CN107628646B - A kind of siderochrome mineral black and preparation method thereof - Google Patents
A kind of siderochrome mineral black and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of siderochrome mineral black and preparation method thereof, include the following steps: to weigh Cr (NO with Cr:Fe 1~1.85:1 of molar ratio3)3·9H2O and Fe (NO3)3·9H2O is simultaneously added in the water that heating temperature is 50~70 DEG C, stirs and Cr/Fe aqueous solution is made；The incendiary agent reacted completely therewith is added, and continues heating stirring until all dissolutions；Mixed liquor heating evaporation is concentrated, then solution is placed in the Muffle furnace of 250~300 DEG C of heat preservations and causes self-propagating combustion；Combustion product is placed in high-temperature calcination stove, is risen to 850~1050 DEG C with 5~10 DEG C/min heating rate and is kept the temperature 1~3h, it is siderochrome mineral black that calcined powder is collected in cooling.The present invention is resulting between 0.1~1.0 μm of pigment particle distribution, the mellow and full rule of shape, and crystallinity is high.Product TSR >=31% is higher than similar products at home and abroad.
Description
Technical field
The invention belongs to inorganic pigment fields, and in particular to a kind of sub-micron crystal grain shape high infrared reflection rate siderochrome mineral black
And preparation method thereof.
Background technique
Pigment is the important component in formulation for coating material, assigns paint colors, tinting strength, tinting power, covering power, increases coating machine
Tool intensity, and can make some special coatings that there are the multiple functions such as conduction, camouflage, photochromic, luminescence generated by light, thermochromism.
According to coating requirement, single may be used in a kind of coating or several different pigment, additional amount account for coating overall quality
Reach as high as 60% or more.Pigment is classified by chemical composition, can be divided mainly into organic pigment and inorganic pigment two major classes.Inorganic face
Material is usually mineral substance, has specific crystal structure, is answered by different oxidation of interim metal via thermal diffusion
Made of conjunction, color depends mainly on brilliant intracorporal electron energy transition, so that absorption spectrum be made to change.With organic face
Material is compared, and the feature of inorganic pigment maximum is remain unchanged for a long period of time under use environment color (good weatherability), and part inorganic pigment has
Unique light, electricity, magnetic property.
Black pigment is that a very widely used colour system is also used to adjust it except production blacking is directly used in
(on the basis of existing color, the black pigment of different proportion is added, so that it may obtain the various of different lightness in the lightness of its pigment
Color).Currently used black inorganic pigment has carbon black, iron oxide black, copper-chrome black, siderochrome black etc..Black pigment why be in
Existing black is primarily due to have high absorptivity (95% or more) to visible light, and (siderochrome is black for most of black pigments
Except) centering near infrared light also has the absorptivity of superelevation.In the gross energy for reaching the sunlight on ground, it is seen that light accounts for 45%, red
Outside line accounts for 50%, and wherein 95% infrared energy concentrates in the range of wavelength is 0.72~2.5 μm, i.e. near-infrared model
In enclosing.And in the outdoor application of some pigment, it shines upon and is difficult to avoid that sometimes, high visible light-near-infrared absorption rate
So that there are contradictory two aspects for black pigment.For example, in northern cold winter, black vehicle (black colored car paint is mostly used carbon black)
More solar heats can be absorbed, so that vehicle interior temperature is relatively high, air-conditioning power consumption can be reduced, play energy-conserving action.But
In summer fair weather, the mean power in ground direct sunlight direction is close to 1.4kW/m2, the raising of illegal vehicle vehicle interior temperature
It is more prominent, uncomfortable occupant, increase air-conditioning power consumption, acceleration interior trim aging can be caused, be very unfavorable in a word.Develop a kind of tool
There is higher solar reflectivity black pigment, instead of the low solar reflectivity pigment such as common carbon black, for reducing sunray pair
Negative effect caused by the mankind is of great significance.
Black siderochrome is by Fe2O3With Cr2O3It is dissolved the mixed phase oxide to be formed with certain proportion, still keeps hematite structure,
Color is the black with red phase, and composition is represented by CrxFe2-xO3.It is that total solar reflectivity is most in existing black pigment that siderochrome is black
The one kind of high (TSR value close to 30%, and carbon black and copper-chrome black TSR are 5% or so), have brilliant weatherability, heat-resisting quantity,
Resistance to acid and alkali, it is environment-protecting and non-poisonous, do not migrate, not bleeding, not soluble in water and organic solvent the advantages that, car paint, exterior coating,
The industries such as coil steel coating, military high reflection camouflage paint, engineering plastics, ink have very big application value.
Currently, the black main technique of production siderochrome has solid-phase synthesis, coprecipitation and sol-gel method, wherein solid phase
Synthetic method is because being convenient for industrialized production and low in cost being widely used by domestic and international major inorganic pigment production firm.In solid phase method
During producing siderochrome mineral black, first iron oxide, chromium oxide and a small amount of auxiliary agent are uniformly mixed, then are crushed-drift through high-temperature calcination-
Wash-dry-ultra-fine grinding finished product.It is restricted by research of super-pine crush equipment grindability, the siderochrome of domestic manufacturer's production is black flat
Equal partial size is mostly at 1.0 μm or more, even if the star enterprise of the inorganic pigments industry such as U.S. ShepherdColor, that releases is same
Class product average grain diameter also can only achieve 0.7 μm.And a kind of conventional process of the sol-gel method as synthetising nanometre powder body, it adopts
It is less than 200nm with the siderochrome mineral black partial size that the method synthesizes more.
For pigment, partial size is to influence factor most outstanding to pigment performance in addition to ingredient and crystal structure.Pigment it
It is granules of pigments to the selective absorbing of light and reflection comprehensive function as a result, wherein selectivity is inhaled so different colours are presented
Receipts are determined by pigment composition and crystal structure, and the size of reflectivity is affected by pigment particle size.Light is dissipated according to particle
Theory is penetrated, is had to incident light best for the incident light of a certain specific wavelength when the half for the wavelength that pigment particle size is light
Dispersion effect.When partial size is less than half-wavelength, the scattering power of light is sharply weakened, into after nanometer range, pigment is to visible
Light (400~760nm) is transparent, and the covering power of pigment is very poor at this time, has not been suitable for coat colorization.And granules of pigments is excessive
When, suspension of the pigment in the systems such as coating is deteriorated, and tinting strength, tinting power also has decline.Bulky grain sets molding when colouring in the plastic
Standby screw rod has larger abrasion, generates free iron and plastics is caused to change colour.And in jetted ink, only due to printer nozzle diameter
It is 10 μm, it is desirable that pigment maximum particle diameter in ink in order to avoid stopped nozzles, and requires granules of pigments granularity no more than 1.0 μm
Distribution is concentrated, and shape is mellow and full.Therefore, good siderochrome mineral black, ideal particle size should be distributed in 0.1~1.0 μm
Within the scope of；Without nano particle, (nanoparticle activated height, stability is poor, causes pigment safety, weatherability, acidproof as far as possible
Alkalinity decline) and partial size be more than 1.0 μm of larger particles.
The process conditions announced are obviously helpless in synthesizing submicron grain type siderochrome mineral black, produce both at home and abroad
Siderochrome mineral black performance on still need to be continuously improved.
Summary of the invention
In order to solve the deficiency of existing production technology, the performance advantage of siderochrome mineral black is excavated, the present invention provides a kind of high
Infrared reflectivity sub-micron crystal grain shape ferrochrome mineral black and preparation method thereof.The present invention is with ferric nitrate, chromic nitrate, the positive fourth of metatitanic acid four
Ester is primary raw material, high-quality siderochrome mineral black is made using continuous self-propagating combustion technique, which has high infrared reflection
Rate, crystal grain are complete and integrated distribution is in sub-micrometer range, are suitable for the industries such as coating, plastics, ink.
Technical solution of the present invention is as follows:
A kind of preparation method of siderochrome mineral black, includes the following steps:
(1) preparation of Cr/Fe aqueous solution
With Cr:Fe 1~1.85:1 of molar ratio, Cr (NO is weighed3)3·9H2O and Fe (NO3)3·9H2O is simultaneously added to heating temperature
Degree is in 50~70 DEG C of water, Cr/Fe aqueous solution is made in stirring；
(2) incendiary agent is added
Since nitrate can only be used as combustion adjuvant, there need to be incendiary agent cooperation to be just able to achieve low temperature self-propagating combustion, therefore root
The total amount of (Cr+Fe) in step (1) solution adds the incendiary agent reacted completely therewith, and continues heating stirring until whole
Dissolution；
(3) self-propagating combustion
Mixed liquor obtained by step (2) is continued to be concentrated with 50~70 DEG C of heating evaporations, to liquor capacity reduction amount >=1/3
Afterwards, solution is placed in the Muffle furnace of 250~300 DEG C of heat preservations and causes self-propagating combustion, post-combustion capture product；
(4) crystallization and thermal treatment
The product that step (3) are collected is placed in high-temperature calcination stove, 850 are risen to 5~10 DEG C/min heating rate~
It 1050 DEG C and 1~3h of heat preservation, is taken out after cooling, collecting calcined powder is siderochrome mineral black.
Preferably, Ti element is introduced in the solution made from step (2).
Preferably, the specific steps for introducing Ti element are as follows: tetra-n-butyl titanate is distributed to the anhydrous second of 5 times of quality
Mixed liquor is made in alcohol, mixed liquor is added dropwise in solution made from step (2), process is added dropwise and continues agitating and heating.
Preferably, molar ratio≤0.04 of the tetra-n-butyl titanate and (Cr+Fe) total amount.
Ideal incendiary agent is component containing only tetra- kinds of elements of C, H, O, N, is had compared with high heating value and soluble easily in water, no
Volatile cheap organic matter, can select citric acid, glycine, glutamic acid, glucose, urea, ammonium hydrogen carbonate and
Any one in ethylene glycol or two or more mixing.According to propellant chemistry theory, each every moles reducing of raw material
Conjunction valence is shown in Table 1, and wherein negative value indicates to be used as oxidant in the reaction, and positive value is reducing agent (incendiary agent).
Each raw material of table 1 aoxidizes reducing and closes valence
According to propellant chemistry theory, when the sum of oxidant and reducing agent chemical valence are 0 in system, indicate that oxidant can
To support incendiary agent to burn completely, reaction can be carried out thoroughly.(Cr+Fe) total amount determined in step (1) is 1.0mol, with
Each incendiary agent dosage reacted completely be shown in Table 2:
2 one-component incendiary agent additional amount of table
The present invention preferably add 30%~50% citric acid, 0%~20% glucose, 20%~50% urea and 0%~
30% ethylene glycol is calculated on the basis of table 2 respectively as incendiary agent, each incendiary agent dosage, be added to after weighing in (1) match it is molten
Liquid simultaneously continues heating stirring until all dissolutions.
Preferably, siderochrome mineral black made from step (4) is also successively post-processed as follows: washing, filters pressing, drying, gas
Stream is crushed, examines and is packed.
Preferably, the solution after step (3) concentration is placed in volume and is more than in 10 times of liquid volume of crucible, then in Muffle furnace
Middle carry out self-propagating combustion.
Siderochrome mineral black of the invention has high near infrared reflectivity, is subject to the factor for influencing the black infrared reflectivity of siderochrome
Illustrate: CrxFe2-xO3Middle Cr/Fe ratio and other elements of doping influence significantly infrared reflectivity, and improve reflectivity
Break-through point.In addition, also needing to improve the particle fraction being distributed in pigment in 0.4~0.9 μ m as far as possible, this size distribution is special
Point can effectively improve 800~1800nm and (arrive while keeping pigment blackness (400~760nm visible reflectance is extremely low)
Up to the main distributed area of infrared ray in surface solar radiation) reflectivity of range.According to infrared physics correlation theory, crystal
The defects of middle crystal boundary, vacancy can to infrared light generate absorption, when crystal structure than it is more complete when, defect concentration is small, to infrared light
Absorption weaken, be conducive to improve infrared reflectivity.Therefore, high infrared reflection rate siderochrome mineral black should be closed through higher temperature
It is a well-developed crystal grain (grain boundary concentration is extremely low) at (the defects of vacancy, dislocation is few), each particle, this is i.e. of the invention
" the grain type siderochrome mineral black " concept proposed.
The resulting high reflectance sub-micron grain sections chrome black pigment of the present invention, SEM photograph show pigment particle distribution 0.1
Between~1.0 μm, the mellow and full rule of shape.XRD analysis shows that pigment is hematite structure, and crystallinity is high, and no other impurity exist.
Pigment may be directly applied to jetted ink pigment, also be more suitable for coloring plastic, have compared with high added value.In addition, this technology from
Ingredient, size distribution, microstructure etc. have carried out the process optimization for being beneficial to improve infrared reflectivity, product near-infrared
Reflectivity is apparently higher than similar products at home and abroad, and solar energy reflection effect is more prominent, especially suitable for modulating solar energy reflection
Coating, can also be in the toning for camouflage coating.
Compared with prior art, the present invention has the following advantages and beneficial effects:
The present invention uses low temperature self-propagating combustion synthesis technology, carries out high temperature crystallization and thermal treatment to combustion product, preparation
Siderochrome mineral black particle size is submicron order (partial size is between 0.1~1.0 μm), and grain structure completely and between crystal grain is adhered
Few, complete grain structure assigns the higher weatherability of siderochrome mineral black, heat-resisting quantity, resistance to acid and alkali, and chromium is precipitated less,
Pigment safety is higher.
2. the present invention is by adjusting Cr/Fe ratio, doping Ti element and optimizes the modes such as granule-morphology, particle diameter distribution, significantly
The performance of siderochrome mineral black is improved, from black to red phase-black transition, infrared reflectivity (NIR) >=51.6%, TSR refer to pigment form and aspect
Mark >=31%, is superior to the similar product of external producer, can be used for modulating sun reflective coating, it can also be used to camouflage coating
Toning.
3. this technique reduces incendiary agent additional amount compared with conventional sol-gel processes and gel self-propagating combustion, drop
Low production cost.This technique using Muffle furnace directly ignite concentration after solution eliminate drying without being prepared into xerogel
Plenty of time needed for process, shorten the production cycle.Compared with solid-phase synthesis, this technique calcination temperature is low, the time is short, energy
It consumes lower.
4. submicron-scale siderochrome mineral black had both been able to satisfy to the lower painting of the index requests such as pigment particle size and size distribution
The industries such as material, plastics are also able to satisfy and require the industries such as high jetted ink, have applications well prospect.
Detailed description of the invention
Fig. 1: the made siderochrome mineral black SEM photograph of embodiment 1, powder group become CrFeO3, 1050 DEG C of heat treatment temperature, powder
Body is without break process.
Fig. 2: the made siderochrome mineral black SEM photograph of embodiment 2, powder group become Cr1.2Fe0.8O3, Ti content is (Cr+Fe)
Total amount 0.04%, 850 DEG C of heat treatment temperature, powder is without break process.
Fig. 3: the made siderochrome mineral black visible light/near-infrared spectral reflectance of embodiment 3, test equipment PERKINELMER
Company produce Lambda950 it is ultraviolet/visible/near infrared spectrophotometer.
Fig. 4: the made siderochrome mineral black XRD diagram of embodiment 3, it is worth mentioning at this point that Cr1.3Fe0.7O3For siderochrome mixed phase oxide
Representative XRD card, Cr:Fe molar ratio be the black diffraction maximum position of siderochrome of 1~1.85:1 and Cr1.3Fe0.7O3Unanimously.
Fig. 5: external product visible light/near-infrared spectral reflectance.
Specific embodiment
With the following Examples, the invention will be further described.
Embodiment 1
A kind of high infrared reflection rate sub-micron grain sections chrome black pigment, Cr:Fe molar ratio are 1:1, are free of Ti element, system
Preparation Method comprises the following steps:
(1) Cr/Fe aqueous solution is prepared
Weigh Cr (NO3)3·9H2O and Fe (NO3)3·9H2Each 0.5mol of O, is successively added in 0.6L deionized water, right
Solution carries out heating stirring, and 50 DEG C of heating temperature, Cr/Fe aqueous solution is made after all dissolving in nitrate.
(2) incendiary agent is added
30% monohydrate potassium, 20% glucose are added, 50% urea is as incendiary agent, specially 0.252mol lemon
Acid, 0.25mol glucose, 1.5mol urea are added to solution in (1) and continue heating stirring until all dissolutions after weighing.
(3) solution is concentrated and causes self-propagating combustion
Mixed liquor obtained by step (2) is continued to be concentrated with 50 DEG C of heating evaporations, it, will after liquor capacity reduces by more than 1/3
It is more than to be placed in solution in 10 times of liquid volume of corundum crucible in the Muffle furnace of 250 DEG C of heat preservations and cause that solution, which is transferred to volume,
Self-propagating combustion, post-combustion capture product are simultaneously packed into mullite sagger.
(4) crystallization and thermal treatment
Crystallization and thermal treatment carries out in high-temperature calcination stove, rises to 1050 DEG C with 10 DEG C/min heating rate and keeps the temperature 1h, drop
Wen Houzhi takes out saggar, collects calcined siderochrome mineral black.
(5) it post-processes
According to the general step in Inorganic Pigment production process, gained siderochrome mineral black is successively washed, is pressed
High reflectance sub-micron grain sections chrome black pigment is finally made in filter, drying, air-flow crushing, inspection, packaging.
Attached drawing 1 is the black primary morphology SEM photograph without break process of the made siderochrome of the present embodiment, it is seen that most of particle
Size is in sub-micrometer range, and particle shape is mellow and full, there is residual adhesion.
Embodiment 2
A kind of high infrared reflection rate sub-micron grain sections chrome black pigment, Cr:Fe molar ratio are 1.5:1, Ti element and (Cr
+ Fe) total amount molar ratio be 0.02:1 preparation method include the following steps:
(1) Cr/Fe aqueous solution is prepared
0.6molCr (NO is weighed respectively3)3·9H2O and 0.4molFe (NO3)3·9H2O is successively added to 0.7L deionization
In water, heating stirring is carried out to solution, 60 DEG C of heating temperature, Cr/Fe aqueous solution is made after all dissolving in nitrate.
(2) incendiary agent is added
50% citric acid, 20% urea, 30% ethylene glycol are added as incendiary agent, specially 0.42mol citric acid,
0.6mol urea, 0.45mol ethylene glycol are added sequentially to solution in (1) and continue heating stirring until all dissolutions after weighing.
(3) Ti element is introduced
It weighs 0.02mol tetra-n-butyl titanate and is distributed in the dehydrated alcohol of 5 times of quality and mixed liquor is made.By mixed liquor
It is added dropwise in step (2) made solution, process is added dropwise and continues agitating and heating.
(4) solution is concentrated and causes self-propagating combustion
Mixed liquor obtained by step (3) is continued to be concentrated with 60 DEG C of heating evaporations, it, will after liquor capacity reduces by more than 1/3
It is more than to be placed in solution in 10 times of liquid volume of corundum crucible in the Muffle furnace of 300 DEG C of heat preservations and cause that solution, which is transferred to volume,
Self-propagating combustion, post-combustion capture product are simultaneously packed into mullite sagger.
(5) crystallization and thermal treatment
Crystallization and thermal treatment carries out in high-temperature calcination stove, rises to 850 DEG C with 7 DEG C/min heating rate and keeps the temperature 3h, cooling
Afterwards to saggar is taken out, calcined siderochrome mineral black is collected.
(6) it post-processes
According to the general step in Inorganic Pigment production process, gained siderochrome mineral black is carried out to wash-filters pressing-baking
High reflectance sub-micron grain sections chrome black pigment is finally made in dry-air-flow crushing-inspection-packaging.
Attached drawing 2 is the black primary morphology SEM photograph without break process of the made siderochrome of the present embodiment, it is seen that granules of pigments is thin
Small uniform, grain development is good and adhesion is less.
Embodiment 3
A kind of high infrared reflection rate sub-micron grain sections chrome black pigment, Cr:Fe molar ratio be 1.85:1, Ti element with
(Cr+Fe) total amount molar ratio is 0.04:1, and preparation method includes the following steps:
(1) Cr/Fe aqueous solution is prepared
0.65molCr (NO is weighed respectively3)3·9H2O and 0.35molFe (NO3)3·9H2O, be successively added to 0.8L go from
In sub- water, heating stirring is carried out to solution, 70 DEG C of heating temperature, Cr/Fe aqueous solution is made after all dissolving in nitrate.
(2) incendiary agent is added
Add 40% citric acid, 20% glucose, 20% urea, 20% ethylene glycol as incendiary agent, specially
0.336mol citric acid, 0.25mol glucose, 0.6mol urea, 0.3mol ethylene glycol are added sequentially to molten in (1) after weighing
Liquid simultaneously continues heating stirring until all dissolutions.
(3) Ti element is introduced
It weighs 0.04mol tetra-n-butyl titanate and is distributed in the dehydrated alcohol of 5 times of quality and mixed liquor is made.By mixed liquor
It is added dropwise in step (2) made solution, process is added dropwise and continues agitating and heating.
(4) solution is concentrated and causes self-propagating combustion
Mixed liquor obtained by step (3) is continued to be concentrated with 70 DEG C of heating evaporations, it, will after liquor capacity reduces by more than 1/3
It is more than to be placed in solution in 10 times of liquid volume of corundum crucible in the Muffle furnace of 300 DEG C of heat preservations and cause that solution, which is transferred to volume,
Self-propagating combustion, post-combustion capture product are simultaneously packed into mullite sagger.
(5) crystallization and thermal treatment
Crystallization and thermal treatment carries out in high-temperature calcination stove, rises to 950 DEG C with 5 DEG C/min heating rate and keeps the temperature 2h, cooling
Afterwards to saggar is taken out, calcined siderochrome mineral black is collected.
(6) it post-processes
According to the general step in Inorganic Pigment production process, gained siderochrome mineral black is carried out to wash-filters pressing-baking
High reflectance sub-micron grain sections chrome black pigment is finally made in dry-air-flow crushing-inspection-packaging.
Fig. 3 is the black visible light/near-infrared spectral reflectance of the made siderochrome of the present embodiment, with the U.S. Fig. 5 Shepherd Color
The comparison of company's infrared external reflection sections chrome black reflectance spectrum, the present embodiment product are obviously high in 800nm~1500nm wave band reflectivity
In the latter, there is infrared external reflection effect more outstanding.Fig. 4 is the black XRD analysis figure of the made siderochrome of the present embodiment, Cr1.3Fe0.7O3Phase
Characteristic diffraction peak cutting edge of a knife or a sword type is sharp, does not detect the object phase diffraction maximum of element containing Ti, illustrates that Ti element is sufficiently solid-solubilized in Cr1.3Fe0.7O3
In crystal grain, unreacting material and other impurity are not detected in product yet.
3 sample CIEL*a*b* parameter of table
4 pigment performance parameter of table
The performance parameter provided according to table 3 and table 4, in above embodiments, the made siderochrome black of embodiment 1 is mutually closer to pure
Black, heat resistance is more preferable, and pigment average grain diameter is about 0.7 μm, is a kind of commercial iron chrome black pigment of balancing performance；Embodiment
The 2 made black SEM photographs of siderochrome show that grain development is good, and partial size is smaller and size distribution is concentrated, finally pigment after crushed
Average grain diameter is 0.4 μm, and the index is better than similar product on sale currently on the market.The made siderochrome mineral black of the present embodiment is special
Suitable for producing jetted ink, it can also be used to infrared reflection coating and coloring plastic；3 black TSR >=31% of made siderochrome of embodiment,
Slightly red phase, infrared external reflection effect is better than similar product on sale, using laying particular emphasis on sun reflective coating and camouflage coating.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of siderochrome mineral black, which comprises the steps of:
(1) preparation of Cr/Fe aqueous solution
With Cr:Fe 1~1.85:1 of molar ratio, Cr (NO is weighed3)3·9H2O and Fe (NO3)3·9H2O is simultaneously added to heating temperature and is
In 50~70 DEG C of water, stirs and Cr/Fe aqueous solution is made；
(2) incendiary agent is added
According to the total amount of (Cr+Fe) in step (1) solution, the incendiary agent reacted completely therewith is added, and it is straight to continue heating stirring
To whole dissolutions；
(3) self-propagating combustion
Mixed liquor obtained by step (2) is continued to be concentrated with 50~70 DEG C of heating evaporations, it, will behind liquor capacity reduction amount >=1/3
Solution, which is placed in the Muffle furnace of 250~300 DEG C of heat preservations, causes self-propagating combustion, post-combustion capture product；
(4) crystallization and thermal treatment
The product that step (3) are collected is placed in high-temperature calcination stove, rises to 850~1050 DEG C with 5~10 DEG C/min heating rate
And 1~3h is kept the temperature, it is taken out after cooling, collecting calcined powder is siderochrome mineral black；
The incendiary agent is citric acid, or is citric acid and glycine, glutamic acid, glucose, urea, ammonium hydrogen carbonate and ethylene glycol
In any one or two or more mixing.
2. preparation method according to claim 1, which is characterized in that introduce Ti element in the solution made from step (2).
3. preparation method according to claim 2, which is characterized in that the specific steps for introducing Ti element are as follows: by titanium
Sour four N-butyls, which are distributed in the dehydrated alcohol of 5 times of quality, is made mixed liquor, and it is obtained that mixed liquor is added dropwise to step (2)
In solution, process is added dropwise and continues agitating and heating.
4. preparation method according to claim 3, which is characterized in that the tetra-n-butyl titanate and (Cr+Fe) total amount
Molar ratio≤0.04.
5. preparation method according to claim 1, which is characterized in that the incendiary agent is by 30%~50% citric acid, 0%
~20% glucose, 20%~50% urea and 0%~30% ethylene glycol composition.
6. preparation method according to claim 5, which is characterized in that siderochrome mineral black made from step (4) also successively into
The following post-processing of row: washing, filters pressing, drying, air-flow crushing, inspection and packaging.
7. preparation method according to claim 6, which is characterized in that the solution after step (3) concentration is placed in volume and is more than
In the crucible that 10 times of liquid volume, then self-propagating combustion is carried out in Muffle furnace.
8. the siderochrome mineral black of claim 1~7 any one the method preparation.
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| CN101768015A (en) * | 2009-12-25 | 2010-07-07 | 华南理工大学 | Black nanophase ceramics pigment and preparation method thereof |
| CN102432341A (en) * | 2011-09-20 | 2012-05-02 | 华东理工大学 | Submicron-nanometer level red ceramic pigment and manufacturing method thereof |
| CN103274761A (en) * | 2013-05-31 | 2013-09-04 | 景德镇陶瓷学院 | Cu-Mn-Fe-Cr cobalt-free black ceramic pigment and preparation method thereof |
| CN103877977A (en) * | 2014-03-24 | 2014-06-25 | 浙江师范大学 | Spinel type catalyst for eliminating halohydrocarbon and preparation method of spinel type catalyst |
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2017
- 2017-10-20 CN CN201710997068.5A patent/CN107628646B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768015A (en) * | 2009-12-25 | 2010-07-07 | 华南理工大学 | Black nanophase ceramics pigment and preparation method thereof |
| CN102432341A (en) * | 2011-09-20 | 2012-05-02 | 华东理工大学 | Submicron-nanometer level red ceramic pigment and manufacturing method thereof |
| CN103274761A (en) * | 2013-05-31 | 2013-09-04 | 景德镇陶瓷学院 | Cu-Mn-Fe-Cr cobalt-free black ceramic pigment and preparation method thereof |
| CN103877977A (en) * | 2014-03-24 | 2014-06-25 | 浙江师范大学 | Spinel type catalyst for eliminating halohydrocarbon and preparation method of spinel type catalyst |
Non-Patent Citations (1)
| Title |
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| Characteristics reproducibility of (Fe, Co)(Cr, Al)2O4 pigments obtained by solution combustion synthesis;J. Gilabert et al.;《Ceramics International》;20160510;第12881页实验部分以及表1 |
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