Phosphorus Research Bulletin

EFFECT OF SULFATE GROUP ON THE FORMATION OF HYDROXYAPATITE IN AN AQUEOUS PHASE

SABURO SHIMABAYASHI, HITOSHI KAWAMURA, TADAYUKI UNO

1993 Volume 3 Pages 1-6
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_1

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Formation of hydroxyapatite(HAP) via amorphous calcium phosphate(ACP) was studied by mixing CaCl₂ with K₂HPO₄ in an aqueous phase in the presence of various sulfate compounds. Sodium sulfate and sodium chondroitin-6-sulfate did not show any effect on the formation of HAP up to ca. 1mM. Transformation of. ACP to HAP was retarded in the presence of potassium polyvinylsulfate(PVSK), while its mother compound, polyvinylalcohol, showed no specific effect over the same concentration range investigated. This result means that sulfate group on PVSK competes significantly with phosphate ion for the active growth sites on the HAP nuclei. Polyvinyl-pyrrolidone(PVP) accelerated the formation of HAP by virtue of its depletion effect. The induction time for the transformation was shortened in the presence of micelle of sodium dodecylsulfate(SDS) owing to its Ca²⁺ condensation effect. This micelle effect gradually diminished with the addition of PVP due to the formation of PVP-SDS complex, which behaved like a polyelectrolyte such as PVSK.

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EFFECT OF PHOSPHORYLATED CELLULOSE AND BOVINE SERUM ALBUMIN ON CRYSTALLIZATION OF HYDROXYAPATITE

SABURO SHIMABAYASHI, NORIYOSHI HASHIMOTO, TADAYUKI UNO

1993 Volume 3 Pages 7-12
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_7

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Effect of partially phosphorylated cellulose(Phos. Cell.) on the transformation of amorphous calcium phosphate(ACP) to hydroxyapatite(HAP) in an aqueous phase was studied. Small amount of Phos. Cell. accelerated the transformation by virtue of the thick and dense clusters of calcium phosphates formed around the Phos. Cell. The clusters played a role of the heterogeneous nucleation sites for HAP. On the other hand, much amount of Phos. Cell. retarded the transformation. This effect was explained mainly in terms of the consumption of Ca²⁺(i. e., decrease in its activity) by the adsorption, where Ca²⁺ was separately bound to phosphate groups of Phos. Cell. The extent of the cluster in this case was small and, therefore, the cluster was less available for the HAP crystal seed.

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ELECTRODEPOSITION AND CHARACTERIZATION OF CALCIUM PHOSPHATES

HIDEKI MONMA, YASUSHI SUETSUGU, KAZUSHI HIROTA

1993 Volume 3 Pages 13-18
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_13

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Electrolytic calcium phosphate depositions were investigated, particularly focusing on apatite. Calcium phosphates were deposited by electrolyzing Ca(H₂PO₄)₂·H₂O (MCP) solutions (0.02-0.20mol/dm³) added with and without NaNO₃ at temperatures (10-50°C) and cathode current densities (5-120mA/cm²). Deposition products changed such as CaHPO₄→CaHPO₄·2H₂O→Apatite with increasing current or decreasing MCP concentration. Adding NaNO₃ or increasing temperature made the apatite deposition easy. At low temperatures or dilute MCP concentrations amorphous calcium phosphate tended to be deposited. The composition of deposited apatite was estimated to be (Ca»Na)_10-x (HPO₄, CO₃)_x(PO₄)_6-x(H₂O» OH)₂·nH₂O; Ca/P-1.5.

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HYDROTHERMAL SYNTHESIS OF COPPER(II) PHOSPHATES

Ka. HASHIMOTO, K. FUJITA, K. MORIO, Y. TODA

1993 Volume 3 Pages 19-24
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_19

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Some copper(II) phosphates have been hydrothermally synthesized by using CuHPO₄·H₂O or Cu₈(HPO₄)₂(PO₄)₄·7H₂O as the starting materials and by treating hydrothermal processing under saturated vapor pressure conditions of 150-350°C.
With CuHPO₄·H₂O as the starting material, when hydrothermal processing in deionized water, octagonal crystals of Cu₂(PO₄)OH were produced in conditions of 150-300°C, and granular crystals of Cu₃(PO₄)₂ were produced in conditions of 350°C for 24 hours or more. In addition, when the processing solution was made into a 1.0 mol·dm^-3H₃PO₄ aqueous solution, a new product Cu₃(PO₄)₂·H₂O was produced in 200°C processing.
When the starting material of Cu₈(HPO₄)₂(PO₄)₄·7H₂O was hydrothermally processed in deionized water, the composition of the hydrothermal product was Cu₂(PO₄)OH under all processing conditions from 150-350°C. However, when 1.0 mol·dm^-3KF aqueous solution was used in the hydrothermal solution, the product became spherulite Cu₅(PO₅)₂(OH)₄ under conditions of 200°C for 10 hours or more and under conditions of 250°C for 10-24 hours.
Copper(II) phosphate shows antibacterial properties, and it is more effective against yellow Staphylococcus than against E. coli.

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INTERCALATION BEHAVIOR OF PYRIDINE AND RELATED COMPOUNDS INTO LAYERED ZIRCONIUM PHOSPHATE

MAYUMI DANJO, YOSHINOBU BABA, MITSUTOMO TSUHAKO, HIROYUKI NARIAI, ITAR ...

1993 Volume 3 Pages 25-30
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_25

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Intercalation of pyridine and its related compounds into layered zirconium phosphate, Zr(HPO₄)₂·H₂O (α-ZrP), was examined for the purpose of discussing the effect of a functional group on the uptake behavior. The acid dissociation constants of pyridines strongly affect the intercalation behavior; nicotinic acid (pKa=2.05) was not intercalated, but nicotinamide (pKa=3.47) was readily intercalated. The uptake behavior was influenced by the amino group position on aminopyridines. The 2-, 3-, and 4-aminopyridine intercalation compounds gave the different X-ray diffraction patterns. The possible arrangement of pyridines between the sheets of α-ZrP will be discussed.

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COMPARISON OF THE COMPLEXATION BEHAVIOR OF CYCLO-IMIDO-TRIPHOSPHATE ANIONS WITH CYCLO-TRIPHOSPHATE ANIONS IN AN AQUEOUS SOLUTION

Tohru Miyajima, Hideshi Maki, Makoto Sakurai, Shoji Sato, Makoto Watan ...

1993 Volume 3 Pages 31-36
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_31

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Proton and metal ion complexation behavior with cyclic triphosphate anions, which constitute P-O-P and/or P-NH-P linkages, were compared with each other in order to see the role of the imido groups on the complexation equilibria. The stability constants of proton and metal ion complexes with the cyclo-triphosphate analogues increases proportionally to the number of the P-NH-P bondings in the phosphate anions, i. e., in the order of cyclo-triphosphate, cyclo-monoimidotriphosphate, cyclo-diimidotriphosphate, and cyclo-triimido triphosphate. The enhancement of the stabilities with the addition of imino groups to the cyclo-triphosphate molecule is pronounced in a Cu²⁺ ion binding. The ²⁷AlNMR spectra of Al³⁺ ion complexes with the series of ligands indicate the direct coordination of the nitrogen atoms of imino groups to Al³⁺ ions.

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COUNTERION BINDING TO INORGANIC POLYPHOSPHATE ANIONS (I)

TOHRU MIYAJIMA, RIE KAKEHASHI

1993 Volume 3 Pages 37-42
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_37

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The change in the Na⁺ ion binding properties of a series of the anions of inorganic phosphates (phosphinate, cyclic polyphosphate, and linear polyphosphate) has been studied in order to see the transition from simple electrolyte to polyelectrolyte. Na⁺ ion activity measurement together with ²³Na NMR peak width measurement gave a consistent conclusion that about 100 of the chain-length is needed to show the binding properties independent of the chain-length in salt-free system.

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COUNTERION BINDING TO INORGANIC POLYPHOSPHATE ANIONS (II)

RIE KAKEHASHI, TOHRU MIYAJIMA

1993 Volume 3 Pages 43-48
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_43

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Metal ion binding properties of a series of inorganic polyphosphate anions has been studied with an excess of uni-univalent salt. The binding equilibria were strongly dependent on the added salt concentration. The concentration dependence of the cyclo-octaphosphate binding was quite close to that of the long-chain polyphosphate binding, whose binding equilibria has been interpreted by a“two-phase model”.

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THERMAL BEHAVIOR OF VARIOUS COPPER CYCLO-PHOSPHATES

HIROYUKI NARIAI, ITARU MOTOOKA, MITSUTOMO TSUHAKO

1993 Volume 3 Pages 49-54
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_49

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The thermal behavior of various copper cyclo-phosphates, Cu₂P₄O₁₂·8H₂O (P_4m), Cu₃P₆O₁₈·12H₂O (P_6m2), and Cu₄P₈O₂₄·18H₂O (P_8m), was investigated using TG-DTA, HPLC, and X-ray diffraction analysis. P_4m decomposed perfectly to ortho-(P₁), pyro-(P₂), and insoluble highpolyphosphates (P_{high poly}) with the elimination of water of crystallization. With an increase in temperature, P₁ and P₂ condensed to Phigh poly, in part, to cyclo-tetraphosphate. The decomposition of P_4m proceeded faster under humid air than dry air. P_6m also decomposed to short-chain phosphates and P_oligo (n=7-14), further to P₁, P₂, and P_{high poly}. Although the water vapor accelerated the decomposition of P_6m, it prevented the formation of cyclo-tetraphosphate. P_8m lost the most of water of crystallization to decompose to P₁ and P₂. The formation of cyclo-tetraphosphate was observed at 300°C. The amount of cyclo-tetraphosphate increased with an increase in temperature. Under a higher water vapor pressure, the decomposition of P_8m proceeded rather faster than under a lower one, while the rate of condensation reactions to P_{high poly} slower than under the higher one. At 450°C, no difference in the effect of atmosphere on the amounts of cyclo-tetraphosphate and P_{high poly} was observed.

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THE SYNTHESIS AND THERMAL BEHAVIOR OF AMMONIUM TETRAIMIDOCYCLOTETRAPHOSPHATE

MAKOTO SAKURAI, MAKOTO WATANABE

1993 Volume 3 Pages 55-60
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_55

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Tetraammonium tetraimidocyclotetraphosphatete tetrahydrate has been prepared by adding aqueous ammonia and ethanol into an aqueous tetraimidocyclotetraphosphoric acid solution. Only the release of the water of crystallization was observed and any decomposition of the imidophosphate did not occur up to 140°C. At a higher temperature, the imidophosphate decomposed to produce many kinds of condensed phosphates with or without NH and NH₂ groups.

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REACTION OF α-AND γ-CYCLODEXTRIN WITH CYCLO-TRIPHOSPHATE

HIDEKO INOUE, YOSHINOBU BABA, MITSUTOMO TSUHAKO

1993 Volume 3 Pages 61-66
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_61

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In an aqueous solution, α- and γ-cyclodextrin (α- and γ-CD) reacted with inorganic sodium cyclo?triphosphate hexahydrate (P_3m), Na₃P₃O₉·6H₂O, to form a triphosphate derivative and three monophosphate derivatives of α-and γ-CD, of which the secondary hydroxyl groups were phosphorylated. The maximum yields of phosphorylated products of α- and γ-CD were 22.6 and 19.0 %, respectively.

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PHOTOCHEMICAL DECOMPOSITION OF ORGANIC PHOSPHORUS COMPOUND INCLUDING POLYPHOSPHATES BY ULTRA-VIOLET RADIATION AND ACID-HYDROLYSIS

Jun-ichi ITOH, Masashi KOMATA

1993 Volume 3 Pages 67-72
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_67

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Total phosphorus in the samples containing organic phosphorus compound, organic polyphosphate and inorganic polyphosphate were determined as orthophosphates by ionchromatography after acid-hydrolysis and photochemical decomposition. With the procedure, oxalic acid was used for thermal acid-hydrolysis of polyphosphate chain, and ultra-violet radiation for photo-oxidation of organic parts of compound and oxalic acid. The method avoids contamination of the final phosphate solution with excess acids those are used in conventional acid-hydrolysis methods.

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SURFACE COATING OF β-TRICALCIUM PHOSPHATE ON THE POROUS HYDROXYAPATITE

Koji IOKU, Kazumichi YANAGISAWA, Nakamichi YAMASAKI, Hisashi KUROSAWA, ...

1993 Volume 3 Pages 73-78
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_73

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Porous hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂; HA) coated with β-tricalcium phosphate (Ca₃(PO₄)₂; TCP) was prepared by our unique method. The porous HA was soaked in diammonium hydrogen phosphate solution, and then the HA was sintered at 900°C for 3 hrs. β-TCP was formed on the surface of HA. It was possible to control the content of surface-formed β-TCP arbitrary by varying the concentration of the solution. The obtained HA coated with 33wt% β-TCP (33TCP) had about 60% open porosity with the pore size from 150 to 400 μm. The average compressive strength of 33TCP was 17.5 MPa. Surface coated HA with β-TCP deprived of the brittleness in handling. From the results of implantation into the femoral condyles of adult rabbits, this porous material showed good bone formation inner and around itself.

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HYDROXYAPATITE COATING ON ALUMINA SUBSTRATE BY SOL-GEL TECHNIQUE

Y. KOJIMA, A. SHIRAISHI, K. ISHII, T. YASUE, Y. ARAI

1993 Volume 3 Pages 79-84
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_79

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The purpose of the present work was to investigate synthetic condition of viscous coating sol by sol-gel technique in reaction of Ca(NO₃)₂-(C₂H₅O)₃PO-C₂H₅OH system, burning temperature after dip-coating the viscous sol onto alumina substrate and thick control of porous hydroxyapatite (HA_p, Ca₁₀(PO₄)₆(OH)₂) coating on the substrate as bone substitute. The products on the substrate were characterized by using X-ray diffraction, scanning electron microscopy, infrared spectroscopy and chemical analysis. The formation of viscous sol as precursor of amorphous calcium phosphate (ACP) was remarkably affected by synthetic conditions such as aging time, Ca/P atomic ratio and pH in an initial mixed solution. In order to stabilize porous HAp coating onto alumina substrate, it was more effective to burn at 1000 °C after dip-coating onto the substrate with viscous sol which formed by aging for 8 days under conditions of Ca/P atomic ratio 1.5 and pH 8 in an initial mixed solution. Also the thickness of HAp layer on the substrate was continuously increased by repeating dip-coating processes 2 to 3 times and developed to about 20μm after repeating 3 times. Consequently, the production of the new artificial biomaterials which joined strongly to the thin layer of HAp on surface of alumina substrate was expected.

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Nasicon-type solid solution in the system Ca-Na-Ti-(PO₄)

Application for the elaboration of multicomponent phosphate bioceramics.

P. VAST, B. DEFFONTAINES, O. MENTRE, F. ABRAHAM

1993 Volume 3 Pages 85-90
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_85

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Nasicon type compounds in the system Ca - Na-Ti-(PO₄) may be obtained by soft chemistry way. We use the phosphate coacervate route and we obtain the same results as by solid chemistry methods. The coacervate route permits us to obtain multicoponent ceramics that may be used in medical applications. This study of the formation of Nasicon solid solution shows the possibility of a sodium ratio control in the glass phasis of multicomponent phosphate ceramic obtained by coacervate process. Thus it is possible to obtain adaptable durability of phosphate ceramic in biomedical application.

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Cu-P-Y-O BASED CERAMIC HUMIDITY SENSOR: SOLID-STATE REACTION BETWEEN Cu₃(PO₄)₂·3H₂O AND Y₂O₃

AKIO TADA, NORIYASU OKAZAKI, MASAKI KAWAI, HIDENOBU ITOH

1993 Volume 3 Pages 91-96
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_91

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The solid-state reaction routes to humudity-sensitive Cu-P-Y-O based subatances, particularly to YPO₄ from Cu₃(PO₄)₂·3H₂O and Y₂O₃ was investigated by XRD, TG-DTA, and SEM. In addition, the sintering temperature of the Cu-P-Y-O based ceramics was correlated with the humidity-sensitive characteristics, and the presence of Cu₂O in the excellent Cu-P-Y-O based humidity sensor was also confirmed.

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Synthesis of Na⁺ Superionic Conductors in the Na₂O-Y₂O₃-P₂O₅-SiO₂ System by using metal alkoxides and Crystallization Processes from Dried Gel

Seiichi SUDA, Kimihiro YAMASHITA, Takao UMEGAKI

1993 Volume 3 Pages 97-102
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_97

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Sodium superionic conductor with the composition of Na_5.2Y_0.8P_0.4Si_3.6O_12.0 was synthesized using metal alkoxides. When a usual synthetic method, using every alkoxide, water, solvent and catalyst directly, was employed as a sol-gel method, the highly conductive silicophosphate was obtained, but a nitrate was precipitated in the dried gel. On the other hand, the dried gel obtained after the gelation was induced by moisture in air was highly homogeneous and showed lowering temperature of crystallization.

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CRYSTALLIZATION AND CONDUCTION PROPERTY OF Na⁺ SUPERIONIC CONDUCTOR NARPSIO-V

Toshiya KAKUTA, Kimihiro YAMASHITA, Motohide MATSUDA, Takao UMEGAKI

1993 Volume 3 Pages 103-108
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_103

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Various Narpsios consisting of the composition formula of Na_3+3x-yR_1-xP_ySi_3-yO₉(R: rare earth, In and Sc) were synthesized by the crystallization of a glass. The formation of Narpsio-V having high conduction property was influenced by the kind of R element. The specimens with single phase of Narpsio-V were obtained in the use of Sm, Eu, Gd, Y and Er. In particular, the Narpsio-V widely yielded on the composition map of [Y] vs. [P]. The R elements also affected the conduction properties. The activation energy for Na⁺ conduction in Narpsio-V was improved with increasing the ionic radius of R element. Although the lowest activation energy was confirmed in the case of Sm, the total conductivity of whole specimen with Sm was lower than that with Gd. This was due to the difference in the grain boundary.

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GRINDING EFFECTS OF SEVERAL PHOSPHATES ON THEIR CATALYTIC ACTIVITIES

AKIO TADA, NORIYASU OKAZAKI, MITSURU OISHI, HIDENOBU ITOH, YUZO IMIZU

1993 Volume 3 Pages 109-114
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_109

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The grinding effects of four kinds of phosphates on their catalytic activities for the isomerization and/or oligomerization of n-butene were investigated; activity-enhancing effect was observed for BPO₄ and Ti(HPO₄)₂·H₂O, while activity-depressing effect for AlPO₄ and Ce(HPO₄)₂·1.33H₂O.

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VAPOR PHASE DECOMPOSITION WITH DECHLORINATION OF ORGANIC CHLORINATED COMPOUNDS OVER CALCIUM-DEFICIENT HYDROXYAPATITE

HARUMITSU NISHIKAWA, HIDEKI MONMA

1993 Volume 3 Pages 115-118
Published: 1993
Released on J-STAGE: October 29, 2012

DOIhttps://doi.org/10.3363/prb1992.3.0_115

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Vapor phase decompositions of trichloro-ethylene(TCE), tetrachloroethylene(PCE) and 1,1,2-trichloro-1, 2, 2-trifluoroethane(CFC113) over calcium-deficient hydroxyapatite(DAp) were investigated in oxidative conditions. The conversions of chlorinated organic compounds were over 90% for TCE at 450°C, over 80% for PCE at 500°C, and 23% for CFC113 at 500°C. In the decomposition of TCE, most of Cl in the compound was captured as Cl^- in DAp.

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