CN1597530A - Biomimetic mintralization in situ preparation method of functional nanometer calcium carbonate - Google Patents
Biomimetic mintralization in situ preparation method of functional nanometer calcium carbonate Download PDFInfo
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- CN1597530A CN1597530A CN 200410011083 CN200410011083A CN1597530A CN 1597530 A CN1597530 A CN 1597530A CN 200410011083 CN200410011083 CN 200410011083 CN 200410011083 A CN200410011083 A CN 200410011083A CN 1597530 A CN1597530 A CN 1597530A
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Abstract
A process for in-situ preparing functional nano-calcium carbonate by bionic mineralizing includes such steps as proportionally mixing the calcium oxide, organic matrix or its solution and calcium hydroxide emulsion, ageing, introducing the mixture of CO2 and air, carbonizing, dewatering, and drying at 80-120 deg.C.
Description
Technical field
The present invention relates to a kind of novel method for preparing functional nano lime carbonate, be specifically related to simulate the method for biomineralization in-situ preparing functional nano lime carbonate.
Background technology
Biomineralization is meant the process that forms mineral substance in vivo, its effect be a kind of extensively and complicated solid-liquid is alternate, the physical and chemical process between organism and inorganics.With a small amount of organic matter is template, carry out molecule manipulation, be combined into inorganic materials high-sequential, inertia substrate or the confined space of mineral precipitation and the surface of nucleation that organic radical mass-energy is supported as structure, determine the form size of mineral particle, spatial disposition, crystalline orientation and polymorphism type, and determine the mechanical properties of biomineral hardware with biocrystal, it not only is heated mechanics factor (as temperature, pressure, concentration, pH and Eh etc.), kinetic factor is (as coring, precipitation and phase transformation etc.) control, also be subjected to biology control (space, framework and chemistry etc.) control.Biomineralization can be divided into 4 stages: pre-organized (2) interface molecular recognition (3) growth modulation (4) cell processing that (1) is organic, its median surface molecular recognition is the key of biomineralization, and cell processing then is the major cause that causes natural biological mineralizing material and artificial material difference.Find after deliberation, biomineral such as tooth, bone, shell, crust etc. all are to be formed on the organic substrate by orderly being embedded in of the inorganic mineral that is rich in lime carbonate, because their sizes are regular, characteristics such as structure, form and crystalline orientation unanimity make them have good performance, so the mineralisation process of these materials is significant in the mimic biology body.
The simulation biomineralization is the research field of forefront in recent years.Biological under the condition of normal temperature and pressure, utilize in the environment extremely simple common component to synthesize structure and the perfect matrix material of performance by a series of energy-conservation, free of contamination processing, the control of biological nucleation, pattern and crystallography orientation etc. to mineral crystal is impayable.People have utilized the principle of biomineralization successfully to synthesize nano material, semiconductor material, organic/inorganic ceramic thin sheet etc. at present, but also do not adopt bionic method synthetic inorganic materials to put on market, but its great application prospect represent to the world.
The active nano-calcium carbonate that obtains through surface treatment is a kind of good reinforcing filler, and the consistency of it and rubber plastic molecule is good, good dispersity during processing, thermostability height.(nano level active calcium carbonate for special use, 02110801.3, Intellectual Property Right Bureau of the RPC, on October 23rd, 2002 in original technology; A kind of production method of active calcium carbonate, 94115875.6, Patent Office of the People's Republic of China (PRC), June 28 nineteen ninety-five), the preparation of active nano-calcium carbonate all is to the nano-calcium carbonate aftertreatment, carries out finishing, its technical process complexity, reaction time is long, and energy consumption is big, the cost height.
In the method for the invention, break through technical barrier, organic substrate plays the control crystal growth and makes the dual function of lime carbonate functionalization, has simplified the condition of preparation nano-calcium carbonate greatly.
Summary of the invention
The object of the present invention is to provide a kind of method by biomimetic mineralization process composite reactive nano-calcium carbonate in the organic and inorganic spacial framework.This method technology is simple, and production cost is low, efficient is high, and reaction time is short, and energy consumption is little, and the lime carbonate particle diameter of production is little, the activation rate height.
The technical solution used in the present invention is: keeping temperature of reaction system is 15～90 ℃, to be that 0.01: 1～0.2: 1 organic substrate or concentration is the solution of 0.1～0.5wt% organic substrate with the calcium oxide mass ratio, mix with calcium hydroxide emulsion, wherein the mass ratio of calcium oxide and water is 0.05: 1～0.3: 1, ageing 0.1～2 hour; Speed with 10～40ml/min feeds carbonic acid gas and the air Mixture that contains 15～40% carbonic acid gas, and carbonization to pH value is 6～9 end, dehydration, and 80～120 ℃ of following drying treatment obtain functional nano lime carbonate.Product is dispersed well white powder, and its particle diameter is 30～100nm, and fineness ratio is 1: 3～1: 20.
Organic substrate of the present invention can be that higher alcohols are (as C
12～C
24Saturated alcohol and C
12～C
24Unsaturated alcohol), higher fatty acid or its esters be (as C
12～C
24Saturated fatty acid and salt and C
12～C
24Unsaturated fatty acids and salt thereof), the aliphatics higher amines is (as C
12～C
24Alkylamine), phosphoric acid ester is (as C
12～C
24The alcohol phosphoric acid ester), sulfuric ester is (as C
12～C
24The alcohol sulfuric ester), the betaine type amphoteric surfac-tant is (as C
12～C
24Alkyl betaine) and water-soluble polymer (as polyacrylamide, polyvinyl alcohol, polyoxyethylene glycol and Polyvinylpyrolidone (PVP)).
The mass ratio of described organic substrate and calcium oxide is 0.01: 1～0.2: 1, and preferred range is that the optimum concn of 0.02: 1～0.04: 1 or organic substrate solution is 0.2wt%.The temperature of described carburizing reagent is between 15～90 ℃, and preferred temperature of reaction (carbonization temperature) is 20～25 ℃, and carbonization to pH value is 7～8 end.
In the present invention, in the middle of calcium hydroxide emulsion adding organic substrate, form orderly system, by organic and inorganic interface molecular recognition, organic optionally the interaction with the veil of inorganics specific direction constitutes spacial framework, by feeding carbon dioxide mix gas, increase partial calcium concentration of reactants to promote the nucleation of lime carbonate, in organic structure by under the kinetic control, carry out the nucleation of calcium carbonate crystal in spacial framework inside, the interaction of growth and lime carbonate and spacial framework, original position composite reactive nano-calcium carbonate, therefore organic substrate not only plays finishing, also plays the control particle diameter, improve dispersed effect.Prepared functional nano lime carbonate through repeatedly the washing and filtration treatment after, stable performance.
The present invention compared with prior art has the following advantages:
1. biomimetic mineralization skilled industryization.The biomimetic mineralization technology is risen to the level of commercial scale production from the level of theoretical investigation and laboratory study.
2. activation rate height.Because organic substrate and the orderly spacial framework of calcium hydroxide formation rule, portion forms lime carbonate within it, and activation rate can reach 99%.
3. method is simple, saves time.No matter method in the past is dry method or wet method, surface treatment all is an experimental procedure that needs additionally carry out separately, and the inventive method is to carry out carbonization in the orderly system inside of organic substrate, original position composite reactive nano-calcium carbonate, simplified technology, easy handling has also shortened reaction time greatly.
4. cost is low.Adopt the inventive method only to need traditional bubbling carbonizing equipment, saved expensive facility investment.Because the reaction times is short, need not heat simultaneously, whole process energy consumption is little, and cost is low.
5. efficient height.The inventive method can realize the industrialization continuous production, and processing power is very high.
6. entire reaction is carried out in aqueous systems, can not cause detrimentally affect to HUMAN HEALTH and environment, has great social significance and wide application prospect.
Description of drawings
Fig. 1: the lime carbonate transmission electron microscope picture (embodiment 20) that 2g octadecanol phosphoric acid ester forms;
Fig. 2: the lime carbonate transmission electron microscope picture (embodiment 21) that 3g octadecanol phosphoric acid ester forms;
Fig. 3: the lime carbonate transmission electron microscope picture (embodiment 22) that 4g octadecanol phosphoric acid ester forms.
Embodiment
Embodiment 1:
The 2g octadecanol is dissolved in the 1L water, the mass ratio that adds calcium oxide and water under room temperature (25 ℃) is 0.1: 1 calcium hydroxide emulsion 1L, ageing was transferred to emulsion in the bubbling carbonizing device after 0.5 hour, speed with 30ml/min feeds carbonic acid gas and the nitrogen mixture that contains 33% carbonic acid gas, carry out carburizing reagent, when the pH of slurries value drops to 7, stop carbonization, with the emulsion dehydration, obtain active nano-calcium carbonate after 120 ℃ of drying treatment.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 40nm, and fineness ratio is 1: 5, and activation rate is 99%.
Embodiment 2:
2g 18 carbon unsaturated alcohols are dissolved in the 1L water, and other condition such as embodiment 1 finally obtain active nano-calcium carbonate, observe under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 38nm, and fineness ratio is 1: 5, and activation rate is 90%.
Embodiment 3:
The mass ratio of calcium oxide and water is 0.05: 1, and other condition such as embodiment 1 finally obtain active nano-calcium carbonate, observes under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 35nm, and fineness ratio is 1: 5, and activation rate is 90%.
Embodiment 4:
The mass ratio of calcium oxide and water is 0.3: 1, and other condition such as embodiment 1 finally obtain active nano-calcium carbonate, observes under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 43nm, and fineness ratio is 1: 4, and activation rate is 99%.
Embodiment 5:
In being dissolved in 1L water, other condition such as embodiment 1 finally obtain active nano-calcium carbonate with the 1g octadecanol, observe under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 40nm, and fineness ratio is 1: 3, and activation rate is 89%.
Embodiment 6:
In being dissolved in 1L water, other condition such as embodiment 1 finally obtain active nano-calcium carbonate with the 5g octadecanol, observe under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 55nm, and fineness ratio is 1: 5, and activation rate is 99.8%.
Embodiment 7:
15 ℃ of maintenance system temperature of reaction, other condition such as embodiment 1 finally obtain active nano-calcium carbonate, observe under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 30nm, and fineness ratio is 1: 4, activation rate is 85%.
Embodiment 8:
90 ℃ of maintenance system temperature of reaction, other condition such as embodiment 1 finally obtain active nano-calcium carbonate, observe under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 90nm, and fineness ratio is 1: 5, activation rate is 99.9%.
Embodiment 9:
Speed with 30ml/min feeds carbonic acid gas and the nitrogen mixture that contains 15% carbonic acid gas, and other is identical with embodiment 1.Observe under transmission electron microscope, the calcium carbonate granule dispersiveness is fine, is shaped as fusiform, and diameter is 60nm, and fineness ratio is 1: 5, and activation rate is 82%.
Embodiment 10:
Speed with 30ml/min feeds carbonic acid gas and the nitrogen mixture that contains 40% carbonic acid gas, and other is identical with embodiment 1.Observe under transmission electron microscope, the calcium carbonate granule dispersiveness is fine, is shaped as fusiform, and diameter is 58nm, and fineness ratio is 1: 5, and activation rate is 90%.
Embodiment 11:
In being dissolved in 1L water, other is identical with embodiment 1 with 2g 12 carbon alcohol.Observe under transmission electron microscope, the calcium carbonate granule dispersiveness is fine, is shaped as fusiform, and diameter is 50nm, and fineness ratio is 1: 5, and activation rate is 80%.
Embodiment 12:
In being dissolved in 1L water, other is identical with embodiment 1 with 2g tetracosa carbon alcohol.Observe under transmission electron microscope, the calcium carbonate granule dispersiveness is fine, is shaped as fusiform, and diameter is 50nm, and fineness ratio is 1: 5, and activation rate is 90%.
Embodiment 13:
Keep system temperature at 90 ℃, the stearic acid of 10g is dissolved in the 1L water, and other is identical with embodiment 1.Observe under transmission electron microscope, the calcium carbonate granule dispersiveness is fine, is shaped as fusiform, and diameter is 85nm, and fineness ratio is 1: 5, and activation rate is 90%.
Embodiment 14:
Keep system temperature at 90 ℃, the stearic acid of 2g and the sodium hydroxide of 2g successively add in the distilled water of 1L, and other is identical with embodiment 1.Observe under transmission electron microscope, the calcium carbonate granule dispersiveness is fine, is shaped as fusiform, and diameter is 80nm, and fineness ratio is 1: 5, and activation rate is 99.9%.
Embodiment 15:
The mass ratio that 10ml oleic acid adds down calcium oxide and water in room temperature (25 ℃) is 0.1: 1 calcium hydroxide emulsion 1L, and other is identical with embodiment 1.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 33nm, and fineness ratio is 1: 4, and activation rate is 99.9%.
Embodiment 16:
The 2g sodium oleate is dissolved in the 1L water, and other is identical with embodiment 1.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 40nm, and fineness ratio is 1: 4, and activation rate is 90%.
Embodiment 17:
The 2g octadecylamine is dissolved in the 1L water, and other is identical with embodiment 1.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 35nm, and fineness ratio is 1: 3, and activation rate is 99%.
Embodiment 18:
The 2g lauryl amine is dissolved in the 1L water, and other is identical with embodiment 17.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 42nm, and fineness ratio is 1: 3, and activation rate is 89%.
Embodiment 19:
2g tetracosyl amine is dissolved in the 1L water, and other is identical with embodiment 17.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 38nm, and fineness ratio is 1: 3, and activation rate is 95%.
Embodiment 20:
2g octadecanol phosphoric acid ester is dissolved in the 1L water, and other is identical with embodiment 1.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 50nm, and fineness ratio is 1: 3, and activation rate is 92%, sees Fig. 1.
Embodiment 21:
3g octadecanol phosphoric acid ester is dissolved in the 1L water, and other is identical with embodiment 20.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 65nm, and fineness ratio is 1: 4, and activation rate is 98%, sees Fig. 2.
Embodiment 22:
4g octadecanol phosphoric acid ester is dissolved in the 1L water, and other is identical with embodiment 20.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 70nm, and fineness ratio is 1: 5, and activation rate is 99.2%, sees Fig. 3.
Embodiment 23:
2g 12 carbon alcohol phosphoric acid ester is dissolved in the 1L water, and other is identical with embodiment 20.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 45nm, and fineness ratio is 1: 3, and activation rate is 85%.
Embodiment 24:
2g tetracosa carbon alcohol phosphoric acid ester is dissolved in the 1L water, and other is identical with embodiment 20.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 50nm, and fineness ratio is 1: 3, and activation rate is 90%.
Embodiment 25:
Described carburizing reagent is carried out under 60 ℃, and other condition is identical with embodiment 20, observes under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 85nm, and fineness ratio is 1: 5, and activation rate is 99.5%.
Embodiment 26:
The temperature of reaction system remains on 80 ℃, and other is identical with embodiment 20.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 98nm, and fineness ratio is 1: 5, and activation rate is 99.6%.
Embodiment 27:
2g octadecanol sulfuric ester is dissolved in the 1L water, and other is identical with embodiment 1.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 55nm, and fineness ratio is 1: 4, and activation rate is 99.5%.
Embodiment 28:
2g 12 carbon alcohol sulfuric ester is dissolved in the 1L water, and other is identical with embodiment 27.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 40nm, and fineness ratio is 1: 4, and activation rate is 88%.
Embodiment 29:
2g tetracosa carbon alcohol sulfuric ester is dissolved in the 1L water, and other is identical with embodiment 27.Observe under transmission electron microscope, calcium carbonate granule is better dispersed, is shaped as fusiform, and diameter is 55nm, and fineness ratio is 1: 4, and activation rate is 95%.
Embodiment 30:
The mass ratio that the 5ml empgen BB adds down calcium oxide and water in room temperature (25 ℃) is 0.1: 1 calcium hydroxide emulsion 1L, and other is identical with embodiment 1.The calcium carbonate product that obtains is water-soluble, observes under transmission electron microscope, and lime carbonate is shaped as cube, and diameter is 50nm.
Embodiment 31:
The mass ratio that 5ml hexadecyl trimethyl-glycine adds down calcium oxide and water in room temperature (25 ℃) is 0.1: 1 calcium hydroxide emulsion 1L, and other is identical with embodiment 30.The calcium carbonate product that obtains is water-soluble, observes under transmission electron microscope, and lime carbonate is shaped as cube, and diameter is 55nm.
Embodiment 32:
The 5ml empgen BB is 0.1: 1 calcium hydroxide emulsion 1L at the following mass ratio that adds calcium oxide and water of room temperature (25 ℃), mechanical stirring was transferred to emulsion in the reactor after 0.5 hour after adding the 1L aqueous solution of 0.1g polyacrylamide preparation then, and other is identical with embodiment 1.The calcium carbonate product that obtains is water-soluble, observes under transmission electron microscope, and lime carbonate is shaped as cube, and diameter is 35nm.
Embodiment 33:
With the 2g molecular weight is that 1,000,000 polyacrylamide is dissolved in the 1L water, and other is identical with embodiment 1.Gained lime carbonate is water-soluble, observes under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as cube, and diameter is 60nm.
Embodiment 34:
The 2g polyvinyl alcohol is dissolved in the 1L water, and other is identical with embodiment 1.Gained lime carbonate is water-soluble, observes under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as cube, and diameter is 70nm.
Embodiment 35:
2g polyoxyethylene glycol-2000 is dissolved in the 1L water, and other is identical with embodiment 1.Gained lime carbonate is water-soluble, observes under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as cube, and diameter is 65nm.
Embodiment 36:
The 2g Polyvinylpyrolidone (PVP) is dissolved in the 1L water, and other is identical with embodiment 1.Gained lime carbonate is water-soluble, observes under transmission electron microscope, and calcium carbonate granule is better dispersed, is shaped as cube, and diameter is 60nm.
Claims (6)
1. the biomimetic mineralization in-situ preparation method of functional nano lime carbonate, the steps include: to keep temperature of reaction system is 15～90 ℃, to be that 0.01: 1～0.2: 1 organic substrate or concentration is the solution of 0.1～0.5wt% organic substrate with the calcium oxide mass ratio, mix with calcium hydroxide emulsion, wherein the mass ratio of calcium oxide and water is 0.05: 1～0.3: 1, ageing 0.1～2 hour; Speed with 10～40ml/min feeds carbonic acid gas and the air Mixture that contains 15～40% carbonic acid gas, and carbonization to pH value is 6～9 end, dehydration, and 80～120 ℃ of following drying treatment obtain functional nano lime carbonate.
2. the biomimetic mineralization in-situ preparation method of functional nano lime carbonate as claimed in claim 1 is characterized in that: organic substrate is higher alcohols, higher fatty acid or its esters, aliphatics higher amines, phosphoric acid ester, betaine type amphoteric surfac-tant or water-soluble polymer.
3. the biomimetic mineralization in-situ preparation method of functional nano lime carbonate as claimed in claim 1 or 2 is characterized in that: organic substrate is C
12～C
24Saturated alcohol, C
12～C
24Unsaturated alcohol, C
12～C
24Saturated fatty acid and salt, C
12～C
24Unsaturated fatty acids and salt, C
12～C
24Alkylamine, C
12～C
24Alcohol phosphoric acid ester, C
12～C
24Alcohol sulfuric ester, C
12～C
24Alkyl betaine, polyacrylamide, polyvinyl alcohol, polyoxyethylene glycol or Polyvinylpyrolidone (PVP).
4. the biomimetic mineralization in-situ preparation method of functional nano lime carbonate as claimed in claim 1 is characterized in that: the mass ratio of organic substrate and calcium oxide is 0.02: 1～0.04: 1.
5. the biomimetic mineralization in-situ preparation method of functional nano lime carbonate as claimed in claim 1 is characterized in that: temperature of reaction system is 20～60 ℃.
6. the biomimetic mineralization in-situ preparation method of functional nano lime carbonate as claimed in claim 1 is characterized in that: carbonization to pH value is 7～8 end.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100427398C (en) * | 2006-04-28 | 2008-10-22 | 湖南大学 | Method for preparing nanometer calcium carbonate |
| CN101580261B (en) * | 2009-06-04 | 2011-01-12 | 河南大学 | Hollow calcium carbonate calcite crystal preparation method |
| CN101570342B (en) * | 2009-06-11 | 2011-08-24 | 福建省万旗非金属材料有限公司 | Method for preparing high-whiteness nanometer calcium carbonate special for silicone sealant by utilizing low-grade limestone by wet method |
| CN103466678A (en) * | 2013-09-27 | 2013-12-25 | 成都新柯力化工科技有限公司 | Preparation method of special-shaped calcium carbonate |
| CN103708520A (en) * | 2013-12-26 | 2014-04-09 | 陕西师范大学 | Green environment-friendly calcium carbonate biomembrane preparation method |
| CN103897438A (en) * | 2014-04-17 | 2014-07-02 | 长春天成高新纳米复合材料有限公司 | Preparation method of composite calcium carbonate |
| CN108324578A (en) * | 2017-01-17 | 2018-07-27 | 武汉大学 | A kind of liquid phase mineralising presoma and the method for repairing demineralization dentine |
| CN108841870A (en) * | 2018-06-04 | 2018-11-20 | 天津大学 | The preparation method of calcium carbonate |
| CN109850938A (en) * | 2019-01-23 | 2019-06-07 | 西安电子科技大学 | The preparation method of the spherical nanocrystal of strontium titanates |
| CN110311146A (en) * | 2019-06-19 | 2019-10-08 | 四川大学 | A kind of carbon dioxide mineralising power generation new method for making catalyst using organic matter |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100427398C (en) * | 2006-04-28 | 2008-10-22 | 湖南大学 | Method for preparing nanometer calcium carbonate |
| CN101580261B (en) * | 2009-06-04 | 2011-01-12 | 河南大学 | Hollow calcium carbonate calcite crystal preparation method |
| CN101570342B (en) * | 2009-06-11 | 2011-08-24 | 福建省万旗非金属材料有限公司 | Method for preparing high-whiteness nanometer calcium carbonate special for silicone sealant by utilizing low-grade limestone by wet method |
| CN103466678A (en) * | 2013-09-27 | 2013-12-25 | 成都新柯力化工科技有限公司 | Preparation method of special-shaped calcium carbonate |
| CN103708520A (en) * | 2013-12-26 | 2014-04-09 | 陕西师范大学 | Green environment-friendly calcium carbonate biomembrane preparation method |
| CN103897438B (en) * | 2014-04-17 | 2016-01-06 | 长春天成高新纳米复合材料有限公司 | A kind of preparation method of composite calcium carbonate |
| CN103897438A (en) * | 2014-04-17 | 2014-07-02 | 长春天成高新纳米复合材料有限公司 | Preparation method of composite calcium carbonate |
| CN108324578A (en) * | 2017-01-17 | 2018-07-27 | 武汉大学 | A kind of liquid phase mineralising presoma and the method for repairing demineralization dentine |
| CN108841870A (en) * | 2018-06-04 | 2018-11-20 | 天津大学 | The preparation method of calcium carbonate |
| CN109850938A (en) * | 2019-01-23 | 2019-06-07 | 西安电子科技大学 | The preparation method of the spherical nanocrystal of strontium titanates |
| CN109850938B (en) * | 2019-01-23 | 2021-07-20 | 西安电子科技大学 | Preparation method of strontium titanate spherical nanocrystal |
| CN110311146A (en) * | 2019-06-19 | 2019-10-08 | 四川大学 | A kind of carbon dioxide mineralising power generation new method for making catalyst using organic matter |
| CN110311146B (en) * | 2019-06-19 | 2020-12-01 | 四川大学 | Carbon dioxide mineralization power generation method using organic matter as catalyst |
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