NIPPON KAGAKU KAISHI
Online ISSN : 2185-0925
Print ISSN : 0369-4577
Volume 1988, Issue 6
Displaying 1-23 of 23 articles from this issue
  • Eishun TSUCHIDA
    1988 Volume 1988 Issue 6 Pages 845-852
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Porphyrin complexes covalently bound to macromolecules bind oxygen reversibly under various conditions. Cobalt porphyrin, fixed to disperse homogeneously and densely in soild polymer matrix, enables the facilitated oxygen transport through successive ligation in a series of complexes with the oxygen concentration gradient. Iron(II) porphyrin is oxidized immediately in an aqueous medium, but ligates oxygen molecule reversibly when it is bound to a macromolecule and accordingly incorporated in hydrophobic environment. A novel iron (II) porphyrin derivative having phospholipid-like substituents (lipid-heme) forms molecu lar assembly with phospholipids (lipid-hemefliposome), and acts as an oxygen carrier in physiological aqueous salt solution, pH 7.4, 37, 40°C, under air. The analyses of oxygen ligation to porphyrin complex is a potential methodology to clarify the molecular environment surrounding the metal complexes.
    Download PDF (3854K)
  • Hiroshi IMAIZUMI, Kazuhito UCHIDA, Minoru OKADA
    1988 Volume 1988 Issue 6 Pages 853-857
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Hydrogen-isotope exchange reaction between organic liquids (unlabeled) and tritium-labeled poly(vinyi alcohol), PVA(T), was investigated. The liquids used were m onosubstituted benzaldehydes, benzaldehyde, nitrobenzene, and benzene. It was found that only monosubstituted benzaldehydes and benzaldehyde had exchangeable 11-1 atoms. Then, the hydrogenisotope exchange reaction between PVA(T) and the excess amount of one of the monosubstituted benzaldehydes or of benzaldehyde was studied in the temperature range of 50-90°C, and the following results were obtained:
    1. A hydrogen atom in a formyl group participates in the reaction.
    2. The order of reactivity is benzaldehyde≈>o->m->p-tolualdehyde
    3. The reactivity of the formyl group in monosubstituted benzaldehydes, except for orthosubstituted benzaldehydes, follows the Hammett rule.
    4. The activation energies for the o-, m-, p-tolu aldehyde and benzaldehyde are 43, 48, 56, and 45 kJ⋅mol-1, respectively.
    Download PDF (1282K)
  • Eiji ENDOH, Hiroshi OTOUMA, Takeshi MORIMOTO, Yoshio ODA
    1988 Volume 1988 Issue 6 Pages 858-863
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    A new Raney nickel composite-coated electrode, which was prepared by a dispersion coating technique from a nickel plating bath in which Raney nickel alloy powder was uniformly dispersed, has been characterized.
    SEM observation showed that the Raney nickel composite-coated layer is microscopically dendritic, although the layer is macroscopically smooth.
    The roughness factor of the electrode was app roximately 8000, which was obtained from the BET surface area measurement.
    ESCA study showed that the surface of the electrode is entirely covered with NiO, which presumably resulted from the exposure of the electrode to air.
    An AC impedance measurement of the electrode showed tha t the phase angle of the electrode impedance which in series consisted of double layer capacitance and solution resistance was ca.45°, which is a typical behavior of a “porous electrode” towards AC.
    The Tafel slope of the polarization curve for hydrogen evolution reaction in a 35 wt% NaOH solution at 90°C was ca.45 mV (2 RT 13 F). Therefore, it was found that the hydrogen evolution reaction mostly occurs on the Raney nickel catalyst not on the nickel matrix of the composite-coating layer.
    Download PDF (3423K)
  • Wakichi KONDO, Toshiya KUMAGAI, Susumu MIZUTA
    1988 Volume 1988 Issue 6 Pages 864-867
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    From a viewpoint of electric power storage, the following iron (III)-iron(II) redox reaction was electrochemically studied.
    By use of a flow cell with gas diffusion electrodes, graphite cloth/FeCl2 (aq), H2 (aq)/ion exchange membrane/FeCl3 (aq), H2(g)/Pt loaded graphite cloth, the voltage-current charatteristics on charging and discharging of the cell were examined at 70°C as a function of (i) total Fe2+/Fe3+ concentration (1.2-2.4 mol/kgH2O), (ii) HCl concentration (1-8 mol/kgH2O), and (iii) the nature of the ion exchange membrane (Neosepta C-66-5 T and Nafion-125)(Figs.2 and 3).
    The voltage -current characteristics were greatly influenced by the HCl concentration. A high HCl concentration favors the charging process because of the cell voltage decrease, while a low HCl concentration favors the discharging process because of the cell voltage increase. Factors (i) and (iii) did not exhibit significant effects on the voltage-current characteristics.
    The power storage efficiency was estimated to be 93-68% at current density of 25-100 mA/cm2 for a solution composition FeCl2/FeCl3/HCl=0.6 /0.6 /5.0 (mol/kgH2O), and 90-57% at 25-100 mA/cm2 for FeCl2/FeCl3/HCl=1.2/1.2/2.5 (mol/kgH2O) (Table 1). If the cell is charged at higher HCl concentration provided by waste heat and discharged at a lower one, higher efficiencies (>100%) could be achieved: this has been experimentally confirmed (Fig.4).
    Download PDF (911K)
  • Susumu MIZUTA, Toshiya KUMAGAI, Wakichi KONDO
    1988 Volume 1988 Issue 6 Pages 868-872
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    A hybrid-type fuel cell system consisting of power generation with the H2/FeCl3 couple and air oxidation of FeCl2,
    was studied. A cell was constructed with graphite gas diffusion electrodes and an ion-exchange membrane.
    The fuel cell characteristics (voltage-current density relationship for Eq.1) was examined for a variety of (i) cell temperature (50-70°C), (ii) ion-exchange membranes (Neosepta C66-5 T, Nafion-125, or Aciplex K-I01), and (iii) the amount of platinum catalyst loaded on the anode (0-45 mgPt/cm2). A typical cell voltage of O.6 V and a current density of 100mA/cm2 were attained at 70°C for 2 mgPt/cm2. Eq.2 was examined with a bubble-type ract or for a variety of (i) bubble diameter (0.9 and O.3 mm), (ii) reaction temperature (70 and 90°C), (iii) oxygen partial pressure (0.8 and 1.8 atm), and (iv) liquid composition (1.5-3.0molFeCl2/kgH2O, 2.0-3.5 mol HCl/kgH2O). The regeneration efficiency was 90% for bubble diameter 0.3 mm, 90°C, 1.8 atm O2, 1.5 mol FeCl2/kgH2O, and 3.5 mol HCl/kgH2O. Based on these experimental results, the feature of the present hybrid-type fuel cell system is discussed in comparison with the phosphoric acid type fuel cell.
    Download PDF (1017K)
  • Akimasa TASAKA, Hiroaki SAKAGUCHI, Hideaki ITO, Takahito NORIMUNE
    1988 Volume 1988 Issue 6 Pages 873-880
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    The anodic reaction of formamide (HCONH2) on amorphous carbon was studied in a molten KH2F3 at 120°C using a few kinds of electrochemical methods. Pt-rod was used as the reference electrode. Anodic products were analyzed by both gas chromatography and infrared spectroscopy.
    The i-E curves obtained by the cyclic voltammetry were divided into four regions with an increase in the potential. The current densities observed in both region I (below ca.2 V vs. Pt) and II (ca.2-3.5 V vs. Pt) were dependent upon the HCONH2-concentration, and, therefore, HCONH2 discharged mainly in these regions. Besides, the (CxF)[x>2] film was formed also on the carbon surface in the region II. In the region III (ca.3.5-6.5 V vs. Pt), HCONH2 was fluorinated and the anode gas was composed of N2(+O2), CF4, NF3, CO2(+COF2), N2O and so on. As H2O in the melt was eliminated by formation of CO2, the content of NF3 in the anode gas increased with the lapse of time of electrolysis and reached the maximum value of 50.9% in the case of 4.0 mol% HCONH2 and the current density of 5.3 mA⋅cm-2. The anode effect occurred in the region IV (over ca.6.5 V vs. Pt). In th is system, however, the peak current density at ca.6.5 V vs. Pt on the i-E curves obtained by scanning the potential to the lower side from 9 V vs. Pt was larger than that in the molten KH2F3 only and it also increased with increasing the number of scan cycles. In electrolysis at the current density of 5.3-11.0 mA⋅cm-2, the anode effect often occurred and the pulsed application of very high voltages (over 40 V) to the electrolytic cell was effective for the decomposition of (CF)n film covering the surface of the carbon anode in every occurrence of the anode effect. This procedure did not decrease the yield of NF3. The addition of 1.0 wt% LiF to the melt was also effective for the prevention of the anode effect, but it decreased the yield of NF3.
    From these results, it is concluded that the surface of the carbon anode would be partially restored through the reduction of (CxF)n and (CF)n films with HCONH2 and that the direct discharge of HCONH3 as well as its electrofluorination would take place on the partially restored surface of the carbon anode. The mechanism of electrochemical fluorination of HCONH2 is also discussed in detail.
    Download PDF (2074K)
  • Masataka SHIMIZU, Keiji KASHIMA, Yoshihisa CHIBA, So TAKEOKA
    1988 Volume 1988 Issue 6 Pages 881-885
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Effects of added K2CO3, CaCO3 and BaCO3 on the activities and selectivities of the Raney nickel alloy catalysts prepared from Ni-Cu-Al alloy were examined. Addition of K2CO3, CaCO3 and BaCO3 was carried out by impregnation of the catalyst with K2CO3, Ca(CH3COO)2 and Ba(CH3COO)2 aq. soln., respectively, followed by calcination in air at 500°C. The improvement of selectivity toward decomposition of methanol and the suppression of dimethyl ether formation were observed for the basic metal carbonates added catalysts (Table 1). Methanol decomposition activities of the catalyst increased with increasing amount of the added basic metal carbonates and reached a maximum at an characteristic value of content for each carbonate (Figs.1, 2, 3). The enhacement of the activity by the addition of CaCO3 and BaCO3 was found to be due to an increase in active sites (Figs.1, 2). For these catalysts, the crystallite size of Ni-Cu alloy decreased with increasing amount of the added carbonates (Figs.1, 2). On the other hand, the addition of K2CO3 caused no increase in active surface area (Fig.3). It could be presumed that K modified the active sites to enhance the activity. The carbon deposition of the catalysts after reaction at 350°C for 30 h increased with the increase of added amount of the carbonates, except the low content regions of CaCO3 and BaCO3 (Table 1). Deactivation was significant for the catalysts on which a large amount of carbon (Fig.4) was deposited.
    Download PDF (1220K)
  • Naohiro SOGA, Yasuhiro SAGAWA, Mamoru YOSHIMOTO, Kazuyuki HIRAO
    1988 Volume 1988 Issue 6 Pages 886-891
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    The mechanical properties such as elastic moduli, Vickers hardness, fracture toughness and percentage crack formation of alkaline earth metaphosphate glasses were systematically measured. In comparison with RO⋅P2O5 (R=Ca, Sr, Ba) glasses, MgO⋅P2O5 glass had a smaller Young′s modulus and Vickers hardness, but larger fracture toughness and crack-forming resistance values even though the ionic radius of Mg2+ is smaller than that of the other alkaline earth ions. This anomaly could be interpreted by considering the structure of metaphosphate glasses, where the coordination number of Mg2+ is four, not six as for Ca2+, Sr2+, and Ba2+. This structure was confirmed by considering the change of interatomic bonds of R-O and P-O, which were obtained from the three-band theory. When the other alkaline earth ions except for Mg2+ were mixed, mixed effects in Young′s modulus and Vickers hardness appeared faintly. On the other hand, when Mg2+ and one of the other alkaline earth ions were mixed, a positive mixed effect was distinctly found. This change was also interpreted in terms of the change of the coordination number of Mg2+.
    Download PDF (1341K)
  • Hiroshi MATSUI, Genzo HASHIZUME, Gin-ya ADACHI, Jiro SHIOKAWA
    1988 Volume 1988 Issue 6 Pages 892-898
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    In order to obtain desired production conditions for prismatic a-calcium sulfate hemihydrate (α-hemihydrate) from calcium sulfite hemihydrate (sulfite), changes in crystal shapes of sulfite and α-hemihydrate and the crystal growth of α-hemihydrate during the oxidation of sulfite suspended in water with sodium citrate and nickel sulfate at 125°C and at 2 kg/cm2 in pressure were studied.
    Plate-like ca lcium sulfate dihydrate (dihydrate) was formed on the surface of spherical sulfite crystals at the temperatures between room temperature and 125°C. Even though the oxidation proceeded at 125°C, the plate-like dihydrate did not transfer rapidly to thea-hemihydrate. After an induction period, the dihydrate rapidly disappeared, and the prismatic ahemihydrate immediately grew in the presence of sodium citrate. Sodium citrate promoted the crystal shape change to the prismatic shape, but slowed down the precipitation of the a-hemihydrate. On the other hand, the nickel sulfate made the precipitation faster a nd promoted the crystal shape change to the needle-like shape,
    Download PDF (8607K)
  • Takeshi OGINO, Noriko TSUNASHIMA, Toshio SUZUKI, Masakazu SAKAGUCHI, K ...
    1988 Volume 1988 Issue 6 Pages 899-905
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    In the formation of calcium carbonate from highly supersaturated aqueous solution, stable calcite is finally formed through a process of the formation of amorphous calcium carbonate (ACC), followed by its transformation to the metastable polymorphs (vaterite at low temperatures or aragonite at high temperatures). The effect of ethylenediamine-N, N, N′, N′tetrakis(methylphosphonic acid) (EDTMP), which is one of the most widely used scale inhibitors, on the above process has been studied as functions of concentration and addition time of EDTMP and of temperature.
    The effect of 10-8.0 to 10-4.0 M(≡mol.⋅dm-3) of EDTMP on the change in the ion product of CO2+ and CO32- in solution, the abundance of polymorphs and the rates of formation and transformation of CaCO3 has been studied by means of potentiometry, X-ray diffractometry and scanning electron microscopy.
    At 25.0°C, although EDTMP up to 10-5.0 M scarcely affected the formation of ACC and its transformation to crystalline CaCO3, the presence of EDTMP strongly inhibited the transformation from vaterite to calcite and the transformation was completely stopped at 10-5.0 M EDTMP (Figs.1 and 2). The transformation of ACC to crystalline CaCO3 was retarded at higher EDTMP concentrations and crystalline CaCO3 was not formed at 10-4.0 M (Fig.1, Table 1). The abundance of calcite formed from ACC increased with increasing EDTMP concentration until 10-5.0 M EDTMP. Its abundance was, however, considerably lowered at 10-4.7-10-4.5 M EDTMP (Table 1), and a very unusual behavior has been observed for the transformation at 10-4.7 M (Fig.1, e). The effect of EDTMP on the process at high ternperature was almost the same as that at 25.0°C, although the metastable polymorph changes to aragonite. The inhibition effect can be explained by the adsorption of EDTMP on the crystal surface of growing polymorphs.
    Download PDF (2843K)
  • Akira Doi, Minekazu FUJIWARA, Minoru FUKUHARA
    1988 Volume 1988 Issue 6 Pages 906-910
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    On the surface of Hidasuli, typical design pattern of Bizen-yaki, the formation of corundum was found in addition to quartz and iron pxide which was responsible for characteristic coloring of Bizen-yaki. It was piesumed that corundum would be formed, in the burning process, through the reaction of Bizen-clay, and potassium, a main alkali composition contained in straw ashes. In this study we investigated chemical, conditions to form the corundum in the reaction of Bizen-clay and potassium, - In the course of our study, we prepared various mixtures of Bizen-clay and potassium chloride in differekrierportion as materials, and burnt them at a constant temparature of 1300°C; then examiged the chemical products created in this process by means of X-ray diffractions. This eiamination showed: for the 3 h burning condition, the more potassium was contained, generally, the less amount of mullite appeared rapidly in the composition of the products. When the 8 wt% potassium chloride sample was used, no more formation of mullite was found out. A material containing 8to 10 wt% potassium chloride has formed the most amount of corundum in a process which was almost the same as that seen of the surface of Hidasuki; furthermdie the higher the potassium content, the more leucite was formed in the reaction of the corundum, the potassium and the quartz.
    Under the conditions where the burning time was longer than 3 h, the corundum reacted with the quartz and the mullite was produced, while the forming range and amount of corundom decreased.
    Download PDF (977K)
  • Chiaki MAEKOYA, Yoshiaki OKAJIMA
    1988 Volume 1988 Issue 6 Pages 911-915
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    An apparatus for the highly sensitive determination of residual organic carbon in highpurity water is described. Organic carbon in high-purity water is converted to carbon dioxide by chemical oxidation (K2S2O8, 200°C, 30 kgf/cm2). The resulting CO2 can be measured directly with a gas chromatograph. The amount of CO2 is directly proportional to the concentration of carbonaceous materials in sample water. The analyzer developed consists of a degasser for removing the dissolved CO2 in sample water, a reactor for converting organic material into CO2, a gas/liquid separator for extraction of CO2 in hot water and vapor, and a gas chromatograph for measuring CO2 in extracting gas.
    The dynamic range for the organic carbon determination was 1-100 ppb and the coefficient of variance at 1 ppb was 20%. The present analytical operation took 20 min per a sample.
    Download PDF (1223K)
  • Tokuhiko OKAMOTO, Kenji FUJITA, Masuhiko KAWAMURA
    1988 Volume 1988 Issue 6 Pages 916-922
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Organo molybdenum compounds are used as an anti-friction additive for fuel-saving engine oils. However, the anti-friction effect of the additive is deteriorated while it is used, to study the mechanism of its deterioration, the local structure around Mo atoms in the compounds have been investigated by an X-ray absorption spectroscopy (EXAFS and XANES)using a laboratory scale equipment.
    The EXAFS results s uggested that the local structure of the Mo atoms in the fresh engine oils is similar to that in the molybdenum 0, 0-dialkyl phosphorodithioate (Mo-DTP)whose structure is expressed by the chemical formula as follows;
    and the molybdenum compound in the oils has changed to Mo oxide in which an Mo atom is coordinated by six oxygen atoms after 2000 km running. XANES spectra of the compounds show that the coordination geometry around Mo atoms in the Mo oxide is similar to that in MoO3 rather than MoO2.
    The deterioration of anti-friction effect of the engine oils after use coincides with Mo oxide formation.
    Download PDF (1632K)
  • Shin-ichi TAKEKUMA, Yoshiharu MATSUBARA, Shuichi MATSUI, Hiroshi YAMAM ...
    1988 Volume 1988 Issue 6 Pages 923-932
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Autoxidation of 1, 5-diisopropylazulene C/A0 at 115°C in HMPA (or DMF) yielded 22separable products. All the compounds were monomeric and dimeric products containing an extra carbon unit ([1G], [1N], [1A2], [1D5], [1D2]), naphthoquinone [1D1], 1 H-inden-1-ones ([1D4], [1H]), azulenylbenzofulvenes ([1B1.2], [1C], [1D8], [1F], [1L], [1M], [1O], [1R1.0], and diazulenylbenzofulvenes ([1E], [1I], [1P], [1S]), structures of which were established on the basis of spectroscopic data (UV, MS, IR, and NMR). Similarly autoxidation of 1, 1′-methylenebis(3, 7-diisopropylazulene) [1A2] at 115°C in HMPA (or DMF) gave 14separable products ([1G], [1N], [1D5], [1D2], [1B1.2], [1C], [1D3], [1F], [1L], [1M], [1O], [1R1.2], which had been previously obtained by the autoxidation of [1A1]. Possible re action pathways through radical reaction schemes are discussed for the formation of all the products.
    Download PDF (2152K)
  • Yukio MIYAMOTO, Yoshiaki OGO
    1988 Volume 1988 Issue 6 Pages 933-939
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Noncatalytic liquefactions of Illinois No.6 coal in tetralin and toluene-tetralin mixture were studied at residence time of 4 to 20 min by continuous flow method. Liquefied products were fractionated into unreacted coal, preasphaltene, asphaltene and oil in order to obtain the yield-time profiles. Chemical reaction engineering analysis was performed for those profiles using the model involving all possible pathways for the formation of preasphaltene, asphaltene and oil from coal. Pseudo-first-order rate constants for each of these mechanistic steps were estimated by nonlinear regression and were compared with those of Wandoan and Morwell coals described previously. In hydrogenative liquefaction at 450°C and 20 MPa, tetralin was unusually converted to isomer 1-methylindan which causes to lose the hydrogen-donor ability as shown in Fig.4. Therefore, noncatalytic reactions with tetralin (hydrogenative liquefaction)were mainly carried out at a temperature of 400°C and pressures of 20 to 60 MPa. The rate constant estimation shown in Table 3 indicated that Illinois No.6 coal liquefaction fairly proceeds via direct formation of asphaltene from parent coal. The largest pressure acceleration for the initial stage of dissolution of Illinois No.6 coal was observed as shown in Fig.8. Comparing with the results of solvent extraction by using toluene-tetralin mixture under the same experimental conditions, the reason for this is that Illinois No.6 coal contains characteristically a fairly large amount of the weak-linked macromolecule as asphaltene, this weakbonded fraction can be easily liquefied by extraction and such a physical process is also accelerated by pressure.
    Download PDF (1711K)
  • Kenji SATO, Takeo KONAKAHARA, Toshio YOSHI, Kazuhiro MARUYAMA
    1988 Volume 1988 Issue 6 Pages 940-945
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Hydroxymethylations of melamine (MH) and acetoguanamine (AGH) with formaldehyde (F) were kinetically investigated in aqueous carboxylate buffers at 40°C. For melamine hydroxymethylation, chloroacetate, 3-chloropropionate, and acetate buffers were used, and for acetoguanamine hydroxymethylation, in addition to above three buffers, formate, and propionate buffers were used. As a result, the second-order rate constant k given by the initial rate R0=k[Mlf]0[F]0 or R0=k[AGHf]0[F]0 was approximately given by k-k′ =kHA[HA]. Here, MHf and AGH f show the free bases of MH and AGH, respectively, and k′ is the rate constant in unbuffered media, HA being the acidic constituent of the buffer. Next, Brφnsted plots obtained by the use of the kHA, values, thus estimated, are linear with the slope of 0.35in each case. From this result, the general acid-catalyzed reaction mechanism was dicussed.
    Download PDF (1317K)
  • Kohei SHIRAISHI, Akihiko SAKAMOTO, Kazuo SUGIYAMA
    1988 Volume 1988 Issue 6 Pages 946-951
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Fifteen kinds of ester derivatives of fumaric acid (F), N-[p-[[(E)-3-(alkoxycarbonyl)acryloylJoxyThenzylidene]-p-alkoxyaniline (R-F-OR′), were p repared. The alkyl group (R)was ethyl, propyl, isopropyl, butyl, and s-butyl. Six kinds of alkoxyl group (OR′) from methoxy to hexyloxy were also employed. All of R-F-OMe showed only the nematic ph ase, while Et-F-OR′ with alkoxyl groups whose carbon number is 3 or above showed smectic phase other than nematic phase. From the electrooptical measurements using the He-Ne laser, electrooptical response time (τr)in nematic phase of R-F-OR′ is found to be 0.68-2.20ms (R: normal chain) and ca 40 ms (R: branched chain). The electrooptical measurement of mixed system of DOBAMBC (2-methylbutyl p-[p-(decyloxy)benzylidene]amino]cinnamate and i-Pr-F-OC6H13n was also carried out.
    Download PDF (1199K)
  • Masanori HASEGAWA, Takashi KAKU, Hiromi KITANO
    1988 Volume 1988 Issue 6 Pages 952-958
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Highly porous poly(styrene-co-divinylbenzene) resins were coupled with 3-chloropropionyl chloride by Friedel-Crafts reaction. The resins obtained were reacted with KSCN in DMF solution at 80°C to introduce isothiocyanato groups. The resin beads were examined for the binding ability with proteins by using batch method and column injection method. Proteins were attracted to the resin beads by the hydrophobic interaction. Subsequently proteins were strongly bound to the resin beads by formation of a stable thiourea structure between amino groups in the proteihs and isothiocyanato groups on the resin beads. These resin beads packed in a column were useful for the pretreatment (removal of proteins) of serum samples in the continuous quantitative analysis of glucose using immobilized enzymes. These resin beads were also useful as the supports of immobilized enzymes.
    Download PDF (1654K)
  • Hiroshi MATSUI, Genzo HASHIZUME, Gin-ya ADACHI, Jiro SHIOKAWA
    1988 Volume 1988 Issue 6 Pages 959-963
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    The hydrolysis process of CaS Ce phosphor under a water vapour pressure was studied by means of exposing CaS: Ce to water vapour.
    CaSO4 and CaSO3 were already obs erved on the surface of the CaS: Ce crystals at the initial period of hydrolysis. While the CaS: Ce was exposed to an atmosphere of 25°C and 40% relative humidity, water was liable to be absorbed in CaS: Ce. The surface of CaS: Ce was surrounded by water in the form of ok, and then molecular water was incorporated into the structure. With the hydrolysis being continued, Ca(OH)2 was partially formed. A small amount of Ca(OH)2 was changed into CaCO3 by absorbing atmospheric CO2. Moreover, CaS: Ce was exposed to a saturated water vapour pressure at 25°C. CaS: Ce was changed into CaSO3.1/2 H2O via II CaSO4. It was found that CaS was transformed to CaSO3, 1/2 H2O while the CaS was stored in a desicator with silica gel.
    Download PDF (3217K)
  • Hiroshi MATSUI, Hironobu OKAMOTO, Genzo HASHIZUME, Gin-ya ADACHI, Jiro ...
    1988 Volume 1988 Issue 6 Pages 964-969
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Effects of reduction conditions on the crystal shapes and the emission intensities of CaS: Ce phosphor have been studied. Needle-like or prismatic α-CaSO4: Ce1/2 H2O including cerium were prepared from CaSO4: Ce2H2O by using sodium succinate. After II⋅CaSO4: Ce was obtained by calcining a-CaSO4: Ce1/2 H2O, CaS: Ce was prepared by the reduction of II⋅CaSO4: Cefat 800, 900 or 1000°C in a stream of H2, in the absence or the presence of sulfur. When It CaSO4: Ce was reduced at 800 or 900°C, needle-like crystal shape of α-CaSO4: Ce⋅1/2H2O was maintained. The products, reduced at 1000°C, consisted of an aggregate of ium spherical CaS: Ce crystals. Grnular CaS: Ce was always obtained from the prismatic α-CaSO4: Ce1/2⋅H2O, regardless of reduction temperature. The emission intensity of CaS: Ce obtained was increased in the presence of sulfur, although the crystal shapes were not different from those obtained in the absence of sulfur.
    Download PDF (5573K)
  • Hisao NISHI, Kiyoshi KITAHARA, Yutaka KUROSAWA, Masaaki IKEDA
    1988 Volume 1988 Issue 6 Pages 970-974
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Syntheses and the structures of carbazole dioxazines (diindolo[3, 2-b: 3′, 2′-/n] and [2, 3-c: 2′, 3′-n]triphenodioxazines) [X b-f] whose two N positions of carbazole rings were covalently substituted by long straight chain alkyl (n-C6-C18) groups were studied. For examining the s tructt ure of [X], carbazole dioxazines in which two N positions were covalently substituted by (n-C3-C12) alkyl, groups having linear type-[6 c-e] and angular type structures [13 c-e] were synthesized from the correspoding 2, 5-bis[9-n-alkyl-2-methoxy-3-carbazolyl)amino)-3, 6-dichloro-1, 4-benzoquinoneg [12 c-d]. It was concluded that [X] does not have the linear type structure by comparing the 'properties of [6] with those of [X] Introduction of long n-alkyl groups on to the carbazole nitrogen of [X] results in lowering the melting and decomposition points, and a small bathochromic shift was observed in the visible spectra. [X] showed an improved dispersion property in poly(vinyl chloride).
    Download PDF (930K)
  • Michiya OTA, Sugio OTANI, Shinji IIZUKA, Takeshi SAWADA, Akira KOJIMA
    1988 Volume 1988 Issue 6 Pages 975-980
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Polycondensed fused polynuclear aromatics (COPNA) resins, previously reported, were carbonized by heat treatment up to 2500°C and carbonization mechanism of COPNA resins linked with dimethyl-substituted of benzenedimethanols (DM-series) was investigated. Discussion was carried out in terms of the structure changes due to heat treatment and the results obtained were compared to those of COPNA resin linked with PXG (PXG-series).
    The starting materials for carbonization were obtained by post-curing DM-series (cured at 120°C for 20 h) 200°C for 1 h.
    The resultant resins were heat-treated, in a stream of nitrogen, to 1400°C at a heating rate of 5°Cimin and then from 1400 to 2500°C at 20°C/min.
    PXG-series was carbonized in solid state through the whole process, while DM-series completely liquefied at 450°C. Optically anisotropic mesophase was observed in a microscopic section of DM-series treated at this temperature.
    X-ray diffraction parameters of DM -series chars produced by the heat treatment at various temperature up to 2500°C revealed that they behave like graphitizing carbon: at 2500°C, d(002)=O.3 36 nm, Lc = 33 rim.
    Download PDF (4000K)
  • Kenzi SUZUKI, Hiroyuki MASUDA, Hisao IMAI, Toshiaki MORI
    1988 Volume 1988 Issue 6 Pages 981-982
    Published: June 10, 1988
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    The interlayer spacing of aluminum-montmorillonite swollen with water (1.13 g-Water/g-Clay) was measured by small angle X-ray scattering. The interlayer spacing of aluminummontmorillonite paste was 19.2Å, and that in the frozen state was 17.3Å. The heat of fusion obtained by differential scanning calorimetry (DSC) was by 72 J/g-Clay smaller than that calculated by assuming that water in the paste was totally frozen. These rcstilts suggested that the amount of unfrozen water at 200 K in aluminum-montmorillonite was 0.22 g-Water/g-Clay.
    Download PDF (459K)
feedback
Top