Phosphorus Research Bulletin

APATITE IN THE PYROCLASTIC FLOW DEPOSIT (1990-1995) OF THE UNZEN VOLCANO, JAPAN, AND ITS UTILIZATION BY BUCKWHEAT

MASAMI NANZYO, YUKO EBUCHI, HITOSHI KANNO

2003 Volume 16 Pages 1-10
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_1

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The dacitic pyroclastic flow deposit (1990-1995) of the Unzen volcano, Japan, contained 1.0-1.6g P₂O₅ kg^-1 of total phosphorus (P). Apatite, a major chemical form of P in the pyroclastic flow deposit, was found as discrete particles and inclusions in various minerals. The dissolution of P from apatite was dependent on pH and chelating organic acids similarly to those in other fresh tephras. However, the ratio of the dilute H₂SO₄-soluble or plant-available P to the total P content was lower in the Unzen pyroclastic flow deposit than in the fresh volcanic ash deposits because of the coarse particle size. Among the tested plants, buckwheat grew best and went to seed without a P fertilizer due to partial dissolution of apatite at a soil pH around 4.

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PHOSPHORYLATION OF MARTOTRIOSE WITH INORGANIC CYCLO-TRIPHOSPHATE

HIDEKO INOUE, NAOTO TONE, HIROKAZU NAKAYAMA, MITSUTOMO TSUHAKO, TARO E ...

2003 Volume 16 Pages 11-18
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_11

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The phosphorylation of maltotriose by cyclo-triphosphate (P_3m) proceeded on not only 1-OH group of a reducing unit, but also 2′-OH and 2″-OH of nonreducing units in aqueous solution. The optimum condition for the phosphorylation of maltotriose with P_3m was a molar ratio of P_3m: maltotriose =1: 4, pH 12, and 25°C.

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INTERCALATION OF 1,3-DIAMINO-2-HYDROXYPROPANE INTO α-ZIRCONIUM PHOSPHATE FOR THE ADSORPTION OF PERFUME GAS

AKI HAYASHI, CHIE SEKIGAWA, SUMIKO KINOSHITA, HIROKAZU NAKAYAMA, MITSU ...

2003 Volume 16 Pages 19-26
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_19

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1,3-Diamino-2-hydroxypropane was intercalated into α-zirconium phosphate to develop the sustained release preparation of perfume. The several phases with different interlayer distances were obtained. Two phases with the interlayer distances (d) of 10.2 and 11.9 Å had a monolayer structure with different inclination angles to the phosphate layer. The amounts of 1, 3- diamino-2-hydroxypropane in two phases were 0.5 and 2.8 mmol/g·α-ZrP. The phase with d=11.9 Å adsorbed (Z)-3-hexen-1-ol gas known as perfume, and its sustaining release from the intercalation compound continued for 40 d.

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SYNTHESIS AND CHARACTERIZATION OF Tm₃H₅(PO₄)₂(P₂O₇)₂, A NEW MIXED-ANION THULIUM MONOPHOSPHATE-DIPHOSPHATE

A. F. SELEVICH, L. S. IVASHKEVICH, K. I. KHURS, A. I. LESNIKOVICH

2003 Volume 16 Pages 27-32
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_27

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Tm₃H₅(PO₄)₂(P₂O₇)₂, mixed-anion thulium hydrogen monophosphate-diphosphate, was synthesized by reaction of Tm₂O₃ with H₃PO₄ at 125°C using thin-layer technique. The compound was identified by chemical analysis, quantitative thin-layer chromatography, thermal analysis, and IR spectroscopy. It was found by preliminary powder XRD study that the obtained thulium phosphate has tetragonal unit cell with a=6.9092 (2), c=17.593 (1) Å; Z=2.

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EFFECT OF ADDITION OF UREA AND ITS THERMAL DERIVATIVES TO A LEAD (II) OXIDE-AMMONIUM DIHYDROGENPHOSPHATE MIXTURE ON YIELD OF CYCLO-OCTAPHOSPHATE PRODUCED BY HEATING

ATSUSHI TAKENAKA, TATSUHIKO ENDO, HIROAKI ONODA

2003 Volume 16 Pages 33-38
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_33

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The yield of cyclo-octaphosphate, obtained by heating a lead (II) oxide-ammonium dihydrogenphosphate mixture with the PbO/NH₄H₂PO₄ mixing molar ratio of 1/2, was affected by addition of urea and its thermal derivatives (biuret and cyanuric acid). The lead (II) oxide-ammonium dihydrogenphosphate mixture gave the highest yield of cyclo-octaphosphate at 500°C, while, by addition of urea or biuret, the yield was appreciably increased and the temperature was lowered to 400°C. Different processes are presented for the formation of cyclo-octaphosphate in the PbO-NH₄H₂PO₄ mixture and in the urea-added or biuret-added mixture. By addition of cyanuric acid, lead (II) polyphosphate with long-chain anion was formed as a main product above 300°C.

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NEW PREPARATION PROCESSES OF PHASES II AND V AMMONIUM POLYPHOSPHATE AND THEIR USE AS FLAME RETARDANTS

MAKOTO WATANABE, MAKOTO SAKURAI, MAKOTO TAKAHASHI

2003 Volume 16 Pages 39-46
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_39

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Ammonium polyphosphate with crystal phases of II and V was prepared by heating a mixture of ammonium orthophosphate and urea under atmospheric condition of wet ammonia at 280 to 305°C and 340 to 350°C, respectively. Form II APP prepared under the reaction condition had a larger average particle size than 10 μm and an average particle size of form V ammonium polyphosphate was 2 to 4 μm. Form II APP with a small average particle size of 2 to 4 μm was produced by heating phase I APP at the same reaction temperature under atmospheric condition of alternate gas flow of wet ammonia and dry air. The solubility of APP with the crystal phases of II and V was very low and the APP worked very well as flame retardants.

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FORMATION AND ADSORPTION OF INTERMOLECULAR COMPLEX BETWEEN ALKYL PHOSPHORIC ACID AND NONIONIC SURFACTANT ON THE SURFACE OF HYDROXYAPATITE IN AN AQUEOUS PHASE

SABURO SHIMABAYASHI, MAKIKO KITA, TOMOAKI HINO

2003 Volume 16 Pages 47-54
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_47

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Dicetyl phosphoric acid (DCP) and monoalkyl phosphoric acid (MAP, carbon number = 12, 14, and 16) are almost insoluble in water, while nonionic surfactants such as Triton X-100 (TX) and Triton N (TN) are soluble but non-adsorbable to hydroxyapatite (HAP) in an aqueous phase. Both DCP and the nonionic surfactant became adsorbable to HAP when these were mixed together in an aqueous phase. The mechanism was as follows; DCP was solubilized in a micelle of the nonionic surfactant and the mixed micelle itself was adsorbed to HAP, forming admicelle. Phosphate groups of DCP exposed on the micelle surface played an important role in the adsorption, because these head groups showed high affinity to the surface of HAP, resulting in adsorption of the micelle (i.e., admicelle). When MAP was used instead of DCP, turbidity or stability of the HAP suspension became high, although single shot of MAP or the nonionic surfactant little affected the stability. These results are showing that the non-adsorbable TX and TN became adsorbable while insoluble alkyl phosphoric acid(DCP, MAP) changed to soluble and adsorbable through their mutual interaction in an aqueous phase and on the surface.

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MECHANISMS OF THE ADSORPTION OF ORGANIC SULFONATED COMPOUNDS BY HYDROXYAPATITE IN AN AQUEOUS PHASE

EFFECTS OF NUMBER OF SULFONATE GROUPS, LATERAL INTERACTION AND COMPLEX FORMATION BETWEEN THE ADSORBATES ON THE SURFACE

SABURO SHIMABAYASHI, YUKARI KATO, MAKIKO FUKUOKA, MASASHI HOSHINO, TOM ...

2003 Volume 16 Pages 55-64
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_55

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Adsorption mechanisms of sulfonated organic compounds by hydroxylapatite (HAP) were studied. Alkylsulfonates such as sodium dodecyl sulfonate were easily adsorbed after ion exchange (i.e.,isomorphous substitution) between their terminal sulfonate groups and phosphate ions on the surface of HAP, because the size of the sulfonate group is quite similar to that of phosphate ion. Azo dyes such as methyl orange (MO) and Ponceau R(PR) were adsorbed, because these compounds also have sulfonate groups in their chemical structure. The adsorption amount of PR was larger than that of MO. This fact is suggesting that the amount increases with the number of sulfonate groups in an adsorbate molecule. The adsorption amount of each of these compounds was, however, smaller than that of a long chain alkylsulfonate. The role of hydrophobic group in an alkyl sulfonate was emphasized. Hydrophobic interaction on the surface of HAP resulted in formation of hemimicelle or admicelle, which accelerated the adsorption. The adsorption amounts of MO and PR were increased in the presence of bovine serum albumin (BSA), because these dyes formed an intermolecular complex with BSA on the surface of HAP which promotes their adsorption.

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ADSORPTION OF HUMIC ACID ON HYDROXYAPATITES

TAKESHI MORIGUCHI, KAZUYUKI YANO, SOUHEI NAKAGAWA, FUMIHIRO KAJI

2003 Volume 16 Pages 65-74
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_65

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Adsorption of humic acid (commercially available) on hydroxyapatites (HAP-100, HAP-200, HAP-300, HAP-400) was investigated in water at 25°C for 6h. Among the apatites, HAP-300, which has the largest specific surface area, indicated the highest adsorbability. Adsorption with HAP-300 within 15 min indicated higher adsorbability than that with charcoal. The isothermic curves according to Langmuir and Freundlich equations revealed that adsorbability of HAP-300 was higher than that of charcoal in the case of low concentration of humic acid (less than 6.56 mg/L). Since the adsorption was improved in NaOH solution than in water, we consider that humic acid is electrostatically adsorbed on Ca sites of hydroxyapatite surface unlike charcoal, which shows physical adsorption into its micro pores. The hydroxyapatite may be applied to an adsorbent alternative for charcoal in water purification plants.

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EFFECT OF HYDROXYAPATITE DOPANT TO YTTRIA STABILIZED ZIRCONIA CERAMICS FOR BIOMEDICAL APPLICATION

Msahiro INUZUKA, Satoshi NAKAMURA, Shigeki KISHI, Katsumi YOSHIDA, Kaz ...

2003 Volume 16 Pages 75-82
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_75

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Lower strength and fracture toughness of hydroxyapatite (HAp) ceramics have reduced the biomedical applications. On the other hand, bioinert yttria-stabilized zirconia ceramics (YSZ), used in hip-joint replacement, have high strength and fracture toughness. We prepared the ceramic HAp-doped YSZ composites (HA-Z) in order to produce high mechanical property and bioactivity materials. The Vickers hardness of the present HA-Z was almost same as YSZ, and larger than that of HAp ceramics. After immersion in simulated body fluid (SBF), the surface of HA-Z was covered by bone like apatite crystal deposited in SBF. The ion conductivity of the HA-Z was decreased with an increasing addition of HAp powders. The reduction of ion conductivity was attributed that the diffusion of calcium ion from HAp to ZrO₂ grains during the solid-state reaction between HAp and ZrO₂. Therefore, the present HA-Z is expected to apply as a new biomaterial.

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EFFECTS OF PREPARATION PROCEDURES OF CALCIUM-LEAD HYDROXYAPATITES ON THERMAL STABILITIES AND CATALYTIC ACTIVITIES FOR OXIDATIVE COUPLING OF METHANE

SHIGERU SUGIYAMA, YOSHIHARU FUJII, HIROMU HAYASHI

2003 Volume 16 Pages 83-90
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_83

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Binary hydroxyapatite, calcium-lead hydroxyapatite, was prepared by three different procedures; (A) the reaction with calcium and lead acetates with disodium hydrogenphosphate, (B) the surface-treatment of calcium hydroxyapatite with aqueous lead cation, and (C) kneading of the component hydroxyapatites. It was revealed that the thermal stability, the nature of the phosphate groups and the catalytic activities for the oxidative coupling of methane of the binary hydroxyapatite were strongly dependent on the preparation procedures.

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SELECTIVE CATALYTIC REDUCTION OF NO WITH HYDROCARBONS OVER Pt/AlPO₄ AND Pt/Al₂O₃: COMPARISON OF PROPENE WITH PROPANE AS A REDUCTANT

RYUTA FUJII, MASASHI SEKI, JUN SHINODA, NORIYASU OKAZAKI, AND TADA

2003 Volume 16 Pages 91-98
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_91

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The catalytic activity of Pt (0.5 wt%)/AlPO₄ for C₃H₆-NO-O₂ was clearly higher than that of Pt (0.5 wt%)/Al₂O₃ in terms of maximum NO conversion and temperature giving the maximum NO conversion, but the former's activity for C₃H₈-NO-O₂ was much lower than the latter's. The feature that Pt (0.5 wt%)/AlPO₄ is much less active for C₃H₈-NO-O₂ was also observed in case of Pt (0.5 wt%)/SiO₂, indicating that the surface and catalytic properties of both supports are partly similar each other.

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HIGH SO₂-TOLERANCE OF Pt-LOADED AlPO₄ CATALYST FOR SELECTIVE CATALYTIC REDUCTION OF NITROGEN MONOXIDE BY ETHENE IN EXCESS OXYGEN

RYUTA FUJII, MASASHI SEKI, JUN SHINODA, NORIYASU OKAZAKI, TADA

2003 Volume 16 Pages 99-106
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_99

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The catalytic activity of Pt/AlPO₄ for C₂H₄-NO-O₂ in the presence of SO₂ was found to be higher in terms of the maximum NO conversion and the corresponding temperature than that of Pt/Al₂O₃. The selectivity toward N₂O (byproduct) of Pt/AlPO₄ was depressed by the presence of SO₂ to its advantage; while the selectivity of Pt/Al₂O₃ was almost unaffected. The XPS spectra of Al, P and O of Pt/AlPO₄ were hardly affected even by the presence of SO₂. On the other hand, the XPS spectra of Al and O of Pt/Al₂O₃ were evidently affected by the presence of SO₂, suggesting that SO₂ interacted strongly with the Al₂O₃ to form aluminum sulfate-like species. The high SO₂-tolerance of Pt/AlPO₄ could be ascribed to the low reactivity of AlPO₄ with SO₂.

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CHEMICAL PREPARATION AND CRYSTAL DATA FOR TWO CONDENSED PHOSPHATES NiCs₄(PO₃)₆ AND NiK₄(P₃O₉)₂

KACEM SBAI, AZEDDINE ATIBI, ABDELKEBIR KENZ, ELMOSTAFA TACE, MALIKA TR ...

2003 Volume 16 Pages 107-111
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_107

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Methods of chemical preparation and crystallographic data are reported for two new condensed phosphates: a polyphosphate of nickel and cesium, NiCs₄(PO₃)₆, and a cyclotriphosphate of nickel and potassium, NiK₄(P₃O₉)₂. NiCs₄(PO₃)₆ is rhombohedral with the following unit-cell dimensions: a=b=11.602(1)Å, c=9.078(1)Å, space group P-3₁c, V=1058.24(1)Å³ and Z=2. NiK₄(P₃O₉)₂ is triclinic with the following unit-cell dimensions: a=6.143(8)Å, b=6.80(1)Å, c=12.80(3)Å, α=102.8(3)°, β=89.7(2)°, γ=66.03(7)°, space group P-1, V=473.56(3)Å₃ and Z=1.

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Addendum(Vol.14 P1~8,2002)

2003 Volume 16 Pages 113
Published: 2003
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.16.0_113

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