By measuring the infrared spectra and laser Raman spectra for various hopeite films and phosphophyllite films, the influence of metal component composition in these films on those spectra can be investigated. In infrared spectra, peaks corresponding to (ν₁ + ₃) andν₄, the fundamental vibrational modes of PO₄^3-, were seen, but the peak patterns ofν₄, were d ifferent for hopeite films containing manganese component from that not containing it (Figs.2, 3, 5 and 6). Raman s pectra for these films were shown in Figs.7-11. Four clear peaks due to PO₄^3-were found in the region of 800-1300 cm^-1. Tetrahedral orthophosphate (PO₄^3-) has four fundamental vibrational modes ofν₁, ν₂, ν₃, and_ν, (Fig.4) ;_ν1, andvν₃are observed in 800-1300 cm^-1. Essentially, ν₃ degenerates triply. But in the crystalline state of zinc phosphate films, the tetrahedral structure of PO₄^3- will be deformed, and the degeneracy of ν₃ is untied and the band is split to three peaks. Accordingly, it was considered that the spectra with four peaks containing ν₁ were generated. Here, main peak corresponds to ν₁ and other th ree peaks correspond toν₃. This consideration was supported by the Raman data for 85%-H₃PO₄solution (Fig.12). The peak fr equencies of Raman bands for various zinc phosphate films were compared (Table 2). For both hopeite films and phosphophyllite films, the Raman peaks shifted to lower wavenumbers with the increase of nickel or manganese component (Fig.13). In particular, the Raman peaks of hopeite C and D was similar to that of phosphophyllite E. The composition of modified hopeite films by the doping of nickel or manganese comp onent has been analyzed as Zn_3-x Me_x(PO₄)₂-4 H₂0 (Me: Ni and/or Mn). This composition is different from neat hopeite films of Zn₃(PO₄)₂4 H₂0 and is modified to the composition as phosphophyllite films. Thus, it was possible to correlate the modification level of zinc phosphate films, for instance, the crystal morphologies of these films or chemical stability like anti-alkaline property with the observation of PO₄^3- peak shift in Raman spectra.

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The structure of hydrothermally synthesized fraipontite was studied in comparison with that of natural fraipontite. Silicon-29 NMR showed a single peak at-83.1 ppm(Fig.1), which revealed much isomorphous replacement of silicon by aluminum. Fraipontite contained nearly equimolar aluminum in both tetrahedral and octahedral sheets (Fig.2), hence the positive charge in the octahedral sheet was mostly compensated by the negative charge in the tetrahedral sheet. Essential water, which was not observed in natural fraipontite, was detected by differential thermal analysis (Fig.3). The chemical analysis and silicon-29 NMR showed that the product contained ca.90% of fraipontite (Table 3), whose composition is shown in equation (2). It was observed by the electron microscope (Fig.4) that the fraipontite crystal was in the form of thin stacked plates, and exhibited a characteristic of phyllosilicates. IR spectrum (Fig.5) indicated that both of the coordinating hydroxyl group and the essential water were in the state of hydrogen bonding. X-Ray diffraction indicated that the (001)spacing of synthesized fraipontite was almost same as that of natural fraipontite. These findings suggested that the essential water was present in the oxygen six membered ring of tetrahedral sheet (Fig.6).

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Magnesium phosphate pentahydrate (TMP5) was prepared from the mixed solution of NaH₂- PO₄⋅2H₂0 and MgCl₂⋅6H₂0 by utilizing the hydrolysis of urea. Amount of urea affecte d the change of pH of the solution. Magnesium hydrogenphosphate trihydrate (DMP 3) was obtained at pH 4.8 by heating the mixed solution containing urea of 0.075 mol/dm³ at 98 °C under the following conditions: Mg²⁺/P mole ratio 1.5 and NaH₂PO₄ concentration 0.1 molf dm³. TMP 5 was easily prepared at pH >5.2 by heating the mixed solution containing urea of 0.45 mol/dm³ at 98 °C. DMP 3 obtained at pH 4.8 was transformed to TMP 5 by ageing at pH >5.2 for 5 h in the presence of Mg²⁺ ions. At the heating rate of 10 °C/min, TMP 5lost three molecules of H₂0 at 220 °C and transformed to amorphous substance. Up to 500 °C two molecules of H₂0 were lost. The amorphous substance was crystallized at 670 °C into anhydrous magnesium phosphate.

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Fluorine in the water samples of a given fluorine concentration has been repeatedly determined, based on the "JIS K 0102 (34.1) " method and it has been found that the fluorine recovery is reduced remarkably when certain kind (SD) of silicon dioxide sample is used. From several experimental results obtained with various kinds (SA, SB, SC, and SD) of silicon dioxide as well as with silica gel (SE), the following (1-6) has been clarified.1. Both SD and SE contain higher moisture than the other kinds.2. The fluorine recovery increases by a factor of two when aliquots of both SD and SE are ignited, based on JIS K 8885 before application to steam distillation based on JIS K 0102 (34.1).3. The materials SD and SE tend to catch fluorine in the water samples during the steam distillation.4. When an aliquot of the sample SD is ignited at 1150°C for 1 h before the distillation, the ignited aliquot hardly catches fluorine during the distillation. As for the sample SE, the same result on its ignited aliquot is consistently obtained.5. The structure of each material is found as follows: SA-SC are α-quartz, SD and SE are α-cristobalitealpha; when an aliquot of the samples (SD and SE) is ignited, both samples (SD and SE) are gradually transformed into α-cristobalite at 1350 °C and at 1300°C, respectively.6. When the α-cristobalite thus obtained is used in the steam distllation, the fluorine recovery obtained is similar to that from the steam distillation where each aliquot of the samples SA-SC is used respectively. From the above-mentioned, the following two points should be examined ur gently.1. The percentage in the provision "ignition loss of silicon dioxide must be no more than 6.0%"(JIS K 8885) is to be changed to a lower percentage.2. A provision for the quality of silicon dioxide is to be inserted into those of JIS K 0102 (34.1).

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Twenty samples of mixed powder of Fe₃O₄ and Fe₂O₃ known content: were measured by Xray diffractometer and the I/I₀ to 2θ of 24 were picked up the measurements. The data filed for multivariate analysis such as cluster analysis, cluster analysis from deviation and principal component analysis was calculated from the matrix of 21×24, and the approximate value of Fe₃O₄ content in a sample was determined.
The accurate Fe₃O₄ content in a sample was calculated from the principal component score. The equations using the calculation are as follows.
D_x is the total principal component score for a sample. D_p-1 and D_p either and of D_x are the total principal component score to data field. M_p-1 and Mp are Fe₃O₄ content corresponding to D_p-1 and D_p X is Fe₃O₄ content of sample. The slope a and the intercept b are calculated from the equations (1) and (2). Differences between the theoretical and calculated values were 97% from calculated of 5 samples (Fe₃O₄ content are 15, 72, 26.04, 35.89, 70.26and 85.88%).

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P-Bis(2-oxooxazolidin-5-ylmethoxy)benzene (PBOB) was prepared by the reaction of tris(2, 3-epoxypropyl)isocyanurate with hydroquinone in the presence of sodium hydroxide as a catalyst in reflux solution of N, N-dimethylformamide. The thermal behavior and the cleavage mechanism by electron impact for PBOB were investigated with the thermal analysis and mass spectrometry, respectively. PBOB gave dimorphic crystals, high temperature- and low temperature-forms. In solid phase two forms gave the identical IR and NMR spectra, b ut they showed marked differences in X-ray diffraction patterns and the activation energies. The activation energies of the pyrolysis was calculated from the TG curves to be 140-460kJ/mol at the high temperature-form and 130-150 kJ/mol at the low temperature -form, respectively. No difference in the pyrolytic behavior was observed in these two forms. In the cleavage by electron impact for PBOB the molecular ion peak was recognized as the base peak. From the TG-GC/MS measurements, the difference between El-cleavage and thermal decomposition for PBOB was elucidated.

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Polyion-complex-type multi-bilayer films were prepared by solvent cast method from cationic bilayer-forming amphiphiles, [CH₃(CH₂)_n-1]₂N⁺(CH₃)₂Br- (2 C_nN, η=14, 16, 18) and various anionic polymers. To clarify the effects of the polymer chains on the bilayer structure in the film, phase transition temperatures (T _c) from solid to liquid-crystalline state of the bilayers, modulus of elasticity of the films, and ESR spectra of the films labeled with a spin probe on the polymer chain, were measured. Disordering effect of polymer chain was observed in the film of the amphiphile with short alkyl chain (2 C₁₄N), resulted in lowerings of T_c, and enthalpy change (The effect was largest in the film prepared from poly (styrene sulfonate)(PSS)). Elasticity of the film mainly depended on the phase of the bilayer matrix (thermal movement of amphiphile molecules). Modulus of elasticity was large below T_c, regardless of the polymer used (Fig.1, 200∼400 MPa). Above T_e, all the films became extremely soft (fluid) not to be measured, though the film prepared from PSS showed the elasticity around 10 MPa (Fig.1). Below T_c, the extrema separation (W) of the ESR spectra was large (more than 6 mT) because of the low thermal movement of the polymer chain, and did not depend on the structure of polymer. On the contrary, aboveT_c, W value (below 5.5 mT) of the film prepared from PSS was larger than that of acrylic polymer (Fig.3). The large disordering effect of PSS on the bilayer, a lack of fluidity of the film in the liquid-crystalline state, and relative large W value in the liquid-crystalline state, were explained on the basis of rigidity of the polymer chain of PSS.

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A polyioncomplex was prepared from a bilayer forming amphiphile, dimethyldioctadecylam-monium bromide, and poly(sodium styrenesulfonate)1abeled with nitroxide radical on a small amount of methacrylate residue in the polymer. Anonbilayerfilm comprised of micro-rods was prepared by usual solvent cast of the polyion complex and cholesterol(80: 20(wlw)). The ESR spectra of thefi1m depended on the direction of applied magnetic field during measurement. Each spectra was changedby uni-axially stretch of the film due to the alternation of the mo1ecular axis of the ionic polymer. The change in the spectra suggested that the longitudinal axis of the ionic polymer was perpendicular to the fi1m surface in a similar manner as the micro-rod. The orientation of the polymer molecule supports an invertedhexagonal type model in which the molecule of ionic polymer would extend linearly along the hydrophilic core of the rod.

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The effect of inorganic salts and humidity on adhesion was discussed in the coating to chromo-plating substrate. Peeling was occurred in the adhesion test of coated film after washing chromo-plating substrate with water containing inorganic salts. Ca²⁺, Na⁺ as cation and NO₃^-, SO₄^2- as anion were detected in the XPS analysis of the peeling area. It was found that inorganic salts with high water absorbability affected the adhesion. Adhesion was poor when coating was applied under high humidity conditions. It was found that surface energy of the back side of coating film was small from the result of measuring of that.

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The superadditivities of reducing agents in the organic solid electrolyte layer have been studied. Tha layer coated onto the electrically conductive film is consisted of poly(vinylbutyral) containing a mixture of benzotriazole (BZT) and silver benzotriazole (BZT-Ag), and reducing agents. On applying a bias, the current flow across the layer forms small Ag nuclei which catalyze the reduction of BZT-Ag by heat development. It is found that t h e reducing agents combined (1) 4-butoxycatechol with P-ethoxyphenol (molar ratio=1: 2) and (2) 4-(methylamino)phenol with hydroquinone (molar ratio=1: 1) exhibit the maximu m superadditivity in the heat development process. The phenomena are elucidated (1) by the regeneration of 4-butoxycatechol and the oxidation of P-ethoxyphenol, and (2) by the regeneration of aminophenol, respectively.

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Heat capacity of several fluoride crystals and glasses has been m easured at various temperatures from 100 to 350 K by using differential scanning calorimetry (DSC). The temperature dependence of the heat capacity has been analyzed in terms of 3-band theory, which was proposed by the present authors previously, in order to examine bonding characteristics in these materials. For the fluoride crystals, the characteristic temperaturesθ₁, and θ₃, which correspond to interatomic vibration between a cation and its nearby anion and intermoleculartype vibration, respectively, are almost identical with each other. Also, for the present fluoride crystals as well as the, oxide crystals reported previously, there exists a proportional relationship between the value ofθ₁, and the bond strength which is estimated from reduced mass and average interatomic separation by assuming electrostatic potential between ions. This fact indicates thatθ₁is a good parameter for evaluation of the interatomic bond strength in fluoride crystals as well as in oxide crystals. On the other hand, θ₁, =θ₃ holds for all of the present fluoride glasses. This fact implies that structure of the present fluoride glasses is describable in terms of random packing of fluoride ions.

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The saturated magnetization (σ) of the ferrite sludge formed by ferrite process treatment of wastewater containing heavy metal and phosphate ions was measured over a wide range of dilution ratio of wastewater (f) (ex. when the heavy metal or phosphate ion concentration of the wastewater reduced to 1/10 of the original one, f=10) and the effects of phosphate ion concentration on the wastewater treatment by ferrite process were discussed quantitatively. Theσ -f curves for various heavy metal and phosphate are similar to each other (Figs.1and 4), are located in variousf regions and depend on the kind of heavy metal and phosphate ions (Figs.2, 3 and 5, and Table 1). The curves have the slopes of 1.0 in low f region and 2.6 in middle f region, and the values of a approach asymptotically to 92 emu/g of Fe₃0₄with increasingf. The rapid decrease ofσ with decreasing f may have resulted from the formation of iron phosphates and/or by-products in ferrite process. The ferrite process requires the value of σ above 60 emu/g for good magnetic separation, steady operation of the process, industrial applications of the sludge and good quality of the treated water (Fig.1). t Treatment of Wastewater Containing Heavy Metal Ion by Ferrite Process. II.

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Quenching distances have been measured between parallel electrode flang es (Fig.1) for methane through heptane (Fig.2), diethyl ether, ethylene oxide (Fig.3), and carbon monoxide (Fig.4). For each of these gases, the value of equivalence ratioΦ_d, has been de termined which corresponds to the minimum quenching distance (Table 1). It has been found that the value of Φ_d is smaller than the equivalence ratioΦ₁, which gives the smallest value of the minimum ignition energy of the gas (Table 2 and Fig.5), the ratio being approximately 1.55, and that the value is about the same as or a little larger than the equ ivalence ratioΦ_xwhich corresponds to the mean concentration of the flammable range of the gas (Tab le 2and Fig.5), where the ratio is 0.95. These findings can be explained in terms of the flame size used in measuring each of these quantities. However, the latter correlation becomes faulse if the corresponding fuel can sustain cool flame or other unusual burning (Fig.5), because the flammability limit (in particular the upper limit) is affected by these phenomena (Table 3) while the value of Φ_d, does not seem to be. If the quenching distances and the flammability limits are measured for downward propagation flames, effect of selective diffusion on their values may become small (Table 4).

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A temperature programmable Langmuir trough using a larg e number of Peltier elements has been developed. Surface temperature of the subphase water in the trough can be changed at a maximum rate of 8°C/min linearly with time in both heating and cooling. Fluc tuation of the surface temperature was within ;± 0.0 2 °C at a constant temperature control. heatingrate dependence and surface-pressure dependence of A-T isobars of myristic acid mo nolayers at the air/water interface were measured with this instrument. The first-order ph ase transition from liquid-condensed to liquid-expanded state of monolayers considerably depend ed on the heating rate. The transition temperature also depended on the surface pressure. This trough will be especially useful for making defect-free LB films by the "isobaric ther mal treatment" of monolayers.

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Variation for 10 years of CH₄ concentration was analyzed b y use of yearly mean, monthly mean, monthly 1 h max. and monthly 1 h min. value, mesured at 16 national air mon itoring stations. CH_∼4 concentration tended to yearly increase. For yearly mean value, increasing ratio was 0.003-0.021 ppm (mean 0.011 ppm) per year. Monthly 1 h max. was in the range of 1.60∼4.53 ppm. High concentrations were measured at urbanized area, that was affe cted by local emission sources. Monthly 1 h min., which was considered as background value, showed yearly increase from 1.58∼1.59 ppm in 1979 to 1.72∼1.73 ppm in 1988.

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Changes in crystal phase and electric resistivity of Mn-Co-Ni oxide were investi g ated in the temperature range of 600 to 1000 °. The starting material was prepared by firing th e Mn-Co-Ni oxide with a composition of 3.0: 1.9: 1.1 at 1400 °. Refiring between 600 a nd 1000° was carried out in an atmosphere of prepurified nitrogen. As a result, it was fou nd that the electric resistivity depended on the type of crystal phases, and the tetragonal s pinel of high temperature form had much higher electric resistivity than that of the cubic spinel.

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Reaction of zinc acetate with aluminum isopropoxide (or galli u m acetylacetonate) in 1, 4-butanediol at 300°C under the spontaneous vapor pressure of the glycol (glycothermal reaction )yielded single-phase zinc aluminate, ZnAl2O4, (or zinc gallate, ZnGa₂O₄), having a spine!structure. The product had a high surface area, 290 m²/g, and the TEM observation sh o wed the product was comprised of agglomerates of fine particles (diameter, ca.5 nm). T husobtained zinc aluminate maintained its large surface area at relatively high temperatures (up to 700°C), and therefore, it has potential use for catalyst materials.

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