DE1417246C - Mixed phases based on titanium dioxide - Google Patents

Description

I 417 246

Mixed phases, titanium dioxide as the host component contained in the crystal modification of rutile or anatase are from German patent I 080 245 known. The mixed phases described in this patent have cations as guest components with a radius between about 0.54 and 0.96 Å and the anions of fluorine and optionally oxygen ions on. The ratio of the sum of the guest cations to the sum of the guest anions is 1: 2.

Mixed crystals of titanium dioxide with a content of tungsten trioxide or mixtures of tungsten trioxide and antimony oxide, bismuth oxide, vanadium pentoxide, Molybdenum oxide and / or uranium oxide and oxides of lithium, magnesium, zinc, manganese (II), iron (II), Kov balt (II), nickel (H), copper (II), aluminum, gallium, Titanium (III), chromium (III), manganese (III) and iron (III) or mixtures of such oxides are from the German Patent specification 1,287,236 is known. The amounts of 6 and / or 5 valent cations and behave of the 1-, 2- or / and 3-valent cations relative to one another in such a way that a mean statistical Valency of - | -4 results.

The present invention relates to mixed phases which are titanium dioxide as the host component in the Contains crystal modification of rutile or anatase. As guest components, these mixed phases lead to Amounts from 0.5 to 50 percent by weight of at least one oxide of one of the pentavalent or ovalent metals antimony, Bismuth, niobium, tantalum, molybdenum and uranium and at least one of the colored oxides. Trivalent metals manganese (II), iron (II), copper (II), Vanadia (IlI), Chromium (IlI), Manganese (IlI), Iron (III) and Rhodium (III) and optionally oxides of 1-, 2-, 3- or / and tetravalent metals, the cations of which have radii between 0.53 and 0.90 Å, the amounts of the metal oxides occurring as guest components behave relative to one another in such a way that the cations have a mean statistical value of +4 results.

Oxides of monovalent metals that meet the conditions just mentioned come mainly from Lithium oxide iii question.

On suitable oxides of divalent metals, which may be included in the mixed phases can, be magnesium and zinc oxide, on suitable oxides of trivalent metals aluminum, gallium and antimony (HI) oxide and appropriate oxides tetravalent metals called germanium, tin, lead, zirconium and hafnium dioxide.

The ion radii of the underlying oxides Metal ions are:

Antimony (V) 0.62 A, bismuth (V) = 0.74 A, niobium (V)

0.69 A, tantalum (V) ■ -. 0.68 A, molybdenum (VI)

0.62 A, uranium (VI) --- = 0.90 A, lithium = 0.78 A,

Magnesium 0.78 A, zinc = 0.83 A, aluminum

0.57 A, gallium 0.62 A, antiiium (lII) = - 0.90 A, Germanium (IV) ■ 0.53 A, tin (IV) == 0.74 A.

Lead (IV) -r: 0.84 A, zircon (IV) = -. 0.87 A, hafnium (IV)

·· ■ - · 0.84 A. The radius of tetravalent titanium is

for comparison 0.64 A.

In order to meet the requirement that the cations of the guest components have a mean statistical Valence of 1-4 results are therefore according to the invention for example on L moles of manganese (II), iron (II) or copper (II) oxide I mol of antimony and / or bismuth and / or niobium and / or tantalum pentoxide and / or molybdenum and / or uranium trioxide, or to 1 mole of vanadium (III) - and / or chromium (III) - and / or manganese (III) - and / or iron (III) - 1 Mo 'antimony and / or bismuth and / or niobium and / or Tantalum pentoxide and / or 1 mol of molybdenum and / or uranium trioxide to build up the mixed phases with Use titanium dioxide; also germanium and / or tin and / or zirconium and / or Hafnium and / or lead dioxide can also be used. It can be bivalent, trivalent and tetravalent Oxides of the type mentioned with the ones mentioned

ίο pentavalent and hexavalent oxides in any arbitrary Way to be combined; but it can also be done individually or several times with the systems mentioned those colorless mixed phases are combined with titanium dioxide in which, for example, 1 mol of lithium oxide 3 moles of antimony and / or niobium and / or tantalum pentoxide or to 1 mole of magnesium and / or Zinc oxide 1 mole of antimony and / or niobium and / or tantalum pentoxide and 1 mole of aluminum and / or Gallium and / or antimony (III) oxide also 1 mole of antimony and / or niobium and / or tantalum pentoxide come. In all cases, however, the law that the mean statistical value of all Cations is +4 and that there is statistical electrical neutrality in the lattice.

Thus are the amounts of the two or more metal oxides that are used as guest components in the mixed phases may be contained, determined relative to one another, so the ratio of the host component titanium dioxide assume virtually any value between 0.5 and 50% for the guest components.

The production of the mixed phases basically means that a mixture of the components is converted into the mixed phases at an elevated temperature, in particular by annealing. In this case, instead of the oxidic components, heat-unstable compounds of the metals on which the components are based can be used, which are converted into the components of the mixed phases when heated. So z. B. instead of titanium dioxide, the hydrate of titanium dioxide which passes into this dioxide during heating can be used. Instead of the oxides of the metals, such as magnesium oxide and zinc oxide, for example, their carbonates, acetates, nitrates or formates can be used. If necessary, small amounts of a flux, such as lithium fluoride, can be added to the mixtures to facilitate the formation of mixed crystals.
The new mixed phases based on

so titanium dioxide make high quality pigments of various kinds Colors and color nuances are represented by advantageous properties, such as B. their refractive index and thus particularly distinguish their color strength and opacity as well as their lightfastness.

The starting materials for the production of some typical representatives of the new mixed phases are given in the following examples. The constituents mentioned are mixed and at 800 ⁰ C and after pulverizing i ₂ hour / annealed ₂ hours at 1000 ° C generally V.

example 1

5,000 g anatase + 0.500 g MnO (converted from MnCO ₃ ) + 2.280 g Sb ₂ O ₅ . A reddish-tinged, medium-brown pigment with a rutile or trirutile structure is obtained.

■ Ζ 7 Example 2> - · ■ ·. "'· ■. ■ -

5,000 g anatase 4- 0.100 g FeO (converted from FeCO ₃ ) + '0.450 g Sb ₂ O ₅ . There is obtained a greenish 'gray pigment from which have approximately 20 ° / ₀ anatase and about 80% Rutilstriiktur.

Example 3

5.000 g anatase + 0.50 g FeO (converted from TeCO ₃ ) 4- 2.250 g "Sb ₂ O _5. A greenish gray pigment with a pure rutile structure is obtained. ■.: ■, -.

B e i s ρ i e 1 4 '

5.000 g anatase + 0.500 g CuO (converted from CuCO _? ) H 2.030 g Sb ₂ O ₅ . A lemon-yellow pigment with a rutile structure is obtained. - - -,

. B e i s ρ ie I 5

5,000 grams of anatase 4; 0.200 g CuO (converted from CuCO ₃ ) -I- 0.812 g 'Sb ₂ O ₅ 4- 0.050 g NaF. A yellowish lime green pigment with a rutile structure is obtained.

Examples

5.000 g anatase + 0.500 g V ₂ O ₅ (as a source for V ₂ O ₃ ) 4- 0.889 g Sb ₂ O ₅ . A black-brown pigment with a rutile structure is obtained. . ■ ■

B e i s ρ ie I 7

5.000 g anatase + 0.100 g Cr ₂ O ₃ 4- 0.213 g Sb ₂ O ₅ . A yellow-olive colored pigment with the structure of rutile is obtained.

Example

5,000 g anatase + 0.500 g Cr ₂ O ₃ 4- 1.070 g Sb ₂ O ₅ . A yellow-brown pigment with a rutile structure is obtained:

. ';.-... B e i s ρ i e 1 9

5,000 g anatase 4- 0.556 g Mn ₂ O ₃ (Mn (III) -) (converted from MnCO ₃ ) + 1.140 g Sb ₂ O ₅ . A chocolate-brown pigment with a rutile structure is obtained.

"Example 10

5,000 g anatase 4-0,200 g Fe ₂ O ₃ 4- 0.405 g Sb ₂ O ₅ . A gray-olive pigment is obtained with about 30% anatase and about 70% rutile structure.

ν "Example 11

5.000 g anatase + 0.200 g Fe ₂ O ₃ + 0.405 g Sb ₂ O ₅ · ■ + 0.200 g NaF. A greenish yellow pigment with a rutile structure is obtained. '-J; · ■ '-

', · Λ Example 12 r-- "- V": ■'"■

.5.000 g anatase + 0.250 g Cr ₂ O ₃ -f- 0.250 g CuO (converted from -CuCO ₃ ) + 1.550 g Sb ₂ O ₅ . A beige-colored pigment with a rutile structure is obtained.

■;, "■■ ■■; .. ■. '. · ^::; Ϊ́ΐΓ. B eis ρ ie 1 13 ·,"^; · ■

- -5.000 g anatase + 0.250 g Fe ₂ O ₃ + 0.250 g MnO converted from MnCO ₃ ) 1 1.645 g Sb ₂ O ₅ . A reddish brown pigment of rutile structure is obtained. ,

Example 14

- 5,000 g anatase -r 0.200 g Fe ₂ O ₃ -, 0.156 g Bi ₂ O ₅ (from nitrate) 4- 0.303 g Sb ₂ O ₅ . One receives a. yellow-beige pigment of rutile structure.

B is ρ i el 15 ' _r

5.000 g anatase f- 0.500 g CuO (converted from CuCO ₃ ) i- 1.015 g Sb ₂ O ₃ i- 0.835 g Nb ₂ O ₅ . A light greenish yellow pigment of rutile structure is obtained.

O:, example 16:

5.000 g anatase .4- 0.500 g Cr ₂ O ₃ ; - 0.268 g Sb ₂ O ₅ 4- 1.091 g Ta ₂ O ₅ . A gray-tinged olive-colored pigment with a rutile structure is obtained.

Example 17

Titanium oxide hydrate sludge with 5,000 g TiO ₂ solid substance is mixed with 0.500 g CuO (converted from CuCO ₃ ) 1- 0.508 g Sb ₂ O ₅ : ■■■ 0.678 g MoO ₃ . _{Calcined 1/2} hour at 700 ° C., after pulverization 1/2 hour at 800 ° C. This gives a green olive pigment with a rutile structure.

Example 18

5.00OgTiO ₂ r 0.500 g MnO (converted from MnCO ₃ ) 4- 1.140 g Sb ₂ O ₅ 4- 1.010 g UO ₃ (from uranyl nitrate). A red-brown pigment of a mixture of rutile and trirutile structure is obtained.

Example 19

. 5.000 g anatase ■ - ■■ 0.100 g MgO (converted from MgCO ₃ ) 4- 0.100 g MnO (from MnCO ₁ ) _{0.010 g Fe 2} O ₃ 4- 0.010 g Cr ₂ O ₃ - 0.452 g V ₂ O ₅ (from NH, YO ₃ ) 4- 0.456 g Sb ₂ O ₅ - 0.0654 g Bi ₂ O, (from nitrate) 4- 0.0179 g UO ₃ (from nitrate) _: 0.0175 g Nb ₂ O ₅ . A dark brown pigment of rutile structure is obtained.

Claims (1)

Claim: That contain mixed-phase titanium dioxide as the host component in the modification of the rutile or anatase, characterized in that it contains as host components in amounts of 0.5 to 50 weight percent of at least one oxide _of: the 5- or 6wertigen metals antimony, bismuth. Niobium, tantalum, molybdenum and uranium and at least one colored oxide of the bivalent or trivalent metals manganese (U), iron (II), copper (II), vanadium (III), chromium (III), manganese (III ), Iron (III) and rhodium (III) and optionally. Oxides of 1-, 2-, 3- or / and tetravalent metals, the cations of which have radii between 0.53 and 0.90 Å, the amounts of metal oxides occurring as guest components being relative to one another in such a way that the cations an average value of 4 4 results.