DE1417251C - Mixed phases with pigment properties based on tin dioxide - Google Patents

Description

• 1 2

It is known to produce white tin dioxide by adding (0.78), copper (I) - (0.96), magnesium (II) - (0.78), zinc (II) compounds small amounts of oxides of vanadium and / (0.83), manganese (II) - (0.91), iron (II) - (0.82), cobalt (II) -. or molybdenum or of such compounds (0.82), nickel (II) - (0.78), vanadium (II) - (0.72), copper (II) - these Elements which, when heated, turn into oxides - (0.72), palladium (II) - (0.80), aluminum (III) - (0.57), go ability, fire-resistant, yellow color bodies 5 gallium (III) - (0.62), titanium (III) - (0.69), arsenic (III) - (0.69), manufacture by annealing, the ceramic and antimony (III) - (0.90), vanadium (III) - (0.65), niobium (III) - enamel technical Can be used. At (> 0.69), tantalum (III> (> 0.68), chromium (III) - (0.64), Mandiesen Procedure, however, the surcharges in quali- gan (IIl) - (0.70), iron (III) - (0.67), rhodium (III) - (0.68), in terms of both quantity and quantity, germanium (IV) - (O, 53), lead (IV) - (0.84), vanadium (IV) - selected, so that crystallographically no defined io (0.61), tellurium (IV) - (0.89), chromium (IV) - (> 0.64), ruthe structures and optimal pigments are not obtained nium (IV) - (0.68), osmium (IV) - (0.67), iriduim (IV) - will (0.66), zircon (IV) - (0.87), hafnium (IV) - (0.84), arsenic-From the tlSA.-Patent 2,534,390 is a kera- (V) - (0, 46), antimony (V) - (0.62), bismuth (V) - (0.74, Vamisches Insulating material known, which consists of tin dioxide nadin (V) - (0.59), niobium (V) - (0.69), tantalum (V) - (0.68), Mound Titanium dioxide consists. Such mixed phases are 15 lybdenum (VI) - (0.62), tungsten (VI) - (0.62),. Uranium (VI) - however in no way suitable as pigments. (0.80) and tellurium (VI) - (0.56).

Furthermore, it is from the German patent specification 1080 245 other metal compounds, such as those

known, mixed phases, which are used as host components of sodium, potassium, calcium, strontium, barium,

Titanium dioxide in the crystal modification of rutile or boron, beryllium, silicon, cerium (IV), phosphorus (V),

Contain anatase. As guest components, 20 chromium (VI), sulfur (VI) and Mn (VII), come for

d. H. so in amounts of less than 50%, real mixed phases are out of the question, because, if necessary

cations with a radius between about 0.54 apart from their insufficient temperature

and about 0.96 Å and the anions of fluorine as well as permanent, their ionic radii either too large or

of divalent oxygen in question. are too small.

Subject of the present application are as So that the requirement is still met that

Mixed phases with pigment properties, the rutile components in the guest components the sum of the added

or have a polyrutile structure, the cations thereby marked to the sum of the added anions below

are characterized by the fact that, as a host component, tin dioxide maintains statistical electrical neutrality in the

and 6 or / and 5-valent lattices such as about 1: 2 behaving as guest components are according to the invention

or / and 3-, 2- or / and l-valent cations, whose 30 z. B. on 1 molecule of nickel (II) -, cobalt (II) -, magnetic

Ionic radius between 0.45 and 0.97 Å, and as sium, zinc, manganese (II) -, iron (II) - or copper (II) -

Anions contain oxygen or fluorine, the oxide 1 molecule arsenic (V) -, antimony (V) - and / or

Sum of the added cations to the sum of the bismuth (V) - or / and vanadium (V) - or / and niobium (V) -

set anions while maintaining statistical elec- or / and tantalum (V) - or / and 1 molecule of molyb-

troneutrality in the lattice about the ratio 1: 2 ent- 35 Danish (VI) - or / and tungsten (VI) - or / and uranium (VI) -

speaks, the amount of guest components in total and / or tellurium (VI) oxide or on 1 molecule of aluminum

however, any, but not greater than the amount of nium, gallium, arsenic (III), antimony (III), van

is the host component. din (III) -, chromium (III) -, manganese (III) -, iron (III) - or

In addition, these mixed phases of tin-rhodium (III) oxide molecules arsenic (V) -, antimony (V) -

dioxids nor such 4-valent metal ions as guest 40 or / and bismuth (V) - or / and vanadium (V) - and / or

contain components with an ionic radius between niobium (V) -or / and tantalum (V) -or / and molybdenum (VI) -

0.45 and 0.97 A. or / and tungsten (VI> or / and uranium (VI) - or / and

Such real mixed phases represent white or tellurium (VI) oxide or on 1 molecule of lithium oxide or

colored pigments, which in their own pigment - 1 molecule of copper (I) oxide 3 molecules of arsenic (V) -, an

properties, especially with regard to color strength and 45 timon (V) -, bismuth (V) -, vanadium (V) -, niobium (V) - or

Color purity, compared to the mixed products - tantalum (V) - or / and 3 molecules of molybdenum (VI) - or /

distinguish remarkably. and tungsten (VI) - or / and uranium (VI) - or / and

The rutile lattice of tin dioxide consists of a tellurium (VI) - and optionally one or more

tetragonal unit cell with the constants O ₀ = molecules germanium (IV) -, lead (IV) -, zircon (IV) -

4.73 and C ₀ = 3.18 A; the cell contains 2 molecules 50 or / and hafnium (IV) oxide as guest components

"SnO _2. The tetravalent positively charged tin with which to use to build up the mixed phases. Es

The ionic radius of 0.74 A is somewhat distorted in the mono-, di-, tri- and tetravalent oxides

• Octahedron of 6 doubly negatively charged acid - of the type mentioned with the mentioned five- and six-

surrounded by fabric. Combined in any desired way through the incorporation of certain foreign-valued oxides

, cations can optionally become an order of the Ca- ₅₅ . In all cases, however, the law must be fulfilled

tions take place in such a way that the c _o -axis of the tetra- remain, that the sum of the added cations

'. gonal cell doubled, tripled or quadrupled to the sum of the added anions while preserving

is multiplied, Such rutile phases are called di-, tri- a statistical electroneutrality in the lattice for example

or polyrutile structures. behaves like 1: 2.

It has now been found, as mentioned above, that 60 mixed phases of tin dioxide and

such metal oxides or / and fluorides in the aforementioned the difluorides of divalent metals, eg. B. Mg, Zn,

Rutile lattice of tin dioxide can be incorporated, Mn (II), Fe (II), Co (II), Ni (II), Cu (II), are made. In

. the cation radii of which are between 0.45 and 0.97 Å. In this case, the added difluorides crystallize

and thus in the crystal-chemical sense with the ionic, with the exception of CuF _2, already in the rutile lattice. the

radius of tetravalent tin are comparable. Me- 65 above-mentioned difluorides can be used individually, to multiply

tallow oxides and fluorides of this type are z. B. the torture or all combined side by side in the rutile

(the ionic radii of the elements concerned are built into a grid.

A are each added in brackets): Lithium (I) - Other mixed phases can also be used with mixtures

3 4

equimolecular parts of a trifluoride and a statistical electroneutrality. Suitable for installation

Fluorides of a monovalent metal, e.g. B. AlF ₃ + LiF, are z. B. the pentoxides of arsenic, antimony, bismuth,

GaF ₃ + LiF, CrF ₃ +, LiF, MnF ₃ + LiF, FeF ₃ + LiF, vanadium, niobium and tantalum. Here too you can

be formed as guest components. , Lithium fluoride one, some or all of the above-mentioned

The simultaneous installation of z. B. 1 LiF + 5 th pentoxides can be combined. ^! . 1 AlF ₃ occur a total of 2 cations and 4 anions. B. from the host into the host lattice; the sum of the component cation charges and an equimolecular mixture is +4, the sum of the anion charges is -4; of hexavalent metal oxide and monovalent! The statistical electro-neutrality is preserved. The tallfluorid consist. A simple example of these additives mentioned above can be added individually, in io sets is the system WO ₃ with LiF. Thereby, in combination with several or all of them, an IW ⁶⁺ and ILi ¹⁺ = 2 Kagitter are built into the host-host grid as guests. . ions and 3 O ² ~ and 1 F ^1- = 4 anions. The sum

Mixed phases can also contain a mixture of the incoming cation charges which is +7

3 molecules of metal trifluoride with 1 molecule of incoming anion charges —7; it prevails

tigern metal oxide, e.g. B. the combination of 3 metal 15 ie statistical electrical neutrality. As trioxides

trifluoride + lithium oxide. Are z. B. come z. B-. those of molybdenum, tungsten,

3 molecules of CrF ₃ with 1 molecule of Li ₂ O at the same time in that of uranium and that of tellurium in question,

the tin dioxide grid built in, so 3Cr ³⁺ + can occur here, too, the various trioxides

2Li ¹⁺ , i.e. 5 cations, and 9 F ^1- +! O ² -, i.e. individually or all together with lithium fluoride

10 anions, in the lattice; the sum of the an ao. V

, built cation charges is + 11, the sum. Finally, let mixed phases with a com-

The amount of the incoming anion charges is -11, it is a combination of some or all of the above

So there is statistical electrical neutrality. Suitable systems listed together. The above individually

Trifluorides for this type of installation are AlF ₃ , GaF ₃ , CrF ₃ .

MnF ₃ and FeF ₃ . One can increase the individual trifluoride 35 by especially that individual or

alone, in several or all at the same time in the host all of the large series of variations listed above

install grille. can be combined with each other again

Further mixed phases can, for. B. a mixed phase in the structure of the parts of a trifluoride and a divalent metal rutile or polyrutile always arises from the host component and despite this large number of possible variations and a mixture of equimolar capacities,
oxides, e.g. B. the combination of 1 FeF ₃ and 1 ZnO, are thus the amounts of two or more 5- or / consist. 1 Fe ³⁺ and 1 Zn ^{a +} = 2 cations and 3 F ^1- and 6- and 3-, 2- or / and 1-valent metal oxides: or and 1 O ^2- = 4 anions occur simultaneously in the fluoride, which as Guest components in the mixed host lattice; the sum of the entered ka-phases can be contained, relative to each other fixed ion charges is +5, that of the entered 35, the ratio of the host component anion charges can be -5, so there is statistical to the guest components overall electroneutrality within wide limits. The trifluorides are the same as fluctuate; the content of guest components is as mentioned above; as metal oxides are, for. B. which, by definition, does not exceed 50%
Oxides of Mg, Zn, Mn (II), Fe (II), Co (II), Ni (II) and The production of the mixed phases is in principle Cu (II) suitable. The trifluoride and the bivalent 40 add to the fact that a mixture of the components metal oxides can each be combined individually or all grain at elevated temperature, in particular by annealing, without the mixed phase being converted into the mixed phases. In doing so, the crystal structure can change. V ^:. \ ', Instead of the oxidic components also' heat-

There is also a mixed phase with equimolecular unstable connections between the components

lar mixture of metal trifluoride and trivalent 45 underlying metals are used

Metal oxide as guest components. As a simple addition to the components of the mixed phases when heated

With this type of installation, the CrF ₃ + Cr ₂ O ₃ system should be ignored. So z. B. instead of tin dioxide

called. At the same time, 3Cr ³⁺ = hydrate which is converted into this dioxide when heated, enters the grid

3 cations and 3 F ¹ "" and 3O ^2- = 6 anions. of tin dioxide can be used. ,Instead of

The sum of the incoming cation charges is 50 oxides of the metals, e.g. B ... of magnesium oxide and

carries +9, the corresponding sum of the anions zinc oxide, for example their hydroxides,

charges —9. Here, too, there are statistical electro-carbonates, acetates, or nitrates. Fonniate Ver

neutrality. Find a twist. Next can also be aqueous or

The above-mentioned other solutions of all substances involved come back as trifluorides through al-

in question; The trivalent metal oxides contain 55 Jcalically reacting substances (e.g. NH ₃ ) which precipitate

the same metals as those of the trifluorides mentioned. Evaporated saline solution or partially or entirely brine

The trifluorides can be used individually or all with or gels of the substances involved. Ge

A sesquioxide, some or all of the sesquioxides, if necessary, can be added to the mixtures for relief

be combined, the ■ corresponding rutile phase of the mixed crystal formation small amounts of a

is retained anyway. "'' 60 flux, such as sodium fluoride, can be added

Other mixed phases can be an equimolecular den.

Mixture of pentavalent metal oxide and lower when using metal compounds

contain valuable metal fluoride. In the case of the valence as output components that these values

Mixing Sb ₁ O ₅ with LiF, 2 Sb ⁸⁺ and 1 Li ¹⁺ occur in the end product, i.e. in the mixed phase.

= ι ·,; '3 cations, and 5Ö ² ~ and ί FK = 6 anions 65 should; it may be necessary to heat

at the same time in., the grid a. The sum of one of the mixtures with the exclusion of oxygen in

occurring "cation charges is +11, that of the inert gas atmosphere,

incoming anion charges —11; Here, too, the following examples show the production

typical representatives of the new mixed phases described. . ..- .. ■ · ...- example 1

5.000 g of SnO ₂ + 0.020 g of Li ₂ O (from Li ₂ CO ₃₎ + 0,650g Sb ₂ O ₅ are mixed, Va hour bei.800 ⁰ C, after pulverizing V ₂ hour at 1000 ⁰ C, after pulverizing V2 hour at Annealed at 1150 ° C. A light gray-blue pigment with a rutile structure is obtained.

Example!

5,00OgSnO ₂ + 0.100 g MgO (from MgCO ₃₎ + 0,802g Sb ₂ O ₅ are mixed, V ₂ hour at 1000 ° C, pulverizing after ¹ J ₂ hours at 1150 ⁰ C, after pulverizing ¹ I ₂ hour at 135o Annealed to ^{0 C.} A greenish gray-blue pigment with a rutile structure is obtained. Example 10; V

5.000 g of SnO ₂ + 0.500 g of Ga ₂ O ₃ + 0.863 g Sb ₂ O ₅ are mixed at 800 ° C, after pulverizing ¹ I ₂ hour at 100O ⁰ C, after pulverizing V ¹ I ₂ Hour ₂ hour at 1150 ° C , after pulverization calcined at 135O ⁰ C for ¹ _{l for 2 hours.} A light gray-blue pigment with a rutile structure is obtained. , ■

Example 11

5.000 g of SnO ₂ + 0.500 g Cr ₂ O ₃ + 1.065 g Sb ₂ O ₃ are mixed, -V ₂ hour at 800 ° C, after pulverizing Vs hour at 100O ⁰ C, after pulverizing V2 hour at 1150 ⁰ C, after pulverization Annealed at 135O ⁰ C for 1 hour. A yellowish brown pigment with a rutile structure is obtained. .

• B e i s ρ i e 1 3

5.000 g of SnO ₂ + 0.200g ZnO (from ZnCO ₃₎ + 0.795 g Sb ₂ O ₅ are mixed, annealed Va hour at 1000 ⁰ C, after pulverizing βο Va hour at 115o C ^0. A greenish white-blue pigment with a rutile structure is obtained.

B e i s ρ i el 4

5.000 g of SnO ₂ + MnO 0.200 g (from MnCO ₃₎ + 0,912g Sb ₂ O ₅ are mixed, annealed Va hour at 80O ⁰ C, after pulverizing Va hour at 100O ⁰ C, after pulverizing Va hour at 1150 ⁰ C. A light gray-brown pigment with a rutile structure is obtained.

B e i s ρ i el 5

5.000 g of SnO ₂ + 0.200 g FeO (from FeCO ₃₎ + 0.900 g Sb ₂ O ₅ are mixed, V2 hour at 80O ⁰ C, annealed at 1150 ⁰ C V2 hour after pulverizing V2 hour at 1000 ° C after pulverizing _r. A light gray pigment with a rutile structure is obtained.

Example I * 6 <

5.000g SnO ₂ + 0.200g CoO (from CoCO ₃ ) + 0.864g Sb ₂ O ₅ are mixed, Va hour at 80O ⁰ C, after pulverization Va hour at 100O ⁰ C, after pulverization V2 hour at 1150 ⁰ C annealed. * A brownish-yellow-gray pigment with a rutile structure is obtained.

Example 7,

5.000 g SnO ₂ + 0.200 g NiO (from NiCO ₃ ) + 0.866 g Sb ₂ O ₅ are mixed, Va hour to 80O ⁰ C, after pulverization Va hour to 100O ⁰ C, after pulverization Va hour to 1150 ⁰ C, after pulverization V heated to 135O ⁰ C for _{2 hours.} An olive-green pigment with a rutile structure is obtained both at 1000 and 1350 ^° C.

Examples

5.000 g of SnO ₂ + 0.500 g of CuO (from CuCO ₃₎ + 2.033 g Sb ₂ O ₅ are mixed, V2 hour at 800 ⁰ C, annealed at 1000 ⁰ C hour, after pulverizing Va hour at 115o C ⁰ after pulverizing Va. A brownish, olive-colored pigment with a rutile structure is obtained.

Example 9 ^ ·

5.000 g SnO ₂ +0.200 g Al ₂ O ₃ g (from Al (OH) ₃₎ + 0.634 Sb ₂ O ₅ are mixed, V ₂ hour at 800 ⁰ C, after pulverizing V2 hour at 1000 ° C, according to Pulverisiercn ¹ I ₂ hours at 1150 ⁰ C, after pulverizing for 1 hour at 1350 ° C annealed. A pale dove-blue pigment with a rutile structure is obtained.

Example 12

5.000 g SnO ₂ +0.500 g Mn ₂ O ₃ (from MnCO ₃ ) + 1.025 g Sb ₂ O ₅ are mixed, Va hour at 800 ° C. after pulverizing Va hour at 100O ⁰ C, after PUL- ', verisieren Va hour at 1150 ⁰ C annealed. A gray-brown pigment with a predominantly rutile structure is obtained.

Example 13

5.000 g SnO ₂ + 0.500 g Fe ₂ O ₃ + 1.013 g Sb ₂ O ₅ are mixed, Va hour to 800 ^° C., after pulverization V2 hour to 1000 ^° C., after pulverization V ₂ hours to 1150 ^° C., after pulverization Heated to 1350 ° C for 1 hour. A light gray-yellow pigment with a rutile structure is obtained.

B e i s ρ i e I 14

5.000 g of SnO ₂ + 0.050 g Li ₂ O (from Li ₂ CO ₃₎ + 0,913g V ₂ O ₅ are mixed, annealed Va hour at 1000 ⁰ C, after pulverizing Va hour at 1150 ⁰ C. A blackish red-brown pigment with a rutile structure is obtained. . ,

Example 15

5.000 g of SnO ₂ + LiF + 0.100 g 0.701 g V ₂ O ₅ are mixed, Va hour at 1000 ⁰ C, after pulverizing V annealed ₂ hours at 1150 ° C. A reddish dark brown pigment with a rutile structure is obtained.

Example 16.

5.000 g SnO ₂ +0.200 g MgO (from MgCO ₃₎ + 0.903 g of V ₂ O ₅ are mixed, Va hour at 1000 ⁰ C, annealed at 1150 ⁰ C V2 hour after pulverization. An olive-brown pigment with a rutile structure is obtained.

Example 17

5.000 g of SnO ₂ + 0.500g ZnO (from ZnCO ₃₎ + 1.118 g of V ₂ O ₅ are mixed, annealed V2 hour at 1000 ⁰ C, after pulverizing Va hour at 1150 ⁰ C. A yellowish ^/ olive-colored pigment with a rutile structure is obtained.

Example 18

5.000 g of SnO ₂ + 0.500 g Al ₂ O ₃ (Al (OH) ₃₎ + 0.892 g of V ₂ O ₅ are mixed, Va hour at 1000 ° C, after pulverizing V annealed ₂ hours at 1150 ⁰ C. A brownish, yellow-olive pigment with a rutile structure is obtained. ■

Example 19 Example 28

5.000 g SnO ₂ + 0.500 g Al ₂ O ₃ (from Al (OH) ₃ ) + 5.000 g SnO ₂ + 1.00Og ZnF ₂ become. mixed,

1.304 g of Nb ₂ O ₅ are mixed, V ₂ hours at 1000 ° C, V ₂ hours at 800 ° C, after pulverization V ₂ hours at

after pulverizing V ₂ hours at 1150 ⁰ C, annealed by PUL- 5 1000 ⁰ C. A white-gray pigment is obtained

verize annealed at 1350 ° C for 1 hour. One obtains from a disturbed rutile structure.

a white pigment of rutile structure both at ■ '- .: ■ ■ ... "

1150 as well as at 1350 ° C. ■ M - ^ -.-: J ■■■■ '■■. , Example 29 ..__. , ..; ....,.,

. . 5,000g SnO ₂ + 1,00Og CoF ₂ are mixed,

Example 20, 10 V ₂ hours at 1000 ° C., after pulverization V ₂ hours

5,000g SnO ₂ + 0.200 g Al ₂ O ₃ (Al (OH) ₃₎ + annealed at 1150 ⁰ C. A dark green-blue color is obtained

0.866 g of Ta ₂ O ₅ are mixed, V ₂ hours at 1000 ° C., pigment of roughly disrupted rutile structure.

after pulverization V ₂ hours at 1150 ° C, after Pul-. .

Verize annealed at 135O ⁰ C for 1 hour. Example ju is obtained

a gray-white pigment of rutile structure both at 15 5,000 g SnO ₂ + 1,000 g MnF ₂ are mixed,

1150 as well as at 1350 ⁰ C. / V ₂ hours at 800 ⁰ C, after pulverization V ₂ hours at

_. . V ₁ 1000 ⁰ C annealed. A gray-brown pigment is obtained

■ Example 21: _: .-, ■ ..; of rutile structure. ; .. ■■■■ ,,. ■■

5.000g SnO ₂ + 0.200g MnO (from MnCO ₃ ) + ".",. *.,; -

0.654g WO ₃ + 0.20Og NaF as flux are 20 Example ji

"! Mixed V ₂ hours at 1000 ⁰ C, g after pulverization 5,000 SnO ₂ + 2.000 g of NiF ₂ are mixed,

Annealed \ Va hour at 1150 ° C -. One receives a light V2 hour at 1000 ° C, after pulverization Va hour

gray pigment of rutile structure. . annealed at 1150 ^{° C.} A gray-yellow pigment is obtained

". . , ■ 'of rutile or. Rutile superstructure.

Example 22. _a5

5.000g SnO ₂ + 0.20OgFeQ (from FeCO ₃ ) + 0.646g Example 32
WO mixed _3, V g ₂ hour at 1000 ° C, g after 5,000 Pulveri- SnO ₂ + 2,000 CuF ₂ are mixed, V ₂ Sieren hour at 1150 ° C, after pulverizing V ₂ hour at 1000 ⁰ C, after pulverizing V ₂ Annealed at 1350 ^° C. for 1 hour. A brown-calcined at 1150 ° C. in air is obtained. A violet-tinged gray pigment with a rutile structure is obtained as well as a 30-tinged gray-brown pigment with a rutile structure.

1150 as well as at 1350 ° C.,, _. . . "

■ B e 1 s ρ 1 e 1 33

Example 23 5.000 g SnO ₂ + 0.476 g LiF + 2.000 g CrF ₃ become

5.000 g of SnO ₂ + 0.200 g CoO (from CoCO ₃₎ + 0,618g mixed, V ₂ hour at 1000 ° C, after pulverizing WO ₃ +0.200 g NaF as the flux are mixed, annealed 35 V ₂ hours at 1150 ⁰ C. A violet V is obtained for ₂ hours at 1000 ° C., after pulverization V has a red pigment with a rutile or rutile superstructure for _{2 hours.} , annealed at 1150 ^{0 C.} The result is a greenish gray. . .._, ·. ·.

blue pigment of rutile structure. .,:. . V ^at } ^s ?} ^E -. ^M '.''■■'

... '■ :.' - ^ ₁ O.- 5,000 g SnO ₂ + 0,460 g LiF + 2,000 g FeF ₃ will be

■ · - · · ■■■ Example 24, mixed _40, V ₂ hour at 1000 ⁰ C, after pulverizing.

5.000g SnO ₂ + 0.200g NiO (from NiCO ₃ ) + 0.620g 'V _{annealed for 2} hours at 1150 ° C. A medium WO _{3 is obtained} , mixed for ₂ hours at 1000 ^° C., according to gray pigment yori rutile structure. . '..
Pulverize V for ₂ hours at 115O ⁰ C, after pulverization. ~ ·, _{0 <}

Annealed at 135O ⁰ C for one hour. Example 35 is obtained

yellow-gray pigment of rutile structure both at 45 5.000 g SnO ₂ + 0.1765 g Li ₂ O (from Li ₂ CO ₃ ) + 2.000 g 115OaIs also at 135O ⁰ C. FeF ₃ are mixed, V ₂ hours at 1000 ⁰ C, after

. . . ' Pulverize V annealed at 1150 ^° C. for _{2 hours.} Man

Example ^ receives a gray, slightly greenish pigment from

5.000 g SnO ₂ + 0.50 g Cr ₂ O ₃ +0.763 g WO ₃ have a rutile structure. .

the mixed, V ₂ hours at 1000 ⁰ C, according to Pulveri- 50, example 36

sizing V2 hour at 1150 ⁰ C, after pulverizing ^:

Annealed for 1 hour at 135O ° C. A gray 5.00OgSnO ₂ + 0.0913gLi ₂ O (from Li ₂ CO ₃ ) + 1,000g is obtained

Pigment of rutile structure. . CrF ₃ are mixed, V ₂ hours at 1000 ⁰ C, after

. ; Of, pulverizing V, calcined at 1150 ^° C. for _{2 hours.} Man he.

Example Zb 55 holds a violet-red pigment with a rutile structure.

5.000g SnO ₂ + 0.500g Fe ₂ O ₃ + 0.726g WO ₃ are _.

the mixed, V * hour at 1000 ⁰ C, according to powder. _: Example 37.

sieren Vz hour at 1150 ⁰ C, after pulverization 5.000 g SnO ₂ + 2.000 g FeF ₃ + 1.410 g CuO (from

Annealed at 1350 ^° C. for 1 hour. A dark CuCO ₃ ) is obtained, mixed for ₂ hours at 1000.degree. C., after a gray pigment of rutile structure and pulverization at 1150 60, for ₂ hours at 1150 ⁰ C calcined. It is also found at 135O ⁰ C. holds a blackish gray pigment of rutile structure.

B e i s ρ i e 1 27 «· '·.,"

Example 38
5.000 g SnO ₂ + 0.050 g Li ₂ O (from Li ₂ CO ₃ ) + 1.436 g -

UO ₃ (converted from uranyl nitrate) are mixed, 65 5,000 g SnO ₂ + 0.224 g LiF + 2,000 g WO ₃

V ₂ hours at 1000 ⁰ C, mixed for ₂ hour after pulverizing V, Va hour at 1000 ° C, after pulverization

annealed at 1150 ^{° C.} A greenish gray V is obtained which has been calcined at 1150 ° C. for _{2 hours.} You get a green

Pigment of rutile structure. pungent gray-blue pigment of rutile structure.

Example 39

5.000 g SnO ₁ + 0.0907 g of LiF + 1.000 g UO ₃ (from uranyl nitrate) are mixed, annealed Va hour at 1000 ° C, pulverizing after Vi hour at 115o C ^0. A gray-beige pigment with a rutile structure is obtained.

Example40.

5.000 g SnO, + 0.411 g Cu ₈ O + 2.000 g of WO ₃ are mixed and in pure nitrogen stream V "hour at 800 ⁰ C, after pulverizing Va hour at 1000 ⁰ C ίο overall glows. A dark gray pigment with a rutile structure is obtained.

B e i s ρ i e 1 41

5.000 g SnO, + 0.359 g Cu ₁ O + 2.000 g Nb ₂ O ₈ are mixed and calcined in a pure nitrogen stream for Va hour at 800 ^° C., after pulverization Va hour at 1000 ^° C. A completely brown-orange pigment with a rutile structure is obtained.

Example 42

ao

5.000 g SnO + 0.500g ZnO (from ZnCO ₃₎ + 1.412 g As ₁ O ₆ are mixed Vi hour at 900 ⁰ C, annealed hour at 1000 ° C after pulverizing Vi. A yellowish white pigment with a rutile structure, as is obtained

Example 43

5.000 g SnO, NiO + 0.500 g (from NiCO ₃₎ + 1.538 g As ₁ O ₅ are mixed, Vi hour at 900 ⁰ C, after pulverizing Vi hour annealed at 1000 ° C. A light green-yellow pigment with a somewhat disturbed rutile structure is obtained.

Example 44

5.000 g SnO, + 0.500 g CoO (from CoCO ₃₎ + 1.533 g As ₁ O _1, are mixed, V · hour at 900 ⁰ C, after pulverizing Vi hour annealed at 1000 ⁰ C. A violet pigment with a rutile structure is obtained.

- Example 45

5.000 g SnO, + 0.200 g MnO (from MnCO ₃ ) + 0.648 g As ₁ O ₅ are mixed, annealed for Vi hour at 90O ⁰ C, after pulverization V for ₁ hour at 1000 ° C. A yellowish gray-brown pigment with a rutile structure is obtained.

B e i s ρ i e 1 46

5.000 g SnO ₂ + 0.500 g CuO (from CuCO ₃ ) + 1.444 g As ₂ O ₅ are mixed, Va hour at 90O ⁰ C, after pulverization V _{calcined for 2} hours at 100O ⁰ C. A blue-green pigment with a rutile structure is obtained.

Example 47

5.000 g SnO ₂ H- 1.000 g Fe ₂ O ₃ + 1.439 g As ₁ O ₅ are mixed, annealed Va hour at 90O ⁰ C, after pulverizing Va hour at 100O ⁰ C. A black-gray pigment with a rutile structure is obtained.

Example 48

5.000 g SnO ₁ + 0.500 g Cr ₁ O ₃ + 0.756 g As ₁ O ₅ are mixed, Va hour at 90O ⁰ C, after pulverization annealed ^{Va hour at 100O 0 C.} A green-gray pigment with a rutile structure is obtained. _f

Claims (2)

Patent claims: 1. Mixed phases with pigment properties that have a rutile or polyrutile structure, thereby characterized in that they are tin dioxide as the host component and 6-or / and as guest components 5-valent or / and 3-, 2- or / and l-valent cations, the ionic radius of which is between 0.45 and 0.97 A, and oxygen as anions or fluorine, the sum of the added cations to the sum of the added Anions corresponds approximately to the ratio 1: 2 while maintaining statistical electrical neutrality in the lattice, however, the total amount of guest components is arbitrary, but not greater than that Amount of host component is. 2. mixed phases according to claim 1, characterized in that they are additionally used as guest components still contain tetravalent metal ions with an ionic radius between 0.45 and 0.97 A.