Phosphorus Research Bulletin

AMORPHOUS CALCIUM PHOSPHATE PRECIPITATION IN AQUEOUS SUPERSATURATED SOLUTIONS: THE INFLUENCE OF NATURAL AND SYNTHETIC INHIBITORS

ZAHID AMJAD

2005 年 18 巻 p. 1-6
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_1

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The induction time for the transformation reaction of amorphous calcium phosphate (ACP) to hydroxyapatite (HAP) was investigated at pH 7.40, 37 °C, and calcium = phosphate 3.20 mM, in the presence of natural and synthetic inhibitors containing phenolic and carboxyl groups. The inhibitors tested include: natural materials containing phenolic and carboxyl groups i.e., green tea extract, GT; lignosulfonate, LS; fulvic acid, FA; tannic acid, TA; and synthetic material containing carboxyl group i.e., polyacrylic acid. It has been found that all inhibitors were effective in delaying the transformation reaction. The inhibitor effectiveness was greatly affected by inhibitor concentration and the presence of functional groups i.e., phenolic and carboxyl. For natural and synthetic inhibitors the order in terms of decreasing effectiveness is: PA >> FA > TA > GT > LS.

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INFLUENCE OF POLYMERIC ADDITIVES ON THE PRECIPITATION AND STABILIZATION OF AMORPHOUS CALCIUM PHOSPHATE

ZAHID AMJAD

2005 年 18 巻 p. 7-14
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_7

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The stabilization effects of poly(acrylic acids) of varying molecular weights and made in different polymerization solvents on the precipitation of amorphous calcium phosphate (ACP) were investigated using a pH-stat method (Ca = PO₄ = 3.2 mM, pH 7.40, 37 °C). It has been found that addition of low concentrations of polymers delays the conversion of ACP to thermodynamically stable hydroxyapatite. Additionally, it has been observed that the stabilization of ACP increases with increasing polymer concentration and decreases with decreasing molecular weight (5,000 to 2,000 Dalton).

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RESEARCH ON INFLUENCE OF TEMPERATURE (20°-1000°C) ON BINARY MIXTURES OF SOLID SOLUTIONS OF Li₃PO₄ - Mg₃(PO₄)₂·8H2O

MICHAL HENRYK UMBREIT, AGNIESZKA JEDRASIEWICZ, JOLANTA KLOS, MONIKA ZA ...

2005 年 18 巻 p. 15-24
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_15

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We analysed thermal phase changes of substrates (20°-1000°C) of binary mixtures Li₃PO₄ - Mg₃(PO₄)₂·8H₂O. Changes during dehydration and thermal dissociation process in binary mixtures prepared with percentage molar ratio 90%-10% were studied. The researches were done by means of differential thermal analysis (TG, DTG, DTA), IR-spectroscopy and WAXS. The above mentioned substances heated for 1 hour up to 500° and 1000°C changed the structure. Mg₃(PO₄)·8H₂O (Bobierite) changes the structure at 500°C into amorphous phase and Farringtonite (in traces) and at 1000°C into Mg₃(PO₄)₂(Farringtonite). Heating Li₃PO₄ (Lithiophosphate) oven at 1000°C do not cause the transformation. Binary mixtures containing 70% - 30% Li₃PO₄ change the structure and double salt LiMgPO₄ is formed.

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EXPERIMENTAL STUDIES OF THE INFLUENCE OF MIX OF THE CALCIUM AND MAGNESIUM SALTS OF INOSITOLHEXAPHOSPHATE ACID ON BILIATION FUNCTION OF A LIVER AT THE ACUTE HEPATITIS

Z. Z. KHAKIMOV, S. S. KASIMOVA, B. M. ASCAMOV, J. Z. AKRAMOVA

2005 年 18 巻 p. 25-29
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_25

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For white pubertal male-rats was reproduced the model of acute necrosis a hepatitis by way of hypodermic inoculation of the acetothioamide and investigated the influencing a mix of calcium and magnesium salts of the inositolhexaphosphate acid on the excretive function of a liver and elemental composition of bile. It is established that the mix of salts of the inositolhexaphosphate acid at an acute hepatitis is remove considerable disturbance on excretive function of a liver and elemental composition of bile. The studied compound has a cholagogic, hypobilirubinic and hepatoprotective properties and present the important interest as a drug for treatment of acute and chronic defects of a liver.

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SURFACE MODIFICATION OF CALCIUM HYDROXYAPATITE WITH 3-AMINOPROPYLTRIETHOXYSILANE

HIDEKAZU TANAKA, MASAYUKI BABA, RYOZI HINO

2005 年 18 巻 p. 31-36
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_31

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The surface of synthetic calcium hydroxyapatite (Hap) particles was modified with 3-aminopropyltriethoxysilane (APS: NH₂(CH₃)₃ Si(OC₂H₅)₃) in 95% ethanol solutions and the resulting materials were characterized by various means. No remarkable change in XRD pattern, molar ratio Ca/P, specific surface area and particle morphology of the Hap was recognized by the modification. The number of surface aminolpropyl group of Hap increased from 0 to 4.2 molecules nm^-2 as the APS concentration increases. IR results indicated that APS reacted with surface P-OH groups of Hap and formed -Si-OH groups.

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MECHANOCHEMICAL EFFECTS ON FORMATION AND PROPERTIES OF VARIOUS COPPER PHOSPHATES

HIROAKI ONONA, KAZUO KOJIMA, HIROYUKI NARIAI

2005 年 18 巻 p. 37-46
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_37

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INFLUENCE OF POLYMER ARCHITECTURE ON THE TOLERANCE OF POLYPHOSPHATES AND PHOSPHONATES WITH CALCIUM IONS IN AQUEOUS SOLUTIONS

ZAHID AMJAD

2005 年 18 巻 p. 47-54
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_47

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THE WET METHOD OF SYNTHESIZING HYDROXYAPATITE FROM AQUEOUS SOLUTIONS AT VARIOUS pH RANGES WHICH MADE ORGANISM TEMPERATURE MAIN

OSAMU FUJINO, HIROYUKI TAMURA

2005 年 18 巻 p. 55-64
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_55

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Hydroxyapatite was formed by the extremely slow addition of diammonium hydrogenphosphate to a solution of calcium nitrate at pH9 buffered with ethylenediamine at 36.5°C. The Ca/P molar ratio in the precipitate yielded was measured by inductively coupled plasma atomic emission spectrometry and the condition of the crystals was examined by X-ray diffraction. This synthetic apatite was compared with human tooth and bones from cattle and pigs. The crystallization condition and Ca/P molar ratio were extremely similar to those of human tooth.

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INTERMOLECULAR COMPLEX FORMATION BETWEEN METHYL ORANGE AND BOVINE SERUM ALBUMIN ON THE SURFACE OF HYDROXYAPATITE IN AN AQUEOUS PHASE

SABURO SHIMABAYASHI, MAKIKO FUKUOKA, TOMOAKI HINO

2005 年 18 巻 p. 65-74
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_65

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Methyl orange (MO) was not adsorbed directly to hydroxyapatite (HAP) when the concentration of MO was low, while bovine serum albumin (BSA) was adsorbed by HAP in the presence or absence of MO. Formation of the intermolecular complex between MO and BSA both in an aqueous phase and on the surface of HAP was discussed in the present paper. Apparent adsorption amount of MO to HAP increased with a concentration of BSA due to the adsorption of BSA and formation of the complex of MO-BSA on the surface when the [BSA] was low. The adsorption amount of MO, however, decreased with a concentration of BSA when the [BSA] was high. This fact was explained in terms of an increase in the concentration of BSA free from HAP, i.e., formation of the complex of MO-BSA in the mother solution.

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EFFECT OF WATER-SOLUBLE ORGANIC POLYMER ON HARDENING OF CALCIUM PHOSPHATE CEMENT

MAKOTO WATANABE, HIDENAO SUZUKI, KENTA MIZUNO, TAKASHI TERADA, MIOKO M ...

2005 年 18 巻 p. 75-81
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_75

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A hard body of calcium phosphate cement was prepared by mixing α-type tricalcium phosphate or tetracalcium phosphate and a polyacrylic acid solution and then hardening the paste. Mechanical strength of the hard body increased with increasing concentration of polyacrylic acid and pH value of the solution. Hardening time to cure the paste decreased with increasing concentration of polyacrylic acid and increased with increasing pH value of a polyacrylic acid solution. The calcium phosphate cement of α -type tricalcium phosphate gave stronger mechanical strength than that of tetracalcium phosphate. The highest compressive strength of 67.3 and 47.1 MPa were given for the hardened cements of α -type tricalcium phosphate and tetracalcium phosphate, respectively. Mechanical strength of the cement increased with the passage of time at the first step and then decreased after one month.

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ADSORPTION OF AQUATIC HUMIC SUBSTANCES ON HYDROXYAPATITE IN WATER

TAKESHI MORIGUCHI, KAZUYUKI YANO, SOUHEI NAKAGAWA, FUMIHIRO KAJI

2005 年 18 巻 p. 83-92
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_83

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Aquatic humic substances, humic acid (Nordic-HA) and fulvic acids (Nordic-FA and Suwannee-FA), were investigated in adsorption on hydroxyapatite (HAP) in water at 25°C for 15 min or 6 h. Adsorbability of HAP to the humic acid was higher than that to the fulvic acids. HAPs calcined at 600°C and 1200°C, HAP-C600 and HAP-C1200, indicated lower adsorbabilities than the raw HAP in the case of adsorption time 6 h. Calcination of HAP resulted in shrinkage of the pores and fusion of the surface, and affected lowering the adsorbability. Actually, judging from evaluation of Freundlich constants, K_F and 1/n, we found that the raw HAP has larger adsorption capacity than the calcined HAPs. Although HAP has smaller surface area than charcoal, the K_F values of HAP were larger than those of charcoal. In addition, by comparison with adsorption of alizarin red S, we found that Ca sites on HAP surface facilely interact with phenolic OH rather than COOH groups of humic substances.

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SYNTHESIS IN THE AMMONIUM POLYPHOSPHATE MELT AND THERMAL BEHAVIOUR OF BINARY POLYPHOSPHATES Mg(NH₄)₂(PO₃)₄ AND Ca(NH₄)₂(PO₃)₄

A.F. SELEVICH, L.S. IVASHKEVICH, E.V. GRUSHEVICH, A.I. LESNIKOVICH

2005 年 18 巻 p. 93-98
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_93

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Reactions of Mg(OH)₂ and Ca(OH)₂ with NH₄PO₃ have been studied in the 300-400 °C range at the molar ratio P₂O₅ : MO = 4:1. Conditions of formation for two new isotypic polyphosphates M(NH₄)₂(PO₃)₄ (M = Mg, Ca) have been elaborated. The compounds are found to be isostructural with binary metaldiammonium polyphosphates M(NH₄)₂(PO₃)₄ (M = Mn, Co, Cd), monoclinic system, the space group P2₁/n, Z = 4. XRD studies have been performed for powder samples of Mg(NH₄)₂(PO₃)₄ [the unit cell dimensions are a = 11.233(6), b = 12.738(5), c = 7.761(4) Å; β = 101.32(5)°] and Ca(NH₄)₂(PO₃)₄ [the unit cell dimensions are a = 11.412(4), b = 13.372(8), c = 7.935(4) Å; β = 101.73(3)°]. Thermal behaviour of the polyphosphates has been investigated in the 20-1000 °C temperature range.

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INVESTIGATION OF BINARY MIXTURES OF SOLID SOLUTIONS Al₂(SO₄)₃·16 H₂O, CaSO₄·2H₂O AND Na₂SO₄ WITH MgHPO₄?3H₂O

MICHAL H. UMBREIT, JEAN P. AUFFREDIC, AGNIESZKA JEDRASIEWICZ

2005 年 18 巻 p. 99-108
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_99

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We analyzed thermal phase changes (20°-1000°C) of binary mixtures of Al₂(SO₄)₃·16 H₂O(I), CaSO₄·2H₂O (II) and Na₂SO₄ (III) with MgHPO₄·3H₂O (IV). Thermal differential analyses (TG, DTG, DTA), IR, WAXS and thermorentgenography revealed that above mentioned mixtures heated during one hour up to 500°C and to 1000°C changed their structures. From among these three system of binary mixtures (I-IV; II-TV, III-IV) only (Na₂SO₄-MgHPO₄· 3H₂O), when the participation share of Na₂SO₄ was from 80 to 30% in the binary mixture, showed the formation NaMg₄(PO₄)₃ with coexistence Na₂SO₄-Mg₂P₂O₇ in samples.

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ACTIVE BPO₄ CATALYST FOR OLIGOMERIZATION OF LIGHT OLEFINS

MOTOI TAKAHASHI, TOMOYA SAKAGUCHI, NORIYASU OKAZAKI, AKIO TADA

2005 年 18 巻 p. 109-114
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_109

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BPO₄ catalysts were prepared under different preparation conditions from an equimolar mixture of boric acid and phosphoric acid, and the activity was investigated for the oligomerization of light olefins. It was found that a BPO₄ catalyst which was prepared by mixing those reagents at 0°C in a rotary evaporator, followed by warming the resulting viscous liquid at around 40°C under controlled pressure (first normal, then reduced pressure) for 1-9h, showed much higher activity than conventional BPO₄ catalysts.

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CHARACTERIZATION OF BPO₄ CATALYST FOR OLIGOMERIZATION OF LIGHT OLEFINS

MOTOI TAKAHASHI, TOMOYA SAKAGUCHI, NORIYASU OKAZAKI, AKIO TADA

2005 年 18 巻 p. 115-120
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_115

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BPO₄ catalysts which were prepared under different conditions from a mixture of boric acid and phosphoric acid were characterized in terms of specific surface area, amounts of the residual reactants unreacted, and acidic properties. Then the correlation between those physicochemical properties and those catalytic activity. It was revealed that the most important factor was to dissolve boric acid in phosphoric acid as completely as possible, avoiding the condensation of boric acid and/or that of phosphoric acid, because those condensates are catalytically inactive and in addition they block the active sites of BPO₄ catalysts. The active sites were also revealed to be Bronsted acid sites by their measurement of pyridine adsorbed on BPO₄ catalysts.

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ACTIVITY OF ALUMINUM PHOSPHATE FOR SELECTIVE CATALYTIC REDUCTION OF NITROGEN MONOXIDE WITH PROPENE OR PROPANE

JUN SHINODA, NORIYASU OKAZAKI, AKIO TADA

2005 年 18 巻 p. 121-126
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_121

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The activity of AlPO₄ for C₃H₆-SCR-NO, C₃H₆-SCR-NO, and several related reactions were investigated and discussed by comparison with those of alumina and silica. The activity of AlPO₄ for C₃H₈-SCR-NO and C₃H₈-SCR-NO was lower than that of Al₂O₃, and silica was inactive. The activity differences between AlPO₄ and Al₂O₃ can be mainly ascribed to those for NO oxidation to NO₂. Over both AlPO₄ and Al₂O₃, the maximum NO conversion in C₃H₆-SCR-NO was located at lower temperature side than that in C₃H₈-SCR-NO. These results can be ascribed to activity differences for the oxidation of C₃H₆ and C₃H₈ with both O₂ and NO.

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CHARACTERIZATION OF LAYER-STRUCTURED OCTACALCIUM PHOSPHATE/DWARBOXYLATE COMPOSITE

HIDEKI MONMA, YUSUKE NISHIMURA, TOSHINORI OKURA

2005 年 18 巻 p. 127-134
発行日: 2005年
公開日: 2012/10/29

DOIhttps://doi.org/10.3363/prb1992.18.0_127

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Layer-structured octacalcium phosphate (OCP)/dicarboxylate composite has become of interest as a new type of calcium phosphate compounds. In the present paper, the inorganic/organic composite has been reviewed for some development of materials science and applications of calcium phosphates. Three kinds of configuration models of intercalated dicarboxylate ions proposed in the literature are described. The interplanar spacing (d₁₀₀) of OCP/dicarboxylate composites increased with increasing in principal chain length of intercalated linear aliphatic dicarboxylate ions. Addition of side chain groups to the principal chains of dicarboxylate ions caused contractions of d₁₀₀ in many cases. Some OCP/dicarboxylate composites were characterized with respect to particle morphology, zeolitic dehydration-rehydration accompanying contraction-recovery of d₁₀₀, catalytic dehydration of 2-propanol, and powder properties.

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