CN103601243B - A kind of sol-gel auto-combustion prepares the method for copper-chrome black - Google Patents
A kind of sol-gel auto-combustion prepares the method for copper-chrome black Download PDFInfo
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Abstract
The present invention discloses a kind of method that sol-gel auto-combustion prepares copper-chrome black.Cupric oxide and chromium sesquioxide is adopted to be raw material, by adding stearic acid and acrylicstyrene segmented copolymer mixing solutions, regulate the pH value of mixed solution to make sol-gel with hydrochloric acid again, then drying makes xerogel, then prepares copper-chrome black by self-propagating combustion.Achieve with oxide compound is that sol-gel prepared by raw material; By the synergy of carboxyl on stearic acid and acrylicstyrene segmented copolymer, decrease the segregation phenomena of metal ion, effectively stop reunion nanocrystalline in thermal decomposition process, the product purity obtained is high, and particle diameter is thin and be evenly distributed, and crystalline form is regular.Overcome that conventional solid calcination method product particle is thick and size-grade distribution is wide, the shortcomings such as crystalline form need be destroyed to product grinding; Decrease atmospheric pollution, eliminate the contaminated wastewater that washing negatively charged ion brings; Reduce calcining temperature and soaking time, save the energy.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind of method that sol-gel auto-combustion prepares copper-chrome black.
Background technology
Copper-chrome black (CuCr
2o
4) pigment is a kind of In The Mixed Metal Oxide Pigments with spinel type crystal structure, there is the performances such as excellent opacifying power, chemical resistance, resistance to elevated temperatures, outdoor stable and indiffusion, be usually used in the fields such as pottery, enamel, coating and plastics.Copper-chrome black mainly plays the effects such as painted and protection against corrosion in pottery and enamel.Because copper-chrome black has remarkable high temperature resistant and weather resistance, be widely used in the coil of strip coating of outdoor use, also in heat-resisting, the weather-proof vanish system such as fluoro-resin, organosilicon, polyester, also can be applicable in long-acting coating and engineering plastics.In addition, copper-chrome black also has excellent visible light-responded property and photochemical stability, have broad application prospects in photocatalytic hydrogen production by water decomposition, photodegradation organism etc., as the decolored degradation to organic dye such as tropeolin-D, Acid Red B, reactive brilliant red k-2gs.
The traditional method preparing copper-chrome black mainly contains solid phase method and hydroxide coprecipitation step.Solid phase method is often with the higher solid carbonic acid copper of purity and sodium dichromate 99, or cupric oxide and chromium sesquioxide mix by a certain percentage, grind to form fine powder, then put into calcining furnace and calcine for some time, then through rinsing, filtration, drying, grind to obtain finished product.Hydroxide coprecipitation step mixes by a certain percentage with the processable salts solution of copper and chromium, then adds alkali and carry out co-precipitation, and throw out is through rinsing, filtration, drying, then product is made in calcining in calcining furnace.In addition, the methods such as hydrothermal method, microemulsion method and sol-gel method are also had.Solid phase method is prepared copper-chrome black and be there is following problem: (1) due to raw material be solid, even if also uneven through the ground and mixed of long period, cause reactant particle contacts area little, reactive behavior is lower, reacts uneven, abundant; (2) for reacting fully, evenly, temperature of reaction is higher, generally need reach about 1200 DEG C, energy consumption is high, and makes pigment agglomeration serious, the comparatively thick and skewness of particle; (3) for meeting the granularity requirements of application, often needing again to grind, easily causing lattice damage, bringing impurity, reducing its chemical resistance.Adopt hydroxide coprecipitation step ingredient requirement processable salt, as the nitrate, vitriol etc. of copper, chromium, require higher; Production process is more complicated, and product particle is thick and size distribution is uneven, and product purity is not high.And other chemical process, as hydrothermal method, microemulsion method and sol-gel method, also higher to ingredient requirement, complex technical process, often needs High Temperature High Pressure, higher to the requirement of equipment, and the reaction times is longer, and production cost is higher, is unfavorable for suitability for industrialized production.
Summary of the invention
For the existing preparation method's Problems existing of above-mentioned copper-chrome black, the invention provides that a kind of product purity is high, comparatively thin, distribution uniform, complete crystal form the sol-gel auto-combustion of particle prepares the method for copper-chrome black.
The technical scheme that the present invention solves the problems of the technologies described above is: a kind of sol-gel auto-combustion prepares the method for copper-chrome black, and its preparation method comprises the following steps:
(1) preparation of sol-gel
Stoichiometrically n (Cu): n (Cr)=1: 2 ~ 2.20 takes a certain amount of cupric oxide and chromium sesquioxide, mix with the water of cupric oxide and chromium sesquioxide total mass 5 ~ 6 times and stir evenly, mix with stearic acid and acrylicstyrene segmented copolymer mixing solutions again, keep temperature 85 ~ 90 DEG C.Under constantly stirring, slowly add hydrochloric acid maintain pH value 3.5 ~ 4.5, gradually become green transparent colloidal sol to mixing solutions, then transpiring moisture is transformed into blackish green gel.
(2) preparation of xerogel precursor
Step (1) gained gel is placed in electric drying oven with forced convection, and at 110 ~ 120 DEG C, dry 1.5 ~ 2.5h makes xerogel presoma.
(3) self-propagating combustion prepares copper-chrome black
Step (2) gained xerogel precursor is placed in retort furnace, and ignition combustion becomes dark gray powder in air atmosphere, then is warming up to 600 ~ 1000 DEG C, and insulation 2 ~ 4h, comes out of the stove and cool to obtain copper-chrome black product.
Above-mentioned sol-gel auto-combustion prepares the method for copper-chrome black, and the stearic acid in described step (1) and the mass ratio of acrylicstyrene segmented copolymer are 5 ~ 10: 1, and stearic acid is 4 ~ 5: 1 to the mass ratio of cupric oxide; The relative molecular mass of acrylicstyrene segmented copolymer is 10000 ~ 100000.
Product of the present invention is suitable for pottery, enamel, coating, plastics, coil of strip coating, and in heat-resisting, the weather-proof vanish system such as fluoro-resin, organosilicon, polyester, also can be applicable in long-acting coating and engineering plastics.
Compared with prior art, beneficial effect of the present invention is:
(1) the present invention is by adding stearic acid and acrylicstyrene segmented copolymer mixing solutions and adding hydrochloric acid, and successfully achieving with oxide compound is that sol-gel prepared by raw material, overcome traditional method prepare sol-gel need by the defect of soluble salt.
(2) the present invention adopts the oxide compound such as cupric oxide and chromium sesquioxide to be raw material, overcome with soluble salt, as the topsoil that to be raw material produce when high-temp combustion of nitrate and hydrochloride, and vitriol is adopted to be that raw material need wash to product the water pollutions brought.
(3) the present invention is by adding stearic acid and acrylicstyrene segmented copolymer, make metal ion and carboxyl complexing, utilize the regular distribution of carboxyl on acrylicstyrene block copolymer chain, and act synergistically with stearic acid, make copper, what the element formation such as chromium were core with carboxyl on acrylicstyrene block copolymer chain is uniformly distributed, not only reduce the segregation phenomena of metal ion, reunion nanocrystalline in effective prevention thermal decomposition process, make product purity high, particle is thinner, complete crystal form, and make product particle even particle size distribution, overcome that conventional solid calcination method product particle is thick and size-grade distribution is wide, the shortcomings such as crystalline form need be destroyed to product grinding, therefore, the product adopting the inventive method to prepare has more excellent technical performance index and use properties.
(4) the inventive method does not need the product after to calcining to carry out aftertreatment, greatly reduces calcining temperature and soaking time prepared by product, has saved the energy.
(5) preparation technology of the present invention is simple, and reaction conditions is gentle, is easy to operate and control, and " three wastes " are few, and required equipment is conventional equipment, is easy to realize suitability for industrialized production, has broad application prospects.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Fig. 1 is process flow sheet of the present invention.
Fig. 2 is the x-ray diffraction pattern of embodiment 2 products obtained therefrom.
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment 2 products obtained therefrom.
Fig. 4 is the energy spectrum analysis figure of embodiment 2 products obtained therefrom.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1
(1) get 100g content be 98.0% cupric oxide and 189.1g content be the chromium sesquioxide of 99.0%, the water mixing adding 1450mL stirs evenly, with 400g stearic acid and 80g relative molecular mass be again 10210 acrylicstyrene segmented copolymer mixing solutions mix, keep temperature 85 DEG C, under constantly stirring, slowly add hydrochloric acid maintain solution ph 3.5 ~ 4.5, gradually become green transparent colloidal sol to mixing solutions, then transpiring moisture is transformed into blackish green gel.
(2) step (1) gained gel is placed in electric drying oven with forced convection, at 110 DEG C, dry 2.5h makes xerogel presoma.
(3) step (2) gained xerogel precursor is placed in retort furnace, ignition combustion becomes dark gray powder in air atmosphere, then is warming up to 600 DEG C, insulation 4h, cooling of coming out of the stove, press thin must copper-chrome black product.
Embodiment 2
(1) get 100g content be 98.0% cupric oxide and 189.1g content be the chromium sesquioxide of 99.0%, the water mixing adding 1735mL stirs evenly, with 450g stearic acid and 60g relative molecular mass be again 31831 acrylicstyrene segmented copolymer mixing solutions mix, keep temperature 90 DEG C, under constantly stirring, slowly add hydrochloric acid maintain solution ph 3.5 ~ 4.5, gradually become green transparent colloidal sol to mixing solutions, then transpiring moisture is transformed into blackish green gel.
(2) step (1) gained gel is placed in electric drying oven with forced convection, at 115 DEG C, dry 2h makes xerogel presoma.
(3) step (2) gained xerogel precursor is placed in retort furnace, ignition combustion becomes dark gray powder in air atmosphere, then is warming up to 800 DEG C, insulation 3.5h, cooling of coming out of the stove, press thin must copper-chrome black product.
Embodiment 3
(1) get 100g content be 98.0% cupric oxide and 198.6g content be the chromium sesquioxide of 99.0%, the water mixing adding 1640mL stirs evenly, with 480g stearic acid and 70g relative molecular mass be again 52356 acrylicstyrene segmented copolymer mixing solutions mix, keep temperature 88 DEG C, under constantly stirring, slowly add hydrochloric acid maintain solution ph 3.5 ~ 4.5, gradually become green transparent colloidal sol to mixing solutions, then transpiring moisture is transformed into blackish green gel.
(2) step (1) gained gel is placed in electric drying oven with forced convection, at 115 DEG C, dry 2h makes xerogel presoma.
(3) step (2) gained xerogel precursor is placed in retort furnace, ignition combustion becomes dark gray powder in air atmosphere, then is warming up to 900 DEG C, insulation 3h, cooling of coming out of the stove, press thin must copper-chrome black product.
Embodiment 4
(1) get 100g content be 98.0% cupric oxide and 208.0g content be the chromium sesquioxide of 99.0%, the water mixing adding 1850mL stirs evenly, with 500g stearic acid and 100g relative molecular mass be again 75484 acrylicstyrene segmented copolymer mixing solutions mix, keep temperature 90 DEG C, under constantly stirring, slowly add hydrochloric acid maintain solution ph 3.5 ~ 4.5, gradually become green transparent colloidal sol to mixing solutions, then transpiring moisture is transformed into blackish green gel.
(2) step (1) gained gel is placed in electric drying oven with forced convection, at 120 DEG C, dry 2h makes xerogel presoma.
(3) step (2) gained xerogel precursor is placed in retort furnace, ignition combustion becomes dark gray powder in air atmosphere, then is warming up to 800 DEG C, insulation 3.5h, cooling of coming out of the stove, press thin must copper-chrome black product.
Embodiment 5
(1) get 100g content be 98.0% cupric oxide and 189.1g content be the chromium sesquioxide of 99.0%, the water mixing adding 1580mL stirs evenly, with 500g stearic acid and 50g relative molecular mass be again 75484 acrylicstyrene segmented copolymer mixing solutions mix, keep temperature 88 DEG C, under constantly stirring, slowly add hydrochloric acid maintain solution ph 3.5 ~ 4.5, gradually become green transparent colloidal sol to mixing solutions, then transpiring moisture is transformed into blackish green gel.
(2) step (1) gained gel is placed in electric drying oven with forced convection, at 120 DEG C, dry 2h makes xerogel presoma.
(3) step (2) gained xerogel precursor is placed in retort furnace, ignition combustion becomes dark gray powder in air atmosphere, then is warming up to 900 DEG C, insulation 2.5h, cooling of coming out of the stove, press thin must copper-chrome black product.Embodiment 6
(1) get 100g content be 98.0% cupric oxide and 189.1g content be the chromium sesquioxide of 99.0%, the water mixing adding 1500mL stirs evenly, with 420g stearic acid and 70g relative molecular mass be again 99169 acrylicstyrene segmented copolymer mixing solutions mix, keep temperature 90 DEG C, under constantly stirring, slowly add hydrochloric acid maintain solution ph 3.5 ~ 4.5, gradually become green transparent colloidal sol to mixing solutions, then transpiring moisture is transformed into blackish green gel.
(2) step (1) gained gel is placed in electric drying oven with forced convection, at 120 DEG C, dry 1.5h makes xerogel presoma.
(3) step (2) gained xerogel precursor is placed in retort furnace, ignition combustion becomes dark gray powder in air atmosphere, then is warming up to 1000 DEG C, insulation 2h, cooling of coming out of the stove, press thin must copper-chrome black product.
Embodiment 2 products obtained therefrom is carried out multinomial sign, adopts Rigaku D/max-2550VB
+18KW turns target X-ray diffractometer, JMS-6380LV type scanning electronic microscope, INCAX-SIGHT energy depressive spectroscopy and SKC-2000 type light transmission formula grain-distribution detection instrument etc. and measures.Respectively as shown in Figures 2 and 3, respectively as shown in Figure 4 and Table 1, granularity and distribute as shown in table 2, product performance index test result is as shown in table 3 for surface-element compositional analysis for X-ray diffraction and Analysis of Surface Topography.
As can be seen from Figure 2, the characteristic diffraction peak of product and CuCr
2o
4standard card data (PDF card 34-0424) are completely the same, show that crystal development is good.As can be seen from Figure 3, crystal is the cubic spinel type pattern of well-crystallized, and particle is more even.From Fig. 4 and table 1, each element ratio of product and CuCr
2o
4in molecular formula, theoretical elemental ratio is very close, illustrates that product purity is high, and the copper-chrome black product of synthesis is pure spinel type CuCr
2o
4.Table 2 shows, the particle of product mainly concentrates between 0.10 ~ 1.00 μm.
Table 1 EDAX results
| Element | Cu | Cr | O |
| Product atomic percentage/% | 13.85 | 27.56 | 58.59 |
| CuCr 2O 4Atomic percentage/% | 14.29 | 28.57 | 57.14 |
Table 2 product granularity and distribution thereof
| Granularity/μm | ≤0.01 | 0.01～0.10 | 0.10～0.50 | 0.50～1.00 |
| Mass percent/% | 3.807 | 7.743 | 27.465 | 43.989 |
| Granularity/μm | 1.00～1.50 | 1.50～2.50 | 2.50～10.00 | ≥10.00 |
| Mass percent/% | 10.422 | 5.831 | 0.742 | 0.001 |
Table 3 product performance index
| Project | Index |
| Color | Blue phase-black |
| Density/(g/cm 3) | 5.4 |
| PH value | 7.2 |
| Oil number/(g/100g) | 19 |
| 105 DEG C of volatile matter/% | ≤0.02 |
| The water solubles/% | ≤0.01 |
| Median size/μm | 0.8 |
| Screenings (10 μm of square hole sieves)/% | ≤0.001 |
| Temperature tolerance/DEG C | Average 1050 DEG C, the highest 1250 DEG C |
| Photostabilization | 8 |
| Acid resistance | 5 |
| Alkali resistance | 5 |
| Resistance to migration | 5 |
| Weathering resistance | 5 |
| Dispersed | Very easily disperse |
Claims (4)
1. sol-gel auto-combustion prepares a method for copper-chrome black, it is characterized in that, comprises the following steps:
(1) preparation of sol-gel
Stoichiometrically
n(Cu):
n(Cr)=1: 2 ~ 2.20 take a certain amount of cupric oxide and chromium sesquioxide, mix with the water of cupric oxide and chromium sesquioxide total mass 5 ~ 6 times and stir evenly, mix with stearic acid and acrylicstyrene segmented copolymer mixing solutions again, keep temperature 85 ~ 90 DEG C, under constantly stirring, slowly add hydrochloric acid maintain pH value 3.5 ~ 4.5, gradually become green transparent colloidal sol to mixing solutions, then transpiring moisture is transformed into blackish green gel;
(2) preparation of xerogel presoma
Step (1) gained gel is placed in electric drying oven with forced convection, and at 110 ~ 120 DEG C, dry 1.5 ~ 2.5 h make xerogel presoma;
(3) self-propagating combustion prepares copper-chrome black
Step (2) gained xerogel presoma is placed in retort furnace, and ignition combustion becomes dark gray powder in air atmosphere, then heats up 600 ~ 1000 DEG C, and insulation 2 ~ 4 h, come out of the stove and cool to obtain copper-chrome black product.
2. sol-gel auto-combustion according to claim 1 prepares the method for copper-chrome black, it is characterized in that: the mass ratio of described stearic acid and acrylicstyrene segmented copolymer is 5 ~ 10: 1.
3. sol-gel auto-combustion according to claim 1 prepares the method for copper-chrome black, it is characterized in that: the mass ratio of described stearic acid and cupric oxide is 4 ~ 5: 1.
4. sol-gel auto-combustion according to claim 1 and 2 prepares the method for copper-chrome black, it is characterized in that: the relative molecular mass of described acrylicstyrene segmented copolymer is 10000 ~ 100000.
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