CN100480185C - Novel aragonite calcium carbonate and method for preparing the same - Google Patents
Novel aragonite calcium carbonate and method for preparing the same Download PDFInfo
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- CN100480185C CN100480185C CNB2007100391467A CN200710039146A CN100480185C CN 100480185 C CN100480185 C CN 100480185C CN B2007100391467 A CNB2007100391467 A CN B2007100391467A CN 200710039146 A CN200710039146 A CN 200710039146A CN 100480185 C CN100480185 C CN 100480185C
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- aragonite
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Abstract
This invention relates to a new type of aragonite CaCO3 and its preparation method, which takes active bio-films as the reaction system, adds cooperated reagent NTA almonia three acid to form a cooperated template to be induced to get a flower-state super structure-the aragonite CaCO3 formed by nanometer line sub-structures, and the diameter of the sub-structure is 40-60nm. The method includes the following steps: dipping cleaned bean spouts in a CaCl solution in the mol concentration of 0.1-0.5mol/L for 12-48h, then dipping the bean sprouts in a Na2CO3 solution in the mole concentration of 0.1-0.5mol/L and containing NTA reagent for 24-72h, cutting open the sprouts and processing them in ultrasonic cleaning to get the product.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of novel aragonite calcium carbonate and preparation method thereof.
Background technology
The crystal of lime carbonate generally occurs with three kinds of forms, i.e. calcite, aragonite and vaterite, and also having a kind of is amorphous calcium carbonate.Their stability is the strongest with calcite, and aragonite and vaterite are all metastable crystal formation, and solution reaction can not get metastable crystal formation under the conventional state.In the research report in the past, the control of being adopted generates the aragonite crystalline and mainly contains change thermodynamic condition (as pressure), adds the homogeneity crystal seed and add the crystal formation control agent, and the product for preparing occurs with bar-shaped or needle-like crystal mostly.
As the lime carbonate of usefulness carbonating legal systems such as bavin in 1988 ocean will wherein aragonite content reach 80%, the long 2-4 micron of crystal, diameter are the 0.3-0.7 micron.Employing phosphoric acid-phosphate additives such as the Shang Wenyu of Xi'an Communications University are prepared calcium carbonate crystal whisker, and the aragonite phase content for preparing is about 70%, and mixing has calcite particle.Employing carbonation methods such as Japan Y.Ota are the 5-100 micron having made length more than 65 degrees centigrade.Diameter is the single preparation of aragonite whisker of 0.2-0.5.Also have the people to add excessive magnesium ion in solution, can induce to obtain aragonite, mean length is 50 microns, and length-to-diameter ratio is 26 whisker.It is that 35-50 micron, diameter are the aragonite of 1.5-3 micron that the somebody adds the length that aluminum ion obtains being used for plastics, paint.
And nano material be a kind of be the material of structural system of the different-shapes such as bar-shaped, wire, tubulose, lath-shaped, the poly-ball top shape of rod of yardstick with nanometer (1/1000000000th meter).This material has good photoelectric characteristic, heat conductivity, magnetism characteristic, mechanical property and catalytic performance etc., and they can be used as the construction unit of nano photoelectric of new generation, electrochemistry, electromechanical device.Specific to lime carbonate, because particle is little, it is few to reunite, and is easy to disperse, and relies on high strength, the high-modulus of self, can more effectively bring into play enhancing, toughening effect.And the macrofiber crystal often can increase the aesthetic property and the smoothness of product, thus nanometer aragonite superstructure have common aragonite incomparable particular performances.
Summary of the invention
The object of the present invention is to provide a kind of productive rate height, non-environmental-pollution, novel aragonite calcium carbonate with low cost and preparation method thereof.
The aragonite calcium carbonate that the present invention proposes, utilize active biological film as reaction system, form collaborative template by adding collaborative reagent N TA (nitrilotriacetic acid(NTA)), induce and obtain the flower-shaped superstructure that pattern is formed by the assembling of nano wire substructure, this flower-shaped superstructure is aragonite calcium carbonate, and wherein the diameter of substructure is 40～60nm.
The preparation method of the aragonite calcium carbonate that the present invention proposes, concrete steps are as follows:
(1) get commercially available bean sprouts, it is used distilled water immersion 1-2 hour, clean, stand-by;
(2) prepare sodium carbonate solution and calcium chloride solution respectively, the volumetric molar concentration of sodium carbonate solution and calcium chloride solution is respectively 0.1-0.5mol/L, and step (1) gained bean sprouts is soaked in earlier in the calcium chloride solution, at room temperature soaks and supports reaction 12-48 hour, take out, outside surface is cleaned with deionized water; In sodium carbonate solution, add relatively then and the additive NTA (nitrilotriacetic acid(NTA)) of sodium carbonate solution mass percent 1-2%, the bean sprouts is soaked support in sodium carbonate solution again, at room temperature soak and supported 24-72 hour; The bean sprouts add-on is looked how many an amount of interpolations of solution, can submergence be as the criterion with solution;
(3) step (2) gained is soaked the bean sprouts and take out, the bean sprouts is cut in washing open, and product is handled through ultrasonic apparatus, and washing disperses product with dehydrated alcohol, promptly gets desired product.
Among the present invention, in the step (3), washing can adopt deionized water and dehydrated alcohol alternately to rinse well, and washing times is 3-6 time.
Through discoverys that study for a long period of time: bone of people and animal and tooth, the heavily fortified point of shellfish biology and hard shell all is the masterpiece of the biomineralization under cell is controlled is organism self a synthetic fine nano material.Wherein lime carbonate is exactly a very typical example, and the lime carbonate of natural formation is many to be occurred with metastable aragonite and vaterite, and mostly is multilevel ordered nano-superstructure, pearl for example, and the performance that this structure is brought is that ordinary construction is incomparable.But the out-of-control words of the lime carbonate of prepared in laboratory then must be calcite, how much all are needle-like or rhabdolith, can't embody special pattern and excellent shape energy that natural synthetic aragonite is had and control the aragonite for preparing big extremely.
Gained aragonite calcium carbonate of the present invention is observed with scanning electronic microscope (SEM), finds all flower-shaped superstructures for being formed by the assembling of substructures such as nano wire of product pattern, and wherein the diameter of substructure is 40～60nm.From X-ray powder diffraction figure, as can be known, do not have assorted peak in the collection of illustrative plates of above-mentioned product and occur, illustrate that product all is the aragonite structure.Infared spectrum shows the red shift phenomenon, is the quantum size benefit of product nanometer substructure.
The present invention has following advantage:
1, because the aragonite that the present invention prepares is a kind of new nano-superstructure aragonite, has the unexistent nano effect of common aragonite.
2, preparation method of the present invention is simple, and productive rate height, and non-environmental-pollution are with low cost, realizes being easy to the suitability for industrialized production future.
Description of drawings
Fig. 1 is the aragonite calcium carbonate structure sem photograph of embodiment 1.Wherein, a is the whole shape appearance figure (250X) of product, and b is that product amplifies shape appearance figure, and (2000X), c is square frame part details enlarged view (5000X) among the figure b, and d is circle part details enlarged view (20000X) among the figure b.
Fig. 2 is the aragonite calcium carbonate structure sem photograph (5000X) of embodiment 2.
Fig. 3 is products therefrom X-ray powder diffraction figure among the embodiment 1.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1:
At first, get commercially available bean sprouts, it is used distilled water immersion 1 hour, washes clean, stand-by.
Then, preparation 100ml (0.1mol/L) CaCl
2The aqueous solution and 0.1mol/LNa
2CO
3Aqueous solution 100ml (reagent of employing all is to analyze alcohol).Place two 250ml tall form beaker respectively.After above-mentioned commercially available Semen Phaseoli radiati Germinatus (100 ml solns add 8～10) through washing cleaned with deionized water again, root was vertically put into down and is filled CaCl
2In the beaker of solution, and make its rhizome, only expose blade all by the solution submergence.Take out behind the 12h, rinse out the CaCl of outside, bean sprouts with deionized water
2Solution, the additive NTA of adding about 1% in sodium carbonate solution soaks the bean sprouts and supports in sodium carbonate solution then, at room temperature soaks equally and supports 24 hours.Take out the bean sprouts, rinse well with deionized water and dehydrated alcohol respectively, wash 3-4 time, cut the bean sprouts open,, clean respectively, for washing 3-4 time, disperse product with dehydrated alcohol at last when handing over zero with deionized water, acetone, dehydrated alcohol with the ultrasonic taking-up of product.From the aragonite calcium carbonate structure sem photograph of Fig. 1 as can be seen, the product pattern is the flower-shaped superstructure that is formed by the assembling of substructures such as nano wire, and wherein the diameter of substructure is 40～60nm.From the X-ray powder diffraction figure of Fig. 3, as can be known, do not have assorted peak in the collection of illustrative plates of above-mentioned product and occur, illustrate that product all is the aragonite structure.Infared spectrum shows the red shift phenomenon, is the quantum size benefit of product nanometer substructure.
Embodiment 2:
At first, get commercially available bean sprouts, it is used distilled water immersion 1 hour, washes clean, stand-by.
Then, preparation 100ml (0.15mol/L) CaCl
2The aqueous solution and 0.15mol/LNa
2CO
3Aqueous solution 100ml (reagent of employing all is to analyze alcohol).Place two 250ml tall form beaker respectively.After above-mentioned commercially available Semen Phaseoli radiati Germinatus (100 ml solns add 8～10) through washing cleaned with deionized water again, root was vertically put into down and is filled CaCl
2In the beaker of solution, and make its rhizome, only expose blade all by the solution submergence.Take out behind the 24h, rinse out the CaCl of outside, bean sprouts with deionized water
2Solution, the additive NTA of adding about 1.5% in sodium carbonate solution soaks the bean sprouts and supports in sodium carbonate solution then, at room temperature soaks equally and supports 48 hours.Take out the bean sprouts, rinse well with deionized water and dehydrated alcohol respectively, wash 4-6 time, cut the bean sprouts open,, clean respectively, wash 4-6 time, disperse product with dehydrated alcohol at last with deionized water, acetone, dehydrated alcohol with the ultrasonic taking-up of product.From the aragonite calcium carbonate structure sem photograph of Fig. 2 as can be seen, the product pattern is the flower-shaped superstructure that is formed by the assembling of substructures such as nano wire, and wherein the diameter of substructure is 40～60nm.Equally can be from X-ray powder diffraction figure as can be known, product all is the aragonite structure.
Embodiment 3:
At first, get commercially available bean sprouts, it is used distilled water immersion 1 hour, washes clean, stand-by.
Then, preparation 100ml (0.2mol/L) CaCl
2The aqueous solution and 0.2mol/LNa
2CO
3Aqueous solution 100ml (reagent of employing all is to analyze alcohol).Place two 250ml tall form beaker respectively.After above-mentioned commercially available Semen Phaseoli radiati Germinatus (100 ml solns add 8～10) through washing cleaned with deionized water again, root was vertically put into down and is filled CaCl
2In the beaker of solution, and make its rhizome, only expose blade all by the solution submergence.Take out behind the 24h, rinse out the CaCl of outside, bean sprouts with deionized water
2Solution, the additive NTA of adding about 2% in sodium carbonate solution soaks the bean sprouts and supports in sodium carbonate solution then, at room temperature soaks equally and supports 72 hours.Take out the bean sprouts, rinse well with deionized water and dehydrated alcohol respectively, wash 3-5 time, cut the bean sprouts open,, clean respectively, wash 3-5 time, disperse product with dehydrated alcohol at last with deionized water, acetone, dehydrated alcohol with the ultrasonic taking-up of product.
Claims (3)
1, a kind of preparation method of aragonite calcium carbonate is characterized in that concrete steps are as follows:
(1) get commercially available bean sprouts, it is used distilled water immersion 1-2 hour, clean, stand-by;
(2) prepare sodium carbonate solution and calcium chloride solution respectively, the volumetric molar concentration of sodium carbonate solution and calcium chloride solution is respectively 0.1-0.5mol/L, and step (1) gained bean sprouts is soaked in earlier in the calcium chloride solution, at room temperature soaks and supports reaction 12-48 hour, take out, outside surface is cleaned with deionized water; In sodium carbonate solution, add additive NTA nitrilotriacetic acid(NTA) then, the bean sprouts is soaked support in sodium carbonate solution again, at room temperature soak and supported 24-72 hour with respect to sodium carbonate solution mass percent 1-2%;
(3) step (2) gained is soaked the bean sprouts and take out, the bean sprouts is cut in washing open, and product is handled through ultrasonic apparatus, and washing disperses product with dehydrated alcohol, promptly gets desired product.
2, the preparation method of aragonite calcium carbonate according to claim 1 is characterized in that in the step (3), and washing adopts deionized water and dehydrated alcohol alternately to rinse well, and washing times is 3-6 time.
3, the aragonite calcium carbonate that obtains of a kind of preparation method according to claim 1, it is characterized in that utilizing active biological film as reaction system, form collaborative template by adding collaborative reagent N TA nitrilotriacetic acid(NTA), induce and obtain the flower-shaped superstructure that pattern is formed by the assembling of nano wire substructure, this flower-shaped superstructure is aragonite calcium carbonate, and wherein the diameter of substructure is 40～60nm.
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| CNB2007100391467A CN100480185C (en) | 2007-04-05 | 2007-04-05 | Novel aragonite calcium carbonate and method for preparing the same |
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| CNB2007100391467A CN100480185C (en) | 2007-04-05 | 2007-04-05 | Novel aragonite calcium carbonate and method for preparing the same |
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| CN100480185C true CN100480185C (en) | 2009-04-22 |
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| CN102743090A (en) * | 2012-07-31 | 2012-10-24 | 陈姬 | Method for manufacturing pearl relic flowers in water |
| CN107140937B (en) * | 2017-07-13 | 2018-10-23 | 广东海洋大学 | One type pearly layer material and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6071336A (en) * | 1996-09-05 | 2000-06-06 | Minerals Technologies Inc. | Acicular calcite and aragonite calcium carbonate |
| CN1641077A (en) * | 2004-01-13 | 2005-07-20 | 中国人民解放军国防科学技术大学 | Method for preparing aragonite type calcium carbonate whisker |
| CN1800451A (en) * | 2005-11-03 | 2006-07-12 | 福建师范大学 | Crystal whisker calcium carbonate preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6071336A (en) * | 1996-09-05 | 2000-06-06 | Minerals Technologies Inc. | Acicular calcite and aragonite calcium carbonate |
| CN1641077A (en) * | 2004-01-13 | 2005-07-20 | 中国人民解放军国防科学技术大学 | Method for preparing aragonite type calcium carbonate whisker |
| CN1800451A (en) * | 2005-11-03 | 2006-07-12 | 福建师范大学 | Crystal whisker calcium carbonate preparation method |
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Granted publication date: 20090422 Termination date: 20120405 |