CN102381844A - Method for modifying hollow glass microspheres by chemical precipitation process - Google Patents
Method for modifying hollow glass microspheres by chemical precipitation process Download PDFInfo
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- CN102381844A CN102381844A CN2011102105714A CN201110210571A CN102381844A CN 102381844 A CN102381844 A CN 102381844A CN 2011102105714 A CN2011102105714 A CN 2011102105714A CN 201110210571 A CN201110210571 A CN 201110210571A CN 102381844 A CN102381844 A CN 102381844A
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- glass micropearl
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Abstract
The invention discloses a method for modifying hollow glass microspheres by a chemical precipitation process. The method comprises the following steps: firstly weighing the hollow glass microspheres with mass-volume concentration of 10-20g/L into a deoiling liquid, stirring for reacting at the temperature of 80-100 DEG C for 20-30 minutes, filtering and washing the hollow glass microspheres, and then drying at the temperature of 110 DEG C for 1-2 hours; and then coating a ferroferric oxide magnetic nanoparticle film on the surfaces of the hollow glass microspheres by adopting ferrous chloride and ferric trichloride. In the method, while the ferroferric oxide magnetic nanoparticles are prepared by the chemical precipitation process, a ferroferric oxide magnetic nanoparticle film layer is directly coated on the surfaces of the hollow glass microspheres so that the hollow glass microspheres have magnetic properties. The method is economical in raw materials and is simple and convenient in operation. Test results show that the hollow glass microspheres modified by the ferroferric oxide magnetic nanoparticles have the advantages of excellent magnetic properties and certain bonding firmness, thus meeting the actual demand.
Description
Technical field
The invention belongs to the function technical field of inorganic nonmetallic materials, relate to a kind of method of modifying of hollow glass micropearl, be specifically related to a kind of method that adopts chemical precipitation method hollow glass micropearl to be carried out modification.
Background technology
Z 250 (Fe
3O
4) be a kind of important spinels ferrite; Have many characteristics such as light, electricity, sound, heat and magnetic that are different from conventional material; Be to use one of soft magnetic material the most widely, note down material, pigment, magnetic fluid material commonly used, catalyzer; Magnetic macromolecular microsphere and electronic material etc. also have good application prospects at biological technical field and medical field.At present; Preparation magnetic Nano ferriferrous oxide particles method mainly contains hydro-thermal reaction method, neutralization precipitation method, chemical coprecipitation, deposition oxidation style and microwave irradiation etc.; Wherein chemical precipitation method has environmental friendliness, purity is high, and the nano particle of preparing is even, good dispersivity, without high temperature sintering; Simple to operate, be prone to realize advantages such as suitability for industrialized production.Hollow glass micropearl is the small hollow glass spheroid of a kind of size; Having advantages such as light weight, low heat conduction, resistance to compression, high dispersive, sound insulation, electrical insulating property and Heat stability is good, is the novel light material of a kind of of many uses, the excellent performance that gets up of development in recent years.Utilize the characteristics of hollow glass micropearl light weight, hollow, it is carried out surface modification treatment, can access and have property the novel material of (as inhaling ripple, reflective, wear-resisting and catalysis etc.).Adopt chemical precipitation method that the correlation technique of hollow glass micropearl coated magnetic nano ferriferrous oxide granule film is not also had at present.Existing method of modifying mainly contains the use chemical coprecipitation, coat one deck spinel type ferrite or magneto-plumbite type ferrite on the hollow glass micropearl surface, but processing unit requires height, is difficult for realization of industrialization.
Summary of the invention
The purpose of this invention is to provide a kind of chemical precipitation method that adopts to the method that hollow glass micropearl carries out modification, solved the hollow glass micropearl that existing method of modifying obtains and do not had magnetic or the relatively poor problem of magnetic.
The technical scheme that the present invention adopted is, the method that adopts chemical precipitation method that hollow glass micropearl is carried out modification is specifically implemented according to following steps:
Step 1: according to quality-volumetric concentration; The hollow glass micropearl that takes by weighing 10-20g/L joins in the degreasing fluid, is under 80-100 ℃ the condition in temperature, stirs; Hollow glass micropearl is filtered, washes, dry 1-2h under 110 ℃ of conditions behind the reaction 20-30min;
Step 2: according to total concentration of iron is 0.01-0.1mol/L, and iron protochloride and iron trichloride mass ratio are Fe
2+: Fe
3+=1:4-4:1 takes by weighing iron protochloride and iron trichloride, uses deionized water dissolving, obtains ferrous iron and ferric mixing solutions; The hollow glass micropearl that then step 1 is obtained is to be immersed in mixing solutions 1-10min under 10-50 ℃ the condition in temperature; Drip mass concentration while stirring and be 28% ammonia soln, keep the pH value at 5-11, with the speed isothermal reaction 1-3h of 100-900r/min; Question response finishes the back separating and filtering and goes out hollow glass micropearl; Use deionized water and absolute ethyl alcohol repetitive scrubbing respectively, drying 30-60min in 60 ℃ of vacuum drying ovens accomplishes the hollow glass micropearl modification.
Characteristics of the present invention also are,
The degreasing fluid in the step 1 wherein according to quality-volumetric concentration, is dissolved in deionized water the water glass of the tsp of the yellow soda ash of the sodium hydroxide of 70g/L, 25g/L, 25g/L and 7.5g/L and is prepared from.
The invention has the beneficial effects as follows, adopt chemical precipitation method in preparation magnetic Nano ferriferrous oxide particles, directly coat one deck magnetic Nano ferriferrous oxide particles film on the hollow glass micropearl surface; Give the hollow glass micropearl magnetic property; Through control reaction temperature and time, processing parameters such as ferrous iron and ferric amount ratio, total concentration of iron have been optimized finishing technique; This method is saved starting material, and is easy and simple to handle.Test result shows that the hollow glass micropearl after the modification of magnetic Nano Z 250 has excellent magnetic and certain combination fastness, can satisfy actual needs.
Description of drawings
Fig. 1 is the stereoscan photograph before the modification of hollow glass micropearl magnetic Nano Z 250;
Fig. 2 is the stereoscan photograph after adopting the inventive method to the modification of hollow glass micropearl coated magnetic nano ferriferrous oxide;
Fig. 3 is the X-ray diffraction spectrogram after adopting the inventive method to the modification of hollow glass micropearl coated magnetic nano ferriferrous oxide;
Fig. 4 is the hysteresis curve after adopting the inventive method to the modification of hollow glass micropearl coated magnetic nano ferriferrous oxide.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.
The method that the present invention adopts chemical precipitation method that hollow glass micropearl is carried out modification, specifically implement according to following steps:
Step 1: according to quality-volumetric concentration, take by weighing the sodium hydroxide of 70g/L, the yellow soda ash of 25g/L, the tsp of 25g/L and the water glass of 7.5g/L and be dissolved in the deionized water, obtain degreasing fluid, be heated to 80-100 ℃; Take by weighing hollow glass micropearl 10-20g, add in the 1L degreasing fluid, adopt the mechanical stirring method that cenosphere is fully disperseed in degreasing fluid, reaction 20-30min after-filtration, washing, the dry 1-2h under 110 ℃ of conditions of the cenosphere after will filtering at last.
Step 2: according to total concentration of iron is 0.01-0.1mol/L, and iron protochloride and iron trichloride mass ratio are Fe
2+: Fe
3+=1:4-4:1 takes by weighing iron protochloride and iron trichloride, uses deionized water dissolving, obtains ferrous iron and ferric mixing solutions; The cenosphere that then step 1 is obtained is immersed in 1-10min in 10-50 ℃ the mixing solutions; Slowly drip mass concentration while stirring and be 28% ammonia soln, make the pH value of solution value, handle 1-3h with 100-900r/min speed constant temperature at 5-11; Question response finishes the back separating and filtering and goes out hollow glass micropearl; Repeatedly wash with deionized water and absolute ethyl alcohol, drying 30-60min in 60 ℃ of vacuum drying ovens promptly accomplishes the coated magnetic nano ferriferrous oxide granule film on the hollow glass micropearl surface.
Fig. 1 and Fig. 2 are the forward and backward stereoscan photographs of hollow glass micropearl coated magnetic nano ferriferrous oxide modification.Can find out; Unmodified hollow glass micropearl surface is very clean, does not have other materials to adhere to, and the hollow glass micropearl surface after the modification has coated thin film shape material; Also be studded with some tiny particles, the high power electromicroscopic photograph shows that this film is to be made up of nano-scale particle.Fig. 3 is the X-ray diffraction spectrogram after the modification of hollow glass micropearl coated magnetic nano ferriferrous oxide.Can find out that the surface coated nano ferriferrous oxide granule of the hollow glass micropearl after the modification has a cube inverse spinel structure, with magnetite Fe among the standard diagram JCPDS
3O
4(No.19-0629) consistent.Fig. 4 is the hysteresis curve of surperficial clad nano Z 250 cenosphere after the modification.Test result shows that the hollow glass micropearl of clad nano Z 250 has superparamagnetism.
Magnetic hysteresis loop with VSM multifunction vibration sample magnetometer (U.S. Quantum Design company) mensuration clad nano Z 250 hollow glass micropearl calculates saturation magnetization and residual magnetization.
Beneficial effect of the present invention place is described from the principle aspect:
1. the present invention is through the total concentration of iron of control, the ratio of iron protochloride and iron trichloride quality, pH value of solution value; Temperature of reaction; Reaction times and stirring velocity make that the ferriferrous oxide film that is coated on the hollow glass micropearl surface is even, and particle is a nano level; Combine fastness good with hollow glass micropearl, have certain magnetic.Because total concentration of iron, the ratio of iron protochloride and iron trichloride quality, the pH value of solution value, temperature of reaction and time, stirring velocity all affects magnetic, purity, crystallization degree, pattern and the size of particles of Z 250.When total concentration of iron during at 0.01-0.1mol/L; The hollow glass micropearl surface can coat certain thickness magnetic Nano ferriferrous oxide particles film; The rare agglomeration of particle can not deposit too many nano particle in the solution simultaneously, combines with hollow glass micropearl firmly; When less than 0.01mol/L, in the solution iron ion very little, the cenosphere surface can not form continuous thin film, influences magnetic property; When greater than 0.1mol/L, iron concentration is excessive to be prone to cause waste, and the magnetic Nano ferriferrous oxide particles film of hollow glass micropearl surface adhesion is too thick, and attachment fastness is bad, and nano particle is prone to come off in the use.
2. when the ratio of iron protochloride and iron trichloride quality during at 1:4-4:1, the hollow glass micropearl surface can coat certain thickness film, and nano particle combines with hollow glass micropearl firmly; When less than 1:4, the ferric ion consumption is too big, prepare to contain the more impurity of ferric iron, magnetic property very a little less than; When greater than 4:1, the ferric ion consumption is prepared and is contained the more impurity of ferrous iron very little, magnetic property also very a little less than.
3. when temperature of reaction is controlled at 10-50 ℃, can generate the magnetic Nano ferriferrous oxide particles; When temperature was lower than 10 ℃, the growth of magnetic Nano Z 250 was very slow; The magnetic Nano ferriferrous oxide particles that when being higher than 50 ℃, generates is very big.
4. when the pH value of solution value is controlled at 5-11, can generate nano ferriferrous oxide granule; When the pH value less than 5 the time, the ferriferrous oxide particles of generation does not have magnetic; When the pH value greater than 11 the time, the ferriferrous oxide particles magnetic of generation very a little less than.
5. reaction times and stirring velocity mainly influence the crystallization degree of Z 250, crystal morphology and size.When the reaction times is controlled at 1-3h, can generate magnetic Nano ferriferrous oxide particles film on the hollow glass micropearl surface; When being lower than 1h, nano ferriferrous oxide combines fastness relatively poor with hollow glass micropearl, also influences the crystallization degree of magnetic Nano Z 250, and magnetic property is bad; When greater than 3h, obvious reunion can take place in the magnetic Nano ferriferrous oxide particles of generation, and granularity obviously increases, and surface irregularity is uneven, and particle comes off easily.
Embodiment 1
Take by weighing hollow glass micropearl 2g, add in the 100ml degreasing fluid, stirring reaction 20min under 80 ℃ of conditions filters then, washes, with the cenosphere dry 1h under 110 ℃ of conditions after filtering.Take by weighing a certain amount of iron protochloride and iron trichloride, use deionized water dissolving, controlling total concentration of iron is 0.01mol/L; Iron protochloride is 1:4 with the ratio of iron trichloride quality, adds the good hollow glass micropearl of pre-treatment, under 10 ℃ of conditions, handles 1min; Slowly drip concentration while stirring and be 28% ammoniacal liquor; Making the pH value of solution value is 5, and with 100r/min speed constant temperature stir process 1h, question response finishes the back separating and filtering and goes out cenosphere; Extremely neutral with deionized water wash, drying 30min in 60 ℃ of vacuum drying ovens.
The saturation magnetization of coated magnetic nano ferriferrous oxide hollow glass micropearl is 12emu/g, and residual magnetization is zero.
Take by weighing hollow glass micropearl 1g, add in the 100ml degreasing fluid, stirring reaction 30min under 100 ℃ of conditions filters then, washes, with the cenosphere dry 2h under 110 ℃ of conditions after filtering.Take by weighing a certain amount of iron protochloride and iron trichloride, use deionized water dissolving, controlling total concentration of iron is 0.1mol/L; Iron protochloride is 4:1 with the ratio of iron trichloride quality, adds the good hollow glass micropearl of pre-treatment, under 50 ℃ of conditions, handles 10min; Slowly drip concentration while stirring and be 28% ammoniacal liquor; Making the pH value of solution value is 11, handles 3h with 900r/min speed constant temperature, and question response finishes the back separating and filtering and goes out microballon; Extremely neutral with deionized water wash, drying 60min in 60 ℃ of vacuum drying ovens.
The saturation magnetization of coated magnetic nano ferriferrous oxide hollow glass micropearl is 45emu/g, and residual magnetization is zero.
Embodiment 3
Take by weighing hollow glass micropearl 1.5g, add in the 100ml degreasing fluid, stirring reaction 25min under 95 ℃ of conditions filters then, washes, with the cenosphere dry 1.5h under 110 ℃ of conditions after filtering.Take by weighing a certain amount of iron protochloride and iron trichloride, use deionized water dissolving, controlling total concentration of iron is 0.05mol/L; Iron protochloride is 2:1 with the ratio of iron trichloride quality, adds the good hollow glass micropearl of pre-treatment, under 30 ℃ of conditions, handles 5min; Slowly drip concentration while stirring and be 28% ammoniacal liquor; Making the pH value of solution value is 9, handles 2h with 500r/min speed constant temperature, and question response finishes the back separating and filtering and goes out cenosphere; Extremely neutral with deionized water wash, drying 40min in 60 ℃ of vacuum drying ovens.
The saturation magnetization of coated magnetic nano ferriferrous oxide hollow glass micropearl is 23emu/g, and residual magnetization is zero.
Claims (2)
1. adopt chemical precipitation method to the method that hollow glass micropearl carries out modification, it is characterized in that, specifically implement according to following steps:
Step 1: according to quality-volumetric concentration; The hollow glass micropearl that takes by weighing 10-20g/L joins in the degreasing fluid, is under 80-100 ℃ the condition in temperature, stirs; Hollow glass micropearl is filtered, washes, dry 1-2h under 110 ℃ of conditions behind the reaction 20-30min;
Step 2: according to total concentration of iron is 0.01-0.1mol/L, and iron protochloride and iron trichloride mass ratio are Fe
2+: Fe
3+=1:4-4:1 takes by weighing iron protochloride and iron trichloride, uses deionized water dissolving, obtains ferrous iron and ferric mixing solutions; The hollow glass micropearl that then step 1 is obtained is to be immersed in mixing solutions 1-10min under 10-50 ℃ the condition in temperature; Drip mass concentration while stirring and be 28% ammonia soln, keep the pH value at 5-11, with the speed isothermal reaction 1-3h of 100-900r/min; Question response finishes the back separating and filtering and goes out hollow glass micropearl; Use deionized water and absolute ethyl alcohol repetitive scrubbing respectively, drying 30-60min in 60 ℃ of vacuum drying ovens accomplishes the hollow glass micropearl modification.
2. employing chemical precipitation method according to claim 1 is carried out the method for modification to hollow glass micropearl; It is characterized in that; Degreasing fluid in the said step 1; According to quality-volumetric concentration, be dissolved in deionized water the water glass of the tsp of the yellow soda ash of the sodium hydroxide of 70g/L, 25g/L, 25g/L and 7.5g/L and be prepared from.
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| CN104069847B (en) * | 2014-04-10 | 2016-05-25 | 西安工程大学 | Rare-earth europium dopen Nano TiO2The preparation method of hollow glass micropearl |
| CN103964707A (en) * | 2014-05-12 | 2014-08-06 | 中国科学院理化技术研究所 | Method of improving fluidity of hollow glass bead powder |
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