CN110615481B - Silica type Bi24Al2-xMnxO39Grass green inorganic pigment and preparation method thereof - Google Patents
Silica type Bi24Al2-xMnxO39Grass green inorganic pigment and preparation method thereof Download PDFInfo
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- CN110615481B CN110615481B CN201910886710.1A CN201910886710A CN110615481B CN 110615481 B CN110615481 B CN 110615481B CN 201910886710 A CN201910886710 A CN 201910886710A CN 110615481 B CN110615481 B CN 110615481B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
Abstract
The invention discloses a silica type Bi24Al2‑xMnxO39Grass green inorganic pigment and a preparation method thereof. The pigment has bright greenish color, silica-type structure, and chemical composition of Bi24Al2‑xMnxO39Wherein x is more than 0 and less than or equal to 0.8. The pigment is prepared by adopting a high-temperature solid-phase method, and the preparation steps are as follows: with Bi2O3、Al2O3And Mn2O3Or MnO2The raw materials are ground uniformly, pressed into tablets under the pressure of 10-30MPa and then sintered in a muffle furnace, wherein the sintering temperature is 600-800 ℃, the sintering time is 4-10h, the heating rate is 5-10 ℃/min, and the cooling rate is 5-10 ℃/min. The grass green inorganic pigment synthesized by the invention is environment-friendly and nontoxic, has a stable structure and bright color, and the preparation method has a simple process and low requirements on equipment.
Description
Technical Field
The invention belongs to the technical field of inorganic pigments, and particularly relates to an environment-friendly, non-toxic and bright-colored silica type grass green inorganic pigment and a preparation method thereof.
Background
Compared with organic pigments, inorganic pigments have the advantages of excellent stability, strong covering power, acid and alkali resistance, weather resistance and the like, and are widely applied to coatings, printing ink, plastics, rubber, painting pigments, glazes and ceramics. As the application range of inorganic pigments is expanded, the requirements on the properties of inorganic pigments are more stringent. Inorganic pigments are classified into conventional natural inorganic pigments and synthetic inorganic pigments. The traditional natural inorganic pigments are mainly derived from ores in the nature, such as chalcopyrite, bismuth yellow, cinnabar and the like, the natural inorganic pigments are generally low in purity, single in color and relatively dark in color, and hardly meet the current living needs of human beings, and some pigments contain toxic metal elements, such as cadmium, vanadium, lead, chromium and the like, so that the health of the human beings is seriously harmed. The defects of the traditional inorganic pigment seriously limit the application of the traditional inorganic pigment in life, so the research on the inorganic pigment which is environment-friendly, nontoxic and excellent in performance has great scientific research value and social value. Researches show that the transition metal element doped multi-component oxide pigment synthesized by a high-temperature solid phase method has high purity, high crystallinity, stable structure, environmental protection, no toxicity, bright and controllable color, and attracts the wide attention of researchers.
Green is a common color in nature, which symbolizes youth, hope, life, peace, nature. The green pigment is widely applied to human life and national defense construction, so that the research on the novel environment-friendly inorganic green pigment has certain value. In recent years, a multinary matrix oxide exhibits a distinct green color by intramolecular charge-mass transfer due to formation of manganese-oxygen tetrahedrons by substitution of a certain amount of central atoms of tetrahedral structural units by a metal manganese element and crystal field transition due to metal manganese ions. Such as Mn doped Ba2In2O5、Ba3V2O8、BaAl2O4The green pigment has high purity, high thermal stability, acid and alkali resistance and adjustable color, but the application of the pigment is limited because the pigment contains expensive metal In and heavy metal Ba.
Disclosure of Invention
The invention relates to Bi2O3，Al2O3Is used as a matrix raw material and is doped with Mn according to a certain molar ratio2O3Or MnO2Synthesizing a series of grass green inorganic pigments with adjustable chromaticity and a preparation method thereof.
The silica type grass green inorganic pigment prepared by the invention is realized by the following technical scheme.
Silica type Bi24Al2-xMnxO39The preparation method of the grass-green inorganic pigment is characterized in that the structure is a stable silica-type structure, the color is bright grass green, and the chemical composition of the grass green inorganic pigment is Bi24Al2-xMnxO39Wherein x is more than 0 and less than or equal to 0.8.
Furthermore, the doping amount of manganese in the pigment is more than 0 and less than or equal to 0.8, and the valence state of the manganese is + 4.
A silica-type Bi as described above24Al2-xMnxO39The preparation method of the grass green inorganic pigment comprises the following steps:
(1) with Bi2O3，Al2O3，Mn2O3Or MnO2Is used as raw material and has the chemical composition general formula Bi24Al2-xMnxO39The raw materials are accurately weighed by an analytical balance;
(2) manually and fully mixing the weighed powder raw materials in the step (1) in an agate mortar, putting the uniformly mixed raw materials into a stainless steel die, and pressing the uniformly mixed raw materials into a block by a press;
(3) and (3) putting the block prepared in the step (2) into a corundum crucible, sintering in a muffle furnace according to a specific sintering system, and cooling the sample to room temperature after sintering, and grinding the sample to obtain the grass green inorganic pigment.
Further, the purity of each raw material described in the step (1) of the above production method was analytical grade, and the mass error was ± 0.0005 g.
Further, the time for manual grinding in an agate mortar in the step (2) of the above preparation method is 20-40 min.
Further, the diameter of the stainless steel mold in the step (2) of the preparation method is 10-20mm, the pressure of the pressing sample is 10-30MPa, and the pressure maintaining time is 1-3 min.
Further, the sample sintering temperature in the step (3) of the preparation method is 600-.
Compared with the prior art, the invention has the following advantages:
(1) the grass green inorganic pigment has bright color and is environment-friendly and nontoxic.
(2) The grass green inorganic pigment has the advantages of stable structure, high purity, no impurity and high chemical stability.
(3) The preparation method has simple process and low requirement on equipment, and is expected to be applied to industrial production.
Drawings
FIG. 1 shows different doping amounts of Bi24Al2-xMnxO39XRD pattern of the sample.
FIG. 2 shows different doping amounts of Bi24Al2-xMnxO39UV-vis spectrum of (1).
Detailed Description
The technical solution of the present invention is further described in detail below with reference to specific examples and drawings, and the examples are only preferred embodiments of the present invention, but not limiting the present invention. Modifications, additions, simplifications, substitutions of any of the details of the present inventive arrangements are intended to be within the scope of the invention.
Example 1: in MnO2Preparation of 2g Bi for Mn Source24Al1.9Mn0.1O39Inorganic pigments
According to Bi24Al1.9Mn0.1O39The chemical formula of (A) is that Bi is weighed according to a certain stoichiometric ratio2O3，Al2O3， MnO2The mass tolerance was. + -. 0.0005 g. Bi is weighed respectively by an electronic analytical balance2O3(1.9632g)， Al2O3(0.0340g)，MnO2(0.0031 g). Putting the weighed raw materials into an agate mortar, fully grinding and mixing for 20min, putting into a stainless steel die with the diameter of 15mm, and keeping the pressure for 1min under the pressure of 10MPa by a tablet press. And (3) putting the pressed block into a muffle furnace, raising the temperature of the muffle furnace to 750 ℃ at the temperature rise rate of 5 ℃/min, preserving the heat for 6 hours at the temperature of 750 ℃, reducing the temperature to room temperature at the temperature reduction rate of 5 ℃/min after the heat preservation is finished, and finally taking out a sample and grinding to obtain the stable grass green inorganic pigment.
Example 2: with Mn2O3Preparation of 2g Bi for Mn Source24Al1.3Mn0.7O39Inorganic pigments
According to Bi24Al1.3Mn0.7O39The chemical formula of (A) is that Bi is weighed according to a certain stoichiometric ratio2O3，Al2O3， Mn2O3The mass tolerance was. + -. 0.0005 g. Bi is weighed respectively by an electronic analytical balance2O3(1.9574g)， Al2O3(0.0232g)，Mn2O3(0.0193 g). Putting the weighed raw materials into an agate mortar, fully grinding and mixing for 20min, putting into a stainless steel die with the diameter of 15mm, and keeping the pressure for 1min under the pressure of 20MPa by a tablet press. And (3) putting the pressed block into a muffle furnace, raising the temperature of the muffle furnace to 750 ℃ at the temperature rise rate of 5 ℃/min, preserving the heat for 4h at the temperature of 750 ℃, reducing the temperature to room temperature at the temperature reduction rate of 5 ℃/min after the heat preservation is finished, and finally taking out a sample and grinding to obtain the stable grass green inorganic pigment.
Claims (6)
1. Silica type Bi24Al2-xMnxO39A grass-green inorganic pigment characterized by having a stable silica-type structure, a bright grass-green color and a chemical composition of Bi24Al2-xMnxO39Wherein x is more than 0 and less than or equal to 0.8.
2. The silica-type Bi of claim 124Al2-xMnxO39The grass green inorganic pigment is characterized in that the doping amount of manganese is more than 0 and less than or equal to 0.8, and the valence state of the manganese is + 3.
3. The silica-type Bi of claim 124Al2-xMnxO39The preparation method of the grass green inorganic pigment is characterized by comprising the following steps:
(1) with Bi2O3，Al2O3，Mn2O3Is used as raw material and has the chemical composition general formula Bi24Al2-xMnxO39The raw materials are accurately weighed by an analytical balance;
(2) manually and fully mixing the weighed powder raw materials in the step (1) in an agate mortar, putting the uniformly mixed raw materials into a stainless steel die, and pressing the uniformly mixed raw materials into a block by a press;
(3) putting the block prepared in the step (2) into a corundum crucible, sintering in a muffle furnace according to a specific sintering system, and after the sintering is finished, cooling the sample to room temperature and grinding the sample to obtain a grass green inorganic pigment;
the specific firing system in the step (3) is as follows: the sintering temperature of the sample is 600-800 ℃, the sintering time is 4-10h, the heating rate is 5-10 ℃/min, and the cooling rate is 5-10 ℃/min.
4. The silica-type Bi of claim 324Al2-xMnxO39The preparation method of the grass green inorganic pigment is characterized in that the purity of each raw material in the step (1) is analytical pure, and the mass error is +/-0.0005 g.
5. The silica-type Bi of claim 324Al2-xMnxO39The preparation method of the grass green inorganic pigment is characterized in that the time for fully and uniformly mixing in the agate mortar by hand in the step (2) is 20-40 min.
6. The silica-type Bi of claim 324Al2-xMnxO39The preparation method of the grass green inorganic pigment is characterized in that the diameter of the stainless steel die in the step (2) is 10-20mm, the pressure of a sample is 10-30MPa, and the pressure maintaining time is 1-3 min.
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| US6503316B1 (en) * | 2000-09-22 | 2003-01-07 | Dmc2 Degussa Metals Catalysts Cerdec Ag | Bismuth-containing laser markable compositions and methods of making and using same |
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| CN107032405A (en) * | 2016-10-25 | 2017-08-11 | 桂林理工大学 | Manganese perovskite type inorganic pigment |
| CN110092658A (en) * | 2019-05-31 | 2019-08-06 | 新乡学院 | A kind of preparation method of bismuth system ceramics |
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