CN103922368B - The colored form class aggregated(particle) structure magnesium hydrate powder preparation method of nanometer sheet base - Google Patents
The colored form class aggregated(particle) structure magnesium hydrate powder preparation method of nanometer sheet base Download PDFInfo
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- CN103922368B CN103922368B CN201410163628.3A CN201410163628A CN103922368B CN 103922368 B CN103922368 B CN 103922368B CN 201410163628 A CN201410163628 A CN 201410163628A CN 103922368 B CN103922368 B CN 103922368B
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Abstract
A colored form class aggregated(particle) structure magnesium hydrate powder preparation method for nanometer sheet base is under fast stirring, by the MgSO of 1.60 ~ 1.70mol/L
4aqueous solution instillation be added with the PEG aqueous solution, be precipitated system in the ammonia soln of pH value 11.5 ~ 12.5, obtain the colored form class aggregated(particle) structure magnesium hydroxide gelatinous precipitate of nanometer sheet base after precipitation system ageing, wherein the add-on of various raw material meets Mg
2+﹕ OH
-be the mol ratio of 1 ﹕ 2.4 ~ 4.0, the quality of PEG accounts for the Mg of generation (OH)
21.2 ~ 1.5% of total mass.The colored form class aggregated(particle) structure magnesium hydrate powder of nanometer sheet base of the present invention has unique very strong absorption from low ion concns solution and reclaims the ability of rare metal, is also a kind of eco-friendly efficient flame-retarding agent.
Description
Technical field
The invention belongs to materials science field, relate to a kind of preparation method of magnesium hydrate powder, particularly a kind of preparation method with the magnesium hydroxide of colored form class aggregated(particle) structure.
Background technology
Magnesium hydroxide is a kind of environment-friendly material, and the adsorptive power in low ion concns solution is very strong.As everyone knows, the specific surface area of sorbent material is larger, and adsorptive power is stronger.Therefore, preparation has and has important practical significance compared with the magnesium hydrate powder of bigger serface.
The specific surface area of the specific surface area structure more any than other of flower form class aggregated(particle) structure is all large.Flower form class aggregated(particle) structure is a kind of secondary structure (secondary level aggregated(particle) structure), can not direct growth out, its primary structure unit is micron or the nanometer sheet that surface has active group.Appeared in the newspapers lead adopt hydrothermal method about the method overwhelming majority preparing flower form class aggregated(particle) structure, High Temperature High Pressure is utilized to change the crystal habit of crystal, to create the structural unit with surface active groups, under suitable pH condition, the complementary activities group by means of active group takes on a grade aggregated(particle) structure.
Not gentle with the preparation condition of hydrothermal method preparation flower form class aggregated(particle) structure, the reactant concn adopted in the method for all reports is all less, so output is very little, does not have practical production meaning.
Summary of the invention
The object of this invention is to provide one adopts high reactant concn to prepare the method for the colored form class aggregated(particle) structure magnesium hydrate powder of nanometer sheet base under normal temperature and pressure (non-hydrothermal condition).
Preparation method of the present invention is under fast stirring, by the MgSO of 1.60 ~ 1.70mol/L
4aqueous solution instillation be added with the PEG aqueous solution, be precipitated system in the ammonia soln of pH value 11.5 ~ 12.5, obtain the colored form class aggregated(particle) structure magnesium hydroxide gelatinous precipitate of nanometer sheet base after precipitation system ageing, wherein the add-on of various raw material meets Mg
2+﹕ OH
-be the mol ratio of 1 ﹕ 2.4 ~ 4.0, the quality of PEG accounts for the Mg of generation (OH)
21.2 ~ 1.5% of total mass.
The PEG added in the present invention plays finishing and ligand guiding, and the described PEG aqueous solution is preferably respectively the PEG aqueous solution be made into soluble in water of 200,6000 and 20000 by the molecular weight of equal in quality.
In above-mentioned preparation method, the digestion time preferably 1 ~ 2h of described precipitation system.
By described gelatinous precipitate with absolute ethanol washing, extremely without SO
4 2-detect, after drying, obtain the colored form class aggregated(particle) structure magnesium hydrate powder based on nanometer sheet base.Due to Mg (OH)
2dissolve in a large number in water, therefore the present invention adopts dehydrated alcohol to wash gelatinous precipitate, in order to avoid washing process causes Mg (OH)
2loss.
The present invention is by adopting above-mentioned preparation method, obtain the colored form class aggregated(particle) structure magnesium hydrate powder of nanometer sheet base, the magnesium hydrate powder of this colored form class aggregated(particle) structure has unique very strong absorption from low ion concns solution and reclaims the ability of rare metal, is also a kind of eco-friendly efficient flame-retarding agent.
Observe by JEM2100F type high resolution TEM the wet gel that the present invention be scattered in dehydrated alcohol spends the magnesium hydrate powder of form class aggregated(particle) structure, its full-resolution picture is as Fig. 1.Can be clear that from figure many nano particles according to the assembling of unified crystallographic direction in flakes (wherein Fig. 1 b is the amplification of institute's circle part in Fig. 1 a), nanoparticle size is about 3.5nm.
This mode is called " directed attachment (OrientedAttachment) ", is a kind of new crystal growth pattern being different from " slaking (OstwaldRipening) ".So-called " directed attachment ", be growing element with nano particle, have the spontaneous assembling process of the adjacent particle of the corner of the eyes of identical crystallographic direction, the particle of assembling is combined by face and is fused into monocrystalline.From the viewpoint of thermokinetics, the power of directed attachment is that high-energy surface is disappeared by bonding pairing, thus greatly reduces the surface energy of system.Suitable tensio-active agent is the key element of directed attachment.Fig. 1 shows, preparation method of the present invention has obvious directed apposition growth feature, and detailed process is as follows: the non-nucleus of magnesium hydroxide 1. being formed several nanosized in containing the aqueous solution of PEG by homogeneous nucleation.2. due to the strong sucking action between organic molecule and inorganic particle, PEG is adsorbed onto non-nucleating surface (term in orientation attachment is that PEG catches non-nucleus).3. non-nucleus crystallization, the change (this process is called " be situated between to see and change ", and its power is that inorganic lattice energy and organic molecule bend) that shape and size occur simultaneously becomes the nano particle of temporary stabilization.The profile of nano particle is little six square pieces (being determined by the inherent structure of brucite), and its side ({ 110}) is high-energy surface, upper bottom surface ({ 001}) is low energy face.Because system surfaces can be tending towards minimum natural character, PEG is adsorbed on the side (high-energy surface) of little six square pieces.4. except playing basic reduction surface energy effect, more meaningfully, PEG by with Mg (OH)
2between special coordination and the structure-directing effect of ligand in water, make nano grain surface functionalization, that is, the nano particle wrapped up by PEG is along identical crystallographic direction orientation, then immediately along this direction mutual " attachment " together, this " attachment " is bonding action.
PEG is selected to be one of unique distinction of the present invention.The essential place of the keying action in orientation attachment that makes nano grain surface functionalization be tensio-active agent, because the coordination between different tensio-active agents and different inorganic materials is different, so the tensio-active agent being suitable for the directed attachment of different inorganic materials generation has selectivity.PEG and Mg (OH)
2complement each other.PEG is dibasic alcohol, and the ligand that it provides is two hydroxyls (-OH), has remained appropriate hydroxyl after there is special coordination with magnesium hydroxide, and this part hydroxyl snugly in water has played structure-directing effect.Do not have residual hydroxyl or residual hydroxyl too much all can not produce structure-directing effect, do not have residual hydroxyl then there is no guide frame, when residual hydroxyl is too much, is wound around mutually between hydroxyl and causes nano particle coagulation.
Directed attachment is unique distinction two of the present invention, and it has played the effect of forming a connecting link in the structure of flower form class aggregated(particle) structure: on the one hand, and the primary structure unit nanometer sheet of flower form class aggregated(particle) structure by directed apposition growth out; On the other hand, the surface tissue of the nanometer sheet generated is that the assembling between nanometer sheet provides suitable condition.The upper and lower surface of nanometer sheet is ({ 001}) face, and it has Mg
2+and O
2-; The side of nanometer sheet has the residual hydroxyl of PEG.These residual hydroxyls or each other bridging form hydrogen bond, or with the O on ({ 001}) face
2-form hydrogen bond.The hydroxyl of bridging makes nanometer sheet form Bian-Bian to connect each other, with the O on ({ 001}) face
2-the hydrogen bond formed makes nanometer sheet form limit-face connection.In certain space, continuous print hydroxyl makes nanometer sheet be assembled into flower.Owing to also having a small amount of residual hydroxyl on the edge of petal, the flower of some amount is gathered into a pile by hydrogen bond therebetween again.As shown in Figure 3.
Nanometer sheet is assembled into flower by hydrogen bond, is unique distinction three of the present invention, and due to hydrogen bond action, nanometer sheet must be assembled into colored shape.
Select ammoniacal liquor to do precipitation agent, because mitigation (compared with sodium hydroxide pellets agent) is compared in the reaction between magnesium sulfate with ammoniacal liquor, be equivalent to the mobility that improve nanoparticle growth unit, high mobility is the prerequisite that directed attachment occurs.Therefore, selecting ammoniacal liquor to do precipitation agent is unique distinction four of the present invention.
Five of unique distinction of the present invention is the reactant solutions that have employed high density.Because the solubleness of magnesium sulfate is high, the reactant solution of configuration high density is possible, and this has established practical basis for industrialization.On the other hand, reaction is made just can to carry out at normal temperatures and pressures.
Adopt Rigaku Dmax-rB type diffractometer, under voltage 40kv, electric current 100mA condition, with Cu target, K
αray carries out X-ray diffraction analysis to the magnesium hydrate powder obtained, and obtains the XRD spectrum of Fig. 2 a.Adopt QUANTAX200 energy spectrometer to carry out chemical composition analysis to the magnesium hydrate powder obtained, obtain the EDS spectrogram of Fig. 2 b.
Compared with the JCPDF card (card 07-0239) of brucite (the mineral formal name used at school of magnesium hydroxide) by Fig. 2 a, diffraction peak is very identical, and peak shape is intact, illustrates that the crystalline structure of magnesium hydroxide is intact.Fig. 2 b shows, prepared powder contains " Mg " and " O " element except " H " element, illustrates that the chemical composition of prepared powder is Mg (OH)
2, " Pt " element in Fig. 2 b comes from conducting film.
Fig. 3 is the magnesium hydrate powder pattern observed on S4800 type field emission scanning electron microscope.From Fig. 3 a, prepared powder is the even bead with colored shape outward appearance, grain diameter 2 ~ 3 μm, and a flower (particle) is made up of tens nanometer sheet, and the bead of some amount is gathered into a pile; The colored shape lines of bead surface can have been found out from Fig. 3 b; Fig. 3 c is the pattern of a flower, orderly the linking together of many nanometer sheet, the thick 25 ~ 40nm of nanometer sheet; Fig. 3 d is the internal morphology of the flower amplified further, therefrom can see and being linked together by Bian-Bian or limit-face between nanometer sheet.
Adopt the pattern of TECNAIG2F20 type Flied emission transmission electron microscope observing flower and the deep structure of research flower, as Fig. 4, voltage 200Kv.Fig. 4 a is the transmission electron microscope X rays topographs of a flower, and its shape characteristic and Fig. 3 c fit like a glove.Strongly ultrasonic does not break into pieces flower, illustrates that flower is a firmly entirety, instead of the aggregate of nanometer sheet.Fig. 4 b is the electron diffraction picture of a flower, and the feature of concentric ring shows that a flower is polycrystalline.Fig. 4 c-g indicates the constitutional features of a nanometer sheet.The HRTEM X rays topographs at a nanometer sheet edge and its diffraction spot illustrate that nanometer sheet is monocrystalline, and this has affirmed that " directed attachment " growth mechanism of nanometer sheet is correct again.
Fig. 5 gives the overall building schematic diagram of the colored form class aggregated(particle) structure magnesium hydroxide of nanometer sheet base.In figure, (a) non-nucleus; B () non-nucleus is caught by PEG, straight line double-headed arrow represents inorganic lattice energy, and curve double-headed arrow represents organic molecule and bends; C () is situated between to see and changes rear stable hexagonal nano particle; D nanometer sheet that the attachment of () orientation is formed; E colored form class aggregated(particle) structure that () is assembled into by hydrogen bond.
Accompanying drawing explanation
Fig. 1 is the full-resolution picture that magnesium hydroxide gelatinous precipitate that the present invention prepares is dispersed in the directed apposition growth in dehydrated alcohol.
Fig. 2 is XRD figure spectrum and the EDS collection of illustrative plates of the magnesium hydrate powder that the present invention prepares.
Fig. 3 is the scanning electron microscope X rays topographs of the magnesium hydrate powder that the present invention prepares.
Fig. 4 is the transmission electron microscope X rays topographs of the magnesium hydrate powder that the present invention prepares.
Fig. 5 is the schematic diagram of the m of the magnesium hydroxide of the colored form class aggregated(particle) structure of nanometer sheet base.
Embodiment
Embodiment 1
Take 20.5gMgSO
4be dissolved in distilled water, be made into 100mL solution.
Strong aqua is diluted to the ammonia soln that pH value is 11.5, gets 182mL, add each 13.6mg of PEG200, PEG6000 and PEG20000 as finishing and ligand directed agents, after fully dissolving, be made into precipitant solution.
By 30mLMgSO
4solution is added dropwise in above-mentioned precipitant solution under fast stirring, drips after terminating, by still aging for precipitation system 2h.
By system suction filtration good for ageing, use absolute ethanol washing gelatinous precipitate, wash 3 times altogether, each 50mL.With BaCl
2solution inspection washings, to separating out without white precipitate.
The clean wet gel that takes a morsel is dispersed in dehydrated alcohol, obtains translucent solution, gets it and carries out high resolution TEM (HRTEM) observation.
Remaining clean wet gel is extremely absolutely dry 120 DEG C of forced air dryings, obtain the magnesium hydrate powder of flower form class aggregated(particle) structure.
Embodiment 2
Take 20.5gMgSO
4be dissolved in distilled water, be made into 100mL solution.
Strong aqua is diluted to the ammonia soln that pH value is 12.0, gets 30.4mL, add each 13.6mg of PEG200, PEG6000 and PEG20000 as finishing and ligand directed agents, after fully dissolving, be made into precipitant solution.
By 30mLMgSO
4solution is added dropwise in above-mentioned precipitant solution under fast stirring, drips after terminating, by still aging for precipitation system 1.5h.
By system suction filtration good for ageing, use absolute ethanol washing gelatinous precipitate, wash 3 times altogether, each 50mL.With BaCl
2solution inspection washings, to separating out without white precipitate.Wet gel will be cleaned extremely absolutely dry 120 DEG C of forced air dryings, obtain the magnesium hydrate powder of flower form class aggregated(particle) structure.
Embodiment 3
Take 20.5gMgSO
4be dissolved in distilled water, be made into 100mL solution.
Strong aqua is diluted to the ammonia soln that pH value is 12.5, gets 29.1mL, add each 27.2mg of PEG200, PEG6000 and PEG20000 as finishing and ligand directed agents, after fully dissolving, be made into precipitant solution.
By 60mLMgSO
4solution is added dropwise in above-mentioned precipitant solution under fast stirring, drips after terminating, by still aging for precipitation system 1h.
By system suction filtration good for ageing, use absolute ethanol washing gelatinous precipitate, wash 3 times altogether, each 50mL.With BaCl
2solution inspection washings, to separating out without white precipitate.Wet gel will be cleaned extremely absolutely dry 120 DEG C of forced air dryings, obtain the magnesium hydrate powder of flower form class aggregated(particle) structure.
Embodiment 4
Take 19.3gMgSO
4be dissolved in distilled water, be made into 100mL solution.
Strong aqua is diluted to the ammonia soln that pH value is 11.5, gets 171mL, add each 12.8mg of PEG200, PEG6000 and PEG20000 as finishing and ligand directed agents, after fully dissolving, be made into precipitant solution.
By 30mLMgSO
4solution is added dropwise in above-mentioned precipitant solution under fast stirring, drips after terminating, by still aging for precipitation system 2h.
By system suction filtration good for ageing, use absolute ethanol washing gelatinous precipitate, wash 3 times altogether, each 45mL.With BaCl
2solution inspection washings, separates out to without white precipitate, will clean wet gel extremely absolutely dry 120 DEG C of forced air dryings, obtains the magnesium hydrate powder of flower form class aggregated(particle) structure.
Embodiment 5
Take 19.3gMgSO
4be dissolved in distilled water, be made into 100mL solution.
Strong aqua is diluted to the ammonia soln that pH value is 11.5, gets 28.6mL, add each 12.8mg of PEG200, PEG6000 and PEG20000 as finishing and ligand directed agents, after fully dissolving, be made into precipitant solution.
By 30mLMgSO
4solution is added dropwise in above-mentioned precipitant solution under fast stirring, drips after terminating, by still aging for precipitation system 1.5h.
By system suction filtration good for ageing, use absolute ethanol washing gelatinous precipitate, wash 3 times altogether, each 45mL.With BaCl
2solution inspection washings, separates out to without white precipitate, will clean wet gel extremely absolutely dry 120 DEG C of forced air dryings, obtains the magnesium hydrate powder of flower form class aggregated(particle) structure.
Claims (1)
1. a preparation method for the colored form class aggregated(particle) structure magnesium hydrate powder of nanometer sheet base, is under fast stirring, by the MgSO of 1.60 ~ 1.70mol/L
4aqueous solution instillation be added with the PEG aqueous solution, be precipitated system in the ammonia soln of pH value 11.5 ~ 12.5, the colored form class aggregated(particle) structure magnesium hydroxide gelatinous precipitate of nanometer sheet base will be obtained after precipitation system ageing 1 ~ 2h, wherein, the add-on of various raw material meets Mg
2+﹕ OH
-be the mol ratio of 1 ﹕ 2.4 ~ 4.0, the PEG that the described PEG aqueous solution is respectively 200,6000 and 20000 by the molecular weight of equal in quality is soluble in waterly made into, and the total mass of PEG accounts for the Mg (OH) of generation
21.2 ~ 1.5% of total mass.
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| CN105197967B (en) * | 2015-09-17 | 2016-10-12 | 南昌大学 | A kind of preparation method of the flower-shaped magnesium oxide of carrying transition metal oxide |
| CN116835616A (en) * | 2023-08-30 | 2023-10-03 | 山东艾科高分子材料有限公司 | Method for preparing high-dispersion hexagonal flaky magnesium hydroxide by high-activity light-burned magnesium oxide through one-step hydrothermal method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1458066A (en) * | 2002-05-17 | 2003-11-26 | 隗学礼 | Process for preparing magnesium hydroxide whisker |
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2014
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1458066A (en) * | 2002-05-17 | 2003-11-26 | 隗学礼 | Process for preparing magnesium hydroxide whisker |
Non-Patent Citations (4)
| Title |
|---|
| Investigation of Antibacterial Activity and Related Mechanism of a Series of Nano-Mg(OH)2;Xiaohong Pan等;《ACS Applied Materials & Interfaces》;20130109;第5卷;1137？1142页 * |
| Mg(OH)2纳米晶的可控制备;孙灵娜等;《深圳大学学报理工版》;20130331;第30卷(第2期);205-209页 * |
| Preparation of magnesium hydroxide nanoflowers;Chenglin Yan等;《Journal of Crystal Growth》;20050714;第282卷;448-454页 * |
| SYNTHESIS OF Mg(OH)2 FROM MAGNESIUM SALTS AND NH4OH BY DIRECT FUNCTIONALISATION WITH POLY(ETHYLENE GLYCOLS);A. Pilarska等;《Physicochemical Problems of Mineral Processing》;20121231;第48卷(第2期);第632页2. Experimental，第634页表1，第637页图4(a) * |
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