OPTIMIZATION OF TECHNOLOGY FOR PRODUCING A COMPOSITE BASED ON BARIUM FERRITE AND BARIUM TITANATE

В работе показано, что в результате спекания образцов композита титанат бария (80 объемных %) - феррит бария (20 объемных %) в фарфоровом тигле при температуре 1300 °С возникает эвтектика. В результате сравнения свойств образцов, полученных при различных температурах спекания, установлено, что оптимальные свойства имеют образцы, спеченные при 1250 °С. Проведено сравнение структуры и диэлектрических свойств образцов керамики титаната бария и композита титанат бария (80 объемных %) - феррит бария (20 объемных %), спеченных при температуре 1250°С. Показано, что добавление в состав титаната бария 20% феррита бария повышает значение диэлектрической проницаемости, пироэлектрического коэффициента и пьезоэлектрического модуля d композита в 1,5 - 2 раза по сравнению с керамикой титаната бария, тогда как значение пьезоэлектрического модуля d остается без изменения. Введение в состав керамики титаната бария 20 % феррита бария достаточно для того, чтобы полученный композит имел магнитные характеристики, соответствующий чистому ферриту бария. It is shown in the work that as a result of sintering of composite samples of barium titanate (80 vol. %) - barium ferrite (20 vol. %) in a porcelain crucible at a temperature of 1300 °C, a eutectic appears. As a result of comparing the properties of the samples obtained at different sintering temperatures, it was found that the samples sintered at 1250 °C have optimal properties. The structure and dielectric properties of barium titanate ceramic samples and barium titanate (80 vol. %) - barium ferrite (20 vol. %) composite sintered at a temperature of 1250 °C are compared. It has been shown that the addition of 20% barium ferrite to the composition of barium titanate increases the dielectric constant, pyroelectric coefficient, and piezoelectric modulus d of the composite of 1,5 - 2 times compared to barium titanate ceramics, while the value of the piezoelectric modulus d remains unchanged. The introduction of 20 % barium ferrite into the barium titanate ceramics is sufficient for the resulting composite to have magnetic characteristics corresponding to pure barium ferrite.

Polymorphs of VO(PO3)2: synthesis and crystal structure refinement revisited

The monoclinic α-polymorph of (VIVO)(PO3)2 is obtained reproducibly by reaction of V2O5 and H3PO4 (85%) (Au crucible, 380 °C, 4 d). Its crystal structure was refined from X-ray single-crystal data [C2/c, Z = 4, a = 15.1038(7) Å, b = 4.193(2) Å, c = 9.573(9) Å, β = 126.45(3), R1 = 0.052, wR2 = 0.189 for 976 unique reflections with Fo > 4σ(Fo), 48 variables]. A single-phase powder of the β-polymorph is obtained by the reaction of V2O5, H3PO4 (85%) and oxalic acid, evaporating the mixture, and subsequent annealing (porcelain crucible, 800 °C in air, 2 d). Single crystals of β-(VIVO)(PO3)2 were grown in a sealed silica ampoule with chlorine as mineralizer. The crystal structure of the orthorhombic (pseudo-tetragonal) β-polymorph was refined from X-ray single-crystal data [pseudo-merohedral twin, Fdd2, Z = 8, a = 15.536(2) Å, b = 15.586(2) Å, c = 4.2611(5) Å, R1 = 0.032, wR2 = 0.068 for 1072 unique reflections with Fo > 4σ(Fo), 50 variables]. Earlier reports on a tetragonal polymorph with unusual geometric structure of the [(V≡O)O5] polyhedron are corrected.

X-ray diffraction analysis of the cause of catalyst deactivation

After regeneration, the catalyst UOP-R-62 was used for conversion of reforming benzine. The percentage of conversion benzine fraction was considerably smaller than that of the new catalyst sample. To determine the cause of catalyst deactivation, in addition to standard methods of analysis, X-ray diffraction and scanning electron microscopy were used. Real and model samples of UOP-R-62 were analysed. Real samples were prepared with the new catalyst, a used and regenerated catalyst with good activity and a deactivated catalyst. Model samples were prepared from the new catalyst by heating at 400–1100 °C in a porcelain crucible in a muffle furnace for 1 h. Prepared samples were measured in a Philips diffractometer system and examined in a scanning electron microscope. The obtained diffractometer patterns, FWHM value of the 440 reflection of γAl2O3, electron micrographs and images of emitted characteristic X-rays were mutually compared. Only the values obtained from the deactivated catalyst differed from the others. Besides reduced broadening of the 440 line the material exhibited new X-ray diffraction lines, a change in phase composition, and modifications in morphology and microstructure. These changes are an indication that overheating of individual spheres of catalyst UOP-R-62 to a temperature of 700—1100 °C or higher caused their deactivation.

Qualitative Detection of Titanium Dioxide in Rubber

Titanium dioxide, either as such or in the form of the composite titanium whites, is now used to such an extent as a rubber pigment that a test for titanium is frequently necessary in the analysis of a compounded rubber. Owing to the insoluble nature of titanium dioxide, troublesome fusions are required to detect it by the normal qualitative tests in the ash remaining when a rubber is incinerated. The following method is offered as a quick and easy means of detecting titanium. A small portion (about 0.01 gram usually suffices) of the ash from the sample is placed in a clean glazed 15-cc. Porcelain crucible. One drop of concentrated sulfuric acid is then added, and the whole is heated on a hot plate for 30 seconds, i.e., until most of the acid is evaporated. The crucible is allowed to cool, and 2 drops of 6 N sulfuric acid added, followed by 1 drop of a 5 per cent aqueous solution of the sodium salt of chromotropic acid (1,8-dihydroxynaphthalene-3,6-disulfonic acid). A brownish red to purple coloration is obtained if titanium be present. In place of the chromotropic acid, 1 drop of 10-volume hydrogen peroxide is added in a second test, when the well-known golden yellow color is obtained.

The Quantitative Determination of Zinc in Transparent Rubber Articles

The method to be described is particularly suitable for the quantitative determination of zinc, present in the form of zinc oxide or of zinc salts, in transparent rubber articles. Rubber articles of this type contain very small quantities of zinc compared with the quantities present in non-transparent rubber articles, in fact the lower limit is only 0.05 per cent, i.e., only about one-hundredth as much as the normal content. The analytic determination of the zinc content when present in such extremely low percentages as this is extremely difficult by ordinary, methods, and even with higher but nevertheless small percentages of zinc, the use of relatively large quantities of material is necessary and the analytical results are often far from precise. The ordinary method of incineration in a porcelain crucible does not lend itself to the isolation of small quantities of zinc because the latter is easily fixed by the silica of the crucible. On the other hand incineration in a platinum crucible is not suitable because of the tendency of this metal to form a carbide in contact with the carbonaceous substances in the rubber. The novel feature of the method of analysis to be described is the procedure for obtaining a solution of the inorganic substances in the rubber. This involves destruction of the rubber by concentrated sulfuric acid and subsequent oxidation of the organic residue by concentrated nitric acid. This gives a solution of the zinc in the form of sulfate. It is then isolated as zinc sulfide and is redissolved and determined volumetrically by the already known method of precipitation with a standard solution of potassium ferrocyanide. The most suitable concentration, acidity and temperature to give precise results by this procedure for low percentages of zinc in rubber were established.

IV.—Note on a Perforated Silica Plate for excluding Flame Gases from a Crucible during Ignition

The device shown in the accompanying sketch has been in use in the Chemistry Department of the University of Edinburgh for some time. It consists of a silica plate, 5 inches square, with a hole bored in it of such size as to admit a crucible to one-half of its depth. The silica plate is held in an inclined position by a clamp.By this means the flame gases are excluded from the interior of the crucible during an ignition. With this device calcium carbonate in a platinum crucible is quickly reduced to oxide with a good bunsen burner, while with a Mecker burner the reduction is complete in a few minutes even when a porcelain crucible is used. The device is also useful for cases such as the ignition of nickel oxide, where there is a danger of reduction. For the estimation of sulphur in coal some such device is absolutely necessary to exclude the flame gases.

III. On Magnesium

Iodine and Sulphur . —I find that iodine can be distilled off magnesium without attacking the metal in the least. In the same manner I distilled several portions of sulphur off magnesium without the metal being at all attacked. Decomposition of Silicic Acid. —Heated for some time in a porcelain crucible with excess of anhydrous silica, the metal burns vividly if the air has access; and a certain quantity of amorphous silicium is immediately formed. Magnesium is therefore capable of reducing silicic acid at a high temperature. The reason why potassium and sodium cannot effect this is simply because these metals are highly volatile and fly off before the crucible has attained the proper temperature. Magnesium being much less volatile than the alkaline metals, takes oxygen from silica before volatilizing. If the silicic acid be in excess, a silicate of magnesia is formed at the same time; if the metal is in excess, much siliciuret of magnesium is produced. The presence of the latter is immediately detected by throwing a little of the product into water acidulated with sulphuric acid, when the charac­teristic phosphoric odour of siliciuretted hydrogen is at once perceived.