CN104961148B - The mixing crystal formation nano-calcium carbonate synthetic method that a kind of content is controlled - Google Patents
The mixing crystal formation nano-calcium carbonate synthetic method that a kind of content is controlled Download PDFInfo
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Abstract
The mixing crystal formation nano-calcium carbonate synthetic method that a kind of content is controlled, it relates to the preparation method of a kind of Nano-Calcium Carbonate.The invention aims to solve prior art and can not prepare the nano material of multiple calcium carbonate crystal formation mixing, the problem that also cannot realize the content of the calcium carbonate crystal formation in material cannot be carried out regulation and control.Synthetic method: one, configuration calcium chloride poly-aspartate mixed solution；Two, configuration sodium carbonate liquor；Three, preparation mixing microemulsion；Four, sodium carbonate emulsion is prepared；Five, microemulsion and the mixing of sodium carbonate microemulsion will be mixed, be centrifuged separation, washing with alcohol the most successively and be dried, and i.e. obtain mixing crystal formation nano-calcium carbonate.Advantage: by the concentration of poly-aspartate in calcium chloride poly-aspartate mixed solution in set-up procedure one, reaches the purpose of vaterite-type calcium carbonate content in the nano-calcium carbonate of control calcite and vaterite mixing crystal formation.Master of the present invention is mainly for the preparation of mixing crystal formation nano-calcium carbonate.
Description
Technical field
The invention belongs to inorganic carbonate calcium material preparation field, be specifically related to the preparation method of a kind of Nano-Calcium Carbonate.
Background technology
The aspect extensive application such as it is simple that Nano-Calcium Carbonate has synthesis, porous, and easy surface is modified, polymorphic, nontoxic, the advantage that bio-compatibility is good, and at food, biomedical, filler, chemical industry, environment.
Chu Yanhong et al. (CN201310570950.3) discloses a kind of method that microemulsion prepares single-crystal-form ball aragonite nano calcium carbonate, the method can only obtain pure vaterite-type Nano-Calcium Carbonate, but can not prepare the nano material of multiple calcium carbonate crystal formation mixing, the content to the calcium carbonate crystal formation in material cannot be carried out regulation and control simultaneously.
Summary of the invention
The invention aims to solve prior art and can not prepare the nano material of multiple calcium carbonate crystal formation mixing, also the problem that cannot realize the content of the calcium carbonate crystal formation in material be cannot be carried out regulation and control, and provide a kind of mixture content controlled mixing crystal formation nano-calcium carbonate synthetic method.
The mixing crystal formation nano-calcium carbonate synthetic method that a kind of mixture content is controlled, is specifically realized by the following steps:
One, configuration calcium chloride-poly-aspartate mixed solution: utilize calcium chloride, poly-aspartate and deionized water configuration calcium chloride-poly-aspartate mixed solution, and calcium chloride concentration is 0.3mol/L in described calcium chloride-poly-aspartate mixed solution, poly-aspartate concentration is Mmg/L, wherein 0 < M < 2.5；
Two, configuration sodium carbonate liquor: being dissolved in deionized water by sodium carbonate, obtaining the concentration of sodium carbonate in sodium carbonate liquor, and described sodium carbonate liquor is 0.3mol/L；
Three, preparation mixing microemulsion: 1., weigh: weigh Ag calcium chloride-poly-aspartate mixed solution, Bg hexamethylene, Cg polyoxyethylenated alcohol sodium sulfate, Dg n-amyl alcohol, and meet B/ (A+B) × 100%=85%, C/ (A+B+C) × 100%=15%, D/ (A+B+D) × 100%=15%；2., mix: Ag calcium chloride-poly-aspartate mixed solution, Bg hexamethylene, Cg polyoxyethylenated alcohol sodium sulfate and Dg n-amyl alcohol are mixed, and stirring and evenly mixing, obtain mixing microemulsion；
Four, sodium carbonate emulsion is prepared: 1., weigh: weigh ag sodium carbonate liquor, bg hexamethylene, cg polyoxyethylenated alcohol sodium sulfate, dg n-amyl alcohol, and meet a/ (a+b) × 100%=85%, c/ (a+b+c) × 100%=15%, d/ (a+b+d) × 100%=15%；2., mix: ag sodium carbonate liquor, bg hexamethylene, cg polyoxyethylenated alcohol sodium sulfate and dg n-amyl alcohol are mixed, and stirring and evenly mixing, obtain sodium carbonate microemulsion；
Five, mixing: by mixing microemulsion and the mixing of sodium carbonate microemulsion, react 3h under the conditions of temperature is 20 DEG C and speed of agitator is 200rpm～300rpm, be centrifuged separation, washing with alcohol the most successively and be dried, i.e. obtain mixing crystal formation nano-calcium carbonate；Ca in mixing microemulsion described in step 52+With CO in sodium carbonate microemulsion3 2-Mol ratio be 1:1；Mixing crystal formation nano-calcium carbonate described in step 5 is calcite and the nano-calcium carbonate of vaterite mixing crystal formation.
The invention have the advantages that the present invention uses combining of microemulsion method and soluble additive poly-aspartate, compared with existing synthetic method, use the method synthesis mixing crystal formation nano-calcium carbonate even particle size distribution that the present invention provides, and by the concentration of poly-aspartate in calcium chloride-poly-aspartate mixed solution in set-up procedure one, reach the purpose of vaterite-type calcium carbonate content in the nano-calcium carbonate of control calcite and vaterite mixing crystal formation.
Accompanying drawing explanation
Fig. 1 is the mixing crystal formation nano-calcium carbonate X ray diffracting spectrum of embodiment 1 preparation；
Fig. 2 is the mixing crystal formation nano-calcium carbonate electron scanning micrograph of embodiment 1 preparation；
Fig. 3 is the mixing crystal formation nano-calcium carbonate X ray diffracting spectrum of embodiment 2 preparation；
Fig. 4 is the mixing crystal formation nano-calcium carbonate electron scanning micrograph of embodiment 2 preparation；
Fig. 5 is the mixing crystal formation nano-calcium carbonate X ray diffracting spectrum of embodiment 3 preparation；
Fig. 6 is the mixing crystal formation nano-calcium carbonate electron scanning micrograph of embodiment 3 preparation；
Fig. 7 is the mixing crystal formation nano-calcium carbonate X ray diffracting spectrum of embodiment 4 preparation；
Fig. 8 is the mixing crystal formation nano-calcium carbonate electron scanning micrograph of embodiment 4 preparation；
Fig. 9 is the mixing crystal formation nano-calcium carbonate X ray diffracting spectrum of embodiment 5 preparation；
Figure 10 is the mixing crystal formation nano-calcium carbonate electron scanning micrograph of embodiment 5 preparation；
Figure 11 is the mixing crystal formation nano-calcium carbonate X ray diffracting spectrum of embodiment 6 preparation；
Figure 12 is the mixing crystal formation nano-calcium carbonate electron scanning micrograph of embodiment 6 preparation.
Detailed description of the invention
Detailed description of the invention one: present embodiment is the mixing crystal formation nano-calcium carbonate synthetic method that a kind of content is controlled, is specifically realized by the following steps:
One, configuration calcium chloride-poly-aspartate mixed solution: utilize calcium chloride, poly-aspartate and deionized water configuration calcium chloride-poly-aspartate mixed solution, and calcium chloride concentration is 0.3mol/L in described calcium chloride-poly-aspartate mixed solution, poly-aspartate concentration is M mg/L, wherein 0 < M < 2.5；
Two, configuration sodium carbonate liquor: being dissolved in deionized water by sodium carbonate, obtaining the concentration of sodium carbonate in sodium carbonate liquor, and described sodium carbonate liquor is 0.3mol/L；
Three, preparation mixing microemulsion: 1., weigh: weigh Ag calcium chloride-poly-aspartate mixed solution, Bg hexamethylene, Cg polyoxyethylenated alcohol sodium sulfate, Dg n-amyl alcohol, and meet B/ (A+B) × 100%=85%, C/ (A+B+C) × 100%=15%, D/ (A+B+D) × 100%=15%；2., mix: Ag calcium chloride-poly-aspartate mixed solution, Bg hexamethylene, Cg polyoxyethylenated alcohol sodium sulfate and Dg n-amyl alcohol are mixed, and stirring and evenly mixing, obtain mixing microemulsion；
Four, sodium carbonate emulsion is prepared: 1., weigh: weigh ag sodium carbonate liquor, bg hexamethylene, cg polyoxyethylenated alcohol sodium sulfate, dg n-amyl alcohol, and meet a/ (a+b) × 100%=85%, c/ (a+b+c) × 100%=15%, d/ (a+b+d) × 100%=15%；2., mix: ag sodium carbonate liquor, bg hexamethylene, cg polyoxyethylenated alcohol sodium sulfate and dg n-amyl alcohol are mixed, and stirring and evenly mixing, obtain sodium carbonate microemulsion；
Five, mixing: by mixing microemulsion and the mixing of sodium carbonate microemulsion, react 3h under the conditions of temperature is 20 DEG C and speed of agitator is 200rpm～300rpm, be centrifuged separation, washing with alcohol the most successively and be dried, i.e. obtain mixing crystal formation nano-calcium carbonate；Ca in mixing microemulsion described in step 52+With CO in sodium carbonate microemulsion3 2-Mol ratio be 1:1；Mixing crystal formation nano-calcium carbonate described in step 5 is calcite and the nano-calcium carbonate of vaterite mixing crystal formation.
Present embodiment employing microemulsion method combines with soluble additive poly-aspartate, compared with existing synthetic method, use the method synthesis mixing crystal formation nano-calcium carbonate even particle size distribution that present embodiment provides, prepare mixing crystal formation nano-calcium carbonate be calcite and the nano-calcium carbonate of vaterite mixing crystal formation, i.e. in mixing crystal formation nano-calcium carbonate prepared by present embodiment, there is vaterite-type calcium carbonate and calcite type calcium carbonate simultaneously, and by the concentration of poly-aspartate in calcium chloride-poly-aspartate mixed solution in set-up procedure one, reach the purpose of vaterite-type calcium carbonate content in the nano-calcium carbonate of control calcite and vaterite mixing crystal formation.
The serviceability of Nano-Calcium Carbonate is the structure by granule and surface nature decision, controls different calcium carbonate crystal formations and different ratios thereof in granule and can change material internal structure and granule-morphology, and then improves the serviceability of Nano-Calcium Carbonate.It addition, mixing crystal formation nano-calcium carbonate can suppress the particle aggregation of monocrystalline type Nano-Calcium Carbonate.
Calculating according to formula 1 and obtain calcite and the molar fraction ratio of vaterite in mixing crystal formation nano-calcium carbonate prepared by detailed description of the invention one, formula 1 is as follows:
IV 104/IC 110=7.691 × XC/XV
Wherein, IV 104/IC 110Ratio for (104) crystallographic plane diffraction peak Yu the peak integral area of (110) crystallographic plane diffraction peak；XC/XVMolar fraction ratio for calcite type calcium carbonate with vaterite-type calcium carbonate.
Formula 1 result of calculation being substituted in formula 2, can try to achieve the percentage composition of vaterite-type calcium carbonate in the mixing crystal formation nano-calcium carbonate of detailed description of the invention one preparation, formula 2 is as follows:
Vaterite content=XV/(XC+XV) × 100%
Calculate the content of vaterite-type calcium carbonate in the mixing crystal formation nano-calcium carbonate of detailed description of the invention one preparation.
Detailed description of the invention two: the present embodiment difference from detailed description of the invention one is: when poly-aspartate concentration is 0.25mg/L in the calcium chloride described in step one-poly-aspartate mixed solution, and in the nano-calcium carbonate of the calcite described in step 5 and vaterite mixing crystal formation, vaterite-type calcium carbonate content is 73%～76%.Other are identical with detailed description of the invention one.
Detailed description of the invention three: the present embodiment difference from detailed description of the invention one is: when poly-aspartate concentration is 0.5mg/L in the calcium chloride described in step one-poly-aspartate mixed solution, and in the nano-calcium carbonate of the calcite described in step 5 and vaterite mixing crystal formation, vaterite-type calcium carbonate content is 80%～83%.Other are identical with detailed description of the invention one.
Detailed description of the invention four: the present embodiment difference from detailed description of the invention one is: when poly-aspartate concentration is 1.0mg/L in the calcium chloride described in step one-poly-aspartate mixed solution, and in the nano-calcium carbonate of the calcite described in step 5 and vaterite mixing crystal formation, vaterite-type calcium carbonate content is 85%～88%.Other are identical with detailed description of the invention one.
Detailed description of the invention five: the present embodiment difference from detailed description of the invention one is: when poly-aspartate concentration is 1.25mg/L in the calcium chloride described in step one-poly-aspartate mixed solution, and in the nano-calcium carbonate of the calcite described in step 5 and vaterite mixing crystal formation, vaterite-type calcium carbonate content is 91%～94%.Other are identical with detailed description of the invention one.
Use following verification experimental verification effect of the present invention
Embodiment 1: the mixing crystal formation nano-calcium carbonate synthetic method that a kind of content is controlled, is specifically realized by the following steps:
One, configuration calcium chloride-poly-aspartate mixed solution: utilize calcium chloride, poly-aspartate and deionized water configuration calcium chloride-poly-aspartate mixed solution, and calcium chloride concentration is 0.3mol/L in described calcium chloride-poly-aspartate mixed solution, poly-aspartate concentration is 0.25mg/L；
Two, configuration sodium carbonate liquor: being dissolved in deionized water by sodium carbonate, obtaining the concentration of sodium carbonate in sodium carbonate liquor, and described sodium carbonate liquor is 0.3mol/L；
Three, preparation mixing microemulsion: 1., weigh: weigh 5.06g calcium chloride-poly-aspartate mixed solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g calcium chloride-poly-aspartate mixed solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain mixing microemulsion；
Four, sodium carbonate emulsion is prepared: 1., weigh: weigh 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9 g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain sodium carbonate microemulsion；
Five, mixing: by mixing microemulsion and the mixing of sodium carbonate microemulsion, react 3h under the conditions of temperature is 20 DEG C and speed of agitator is 250rpm, be centrifuged separation, washing with alcohol the most successively and be dried, i.e. obtain mixing crystal formation nano-calcium carbonate；Ca in mixing microemulsion described in step 52+With CO in sodium carbonate microemulsion3 2-Mol ratio be 1:1.
The X ray diffracting spectrum of the mixing crystal formation nano-calcium carbonate of embodiment 1 preparation is as it is shown in figure 1, Fig. 1 is the mixing crystal formation nano-calcium carbonate X ray diffracting spectrum of embodiment 1 preparation；As shown in Figure 1, at 2 θ angles, (104), (108) crystal face of diffraction maximum correspondence calcium carbonate crystal equal to 29.42 °, at 47.6 °, is the characteristic diffraction peak of calcite type calcium carbonate (c).2 θ angles be positioned at 24.9 °, 27.01 °, diffraction maximum correspondence calcium carbonate crystal (100) at 32.6 °, (101), (102) crystal face, it is the characteristic diffraction peak of vaterite-type calcium carbonate (v), it was demonstrated that the mixing crystal formation nano-calcium carbonate of embodiment 1 preparation is calcite and the nano-calcium carbonate of vaterite mixing crystal formation.
Calculating according to formula 1 and formula 2 and obtaining the content of vaterite-type calcium carbonate in mixing crystal formation nano-calcium carbonate prepared by embodiment 1 is 74.7%.
The electron scanning micrograph of the mixing crystal formation nano-calcium carbonate of embodiment 1 preparation is as in figure 2 it is shown, Fig. 2 is the mixing crystal formation nano-calcium carbonate electron scanning micrograph of embodiment 1 preparation；As shown in Figure 2, the mixing crystal formation nano-calcium carbonate of embodiment 1 preparation is to be piled up by ball shaped nano vaterite-type calcium carbonate to form, and oarse-grained calcite type calcium carbonate, Fig. 2 Yu Figure 12 contrast understands, and in the mixing crystal formation nano-calcium carbonate of embodiment 1 preparation, calcite type calcium carbonate size reduces.
Embodiment 2: the mixing crystal formation nano-calcium carbonate synthetic method that a kind of content is controlled, is specifically realized by the following steps:
One, configuration calcium chloride-poly-aspartate mixed solution: utilize calcium chloride, poly-aspartate and deionized water configuration calcium chloride-poly-aspartate mixed solution, and calcium chloride concentration is 0.3mol/L in described calcium chloride-poly-aspartate mixed solution, poly-aspartate concentration is 0.5mg/L；
Two, configuration sodium carbonate liquor: being dissolved in deionized water by sodium carbonate, obtaining the concentration of sodium carbonate in sodium carbonate liquor, and described sodium carbonate liquor is 0.3mol/L；
Three, preparation mixing microemulsion: 1., weigh: weigh 5.06g calcium chloride-poly-aspartate mixed solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g calcium chloride-poly-aspartate mixed solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain mixing microemulsion；
Four, sodium carbonate emulsion is prepared: 1., weigh: weigh 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain sodium carbonate microemulsion；
Five, mixing: by mixing microemulsion and the mixing of sodium carbonate microemulsion, react 3h under the conditions of temperature is 20 DEG C and speed of agitator is 250rpm, be centrifuged separation, washing with alcohol the most successively and be dried, i.e. obtain mixing crystal formation nano-calcium carbonate；Ca in mixing microemulsion described in step 52+With CO in sodium carbonate microemulsion3 2-Mol ratio be 1:1.
The X ray diffracting spectrum of the mixing crystal formation nano-calcium carbonate of embodiment 2 preparation is as it is shown on figure 3, Fig. 3 is the mixing crystal formation nano-calcium carbonate X ray diffracting spectrum of embodiment 2 preparation；From the figure 3, it may be seen that at 2 θ angles (104), (108) crystal face of diffraction maximum correspondence calcium carbonate crystal equal to 29.42 °, at 47.6 °, be the calcite type calcium carbonate (characteristic diffraction peak of c.2 θ angles be positioned at 24.9 °, 27.01 °, diffraction maximum correspondence calcium carbonate crystal (100) at 32.6 °, (101), (102) crystal face, it is the characteristic diffraction peak of vaterite-type calcium carbonate (v), it was demonstrated that the mixing crystal formation nano-calcium carbonate of embodiment 2 preparation is calcite and the nano-calcium carbonate of vaterite mixing crystal formation.
Calculating according to formula 1 and formula 2 and obtaining the content of vaterite-type calcium carbonate in mixing crystal formation nano-calcium carbonate prepared by embodiment 2 is 81.6%.
As shown in Figure 4, Fig. 4 is the mixing crystal formation nano-calcium carbonate electron scanning micrograph of embodiment 2 preparation to the electron scanning micrograph of the mixing crystal formation nano-calcium carbonate of embodiment 2 preparation；As shown in Figure 4, the mixing crystal formation nano-calcium carbonate of embodiment 2 preparation is to be piled up by ball shaped nano vaterite-type calcium carbonate to form, and oarse-grained calcite type calcium carbonate.
Embodiment 3: the mixing crystal formation nano-calcium carbonate synthetic method that a kind of content is controlled, is specifically realized by the following steps:
One, configuration calcium chloride-poly-aspartate mixed solution: utilize calcium chloride, poly-aspartate and deionized water configuration calcium chloride-poly-aspartate mixed solution, and calcium chloride concentration is 0.3mol/L in described calcium chloride-poly-aspartate mixed solution, poly-aspartate concentration is 1.0mg/L；
Two, configuration sodium carbonate liquor: being dissolved in deionized water by sodium carbonate, obtaining the concentration of sodium carbonate in sodium carbonate liquor, and described sodium carbonate liquor is 0.3mol/L；
Three, preparation mixing microemulsion: 1., weigh: weigh 5.06g calcium chloride-poly-aspartate mixed solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g calcium chloride-poly-aspartate mixed solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain mixing microemulsion；
Four, sodium carbonate emulsion is prepared: 1., weigh: weigh 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain sodium carbonate microemulsion；
Five, mixing: by mixing microemulsion and the mixing of sodium carbonate microemulsion, react 3h under the conditions of temperature is 20 DEG C and speed of agitator is 250rpm, be centrifuged separation, washing with alcohol the most successively and be dried, i.e. obtain mixing crystal formation nano-calcium carbonate；Ca in mixing microemulsion described in step 52+With CO in sodium carbonate microemulsion3 2-Mol ratio be 1:1.
The X ray diffracting spectrum of the mixing crystal formation nano-calcium carbonate of embodiment 3 preparation is as it is shown in figure 5, Fig. 5 is the mixing crystal formation nano-calcium carbonate X ray diffracting spectrum of embodiment 3 preparation；As shown in Figure 5, at 2 θ angles, (104), (108) crystal face of diffraction maximum correspondence calcium carbonate crystal equal to 29.42 °, at 47.6 °, is the characteristic diffraction peak of calcite type calcium carbonate (c).2 θ angles be positioned at 24.9 °, 27.01 °, diffraction maximum correspondence calcium carbonate crystal (100) at 32.6 °, (101), (102) crystal face, it is the characteristic diffraction peak of vaterite-type calcium carbonate (v), it was demonstrated that the mixing crystal formation nano-calcium carbonate of embodiment 3 preparation is calcite and the nano-calcium carbonate of vaterite mixing crystal formation.
Calculating according to formula 1 and formula 2 and obtaining the content of vaterite-type calcium carbonate in mixing crystal formation nano-calcium carbonate prepared by embodiment 3 is 86.7%.
As shown in Figure 6, Fig. 6 is the mixing crystal formation nano-calcium carbonate electron scanning micrograph of embodiment 3 preparation to the electron scanning micrograph of the mixing crystal formation nano-calcium carbonate of embodiment 3 preparation；As shown in Figure 6, the mixing crystal formation nano-calcium carbonate of embodiment 4 preparation is to be piled up by ball shaped nano vaterite-type calcium carbonate to form, and oarse-grained calcite type calcium carbonate, Fig. 6 Yu Fig. 4 contrast understands, and in the mixing crystal formation nano-calcium carbonate of embodiment 2 preparation, oarse-grained calcite type calcium carbonate size and content reduce further.
Embodiment 4: the mixing crystal formation nano-calcium carbonate synthetic method that a kind of content is controlled, is specifically realized by the following steps:
One, configuration calcium chloride-poly-aspartate mixed solution: utilize calcium chloride, poly-aspartate and deionized water configuration calcium chloride-poly-aspartate mixed solution, and calcium chloride concentration is 0.3mol/L in described calcium chloride-poly-aspartate mixed solution, poly-aspartate concentration is 1.25mg/L；
Two, configuration sodium carbonate liquor: being dissolved in deionized water by sodium carbonate, obtaining the concentration of sodium carbonate in sodium carbonate liquor, and described sodium carbonate liquor is 0.3mol/L；
Three, preparation mixing microemulsion: 1., weigh: weigh 5.06g calcium chloride-poly-aspartate mixed solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g calcium chloride-poly-aspartate mixed solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain mixing microemulsion；
Four, sodium carbonate emulsion is prepared: 1., weigh: weigh 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain sodium carbonate microemulsion；
Five, mixing: by mixing microemulsion and the mixing of sodium carbonate microemulsion, react 3h under the conditions of temperature is 20 DEG C and speed of agitator is 250rpm, be centrifuged separation, washing with alcohol the most successively and be dried, i.e. obtain mixing crystal formation nano-calcium carbonate；Ca in mixing microemulsion described in step 52+With CO in sodium carbonate microemulsion3 2-Mol ratio be 1:1.
The X ray diffracting spectrum of the mixing crystal formation nano-calcium carbonate of embodiment 4 preparation is as it is shown in fig. 7, Fig. 7 is the mixing crystal formation nano-calcium carbonate X ray diffracting spectrum of embodiment 4 preparation；As shown in Figure 7, at 2 θ angles, (104), (108) crystal face of diffraction maximum correspondence calcium carbonate crystal equal to 29.42 °, at 47.6 °, is the characteristic diffraction peak of calcite type calcium carbonate (c).2 θ angles be positioned at 24.9 °, 27.01 °, diffraction maximum correspondence calcium carbonate crystal (100) at 32.6 °, (101), (102) crystal face, it is the characteristic diffraction peak of vaterite-type calcium carbonate (v), it was demonstrated that the mixing crystal formation nano-calcium carbonate of embodiment 4 preparation is calcite and the nano-calcium carbonate of vaterite mixing crystal formation.
Calculating according to formula 1 and formula 2 and obtaining the content of vaterite-type calcium carbonate in mixing crystal formation nano-calcium carbonate prepared by embodiment 4 is 92.4%.
As shown in Figure 8, Fig. 8 is the mixing crystal formation nano-calcium carbonate electron scanning micrograph of embodiment 4 preparation to the electron scanning micrograph of the mixing crystal formation nano-calcium carbonate of embodiment 4 preparation；As shown in Figure 8, the mixing crystal formation nano-calcium carbonate of embodiment 4 preparation is to be piled up by ball shaped nano vaterite-type calcium carbonate to form, and is little to find the crystal that particle size is inconsistent.
Embodiment 5: a kind of nano-calcium carbonate synthetic method, is specifically realized by the following steps:
One, configuration calcium chloride-poly-aspartate mixed solution: utilize calcium chloride, poly-aspartate and deionized water configuration calcium chloride-poly-aspartate mixed solution, and calcium chloride concentration is 0.3mol/L in described calcium chloride-poly-aspartate mixed solution, poly-aspartate concentration is 2.5mg/L；
Two, configuration sodium carbonate liquor: being dissolved in deionized water by sodium carbonate, obtaining the concentration of sodium carbonate in sodium carbonate liquor, and described sodium carbonate liquor is 0.3mol/L；
Three, preparation mixing microemulsion: 1., weigh: weigh 5.06g calcium chloride-poly-aspartate mixed solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g calcium chloride-poly-aspartate mixed solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain mixing microemulsion；
Four, sodium carbonate emulsion is prepared: 1., weigh: weigh 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain sodium carbonate microemulsion；
Five, mixing: by mixing microemulsion and the mixing of sodium carbonate microemulsion, react 3h under the conditions of temperature is 20 DEG C and speed of agitator is 250rpm, be centrifuged separation, washing with alcohol the most successively and be dried, i.e. obtaining nano-calcium carbonate；Ca in mixing microemulsion described in step 52+With CO in sodium carbonate microemulsion3 2-Mol ratio be 1:1.
The X ray diffracting spectrum of the nano-calcium carbonate of embodiment 5 preparation is as it is shown in figure 9, Fig. 9 is the nano-calcium carbonate X ray diffracting spectrum of embodiment 5 preparation；As shown in Figure 9,2 θ angles be positioned at 24.9 °, 27.01 °, diffraction maximum correspondence calcium carbonate crystal (100) at 32.6 °, (101), (102) crystal face, it it is the characteristic diffraction peak of vaterite-type (v) calcium carbonate, and the diffraction maximum without other stray crystal, it was demonstrated that the nano-calcium carbonate of embodiment 5 preparation is pure crystal formation vaterite-type calcium carbonate.
As shown in Figure 10, Figure 10 is the nano-calcium carbonate electron scanning micrograph of embodiment 5 preparation to the electron scanning micrograph of the nano-calcium carbonate of embodiment 5 preparation；As shown in Figure 10, the nano-calcium carbonate of embodiment 5 preparation is the spherical structure of even particle size distribution.
Embodiment 6: a kind of nano-calcium carbonate synthetic method, is specifically realized by the following steps:
One, configuration calcium chloride solution: utilizing calcium chloride concentration in calcium chloride and deionized water configuration calcium chloride solution, and described calcium chloride solution is 0.3mol/L；
Two, configuration sodium carbonate liquor: being dissolved in deionized water by sodium carbonate, obtaining the concentration of sodium carbonate in sodium carbonate liquor, and described sodium carbonate liquor is 0.3mol/L；
Three, preparation mixing microemulsion: 1., weigh: weigh 5.06g calcium chloride solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g calcium chloride solution, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain calcium chloride microemulsion；
Four, sodium carbonate emulsion is prepared: 1., weigh: weigh 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate, 5.9g n-amyl alcohol；2., mix: 5.06g sodium carbonate liquor, 28.3g hexamethylene, 5.9g polyoxyethylenated alcohol sodium sulfate and 5.9g n-amyl alcohol are mixed, and stirring and evenly mixing, obtain sodium carbonate microemulsion；
Five, mixing: calcium chloride microemulsion and sodium carbonate microemulsion are mixed, reacts 3h under the conditions of temperature is 20 DEG C and speed of agitator is 250rpm, is centrifuged separation, washing with alcohol the most successively and is dried, i.e. obtaining nano-calcium carbonate；Ca in calcium chloride microemulsion described in step 52+With CO in sodium carbonate microemulsion3 2-Mol ratio be 1:1.
As shown in figure 11, Figure 11 is the nano-calcium carbonate X ray diffracting spectrum of embodiment 6 preparation to the X ray diffracting spectrum of the calcium carbonate material of embodiment 6 preparation；As shown in Figure 11, at 2 θ angles, (104), (108) crystal face of diffraction maximum correspondence calcium carbonate crystal equal to 29.42 °, at 47.6 °, is the characteristic diffraction peak of calcite type calcium carbonate (c).Prove that calcium carbonate material prepared by embodiment 6 is pure crystal formation calcite type calcium carbonate.
As shown in figure 12, Figure 12 is the calcium carbonate material electron scanning micrograph of embodiment 6 preparation to the electron scanning micrograph of the calcium carbonate material of embodiment 6 preparation；As shown in Figure 12, the calcium carbonate of embodiment 6 preparation is the calcium carbonate material that particle diameter is relatively large, because pure calcite crystal formation is especially suitable for the growth of crystal, crystal can quickly be grown to the calcite particle that particle diameter is the biggest, is unfavorable for the preparation of nano-calcium carbonate.
Claims (5)
1. the mixing crystal formation nano-calcium carbonate synthetic method that a content is controlled, it is characterised in that it completes according to the following steps:
One, configuration calcium chloride-poly-aspartate mixed solution: utilize calcium chloride, poly-aspartate and deionized water configuration chlorination
In calcium-poly-aspartate mixed solution, and described calcium chloride-poly-aspartate mixed solution, calcium chloride concentration is 0.3mol/L,
Poly-aspartate concentration is M mg/L, wherein 0 < M < 2.5；
Two, configuration sodium carbonate liquor: sodium carbonate is dissolved in deionized water, obtains sodium carbonate liquor, and described sodium carbonate
In solution, the concentration of sodium carbonate is 0.3mol/L；
Three, preparation mixing microemulsion: 1., weigh: weigh Ag calcium chloride-poly-aspartate mixed solution, B g hexamethylene,
C g polyoxyethylenated alcohol sodium sulfate, D g n-amyl alcohol, and meet B/ (A+B) × 100%=85%,
C/ (A+B+C) × 100%=15%, D/ (A+B+D) × 100%=15%；2., mixing: by Ag calcium chloride-
Poly-aspartate mixed solution, B g hexamethylene, C g polyoxyethylenated alcohol sodium sulfate and the mixing of D g n-amyl alcohol, and stir
Mix mixing, obtain mixing microemulsion；
Four, sodium carbonate emulsion is prepared: 1., weigh: weigh ag sodium carbonate liquor, b g hexamethylene, c g fatty alcohol polyoxy second
Alkene ether sodium sulfate, d g n-amyl alcohol, and meet a/ (a+b) × 100%=85%, c/ (a+b+c) × 100%=15%,
D/ (a+b+d) × 100%=15%；2., mixing: by a g sodium carbonate liquor, b g hexamethylene, c g fatty alcohol polyoxy second
Alkene ether sodium sulfate and the mixing of d g n-amyl alcohol, and stirring and evenly mixing, obtain sodium carbonate microemulsion；
Five, mixing: will mix microemulsion and the mixing of sodium carbonate microemulsion, being 20 DEG C in temperature with speed of agitator is
React 3h under the conditions of 200rpm～300rpm, be centrifuged separation, washing with alcohol the most successively and be dried, i.e. obtaining mix-crystal
Type nano-calcium carbonate；Ca in mixing microemulsion described in step 52+With CO in sodium carbonate microemulsion3 2-Mol ratio be 1:1；
Mixing crystal formation nano-calcium carbonate described in step 5 is calcite and the nano-calcium carbonate of vaterite mixing crystal formation.
The mixing crystal formation nano-calcium carbonate synthetic method that a kind of content the most according to claim 1 is controlled, it is characterised in that
When in the calcium chloride described in step one-poly-aspartate mixed solution, poly-aspartate concentration is 0.25mg/L, step 5
Described in calcite and vaterite mixing crystal formation nano-calcium carbonate in vaterite-type calcium carbonate content be 73%～76%.
The mixing crystal formation nano-calcium carbonate synthetic method that a kind of content the most according to claim 1 is controlled, it is characterised in that
When in the calcium chloride described in step one-poly-aspartate mixed solution, poly-aspartate concentration is 0.5mg/L, in step 5
In the nano-calcium carbonate of described calcite and vaterite mixing crystal formation, vaterite-type calcium carbonate content is 80%～83%.
The mixing crystal formation nano-calcium carbonate synthetic method that a kind of content the most according to claim 1 is controlled, it is characterised in that
When in the calcium chloride described in step one-poly-aspartate mixed solution, poly-aspartate concentration is 1.0mg/L, in step 5
In the nano-calcium carbonate of described calcite and vaterite mixing crystal formation, vaterite-type calcium carbonate content is 85%～88%.
The mixing crystal formation nano-calcium carbonate synthetic method that a kind of content the most according to claim 1 is controlled, it is characterised in that
When in the calcium chloride described in step one-poly-aspartate mixed solution, poly-aspartate concentration is 1.25mg/L, step 5
Described in calcite and vaterite mixing crystal formation nano-calcium carbonate in vaterite-type calcium carbonate content be 91%～94%.
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