Beiträge zur systematischen Verwandtschaftslehre. 83. Über die Verbindungsfähigkeit von Titan mit Phosphor

Biltz, Wilhelm; Rink, Anneliese; Wiechmann, Friedel

doi:10.1002/zaac.19382380408

Cited by 18 publications

(6 citation statements)

References 6 publications

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“…The group 4 phosphides are known for their hardness and chemical inertness even at elevated temperatures. − When zirconium phosphide (ZrP) and hafnium phosphide (HfP) are heated above 1425 °C and 1600 °C, respectively, they each undergo a hexagonal (h) to cubic (c) phase transition as demonstrated by Irani and Gingerich . This transition may involve loss of phosphorus .…”

Section: Introductionmentioning

confidence: 99%

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Self-Propagating Metathesis Routes to Metastable Group 4 Phosphides

2000

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Group 4 phosphides, which are typically prepared at high temperatures (> 800 degrees C) over several days, are synthesized in self-propagating metathesis (exchange) reactions in seconds. These reactions produce cubic forms of zirconium phosphide (ZrP) and hafnium phosphide (HfP) which are normally made at temperatures greater than 1425 degrees C and 1600 degrees C, respectively. To test whether the high temperatures reached in the metathesis reactions are responsible for the formation of the cubic phases, inert salts are added to lower the maximum reaction temperatures. The lower temperature reactions still result in cubic phosphides, although smaller crystallites form. Further experiments with phosphorus addition indicate that the phosphorus content is not responsible for cubic phase formation. Templating is ruled out using lattice mismatched KCl and hexagonal ZnS as additives. Therefore, the direct synthesis of the high-temperature cubic phase in metathesis reactions appears to be caused by nucleation of the metastable cubic form that is then trapped by rapid cooling. Heating the cubic phase of either ZrP or HfP to 1000 degrees C for 18 h, or carrying out metathesis reactions in sealed ampules at 1000 degrees C, results only in the hexagonal phase.

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Section: Introductionmentioning

confidence: 99%

“…Other researchers have synthesized group 4 phosphides by a variety of methods including reactions of metals with phosphorus, , metals or metal halides with Ca 3 P 2 , metals with PH 3 , ,,, and ZrCl 4 with PCl 3 , or reduction of metal oxides with aluminum in the presence of phosphorus and iodine …”

Section: Introductionmentioning

confidence: 99%

Self-Propagating Metathesis Routes to Metastable Group 4 Phosphides

2000

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“…The structure solution of Ti 2 P is quite an old structural problem. The ®rst indications for a Ti 2 P phase were reported by Biltz et al (1938) and by Vereikina & Samsonov (1960), but the poor quality of their data prevented them giving any structure information on this new compound. A ®rst structural model was proposed by Yeremenko & Listovnichy (1965).…”

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confidence: 97%

Structure of Ti₂P solved by three-dimensional electron diffraction data collected with the precession technique and high-resolution electron microscopy

et al. 2003

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The crystal structure of Ti(2)P has been analysed using electron diffraction and high-resolution electron-microscopy techniques. A new unit cell was found, the compound is hexagonal with a = 19.969 (1) and c = 3.4589 (1) A. The structure was first solved in space group P-62m in projection using direct methods on electron diffraction data from the [001] zone axis. A three-dimensional solution was obtained using again direct methods but on a three-dimensional set of electron diffraction data recorded with the precession technique. Ti(2)P is a distorted Fe(2)P structure and, based on high-resolution images, it is possible to explain that the tripling of the unit cell is due to the ordering of P vacancies that reduces the symmetry to P-6.

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“…Only a few investigations of the phosphides have been done, although some phosphides have some good physical and chemical properties [1,2], and have extensive applications in many areas. The group 4 phosphides are such transition metal phosphides, which are of much interest in view of its high chemical and thermodynamic stability, its metallic conductivity and its moderately high hardness [3][4][5].…”

Section: Introductionmentioning

confidence: 99%

Low-temperature synthesis of nanocrystalline ZrP via co-reduction of ZrCl4 and PCl3

Chen

Huang

et al. 2004

Materials Letters

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Beiträge zur systematischen Verwandtschaftslehre. 83. Über die Verbindungsfähigkeit von Titan mit Phosphor

Cited by 18 publications

References 6 publications

Self-Propagating Metathesis Routes to Metastable Group 4 Phosphides

Self-Propagating Metathesis Routes to Metastable Group 4 Phosphides

Structure of Ti₂P solved by three-dimensional electron diffraction data collected with the precession technique and high-resolution electron microscopy

Low-temperature synthesis of nanocrystalline ZrP via co-reduction of ZrCl4 and PCl3

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Beiträge zur systematischen Verwandtschaftslehre. 83. Über die Verbindungsfähigkeit von Titan mit Phosphor

Cited by 18 publications

References 6 publications

Self-Propagating Metathesis Routes to Metastable Group 4 Phosphides

Self-Propagating Metathesis Routes to Metastable Group 4 Phosphides

Structure of Ti2P solved by three-dimensional electron diffraction data collected with the precession technique and high-resolution electron microscopy

Low-temperature synthesis of nanocrystalline ZrP via co-reduction of ZrCl4 and PCl3

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Structure of Ti₂P solved by three-dimensional electron diffraction data collected with the precession technique and high-resolution electron microscopy