CN1676681A - Method for preparing high length-diameter ratio magnesia whisker - Google Patents
Method for preparing high length-diameter ratio magnesia whisker Download PDFInfo
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- CN1676681A CN1676681A CN 200510045725 CN200510045725A CN1676681A CN 1676681 A CN1676681 A CN 1676681A CN 200510045725 CN200510045725 CN 200510045725 CN 200510045725 A CN200510045725 A CN 200510045725A CN 1676681 A CN1676681 A CN 1676681A
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Abstract
This invention belongs to the producing field of inorganic non-metal material, referring to the producing method of a kind of high slenderness ratio MgO whisker. This invention chooses soluble magnesium salts and soluble carbonate as crude materials to firstly get MgCO3 predecessor. After processing heating-up calcinations, we will get the MgO whisker. This method is easy, and the product costs little. The product's diameter is 2-5 mum, and its length is 30-50mum, while the whisker has high physical and mechanical nature. It can be used as the enhancer and fire retardant of plastics and the binder of covering material. It is good filter material and assistant, which can be widely used in the fields of cars, electronics and electricity, mechanics, chemical industry and architecture. This method has no defects of the existing methods such as big costs and sophisticated techniques, and the MgO whisker has good dispersity and high purity, so it offers ease to realize commercial process.
Description
Technical field
The invention belongs to the preparation field of ceramic, specifically relate to a kind of preparation method of high length-diameter ratio magnesia whisker.
Background technology
Whisker is a length-to-diameter ratio greater than 10 single crystal fibre material.Whisker atomic structure when crystallization is arranged high-sequential, and subsurface defect is less, so its intensity and modulus are the strengthening and toughening agent of the very excellent matrix material of a kind of mechanical property all near the theoretical value of its perfect crystal material.
The MgO whisker has good thermotolerance, insulativity, heat conductivity, stability and strengthening and toughening, can be used as the properties-correcting agent of matrix material.During the compound use of MgO whisker and polyvinyl chloride, can obviously improve the tensile strength and the resistance to impact shock of base material, improve the physical strength of goods; Be used with cement, can improve the flexural strength and the resistance to impact shock of material of construction.It also can be used as the plasticising strengthening agent of sorbent material, thermal insulation material, sound absorbent material, corrosion resistant material, fire retardant material and unsaturated polyester.Particularly the MgO whisker has dissolved characteristic under certain condition, and is good with physical environment Harmony, thereby the MgO Preparation of Whiskers has become one of focus that the various countries scientist paid close attention to.
The method for preparing the MgO whisker has physics method and chemical reaction method.Physical method is comparatively few to be used.Chemical reaction method comprises: reduction MgO method, magnesium salts hydrolysis method, magnesium salts and halide reaction method, MgCO
3Decomposition method, spinel decomposition method and magnesium hydrolysis method etc.The preparation method commonly used of MgO whisker mainly contains following several at present:
Steaming method (the phase court of a feudal ruler etc. " Preparation of Magnesia Whiskers ", Hebei Normal University's journal, 1997,21 volumes, the first phase) is about to block MgO and in vacuum oven, heats (being lower than 2000 ℃), make block MgO distillation be MgO steam, obtain the MgO whisker after the cooling gradually with graphite heater.It is low, of poor quality and productive rate is low to steam the MgO whisker purity of method gained, and there be limited evidence currently of adopts.
Carbothermic method is (referring to Li Jun " thermomechanical analysis and the experimental verification that prepare the MgO whisker with the C reduction method "; pottery journal 1997; 18 volumes; the second phase) be under the protection of rare gas element; MgO and the reaction of C Hybrid Heating are generated Mg steam; after for some time is carried out in reaction, feed the rare gas element that contains oxygen, can generate the MgO whisker.This method gained MgO whisker productive rate is low, and also needs to feed rare gas element, complex process, production cost height in the process.
Magnesium salts hydrolysis method (referring to Hayashi S, Saito H, Growth of Magnesia Whisker by Vapor Phase Reaction, Journal of Crystal Growth, 1974,24/25,345～349.) is with MgCl
2Be heated into gaseous state, feed argon gas MgCl
2Steam is transported to reaction zone, transports the H that comes at this and with argon gas
2O reacts, and generates the MgO whisker.This method technology, equipment complexity, and need to consume argon gas, production cost height.
The spinel decomposition method is that raw material is placed in the iridium crucible, is heated to 1900 ℃ under normal pressure, feeds the air that contains minor amounts of oxygen and water vapour in the heat-processed.Get final product the MgO whisker.
The characteristics of these methods are: when preparation MgO whisker, need by high temperature (being higher than 850 ℃), through the intermediate stage of Mg steam, whisker is grown out in gas phase, usually in the whisker growth process, add some character and output that some basic metal, alkaline-earth metal and compound thereof change whisker.These methods respectively have relative merits: reduction MgO method, MgCO
3Decomposition method, spinel decomposition method and magnesium hydrolysis method prepare the higher temperature of MgO whisker requirement, and usually more than 1400 ℃, thereby conversion unit is comparatively complicated, and still, the whisker length-to-diameter ratio height, the quality that obtain are good.Magnesium hydrolysis method and magnesium salts and halide reaction method are temperature required corresponding low, and the whisker that obtains is second-rate, in the whisker that makes, there is magnesium salts, the halogenide of complete reaction not and fails to change into the impurity such as MgO powder of whisker, therefore must make with extra care the MgO whisker.
Summary of the invention
The objective of the invention is, complex process low, of poor quality for the MgO whisker purity that solves production and the high shortcoming of cost provides a kind of processing unit simple, is suitable for the preparation method of the high length-diameter ratio magnesia whisker of scale operation.
The present invention solves the technical scheme that its technology adopts: a kind of preparation method of high length-diameter ratio magnesia whisker, be to be raw material with solubility divalence magnesium salts and soluble carbon hydrochlorate, volumetric molar concentration by 1: 0.5～5 is mixed directly synthetic, make the magnesiumcarbonate precursor through ageing, filtration, washing, drying again, this precursor obtains the MgO powder through the temperature programming calcining, and its concrete preparation process is:
1, solubility divalence magnesium salts and solubility dicovalent carbon hydrochlorate all are made into the solution of 0.1～3.0mol/L, at room temperature carbonate solution slowly are added drop-wise in the magnesium salt solution, the add-on of carbonate solution is pressed Mg
2+/ CO
3 2-=1: 0.5～5 molar ratio computing with 50～120 rev/mins of stirring velocity stirring reactions 5～20 minutes, with the emulsion ageing at room temperature that obtains 5～20 hours, filters, washing, promptly gets the magnesiumcarbonate precursor after dry 2～5 hours down in 50～100 ℃;
2, magnesiumcarbonate precursor temperature rise rate with 5～20 ℃/min under 400～800 ℃ temperature of above-mentioned preparation was calcined 3～6 hours, can be obtained the MgO whisker.
Described solubility divalence magnesium salts is any in magnesium chloride, magnesium nitrate and the sal epsom, the soluble carbon hydrochlorate is any in yellow soda ash, salt of wormwood, volatile salt and the bicarbonate of ammonia, and the molar equivalent of soluble carbon hydrochlorate is 0.5～5 times of magnesium ion molar equivalent.
The MgO whisker that obtains is carried out scanning electron microscope (SEM) analysis, and its diameter is between 2～5 μ m as a result, and length is between 30～50 μ m.
The invention has the beneficial effects as follows that adopted a kind of simple and easy to do method to prepare the MgO whisker, the product preparation cost is low, resulting good product dispersibility, the purity height is easy to realize suitability for industrialized production.
Description of drawings
The invention will be further described below in conjunction with the drawings and specific embodiments.
Fig. 1 is the X-ray diffractogram of the magnesia crystal whisker of the present invention's preparation.
Fig. 2 is the SEM shape appearance figure of the magnesia crystal whisker of the present invention's preparation.
Fig. 3 is the SEM shape appearance figure of the magnesia crystal whisker of the present invention's preparation.
Embodiment
Embodiment 1
With concentration is the MgCl of 0.5mol/L
2Solution adds in the reaction vessel, and slowly adding concentration under the room temperature is the Na of 1.0mol/L
2CO
3Solution (Mg
2+/ CO
3 2-=1: 2) pour reactor into, with 120 rev/mins of stirring reactions of stirring velocity 10 minutes.With the emulsion ageing at room temperature that obtains 10 hours, filter, with distilled water and absolute ethanol washing, promptly get the magnesiumcarbonate precursor after 2 hours in 100 ℃ of dryings.Calcining is 3 hours after being warming up to 800 ℃ with the temperature rise rate of 5 ℃/min, obtains the MgO powder.Its diameter is at 3～5 μ m after measured, and length is 40～50 μ m.
Embodiment 2
With concentration is the Mg (NO of 0.5mol/L
3)
2Solution adds in the reaction vessel, and slowly adding concentration under the room temperature is the K of 0.5mol/L
2CO
3Solution (Mg
2+/ CO
3 2-=1: 1) pour reactor into, with 80 rev/mins of stirring reactions of stirring velocity 5 minutes.With the emulsion ageing at room temperature that obtains 16 hours, filter, with distilled water and absolute ethanol washing, promptly get the magnesiumcarbonate precursor after 4 hours in 60 ℃ of dryings.Calcining is 4 hours after being warming up to 500 ℃ with the temperature rise rate of 10 ℃/min, obtains the MgO powder.Its diameter is at 3～5 μ m after measured, and length is 30～40 μ m.
Embodiment 3
With concentration is the MgCl of 1.0mol/L
2Solution adds in the reaction vessel, and slowly adding concentration under the room temperature is the (NH of 1.5mol/L
4)
2CO
3Solution (Mg
2+/ CO
3 2-=1: 1.5) pour reactor into, with 100 rev/mins of stirring reactions of stirring velocity 10 minutes.With the emulsion ageing at room temperature that obtains 20 hours, filter, with distilled water and absolute ethanol washing, promptly get the magnesiumcarbonate precursor after 5 hours in 60 ℃ of dryings.Calcining is 4 hours after being warming up to 500 ℃ with the temperature rise rate of 6 ℃/min, obtains the MgO powder.Its diameter is at 2～3 μ m after measured, and length is 30～50 μ m.
Embodiment 4
With concentration is the MgSO of 1.0mol/L
4Solution adds in the reaction vessel, and slowly adding concentration under the room temperature is the Na of 3.0mol/L
2CO
3Solution (Mg
2+/ CO
3 2-=1: 3) pour reactor into, with 80 rev/mins of stirring reactions of stirring velocity 15 minutes.With the emulsion ageing at room temperature that obtains 12 hours, filter, with distilled water and absolute ethanol washing, promptly get the magnesiumcarbonate precursor after 4 hours in 80 ℃ of dryings.Calcining is 2 hours after being warming up to 700 ℃ with the temperature rise rate of 10 ℃/min, obtains the MgO powder.Its diameter is at 3～5 μ m after measured, and length is 30～40 μ m.
Embodiment 5
With concentration is the MgCl of 1.0mol/L
2Solution adds in the reaction vessel, and slowly adding concentration under the room temperature is the NH of 2.0mol/L
4HCO
3Solution (Mg
2+/ CO
3 2-=1: 2) pour reactor into, with 120 rev/mins of stirring reactions of stirring velocity 20 minutes.With the emulsion ageing at room temperature that obtains 20 hours, filter, with distilled water and absolute ethanol washing, promptly get the magnesiumcarbonate precursor after 4 hours in 80 ℃ of dryings.Calcining is 4 hours after being warming up to 500 ℃ with the temperature rise rate of 5 ℃/min, obtains the MgO powder.Its diameter is at 2～3 μ m after measured, and length is 40～50 μ m.
Claims (4)
1, a kind of preparation method of high length-diameter ratio magnesia whisker, it is characterized in that, be to be raw material with solubility divalence magnesium salts and soluble carbon hydrochlorate, volumetric molar concentration by 1: 0.5～5 is mixed directly synthetic, make the magnesiumcarbonate precursor through ageing, filtration, washing, drying again, this precursor obtains magnesium oxide powder through the temperature programming calcining, and its preparation process is:
A. solubility divalence magnesium salts and solubility dicovalent carbon hydrochlorate all are made into the solution of 0.1～3.0mol/L, at room temperature carbonate solution slowly are added drop-wise in the magnesium salt solution, the add-on of carbonate solution is pressed Mg
2+/ CO
3 2-=1: 0.5～5 molar ratio computing with 50～120 rev/mins of stirring velocity stirring reactions 5～20 minutes, with the emulsion ageing at room temperature that obtains 5～20 hours, filters, washing, promptly gets the magnesiumcarbonate precursor after dry 2～5 hours down in 50～100 ℃;
B. magnesiumcarbonate precursor temperature rise rate with 5～20 ℃/min under 400～800 ℃ temperature of above-mentioned preparation was calcined 3～6 hours, can be obtained the MgO whisker.
2, the preparation method of a kind of high length-diameter ratio magnesia whisker according to claim 1 is characterized in that, described solubility divalence magnesium salts is any in magnesium chloride, magnesium nitrate and the sal epsom.
3, the preparation method of a kind of high length-diameter ratio magnesia whisker according to claim 1 is characterized in that, described soluble carbon hydrochlorate is any in yellow soda ash, salt of wormwood, volatile salt and the bicarbonate of ammonia.
4, the preparation method of a kind of high length-diameter ratio magnesia whisker according to claim 1 is characterized in that, the molar equivalent of described soluble carbon hydrochlorate is 0.5～5 times of magnesium ion molar equivalent.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452675A (en) * | 2010-10-14 | 2012-05-16 | 中国科学院过程工程研究所 | Method for preparing nanometer/micrometer-scale high-purity magnesium oxide |
| CN102936750A (en) * | 2012-11-14 | 2013-02-20 | 辽宁工程技术大学 | Process for preparing trihydrate magnesium carbonate crystal whiskers through microwave method |
| CN105908255A (en) * | 2016-03-24 | 2016-08-31 | 西安建筑科技大学 | Method for preparing magnesium oxide whisker from waste magnesia-carbon brick |
| CN108866634A (en) * | 2018-07-27 | 2018-11-23 | 辽宁科技大学 | A method of magnesia crystal whisker is prepared using waste magnesia carbon brick substrate material as raw material |
| CN111303511A (en) * | 2018-12-12 | 2020-06-19 | 新奥石墨烯技术有限公司 | Polymer composite material containing micro-nano hybrid structure filler and preparation method thereof |
-
2005
- 2005-01-21 CN CN 200510045725 patent/CN1288281C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102452675A (en) * | 2010-10-14 | 2012-05-16 | 中国科学院过程工程研究所 | Method for preparing nanometer/micrometer-scale high-purity magnesium oxide |
| CN102452675B (en) * | 2010-10-14 | 2013-10-16 | 中国科学院过程工程研究所 | Method for preparing nanometer/micrometer-scale high-purity magnesium oxide |
| CN102936750A (en) * | 2012-11-14 | 2013-02-20 | 辽宁工程技术大学 | Process for preparing trihydrate magnesium carbonate crystal whiskers through microwave method |
| CN102936750B (en) * | 2012-11-14 | 2015-04-08 | 辽宁工程技术大学 | Process for preparing trihydrate magnesium carbonate crystal whiskers through microwave method |
| CN105908255A (en) * | 2016-03-24 | 2016-08-31 | 西安建筑科技大学 | Method for preparing magnesium oxide whisker from waste magnesia-carbon brick |
| CN105908255B (en) * | 2016-03-24 | 2018-03-16 | 西安建筑科技大学 | A kind of method that magnesia crystal whisker is prepared using waste magnesia carbon bricks |
| CN108866634A (en) * | 2018-07-27 | 2018-11-23 | 辽宁科技大学 | A method of magnesia crystal whisker is prepared using waste magnesia carbon brick substrate material as raw material |
| CN108866634B (en) * | 2018-07-27 | 2019-11-05 | 辽宁科技大学 | A method of magnesia crystal whisker is prepared using waste magnesia carbon brick substrate material as raw material |
| CN111303511A (en) * | 2018-12-12 | 2020-06-19 | 新奥石墨烯技术有限公司 | Polymer composite material containing micro-nano hybrid structure filler and preparation method thereof |
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|---|---|
| CN1288281C (en) | 2006-12-06 |
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