thermally stable, if degradation reactions are considered; the temperatures of decomposition at the maximum decomposition rate were above 530°C. It has been found that the thermal stability of the SIL–PTFE system is increasing with the increase of the PTFE content. This revised version was published online in August 2006 with corrections to the Cover Date.     

Complex Formation of Cyclodextrins with Various Thiophenes and their Polymerization in Water: Preparation of Poly-pseudo-rotaxanes containing Poly(thiophene)s

Cyclodextrins (α-CD, β-CD and 2,6-di-O-dimethyl-β-CD (DM-β-CD)) were found to form inclusion compounds with thiophenes (thiophene (T), bithiophene (2T)) in water and in crystalline states. The structures of α-CD–T, β-CD–2T, and DM-β-CD–2T inclusion complexes were determined by X-ray crystallography. DM-β-CD forms a 1:1 cage type complex with 2T. In contrast, β-CD formed 2:3 (CD:guest) complexes with thiophene and α-CD formed 2:3 complexes, both of the channel type. These inclusion complexes were found to polymerize by FeCl₃ in the inclusion compounds in water. The products were formed poly-pseudo-rotaxane between cyclodextrins and poly(thiophene) characterized by IR, ¹H-NMR and ¹³C CP/MAS NMR. The molecular weights of the poly-pseudo-rotaxanes with poly(thiophene) were determined by the MALDI-TOF mass spectra to be 3000–5000. In comparison between poly-pseudo-rotaxane (DM-β-CD–poly(thiophene)), authentic poly(thiophene) and the washed DM-β-CD–poly(thiophene) which was washed with DMF to dethread DM-β-CD, these poly-pseudo-rotaxane was characterized by Raman, UV–vis and fluorescence spectra. The maximum emission band of DM-β-CD–poly(thiophene) shifted to a shorter wavelength. The hypsochromic shift was derived from poly-pseudo-rotaxane with DM-β-CD.     

Phytochemical analysis of young fustic (Cotinus coggygria heartwood) and identification of isolated colourants in historical textiles

Young fustic (Cotinus coggygria Scop.; Anacardiaceae) has been used as a dyestuff since antiquity. Phytochemical investigation of the methanol extract of the heartwood has led to the isolation and structure elucidation by nuclear magnetic resonance and mass spectrometry (MS) of 3′,4′,6-trihydroxyaurone (sulfuretin) and 3′,4′,7-trihydroxyflavonol (fisetin) as well as 3′,4′,7-trihydroxyflavanol (fustin), 3′,4′,5,7-tetrahydroxyflavonol (quercetin), 3′,4′,5,7-tetrahydroxyflavanol (taxifolin), 4′,7-dihydroxyflavanol, 3′,4′,7-trihydroxyflavanone (butin), 4′,7-dihydroxyflavanone (liquiritigenin), trans-2′,3,4,4′-tetrahydroxychalcone (butein), 4′,5,7-trihydroxyflavanone and trans-2′,4,4′-trihydroxychalcone (isoliquiritigenin). The isolated compounds were used as reference materials for the development of a high-performance liquid chromatography–diode array detector–MS method, which was then applied to analyse (1) fresh silk samples dyed with young fustic, (2) dyed silk subjected to artificially accelerated light ageing and (3) historical silk micro-samples, extracted from ecclesiastical post-Byzantine garments (fifteenth to eighteenth century), which belong to monasteries of Mount Athos. Sulfuretin and fisetin, which are usually used as markers for the identification of the yellow dye and, for the first time, some of the aforementioned flavonoid components of young fustic were identified in the historical extracts. Furthermore, preliminary experiments suggested that although the amounts of the dye components decrease with light ageing, the relative ratio of fisetin and sulfuretin, after a first step of ageing, seems to be almost unaffected by such degradation processes raised by light. The effect of the latter on the morphology of the dyed silk fibres is briefly investigated by scanning electron microscopy.     

Preparation of nano-sized polybenzimidazole and carbon particles via poly(amino-amide) particles

Poly(amino-amide; PAA) particles consisting of p-phthalyl chloride and 3,3′-diaminobenzidine and 4,4′-diphenyldicarbony chloride and 3,3′-diaminobenzidine were prepared. The particles were then transformed by treatment with heat into poly(p-phenylenebenzimidazole; PPC–PAA) and poly(4,4′-diphenylenebenzimidazole; DPC–PAA) particles, respectively. The number ratio of ring-closing of the obtained product was found to be dependent on the processing temperature. However, the morphology and diameter of the products were not found to be temperature dependent. PPC–PAA particles were amorphous and DPC–PAA particles had a high degree of crystallinity. Further, upon heating up to 1,000 °C, poly(p-phenylenebenzimidazole) and poly(4,4′-diphenylenebenzimidazole) particles were transformed into carbon particles and carbon bulk, respectively. The poly(amino-amide), polybenzimidazole and carbon particles obtained were nano-sized spherical particles with narrow size distributions.     

Unilateral NMR, 13C CPMAS NMR spectroscopy and micro-analytical techniques for studying the materials and state of conservation of an ancient Egyptian wooden sarcophagus

A multi-technique approach was employed to study a decorated Egyptian wooden sarcophagus (XXV–XXVI dynasty, Third Intermediate Period), belonging to the Museo del Vicino Oriente of the Sapienza University of Rome. Portable non-invasive unilateral NMR was applied to evaluate the conservation state of the sarcophagus. Moreover, using unilateral NMR, a non-invasive analytical protocol was established to detect the presence of organic substances on the surface and/or embedded in the wooden matrix. This protocol allowed for an educated sampling campaign aimed at further investigating the state of degradation of the wood and the presence of organic substances by ¹³C cross polarization magic angle spinning (CPMAS) NMR spectroscopy. The composition of the painted layer was analysed by optical microscopy (OM), scanning electron microscopy–energy dispersive spectroscopy (SEM–EDS), Raman and surface enhanced (resonance) Raman spectroscopy (SERS/SERRS), infrared and GC–MS techniques, evidencing original components such as clay minerals, Egyptian green, indigo, natural gums, and also highlighting restoration pigments and alteration compounds. The identification of the wood, of great value for the reconstruction of the history of the artwork, was achieved by means of optical microscopy.     

Synthesis and properties of poly(amide–imide)s containing a N-methylcarbazole group

A new dicarboxylic acid monomer containing the N-methylcarbazole and imide structures, 3,6-bis(trimellitimido)-N-methylcarbazole (I), was prepared from the condensation of 3,6-diamino-N-methylcarbazole (c) and trimellitic anhydride. The diamine c was synthesized in three steps starting from the methylation of carbazole, followed by nitration and catalytic hydrazine reduction. A series of N-methylcarbazole-containing poly(amide–imide)s were synthesized by direct polycondensation from the diimide–diacid I with various aromatic diamines. These poly(amide–imide)s had inherent viscosities of 0.66–1.47 dl/g and were readily soluble in a variety of organic solvents, including N-methyl-2-pyrrolidone and N,N-dimethylacetamide (DMAc). Transparent, flexible, and tough films of these polymers could be cast from DMAc solutions, and these films exhibited excellent mechanical strength. The glass-transition temperatures of these poly(amide–imide)s were in the range 317–362 °C. All the poly (amide–imide) did not degrade noticeably below 480 °C in nitrogen, and the 10% weight loss temperatures and char yields at 800 °C were above 520 °C and 60% in nitrogen, respectively, indicating high thermal stability. Received: 8 February 2000/Accepted: 23 March 2000     

Effect of compatibilization on thermal degradation kinetics of HDPE-based composites containing cellulose reinforcements

Dynamic thermogravimetric analysis under nitrogen flow was used to investigate the thermal decomposition process of high-density poly(ethylene) (HDPE)-based composites reinforced with cellulose fibers obtained from the recycling of multilayer carton scraps, as a function of the cellulose content and the compatibilization. The Friedman, Flynn–Wall–Ozawa, and Coats–Redfern methods were used to determine the apparent activation energy (E _a) of the thermal degradation of the cellulose component into the composites. E _a has been found dependent on the cellulose amount and on the cellulose/polymer matrix interfacial adhesion. In particular, it has been evidenced an increase of the cellulose thermal stability as a consequence of the improved interfacial adhesion between the components in NFR composites.     

UV ageing studies: evaluation of lightfastness declarations of commercial acrylic paints

The lightfastness declarations of several different commercial acrylic paints and different quality series were tested by artificial UV ageing. To evaluate their lightfastness declarations, three acrylic colours (cadmium red, ultramarine blue and chromium oxide green) from six companies (Lascaux, Liquitex, Lukas, Rembrandt, Schmincke, and Winsor & Newton) were analysed before and after UV exposure. Characterisation and identification of these materials were carried out with Py–GC/MS, FTIR–ATR analyses, and colour measurements. Particular attention was focused on the Py–GC/MS measurements and on comparison of the single-shot method for pyrolysis of polymers and the double-shot mode which enables a unique combination of pyrolysis methods for analysis of polymers and thermal desorption for documentation of the volatile compounds. Depending on the particular company and the specific value of the lightfastness declaration, different binding media (i.e. poly(EA/MMA), poly(nBA/MMA), and poly(2-EHA/MMA)), and fillers (i.e. kaolinite, calcium carbonate, barite, and talc) were characterised and identified by Py–GC/MS and FTIR–ATR analyses. After UV exposure, several alteration processes with consequent formation of volatile compounds or new products were observed by both techniques, especially for the blue paints. In particular, the double-shot mode of Py–GC/MS enabled the detection of oxidation products, which could not be detected with the single-shot mode. Comparison of the lightfastness declarations for each of the blue, green, and red paints and the noted alterations broadly agreed for most of the paints.     

Highly Porous Silica Monoliths from Ethyl (L)-Lactate Modified Silanes

Summary. A new type of silica precursor was synthesized by (trans)alkoxylation of alkoxy- and chlorosilanes with ethyl (L)-lactate. This novel ethyl lactate modified silane was hydrolyzed and condensed in the presence of a non-ionic surfactant – poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) triblock copolymer (P123) – to give monolithic silica gels. The wet gels were dried using two different drying techniques resulting in crack-free monoliths: a) supercritical drying with CO₂ to yield a porous inorganic material and b) surface silylation with trimethylchlorosilane to yield an inorganic–organic nanocomposite material. The obtained porous gels were characterized by different techniques including thermal analysis, nitrogen sorption, and electron microscopy (TEM, SEM).     

HPLC–DAD–MS analysis of dyes identified in textiles from Mount Athos

Organic colorants contained in 30 textiles (16th to early 20th century) from the monastery of Simonos Petra (Mount Athos) have been investigated using high-performance liquid chromatography equipped with diode-array detection and mass spectrometry (HPLC–DAD–MS). The components of natural dyes identified in samples treated by the standard HCl dyestuff extraction method were: alizarin, apigenin, butein, carminic acid, chrysoeriol, dcII, dcIV, dcVII, ellagic acid, emodin, fisetin, flavokermesic acid, fustin, genistein, haematein derivative (Hae′), indigotin, indirubin, isoliquiritigenin, isorhamnetin, kaempferide, kaempferol, kermesic acid, luteolin, naringenin, purpurin, quercetin, rhamnazin, rhamnetin, sulfuretin, and type B and type C compounds (last two are markers for Caesalpinia trees). Early, semi-synthetic dyes, for example indigo carmine, fuchsin components, and rhodamine B were identified in objects dated late 19th to early 20th century. A dyestuff extraction method which involves use of TFA, instead of HCl, was applied to selected historical samples, showing that the mild method enables efficient extraction of weld (Reseda luteola L.) and dyer’s broom (Genista tinctoria L.) glycosides. The marker compound (Hae′) for logwood (Haematoxylum campechianum L.) identification after treatment with HCl was investigated by liquid chromatography coupled to mass spectrometry (LC–MS) in negative electrospray ionization (LC–MS-ESI⁻) mode. LC–MS in negative atmospheric pressure chemical ionization (LC–MS-APCI⁻) mode was used, probably for the first time, to investigate cochineal (Dactylopius coccus Costa) samples. Positive electrospray ionization (LC–MS-ESI⁺) mode was used for identification of fuchsin components. Detailed HPLC–DAD studies were performed on young fustic (Cotinus coggygria Scop.) and Persian berries (Rhamnus trees).     

Molecular characteristics of poly(propylene imine) dendrimers as studied with translational diffusion and viscometry

 The generation of dendrimers based on poly(propylene imine) with CN end groups [DAB–dend–(CN) _x ] and with palmitoyl end groups [DAB–dend–(C15) _x ] was studied by methods of translational diffusion and viscometry. The volumes of the DAB–dend–(CN) _x and DAB–dend–(C15) _x dendrimers and the previously studied DAB–dend–(lacto) _x dendrimer were compared to evaluate the volumes of the end groups in hybrid dendrimers. The volume of the hybrid dendrimers compared to that of the initial dendrimers increases proportionally to the number of end groups: this means that the end groups are predominantly located on the periphery of each molecule, thus ensuring this volume will increase. It is shown that the volume of the end groups for DAB–dend–(C15) _x is 3.5 times greater, and for DAB–dend–(lacto) _x it is 5.0 times greater than that occupied by free mole- cules corresponding to the end groups. The values of the intrinsic viscosity were compared with the values of the diffusion coefficient and the chemical formula molecular weight. Received: 7 August 2001 Accepted: 2 November 2001     

Formation of polymer–colloid complexes of aluminoxane particles with poly(acrylic acid) and its copolymers with acrylamide

Formation of polymer–colloid complexes formed by positively charged aluminoxane particles with a size of ~4.6 nm, which constitute the main part of the dispersed phase in aluminum polyhydroxychloride sols with poly(acrylic acid) and acrylic acid copolymers with acrylamide, is studied. Conditions of preparing water-soluble polymer–colloid complexes are determined. It is shown that water-soluble polycomplexes are obtained through the interaction of aluminoxane particles with acrylic acid–acrylamide copolymers containing no more than 0.8 mol% acrylic acid units. In the polymer–colloid complex, aluminoxane particles are uniformly distributed over polyelectrolyte macromolecules and the optimum composition is attained at the molar ratio of components Z equal to 1:1. In semidilute solutions, the addition of aluminoxane particles to the copolymer brings about formation of the gel featuring viscoelastic properties. For all copolymers, the maximally elastic properties of the gels are attained at Z ≈ 1.     

Synthesis of Poly(<Emphasis Type="Italic">o</Emphasis>-anisidine)/H<Subscript>2</Subscript>SO<Subscript>4</Subscript> Film for the Development of Glucose Biosensor

The poly(o-anisidine)–sulfuric acid–glucose oxidase (POA–H₂SO₄–GOx) electrode has been investigated in the present work. Platinum electrode was used for the synthesis of poly (o-anisidine)–sulfuric acid (POA–H₂SO₄) film using galvanostatic method with 0.2 M o-anisidine, 1.0 M H₂SO₄ solution, 1.0 pH and 2 mA/cm² applied current density. The synthesized film was characterized using electrochemical technique, conductivity measurement, UV–visible spectroscopy, Fourier transform infrared spectroscopy, and scanning electron microscopy. GO_X was immobilized on synthesized POA–H₂SO₄ film by cross-linking via glutaraldehyde in phosphate and acetate buffer. The Michaelis–Menten constant ( K_\textm￠K_{\text{m}}^\prime ) was determined for the immobilized enzyme. The glucose oxidase electrode shows the maximum current response at pH 5.5 and potential 0.6 V. The sensitivity of POA–H₂SO₄–GO_X electrode in phosphate and acetate buffer has been recorded. The results of this study reveal that the phosphate buffer gives fast response as compared to acetate buffer in amperometric measurements.     

Phase behavior and interactions in blends of poly[(butylene adipate)-co-poly(butylene terephthalate)] copolyester with poly(4-vinyl phenol)

Miscibility with a linear T _g–composition relationship was proven for blend of poly(butylene adipate-co-butylene terephthalate) [P(BA-co-BT)] with poly(4-vinyl phenol) (PVPh). In comparison to the blends of PBA/PVPh and poly(butylene terephthalate) (PBT)/PVPh, the Kwei’s T _g model fitting on data for the P(BA-co-BT)/PVPh blend yields a q value between those for the PBA/PVPh and PBT/PVPh blends. The q values suggest that the interaction strength in the P(BA-co-BT)/PVPh blend is not as strong as that in the PBT/PVPh blend. Upon mixing the PVPh into the immiscible blend of PBA and PBT, the ternary PBA/PBT/PVPh blends only exhibits partial miscibility. Full-scale ternary miscibility in whole compositions is not possible owing to the significant ∆χ effect (χ _ij  – χ _ik ). The wavenumber shifts of the hydroxyl IR absorbance band indicates that the H-bonding strength is in decreasing order—PBT/PVPh > P(BA-co-BT)/PVPh > PBA/PVPh—and shows that the BA segment in the copolymer tends to defray interactions between P(BA-co-BT) and PVPh in blends.     

Poly(PEGMA) magnetic nanogels: preparation via photochemical method,characterization and application as drug carrier

One-pot synthesis of magnetic nanogels with excellent biocompatibility via the photochemical method is reported in this paper. Poly(PEGMA) modified superparamagnetic nanogels (poly(PEGMA) magnetic nanogels) were synthesized by in-situ polymerization using poly(ethylene glycol) methacrylate (PEGMA) as the monomer and N, N′-methylene-bis-(acrylamide) (MBA) as the cross-linking agent in magnetite aqueous suspension under UV irradiation. The surface functional groups and components of magnetic nanogels were analyzed by Fourier transform infrared spectroscopy (FTIR) and a thermogravimetric analyzer (TGA). The results indicated that the poly(PEGMA) magnetic nanogels were synthesized successfully by coating poly(PEGMA) on the Fe₃O₄ nanoparticles under UV irradiation, and the Fe₃O₄ nanoparticles content in this nanogels was above 50 wt%. The morphology, size, zeta-potential and magnetic property were also characterized. The magnetic nanogels had a nearly spherical shape and core-shell structure, the average size in aqueous system measured by photon correlation spectroscopy (PCS) was 68.4 nm, which was much bigger than that in the dry state, the nanogels behaved superparamagnetically with saturated magnetization of 58.6 emu/g, and the zeta-potential was −16.3–−17.3 mV at physiological pH (6.8–7.4) which could help to maintain stability in blood. The preliminary application as drug carrier was made and the doxorubicin-loaded magnetic nanogels had an excellent property in slow-release. The experiment indicated that the magnetic nanogel was an ideal candidate carrier in target drug delivery systems and other biomedical application. Supported by the Natural Science Foundation of Shandong Province (Grant No. Q2006F01), Scientific and Technological Project of Shandong Province (Grant No. 2007GG3WZ02066) and Scientific and Technological Project of Department of Education, Shandong (Grant No. J07WC01)     

Spectroelectrochemistry of conducting polypyrrole and poly(pyrrole–cyclodextrin) prepared in aqueous and nonaqueous solvents

Conducting polypyrrole (PPy) and poly(pyrrole-2,6-dimethyl-β-cyclodextrin) [poly(Py-β-DMCD)] films were prepared by electrode potential cycling on a gold electrode in aqueous and nonaqueous (acetonitrile) electrolyte solutions containing lithium perchlorate. The resulting products were characterized with cyclic voltammetry, in situ UV–Vis spectroscopy, and in situ conductivity measurements. For the electrosynthesis of poly(Py-β-DMCD), a (1:1) (mole–mole) (Py-β-DMCD) supramolecular cyclodextrin complex of pyrrole previously characterized with proton NMR spectroscopy was used as starting material. A different cyclic voltammetric behavior was observed for pyrrole and the poly(Py-β-DMCD) complex in aqueous and nonaqueous solutions during electrosynthesis. The results show that in both solutions in the presence of cyclodextrin, the oxidation potential of pyrrole monomers increases. However, the difference of oxidation potentials for films prepared in aqueous solution is larger than for the films prepared in nonaqueous solution. In situ conductivity measurements of the films show that films prepared in acetonitrile solution are more conductive than those synthesized in aqueous solutions. Maximum conductivity can be observed for PPy and poly(Py-β-DMCD) films prepared in nonaqueous solution in the range of 0.10 < E _Ag/AgCl < 0.90 V and 0.30 < E _Ag/AgCl < 0.90 V, respectively. In situ UV–Vis spectroelectrochemical data for both films prepared potentiodynamically by cycling the potentials from −0.40 < E _Ag/AgCl < 0.90 V in nonaqueous solutions are reported. This paper is dedicated to Prof. Alan Bond on the occasion of his 65th birthday in recognition of his numerous contributions toward electrochemistry.     

Partial Molar Volumes and Refractions of Aqueous Solutions of Poly[vinyl alcohol]

The partial molar volumes (V ₂) and refractions (R ₂) for poly[vinyl alcohol] (PVOH) in water were determined at 0.00, 5.00, 15.00, 20.00, and 25.00 °C. Each of the partial molar quantities exhibits a small but significant dependence upon concentration which is analyzed using a previously reported model of solvation. This study concludes that the water in the regions surrounding the solute molecules exhibits less hydrogen bonding and as a consequence is denser than the bulk water. In addition, the study finds that the partial molar volume of PVOH at infinite dilution is the simple sum of contributions from its monomer units (–CH₂–CHOH–).     

Mixed layers of DPPC and a linear poly(ethylene glycol)-b-hyperbranched poly(glycerol) block copolymer having a cholesteryl end group

Interactions of the phospholipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) with the amphiphilic diblock copolymer Ch-lPEG₃₀-b-hbPG₂₄ (ChP) are studied at the air–water interface by surface pressure–mean molecular area (π–mmA) measurements of mixed Langmuir films and adsorption measurements of ChP to the air–water interface covered with DPPC monolayers at different initial surface pressure values π ₀. ChP is composed of a single hydrophobic cholesteryl (Ch) moiety covalently bound to a diblock copolymer consisting of a hydrophilic linear poly(ethylene glycol) (lPEG) block and a hydrophilic hyperbranched poly(glycerol) (hbPG) block. Langmuir isotherms and compression moduli of the mixed Langmuir films of different molar ratios reveal distinct interactions between DPPC and ChP during compression. It is demonstrated that the behavior of the DPPC/ChP mixtures is dominated by DPPC up to a molar ratio of 10:1, whereas the behavior is predominantly governed by ChP in mixtures with lower DPPC content (molar ratios of 5:1, 2:1, and 1:1). In adsorption measurements, a strong affinity of ChP to DPPC is observed after injection into the water subphase. The surface pressure value π _in up to which ChP is able to penetrate into DPPC monolayers is determined to the remarkably high value of 48.2 mN/m which attests the favorable interactions between DPPC and the Ch moiety of ChP. Atomic force microscopy on LB films of DPPC/ChP mixtures of different molar ratios transferred onto hydrophilic substrates confirms the presence of two different phases, a DPPC-rich phase and a ChP-rich phase.     

Association in Unsalted and Brine Solutions of a Water-Soluble Terpolymer with <Emphasis Type="Italic">p</Emphasis>-Vinylbenzyl-Terminated Octylphenoxy Poly(ethylene oxide)

An associating terpolymer (PAOE) of acrylamide (AM), sodium 2-acrylamido-2-methylpropane sulphonate (NaAMPS), and a novel macromonomer: p-vinylbenzyl-terminated octylphenoxy poly(ethylene oxide) (VOE, degree of polymerization: 4) was synthesized by aqueous free-radical copolymerization. The PAOE polymer exhibited excellent thickening properties in unsalted and brine solutions. The electrostatic shielding of repulsive interactions of the polymer was much weaker than that of the linear associating polymers with small hydrophobic monomers. This brine solution exhibited unexpected salt-thickening behaviors twice, and good resistance to salt and ageing. The intermolecular hydrophobic association in unsalted and brine PAOE solutions, as functions of polymer and NaCl concentration, were characterized by fluorescence spectroscopy. With the addition of NaCl, the polymer chains were comparatively extended and continuous network structures were formed via the intermolecular hydrophobic association in brine solutions as well as in unsalted solutions at 0.15–0.25 g⋅dL⁻¹ PAOE, as observed by a scanning electron microscope (SEM).