CN110482585A - A kind of synthetic method of amorphous calcium carbonate - Google Patents
A kind of synthetic method of amorphous calcium carbonate Download PDFInfo
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- CN110482585A CN110482585A CN201910718688.XA CN201910718688A CN110482585A CN 110482585 A CN110482585 A CN 110482585A CN 201910718688 A CN201910718688 A CN 201910718688A CN 110482585 A CN110482585 A CN 110482585A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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Abstract
The invention discloses a kind of synthetic methods of amorphous calcium carbonate, it carries out: (1) water-soluble Ca salt being dissolved in deionized water in accordance with the following steps the preparation of solution A:, then ionic surfactant is added, solution A is formed, wherein the molar ratio of water-soluble Ca salt and ionic surfactant is 1:1~100:1；(2) preparation of solution B: water soluble carbonate or bicarbonate are dissolved in deionized water, and adjust solution ph 11~13, form solution B；(3) solution A in step (1) and the solution B in step (2) -5~5 DEG C are placed in refrigerate 40~60 minutes；Then by after refrigeration solution A and solution B mix rapidly, stir 5~60 seconds, then be centrifuged, wash and dry to get amorphous calcium carbonate.Synthetic method of the invention has many advantages, such as that easy to operate, raw material is cheap and easy to get, reaction rate is fast and is not necessarily to complex and expensive apparatus.
Description
(1) technical field
The present invention relates to chemical engineering and field of material engineering technology, more particularly to a kind of synthesis side of unformed calcium carbonate
Method.
(2) background technique
In nature, calcium carbonate shares six kinds of crystal forms, including three kinds of anhydrous crystal forms: calcite (calcite), text
Stone (aragonite) and vaterite (vaterite)；Three kinds of aqueous crystal forms: amorphous calcium carbonate (amorphous calcium
Carbonate), an aqueous carbonate calcium (calcium carbonate monohydrate) and six aqueous carbonate calcium (calcium
carbonate hexahydrate).In this six kinds of calcium carbonate, in addition to amorphous calcium carbonate ACC, remaining five kinds are all crystalline state.
At the standard conditions, calcite and aragonite have similar thermodynamic stability, all relatively conventional in biology and geology field.
Vaterite is in metastable state compared to calcite and aragonite, seldom occurs in nature, only examines in certain biomineralization structures
It measures on a small quantity, did not occurred in geology field also.Presence of the one aqueous carbonate calcium in organism is then more rare, six aqueous carbonates
Calcium was not found also in vivo.Since amorphous calcium carbonate is tended to when the calcium carbonate with other crystalline states coexists
It is ignored, therefore the presence of amorphous calcium carbonate ACC in nature may be more more extensive than in cognition.
Amorphous materials include amorphous calcium phosphate, amorphous calcium carbonate, silica etc., these materials are in biomineralization
In play an important role.Life entity can construct out various inorganic or Inorganic-Organic Hybrid Material using these materials, with
Realize its different function, such as protection, support, gravity sensing etc..The solubility of amorphous calcium carbonate is six kinds of carbonic acid calcium phases
In it is maximum, density is the smallest in six kinds, therefore more difficult deposition.Also, amorphous calcium carbonate is extremely unstable in aqueous solution
It is fixed, will be rapidly to the smaller crystal type calcium carbonate transformation of solubility, this also causes the research to amorphous calcium carbonate compared with crystalline state
The difficulty that calcium carbonate comes.
In recent years, studies have found that amorphous calcium carbonate plays even more important effect during biomineralization, in phase
Directly participate in controlling the arrangement and orientation of crystalline state in transition process.Compared to crystalline state calcium carbonate, amorphous calcium carbonate by
In its isotropism and plasticity the characteristics of, it can be molded various shape, be then converted to the crystalline state carbon of respective shapes
Sour calcium.Since calcium carbonate biogenic mineral has some special properties, such as its mechanical performances ratio such as hardness, intensity and toughness
Most of composite ceramic material will be outstanding, therefore, receives the extensive concern of scholars to the research of biomineralization material,
It is even more wherein the hot spot studied as the amorphous calcium carbonate of precursor.
Currently, the synthetic method of amorphous calcium carbonate is more, such as direct mixing method (Koga N, Nakagoe Y, Tanaka
H.Crystallization of amorphous calcium carbonate.Thermochimica Acta,1998,318
(1): 239-244.), CO2Gaseous diffusion process (G ü nther C, Becker A, Wolf G, Epple M.In vitro
synthesis and structural characterization of amorphous calcium
carbonate.Zeitschrift für anorganische und allgemeine Chemie,2005,631(13):
2830-2835.), hydrolyze carbonation source method (Faatz M,F,Wegner G.Amorphous calcium
carbonate:synthesis and potential intermediate in biomineralization.Advanced
Materials, 2004,16 (12): 996-1000.), Kitano method (Lee H S, Ha T H, Kim K.Fabrication of
unusually stable amorphous calcium carbonate in an ethanol medium.Materials
Chemistry and Physics, 2005,93 (2): 376-382.), but to there is controllability mostly poor for these synthetic methods.
(3) summary of the invention
Existing synthetic method there are aiming at the problem that, the purpose of the present invention is invent a kind of rapidly and efficiently to synthesize amorphous carbon
The method of sour calcium.
In order to achieve the above-mentioned object of the invention, The technical solution adopted by the invention is as follows:
A kind of synthetic method of amorphous calcium carbonate carries out in accordance with the following steps:
(1) preparation of solution A: water-soluble Ca salt is dissolved in deionized water, and ionic surfactant, shape is then added
At solution A, wherein the molar ratio of water-soluble Ca salt and ionic surfactant is 1:1~100:1；
(2) preparation of solution B: water soluble carbonate or bicarbonate are dissolved in deionized water, and adjust solution ph
11~13, solution B is formed；
(3) solution A in step (1) and the solution B in step (2) -5~5 DEG C are placed in refrigerate 40~60 minutes；Then
By after refrigeration solution A and solution B mix rapidly, stir 5~60 seconds, then be centrifuged, wash and dry to get nothing
Shape calcium carbonate.
In the present invention, the water-soluble Ca salt can be following one or any several combination: calcium chloride and its
Hydrate, calcium bromide and its hydrate, calcium nitrate and its hydrate, calcium lactate and its hydrate.The water soluble carbonate
Can be the composition of following one or any of several: sodium carbonate and its hydrate, potassium carbonate and its hydrate, ammonium carbonate and its
Hydrate.The water soluble carbonate hydrogen salt can be the composition of following one or any of several: sodium bicarbonate and its hydrate,
Saleratus and its hydrate, ammonium hydrogen carbonate and its hydrate.
In step (1) of the present invention, the ionic surfactant can be anionic surfactant, cation form
Face activating agent, zwitterionic surfactant are cetyl trimethylammonium bromide in specific embodiment.
Preferably, the molar ratio of water-soluble Ca salt described in step (1) and ionic surfactant be 20:1~
100:1.
Preferably, the concentration of water-soluble Ca salt is 0.01~0.5mol/L in solution A.
Preferably, the concentration of water soluble carbonate is 0.04~0.2mol/L in solution B.
Preferably, the pH value of solution B is adjusted in step (2) with sodium hydrate aqueous solution.
In step (3) of the present invention, for the feed ratio of water-soluble Ca salt and water soluble carbonate in solution A and solution B
Example does not specially require, and water-soluble Ca salt or water soluble carbonate are excessive or both equimolar feeds intake, this field skill
Art personnel can set according to the actual situation.
In step (3) of the present invention, to improve efficiency, the centrifugation is 3000~5000 revs/min of revolving speed in revolving speed
It is carried out in range.
The amorphous calcium carbonate synthesized by the method for the invention can be used in the synthesis application and amorphous carbon of biomimetic material
The crystalline transition of sour calcium is studied.
Compared with existing synthetic method, the method for the present invention, as stabilizer, need to only be added using ionic surfactant
Enter the effect that can reach stable amorphous calcium carbonate on a small quantity, this method is with easy to operate, raw material is cheap and easy to get, reaction rate
The advantages that fastly and being not necessarily to complex and expensive apparatus.
(4) Detailed description of the invention
Fig. 1 is the XRD diagram of product prepared by embodiment 1.
(5) specific embodiment
The present invention is further described below with reference to specific embodiment, the advantages and features of the present invention will be with describing
And it is apparent.But examples are merely exemplary for these, and it is not intended to limit the scope of the present invention in any way.Art technology
Personnel are it is appreciated that can be to the details of technical solution of the present invention under aftermentioned spirit and scope before without departing from the present invention
It modifies or replaces with form, but these modifications and replacement are fallen within the protection scope of the present invention.
Embodiment 1
By 0.111 gram of CaCl2It is dissolved in 100 ml deionized waters and forms solution A, and take 0.018 gram of cetyl front three
Base ammonium bromide is dissolved in solution A；By 0.424 gram of NaCO3It is dissolved in 100 ml deionized waters and forms solution B, and pass through addition
The sodium hydroxide solution of 0.1 mol/L adjusts pH to 11；Two solution of A, B is placed in refrigerator and is refrigerated 40 minutes in 4 DEG C, is taken out
Solution B is added in solution A rapidly afterwards, stirs 1 minute, is then centrifuged, centrifugal rotational speed is 3000 revs/min, right
The solid separated washs 2 times with dehydrated alcohol, finally cold air drying at room temperature, obtains product, utilizes X-ray diffractometer
(XRD) obtained product is characterized, the calcium carbonate in product containing amorphous calcium carbonate and partially crystallizable.
Embodiment 2
By 5.549 grams of CaCl2It is dissolved in 100 ml deionized waters and forms solution A, and take 0.182 gram of cetyl front three
Base ammonium bromide is dissolved in solution A；By 1.325 grams of NaCO3It is dissolved in 100 ml deionized waters and forms solution B, and pass through addition
The sodium hydroxide solution of 0.1 mol/L adjusts pH to 13；Two solution of A, B is placed in refrigerator and is refrigerated 60 minutes in 4 DEG C, is taken out
Solution B is added in solution A rapidly afterwards, stirs 1 minute, is then centrifuged, centrifugal rotational speed is 5000 revs/min, right
The solid separated washs 2 times with dehydrated alcohol, finally cold air drying at room temperature, the XRD diagram similar embodiment 1 of product.
Embodiment 3
By 1.110 grams of CaCl2It is dissolved in 100 ml deionized waters and forms solution A, and take 0.109 gram of cetyl front three
Base ammonium bromide is dissolved in solution A；By 1.060 grams of NaCO3It is dissolved in 100 ml deionized waters and forms solution B, and pass through addition
The sodium hydroxide solution of 0.1 mol/L adjusts pH to 12；Two solution of A, B is placed in refrigerator and is refrigerated 50 minutes in 4 DEG C, is taken out
Solution B is added in solution A rapidly afterwards, stirs 1 minute, is then centrifuged, centrifugal rotational speed is 4000 revs/min, right
The solid separated washs 2 times with dehydrated alcohol, finally cold air drying at room temperature, the XRD diagram similar embodiment 1 of product.
Embodiment 4
By 0.111 gram of CaCl2It is dissolved in 100 ml deionized waters and forms solution A, and take 0.018 gram of cetyl front three
Base ammonium bromide is dissolved in solution A；By 0.106 gram of NaCO3It is dissolved in 100 ml deionized waters and forms solution B, and pass through addition
The sodium hydroxide solution of 0.1 mol/L adjusts pH to 12；Two solution of A, B is placed in refrigerator and is refrigerated 60 minutes in 4 DEG C, is taken out
Solution B is added in solution A rapidly afterwards, stirs 1 minute, is then centrifuged, centrifugal rotational speed is 4000 revs/min, right
The solid separated washs 2 times with dehydrated alcohol, finally cold air drying at room temperature, the XRD diagram similar embodiment 1 of product.
Embodiment 5
By 5.549 grams of CaCl2It is dissolved in 100 ml deionized waters and forms solution A, and take 0.911 gram of cetyl front three
Base ammonium bromide is dissolved in solution A；By 5.300 grams of NaCO3It is dissolved in 100 ml deionized waters and forms solution B, and pass through addition
The sodium hydroxide solution of 0.1 mol/L adjusts pH to 11；Two solution of A, B is placed in refrigerator and is refrigerated 40 minutes in 4 DEG C, is taken out
Solution B is added in solution A rapidly afterwards, stirs 1 minute, is then centrifuged, centrifugal rotational speed is 4000 revs/min, right
The solid separated washs 2 times with dehydrated alcohol, finally cold air drying at room temperature, the XRD diagram similar embodiment 1 of product.
Embodiment 6
By 1.110 grams of CaCl2It is dissolved in 100 ml deionized waters and forms solution A, and take 0.146 gram of cetyl front three
Base ammonium bromide is dissolved in solution A；By 4.240 grams of NaCO3It is dissolved in 100 ml deionized waters and forms solution B, and pass through addition
The sodium hydroxide solution of 0.1 mol/L adjusts pH to 13；Two solution of A, B is placed in refrigerator and is refrigerated 50 minutes in 4 DEG C, is taken out
Solution B is added in solution A rapidly afterwards, stirs 1 minute, is then centrifuged, centrifugal rotational speed is 3000 revs/min, right
The solid separated washs 2 times with dehydrated alcohol, finally cold air drying at room temperature, the XRD diagram similar embodiment 1 of product.
Claims (10)
1. a kind of synthetic method of amorphous calcium carbonate carries out in accordance with the following steps:
(1) preparation of solution A: water-soluble Ca salt is dissolved in deionized water, and ionic surfactant is then added, and is formed molten
Liquid A, wherein the molar ratio of water-soluble Ca salt and ionic surfactant is 1:1~100:1；
(2) preparation of solution B: water soluble carbonate or bicarbonate are dissolved in deionized water, and adjust solution ph 11
~13, form solution B；
(3) solution A in step (1) and the solution B in step (2) -5~5 DEG C are placed in refrigerate 40~60 minutes；It then will be cold
Solution A and solution B behind hiding mix rapidly, stir 5~60 seconds, then be centrifuged, wash and dry to get amorphous
Calcium carbonate.
2. synthetic method as described in claim 1, it is characterised in that: water-soluble Ca salt and ionic described in step (1)
The molar ratio of surfactant is 20:1~100:1.
3. synthetic method as claimed in claim 1 or 2, it is characterised in that: in step (1), the ionic surfactant
Agent is cetyl trimethylammonium bromide.
4. synthetic method as claimed in claim 1 or 2, it is characterised in that: the water-soluble Ca salt be selected from it is following a kind of or
Any several combination: calcium chloride and its hydrate, calcium bromide and its hydrate, calcium nitrate and its hydrate, calcium lactate and its
Hydrate.
5. synthetic method as claimed in claim 1 or 2, it is characterised in that: the water soluble carbonate be it is following a kind of or
Any several composition: sodium carbonate and its hydrate, potassium carbonate and its hydrate, ammonium carbonate and its hydrate.
6. synthetic method as claimed in claim 1 or 2, it is characterised in that: the water soluble carbonate hydrogen salt be it is following a kind of or
Any several composition: sodium bicarbonate and its hydrate, saleratus and its hydrate, ammonium hydrogen carbonate and its hydrate.
7. synthetic method as claimed in claim 1 or 2, it is characterised in that: in solution A, the concentration of water-soluble Ca salt is 0.01
~0.5mol/L.
8. synthetic method as claimed in claim 1 or 2, it is characterised in that: in solution B, the concentration of water soluble carbonate is
0.04~0.2mol/L.
9. synthetic method as claimed in claim 1 or 2, it is characterised in that: molten with sodium hydrate aqueous solution adjusting in step (2)
The pH value of liquid B.
10. synthetic method as claimed in claim 1 or 2, it is characterised in that: in step (3), the centrifugation is in revolving speed
It is carried out in 3000~5000 revs/min of the range of speeds.
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Cited By (3)
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| CN111892076A (en) * | 2020-08-26 | 2020-11-06 | 武汉理工大学 | Preparation method for obtaining amorphous calcium carbonate particles with nano-pore structure by organic solvent induction |
| CN112458534A (en) * | 2020-10-15 | 2021-03-09 | 中国科学技术大学 | Magnesium calcite mesoscopic crystal and preparation method of magnesium calcite crystal with adjustable morphology |
| CN115353137A (en) * | 2022-06-30 | 2022-11-18 | 福建信息职业技术学院 | Preparation method and application of amorphous calcium carbonate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892076A (en) * | 2020-08-26 | 2020-11-06 | 武汉理工大学 | Preparation method for obtaining amorphous calcium carbonate particles with nano-pore structure by organic solvent induction |
| CN112458534A (en) * | 2020-10-15 | 2021-03-09 | 中国科学技术大学 | Magnesium calcite mesoscopic crystal and preparation method of magnesium calcite crystal with adjustable morphology |
| CN112458534B (en) * | 2020-10-15 | 2022-05-13 | 中国科学技术大学 | Magnesium calcite mesoscopic crystal and preparation method of magnesium calcite crystal with adjustable morphology |
| CN115353137A (en) * | 2022-06-30 | 2022-11-18 | 福建信息职业技术学院 | Preparation method and application of amorphous calcium carbonate |
| CN115353137B (en) * | 2022-06-30 | 2023-10-24 | 福建信息职业技术学院 | Preparation method and application of amorphous calcium carbonate |
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