CN102030539A - Method for preparing solid composite particles - Google Patents
Method for preparing solid composite particles Download PDFInfo
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- CN102030539A CN102030539A CN2010105016559A CN201010501655A CN102030539A CN 102030539 A CN102030539 A CN 102030539A CN 2010105016559 A CN2010105016559 A CN 2010105016559A CN 201010501655 A CN201010501655 A CN 201010501655A CN 102030539 A CN102030539 A CN 102030539A
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Abstract
A method for preparing solid composite particles comprises the following steps: according to demand on chemical composition of the composite particles, uniformly mixing two or more kinds of water-based colloids or dispersions having different components into steady mixed dispersion, and regulating pH=2-11, then, containing the mixed dispersion in a container, freezing the dispersion in low-temperature environment and wholly freezing the dispersion into ice solid bodies, after unfreezing, forming a solid deposited layer deposited by schistose granular solid particles of which size is in a range from 1-3mm and particle profile is visible, repeatedly soaking and washing the deposited layer by water, and drying the deposited layer to get the solid composite particles. Different components in the solid composite particles obtained by the invention can implement uniform dispersive mixing in nano size. The method for preparing solid composite particles has the advantages of simple and easy technology and high degree of mixing of the composite particles, so that the method is very suitable for preparation of raw materials of novel functional materials and structural materials.
Description
Technical field
The present invention relates to a kind of method for preparing the solid composite particles.
Background technology
In order to obtain the mixture of solid particulate; the most traditional is the simple mixed method of utilizing manpower or machinery; this method is utilized external force; by rub up, mix and stir, stir, push, shear, knead, different modes such as grinding; at the hygrometric state that contains liquid vehicle or do not contain under the dry state of liquid vehicle; make some kinds of solid particulates intert mutually, disperse, thereby the mixing of the solid particulate of heterogeneity obtain the solid composite particles the most at last, for use in certain products and technology.For example starting from pottery preparation, the brick and tile production of ancient times, all is to adopt similar method to mix the particle of heterogeneity up to neoteric and modern refractory materials, part-structure stupalith, ceramic material, high molecule alloy material, metal alloy compositions, catalyzer, new energy materials etc.This method can not make the solid particulate of heterogeneity reach mixed uniformly on the yardstick of microcosmic, is a kind of more coarse simple mixed, and the compound degree of heterogeneity particulate is very low.Along with development of modern science and technology, new material new process emerges in an endless stream, and people have developed some new mixed methods again, to satisfy the needs of new material development.More representational is sol-gel method and liquid phase chemical coprecipitation method.These methods or the expensive chemical feedstocks of needs perhaps need complicated subsequent treatment process, as numerous and diverse desalination, dehydration etc., are not suitable for large batch of industrial production.And, bring difficulty with regard to the control of giving material property like this because different substances is different to the characteristic that gel transforms by colloidal sol, and the chemical coprecipitation characteristic of different substances is also different, and the composition of the composite particles that obtains and predefined composition have certain deviation.
In a word, still be necessary to seek a kind of method for preparing the solid composite particles efficient, that easily go at present.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing the solid composite particles efficient, that easily go.
Technical solution proposed by the invention is such:
A kind of method for preparing the solid composite particles the steps include:
(1) choose colloid that simplification compound particles dispersed that some kinds of solid matter contents determine forms or dispersion liquid as raw material in water, described colloid or dispersion liquid are that solid particulate that particle diameter is not more than 100nm is dispersed in and forms stable, dispersion system uniformly in the water;
(2) according to the chemical constitution of target composite particles with as the solid matter content of the colloid of raw material or dispersion liquid two kinds, some kinds of colloids or dispersion liquid more than three kinds or three kinds are mixed according to a certain percentage, and pH=2～11 of adjusting mixed dispersion liquid, form stable colloid mixture, mixed dispersion liquid or colloid and the mixture of dispersion liquid, the general designation mixed dispersion liquid;
(3) above-mentioned mixed dispersion liquid is packed into container low temperature resistant, anti-dilatational strain, place low temperature environment freezing, freeze to be ice shape solid up to integral body, should ice the shape solid then shifts out low temperature environment together with container and thaws, after treating to thaw fully, present solid-liquid separation effect in the container, the sedimental form of solid particulate that solid matter can be differentiated appearance profile with size at 0.1～3mm, naked eyes is deposited on the bottom of container, and container top is the clarifying water of water white transparency of separating out;
(4) above-mentioned solid particulate settling is leached, and take out after making the water stirring and washing, dry in moisture eliminator, just obtain by the mixed uniformly composite particles of nano particle different types of nano-solid granulometric composition, different.
Described colloid or the solid matter in the dispersion liquid as raw material comprises the metal oxide that is insoluble in water: silicon-dioxide (SiO
2), aluminium sesquioxide (Al
2O
3), titanium dioxide (TiO
2), ferric oxide (Fe
2O
3), Z 250 (Fe
3O
4), zirconium dioxide (ZrO
2), tindioxide (SnO
2).
Described colloid or the solid matter in the dispersion liquid as raw material can be metal simple-substance or the non-metal simple-substance that is insoluble in water: gold (Au), silver (Ag), palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir), ruthenium (Ru), carbon (C).
Described colloid or the solid matter in the dispersion liquid as raw material can be the metal carbonate that is insoluble in water: magnesiumcarbonate (MgCO
3), lime carbonate (CaCO
3), barium carbonate (BaCO
3), Strontium carbonate powder (SrCO
3).
Described colloid or the solid matter in the dispersion liquid as raw material can be the oxide compound of rare earth element.Described rare earth element is cerium (Ce), yttrium (Y), lanthanum (La), dysprosium (Dy), praseodymium (Pr), neodymium (Nd), europium (Eu), gadolinium (Gd), erbium (Er), ytterbium (Yb).
Described sulfide, selenide or the sulfoselenide that can be metallic element: Cadmium Sulfide (CdS), zinc sulphide (ZnS), lead sulfide (PbS), cadmium selenide (CdSe), cadmium sulfoselenide (CdSe as the colloid or the solid matter in the dispersion liquid of raw material
xS
1-x) (x=0.1～0.9).
In the present invention, the solid composite particles is meant the solid particulate of heterogeneity is realized uniform mixing and a kind of granular mixture of obtaining at the range scale of this particulate initial size.
The solid composite particles of the present invention in order to obtain to form by some kinds of different solid particulates, will choose some kinds earlier is distributed to by single solid particulate and forms in the water, definite colloid or the dispersion liquid of active constituent content (being solids content), according to the requirement of target solids composite particles composition some kinds of colloids or dispersion liquid are mixed according to a certain percentage then and form stable colloid miscellany, colloid-dispersion liquid miscellany, dispersion liquid-dispersion liquid miscellany, at last these miscellanys are frozen into ice shape solid at low temperature environment, thaw again, the bottom of container is the settled layer of solid particulate after thawing, the upper strata is a water, water is shifted out, granular deposit takes out further and handles, just can obtain the solid composite particles of dry state, the solid composite particles of this dry state has and the liquid same dispersing uniformity of single dispersion liquid, and dispersed uniform can realize at the range scale of primary particle.
Compare with traditional simple hybrid system of utilizing manpower or machinery, the present invention has following unusual effect:
(1) mixing of the inner heterogeneity of composite particles is very even.In the simple hybrid system, because the material particles before mixing is thicker, and there are various coacervates inevitably, and these coacervates can not reach to separate completely in simple mixing process and reunite and miniaturization, the final mixture that forms mixes degree very low (available AAABBBAABB represents that A, B represent two kinds of variable grains).And in the method for the invention, solid particulate miniaturization to ten nanometer or dozens of nanometer degree in the employed colloid, even reach below ten nanometers, and the granularity of stablizing the solid particulate in the non-setting dispersion liquid also at tens nanometer to 100 nanometer range, after some kinds of single colloids by heterogeneity or dispersion liquid mix, can in water carrier, realize ten homodisperse to the dozens of nanoscale.By freezing and course of defrosting; this dispersing uniformity is fixed and is kept in follow-up solid composite particles mixed powder; finally obtain the composite particles of dry state; its degree of scatter and traditional simple hybrid system are compared and are had great advantage (available ABABABABAB represents that A, B represent two kinds of variable grains).
(2) structure of solid composite particles is closely knit.Traditional simple hybrid system realizes that under the effect of intensive external force intensive external force effect more just can realize good more dispersion relatively.The mixed powder structure that obtains like this is fluffy, the tap density and the tap density of powder are lower, be unfavorable for that some tap densities to powder, tap density have the composite particles purposes of requirement, as the formation of high density ceramic base substrate, acquisition of the new energy materials of high-energy-density or the like.And in the present invention, through the composite particles settled layer that is deposited on container bottom after thawing is to form under cryogenic freezing and such low-energy state that thaws, single composite particles has than higher density, the mixed powder structure is closely knit, helps obtaining the new energy materials assembly of highdensity ceramic body and high-energy-density.
Compare with chemical coprecipitation with sol-gel method, method of the present invention has following unusual effect:
(1) applied widely.Sol-gel method be because raw material restriction can only be used to prepare the composite grain between limited several oxide compound, and method of the present invention is applicable to compound between nearly all solid particulate that is insoluble in water.So long as be insoluble in water, and can in water, disperse to form stable colloid or a kind of solid particulate of dispersion liquid, can utilize method realization uniform mixing of the present invention and prepare described composite particles with another or some kinds of solid particulates with similar performance.
Above-mentioned can be used for preparing the colloid of composite particles or particle that the diameter in the dispersion liquid is not more than 100nm can belong to following several chemical ingredients: metal oxide: silicon-dioxide (SiO
2), aluminium sesquioxide (Al
2O
3), titanium dioxide (TiO
2), ferric oxide (Fe
2O
3), Z 250 (Fe
3O
4), zirconium dioxide (ZrO
2), tindioxide (SnO
2); Metal or non-metal simple-substance gold (Au), silver (Ag), palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir), ruthenium (Ru), carbon (C); Metal carbonate: magnesiumcarbonate (MgCO
3), lime carbonate (CaCO
3), barium carbonate (BaCO
3), Strontium carbonate powder (SrCO
3); The oxide compound of rare-earth element cerium (Ce), yttrium (Y), lanthanum (La), dysprosium (Dy), praseodymium (Pr), neodymium (Nd), europium (Eu), gadolinium (Gd), erbium (Er), ytterbium (Yb); The sulfide of metallic element, selenide or sulfoselenide: Cadmium Sulfide (CdS), zinc sulphide (ZnS), lead sulfide (PbS), cadmium selenide (CdSe), cadmium sulfoselenide (CdSe
xS
1-x) (x=0.1～0.9).
(2) technology is simple.Sol-gel method and chemical coprecipitation use the organic compound or the inorganic salt of metal, as metal alkoxide, acetate, nitrate, vitriol or muriate or the like, after the reaction of the transformation of going through sol-gel or chemical coprecipitation is finished, also will be through washing, desalination, processes such as oven dry just obtain different components and reach mixed uniformly composite grain, because the pore quantity of gel inside is huge, size is little, and the solid particulate that chemical coprecipitation obtains is fine, throw out is cotton-shaped amorphous body, specific surface area is huge, and the washing of wherein wrapping up the by product salinity of carrying secretly is very difficult.And in the method for the present invention, hybrid dispersions almost completely separates with water through freezing and the deposition of solids layer that obtains that thaws, the deposition of solids layer is closely knit by structure, thick, the piece granular solids composite particles of naked eyes visible particle profile are formed, there are not parcel or entrapped moisture, dispersion agent and other water-soluble impurities are retained in the water, just can make deposition of solids layer and water sepn and obtain clean composite particles through simple solid-liquid separation and water washing process, the simple dry solid composite particles that a small amount of planar water just can obtain dry state of removing.
(3) easy control of components of composite particles.In sol-gel method and the chemical coprecipitation, because the sol-gel characteristic of different substances is different with the response characteristic in the chemical coprecipitation process, chemical constitution has deviation with predefined composition in the composite grain that causes obtaining on micro-scale.And in the method for the invention, the composition of composite particles and homogeneity formed in the liquid-phase mixing stage, were fixed and kept in freezing and the link of thawing, and the composition and the homogeneity of the composite particles that finally obtains are controlled easily.
(4) structure of composite particles is more closely knit.The composite grain structure that chemical coprecipitation obtains is fluffy, and the composite particles compact structure that method of the present invention obtains helps the use occasion of the high packing density of particle of some needs.
Embodiment
By the following examples the present invention is further elaborated.
Embodiment 1
Preparation TiO
2-SiO
2Composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 150gTiO again
2Content is 15%, average particulate diameter is the TiO of 10nm, pH=1.6
2Aqueous dispersions is poured aforementioned SiO into
2In the colloid, use magnetic stirrer 60min, obtain uniform white mixed dispersion liquid, the actual pH=2.3 that records this white mixed dispersion liquid.This white mixed dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, up to the icing ice shape solid that becomes white of integral body, then this white ice shape solid being shifted out refrigeration chamber together with plastic containers thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular white compact grain of particle profile and pile up the settled layer that forms, the water that accounts for solid-liquid cumulative volume about 80% on upper strata is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, adding water so repeatedly cleans four times, then lower floor's solid mixture is taken out in 105 ℃ of dryings 24 hours, just obtain TiO
2-SiO
2Composite particles.The method of present embodiment narration can be used for preparation equally and contain stannic oxide (SnO
2) the solid composite particles of nano particle.
Embodiment 2
Preparation SiO
2-Fe
2O
3Composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 120gFe
2O
3Content is 8%, particle diameter is the Fe of 5～15nm, pH=8.5
2O
3The water base colloid of sorrel is poured aforementioned SiO into
2In the colloid, use magnetic stirrer 60min, obtain uniform sorrel mixed dispersion liquid, the actual pH=7.9 that records this sorrel mixed dispersion liquid.This dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, freezing up to integral body becomes ice shape solid russet, then this sorrel ice shape solid being shifted out refrigeration chamber together with plastic containers thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular sorrel compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10mi n with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, then lower floor's solid mixture is taken out, just obtain SiO 105 ℃ of dryings 24 hours
2-Fe
2O
3Composite particles.
Embodiment 3
Preparation SiO
2-Fe
3O
4Composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 120gFe
3O
4Content is 12%, particle diameter is the Fe of 5～20nm, pH=8.5
3O
4The nearly water base colloid of black is poured aforementioned SiO into
2In the water base colloid, use magnetic stirrer 60min, obtain uniformly nearly black mixed dispersion liquid, the actual pH=7.9 that records this nearly black mixed dispersion liquid.This dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, freezing up to integral body becomes pullous ice shape solid, then should nearly black ice shape solid shifting out refrigeration chamber together with plastic containers thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular black compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, then lower floor's solid mixture is taken out, just obtain SiO 105 ℃ of dryings 24 hours
2-Fe
3O
4Composite particles.
Embodiment 4
Preparation SiO
2-Fe
3O
4-TiO
2Composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 120gFe
3O
4Content is 12%, particle diameter is the Fe of 5～20nm, pH=8.5
3O
4The nearly water base colloid of black is poured aforementioned SiO into
2In the water base colloid, stir 60min, obtain uniformly nearly black mixed dispersion liquid with magnetic stirrer.Get 150gTiO again
2Content is 15%, average particulate diameter is the white TiO of 10nm, pH=1.6
2Dispersion liquid is poured in the aforementioned colloid mixture, with magnetic stirring apparatus restir 60min, obtains uniformly nearly black dispersion liquid, the actual pH=2.4 that records this nearly black mixed dispersion liquid.This nearly black mixed dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, freezing up to integral body becomes pullous ice shape solid, then should nearly black ice shape solid shifting out refrigeration chamber together with plastic containers thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular black compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, lower floor's solid takes out 105 ℃ of dryings 24 hours, just obtains SiO
2-Fe
3O
4-TiO
2Composite particles.
Embodiment 5
Preparation SiO
2-Fe
2O
3-TiO
2Composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 120gFe
2O
3Content is 8%, particle diameter is the Fe of 5～15nm, pH=8.5
2O
3The water base colloid of sorrel is poured aforementioned SiO into
2In the water base colloid, stir 60min, obtain uniform sorrel dispersion liquid with magnetic stirrer.Get 150gTiO again
2Content is 15%, average particulate diameter is the white TiO of 10nm, pH=1.6
2Aqueous dispersions is poured in the aforementioned colloid mixture, with magnetic stirring apparatus restir 60min, obtains uniform sorrel mixed dispersion liquid, the actual pH=2.4 that records this sorrel mixed dispersion liquid.This sorrel mixed dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, freezing up to integral body becomes ice shape solid russet, then this sorrel ice shape solid being shifted out refrigeration chamber together with plastic containers thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular sorrel compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, then lower floor's solid is taken out, just obtain SiO 105 ℃ of dryings 24 hours
2-Fe
2O
3-TiO
2Composite particles.
Embodiment 6
Preparation SiO
2-C composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get the 150g carbon content and be 6%, particle diameter is the black carbon Heisui River dispersion of 10～15nm, pH=5.5, pours aforementioned SiO into
2In the water base colloid, use magnetic stirrer 60min, obtain uniform black mixed dispersion liquid.Actual this black mixed dispersion liquid pH=6.5 that records.This black mixed dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, up to the icing ice shape solid that becomes black of integral body, then this black ice shape solid being shifted out refrigeration chamber together with plastic containers thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular black compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, then lower floor's solid is taken out, just obtain the SiO that outward appearance is black 105 ℃ of dryings 24 hours
2-C composite particles.
Embodiment 7
Preparation SiO
2-ZrO
2Composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 200gZrO
2Content is 20%, average particulate diameter is the ZrO of 50nm, pH=9.5
2The white aqueous dispersions is poured aforementioned SiO into
2In the water base colloid, use magnetic stirrer 60min, obtain white translucent mixed dispersion liquid uniformly.The actual pH=9.1 that records the translucent mixed dispersion liquid of this white.This dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, up to the icing ice shape solid that becomes white of integral body, should ice the shape solid then shifts out refrigeration chamber together with plastic containers and thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 40% by 0.1～2mm side-to-side dimensions, naked eyes can be differentiated the fine sand shape white compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, then lower floor's solid is taken out, just obtain SiO 105 ℃ of dryings 24 hours
2-ZrO
2Composite particles.
Embodiment 8
Preparation ZrO
2-TiO
2Composite particles.Get 100gZrO
2Content is 20%, average particulate diameter is the white translucent ZrO of 50nm, pH=9.5
2Aqueous dispersions, the capacity of putting into are the glass beaker of 2500ml.Get 2000gTiO
2Content is 20%, average particulate diameter is the white TiO of 10nm, pH=7
2Aqueous dispersions is poured aforementioned ZrO into
2In the aqueous dispersions, use magnetic stirrer 60min, obtain uniform white mixed dispersion liquid.The actual pH=8.5 that records this white mixed dispersion liquid.This white mixed dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, up to the icing ice shape solid that becomes white of integral body, should ice the shape solid then shifts out refrigeration chamber together with plastic containers and thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 50% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular white compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 50%, water is inclined to, lower floor's solid particle layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, then lower floor's solid is taken out, just obtain ZrO 105 ℃ of dryings 24 hours
2-TiO
2Composite particles.
Embodiment 9
Preparation SiO
2-Al
2O
3Composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=11.2
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 300gAl
2O
3Content is 20%, average particulate diameter is the Al of 30nm, pH=9.5
2O
3The white aqueous dispersions is poured aforementioned SiO into
2In the water base colloid, use magnetic stirrer 60min, obtain white translucent mixed dispersion liquid uniformly.The actual pH=11.0 that records this mixed dispersion liquid.This dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, up to the icing ice shape solid that becomes white of integral body, should ice the shape solid then shifts out refrigeration chamber together with plastic containers and thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 30% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular white compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 70%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, then lower floor's solid is taken out, just obtain SiO 105 ℃ of dryings 24 hours
2-Al
2O
3Composite particles.
Embodiment 10
Preparation SiO
2-Au composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 100gAu content and be 0.3%, the Au average particulate diameter is the red Au water base sol of 13nm, pH=3.5, pours aforementioned SiO into
2In the water base colloid, use magnetic stirrer 60min, obtain the transparent mixed dispersion liquid of uniform greenish orange redness.The actual pH=3.6 that records this mixed dispersion liquid.This dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, up to the icing ice shape solid that becomes greenish orange redness of integral body, should ice the shape solid then shifts out refrigeration chamber together with plastic containers and thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the greenish orange red compact grain of fine-grannular of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, then lower floor's solid is taken out 105 ℃ of dryings, just obtain SiO
2-Au composite particles.The described method of present embodiment can be used for preparation equally and contain the solid composite particles of other precious metal elements as the nano particle of the simple substance of silver (Ag), palladium (Pd), platinum (Pt), rhodium (Rh), iridium (Ir), ruthenium (Ru).
Embodiment 11
Preparation SiO
2-CdS composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 100gCdS content and be 2%, average particulate diameter is the yellow water base colloid of CdS of 10nm, pH=9.5, use polyphosphoric acid stable sodium, pours aforementioned SiO into
2In the water base colloid, use magnetic stirrer 60min, obtain faint yellow translucent mixed dispersion liquid uniformly.The actual pH=8.7 that records this mixed dispersion liquid.This dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, freezing up to integral body becomes flaxen ice shape solid, should ice the shape solid then shifts out refrigeration chamber together with plastic containers and thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the faint yellow compact grain of fine-grannular of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, lower floor's solid is taken out 105 ℃ of dryings, just obtain SiO
2-CdS composite particles.The described method of present embodiment is equally applicable to prepare contain with CdS has sulfide, selenide or the sulfoselenide of similar performance such as zinc sulphide (ZnS), lead sulfide (PbS), cadmium selenide (CdSe), cadmium sulfoselenide (CdSe
xS
1-x) the solid composite particles of nano particle.
Embodiment 12
Preparation SiO
2-Al
2O
3-MgCO
3Composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 5000ml.Get 1018.4gAl
2O
3Content is 20%, average particulate diameter is the Al of 30nm, pH=9.5
2O
3The white aqueous dispersions is poured above-mentioned SiO into
2In the water base colloid, use magnetic stirrer 60min, obtain uniform and stable white mixed dispersion liquid.Get 841.14gMgCO again
3Content is 20%, average particulate diameter is the MgCO of 20nm, pH=9
3Aqueous dispersions adds in the above-mentioned white mixed dispersion liquid, uses magnetic stirrer 60min again, obtains linen mixed dispersion liquid.Record the pH=9.3 of this mixed dispersion liquid.This canescence mixed dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, freezing up to integral body becomes linen ice shape solid, then this canescence ice shape solid being shifted out refrigeration chamber together with plastic containers thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 40% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular canescence compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 60%, water is inclined to, lower floor's solid particle layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, lower floor's solid is taken out 105 ℃ of dryings, just obtain SiO
2-Al
2O
3-MgCO
3Composite particles.The method that present embodiment is narrated also can be used for preparation and contains lime carbonate (CaCO
3), barium carbonate (BaCO
3), Strontium carbonate powder (SrCO
3) the solid composite particles of nano particle.
Embodiment 13
Preparation SiO
2-CeO
2Composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 80gCeO
2Content is 20%, average particulate diameter is the CeO of 30nm, pH=9
2Yellow aqueous dispersions is poured aforementioned SiO into
2In the water base colloid, use magnetic stirrer 60min, obtain uniform faint yellow mixed dispersion liquid, record the pH=8.3 of this mixed dispersion liquid.This dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, freezing up to integral body becomes flaxen ice shape solid, should ice the shape solid then shifts out refrigeration chamber together with plastic containers and thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the yellow compact grain of fine-grannular of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, lower floor's solid is taken out 105 ℃ of dryings, just obtain TiO
2-CeO
2Composite particles.The described method of present embodiment also is applicable to the solid composite particles of the nano particle of the oxide compound that contains rare earth element yttrium (Y), lanthanum (La), dysprosium (Dy), praseodymium (Pr), neodymium (Nd), europium (Eu), gadolinium (Gd), erbium (Er), ytterbium (Yb).
Embodiment 14
Preparation SiO
2-Fe
3O
4-TiO
2-C composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 120gFe
3O
4Content is 12%, particle diameter is the Fe of 5～20nm, pH=8.5
3O
4The nearly water base colloid of black is poured aforementioned SiO into
2In the water base colloid, stir 60min, obtain uniformly nearly black dispersion liquid with magnetic stirrer.Get 150gTiO again
2Content is 15%, average particulate diameter is the white TiO of 10nm, pH=1.6
2Dispersion liquid is poured in the aforementioned colloid mixture, with magnetic stirring apparatus restir 60min, obtains uniformly nearly black dispersion liquid.Get the 80g carbon content at last and be 6%, particle diameter is the black carbon Heisui River dispersion of 10～15nm, pH=5.5, pours in the aforementioned nearly black dispersion liquid, uses magnetic stirrer 60min, obtains uniform black mixed dispersion liquid.Record the pH=2.0 of this black mixed dispersion liquid.This black mixed dispersion liquid that finally obtains is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, up to the icing ice shape solid that becomes black of integral body, then this black ice shape solid being shifted out refrigeration chamber together with plastic containers thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular black compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, lower floor's solid is taken out 105 ℃ of dryings 24 hours, just obtain SiO
2-Fe
3O
4-TiO
2-C composite particles.
Embodiment 15
Preparation SiO
2-Fe
2O
3-TiO
2-C-CeO
2Composite particles.Get 1000gSiO
2Content is 30%, particle diameter is the transparent SiO of 8～20nm, pH=7.3
2Water base colloid, the capacity of putting into are the glass beaker of 2500ml.Get 120gFe
2O
3Content is 8%, particle diameter is the Fe of 5～15nm, pH=8.5
2O
3The water base colloid of sorrel is poured aforementioned SiO into
2In the water base colloid, stir 60min, obtain uniform sorrel dispersion liquid with magnetic stirrer.Get 150gTiO again
2Content is 15%, average particulate diameter is the white TiO of 10nm, pH=1.6
2Aqueous dispersions is poured in the aforementioned colloid mixture, with magnetic stirring apparatus restir 60min, obtains uniform sorrel dispersion liquid.Get the 60g carbon content again and be 6%, particle diameter is the black carbon Heisui River dispersion of 10～15nm, pH=5.5, pours in the aforementioned sorrel dispersion liquid, uses magnetic stirrer 60min, obtains uniform black mixed dispersion liquid.Get 10gCeO at last
2Content is 20%, the CeO of average particulate diameter 30nm, pH=9
2Yellow aqueous dispersions is poured in the above-mentioned black dispersion liquid, uses magnetic stirrer 60min, obtains uniform black dispersion liquid.Record the pH=2.3 of this black mixed dispersion liquid.This black dispersion liquid is poured in the plastic containers, it is freezing to put into freezer compartment of refrigerator, up to the icing ice shape solid that becomes black of integral body, then this black ice shape solid being shifted out refrigeration chamber together with plastic containers thaws naturally, thaw finish after, container bottom be one deck account for solid-liquid cumulative volume about 20% by the 1mm side-to-side dimensions, naked eyes can be differentiated the fine-grannular black compact grain of particle profile and pile up the settled layer that forms, the upper strata is the clarifying water of water white transparency that accounts for solid-liquid cumulative volume about 80%, water is inclined to, lower floor's granular layer adds 1000ml water, stirring 10min with mechanical stirrer cleans, the water on upper strata is inclined to, add water so repeatedly and clean four times, lower floor's solid is taken out 105 ℃ of dryings 24 hours, just obtain SiO
2-Fe
2O
3-TiO
2-C-CeO
2Composite particles.
Claims (11)
1. method for preparing the solid composite particles, it is characterized in that: this preparation method's step is:
(1) choose colloid that simplification compound particles dispersed that some kinds of solid matter contents determine forms or dispersion liquid as raw material in water, described colloid or dispersion liquid are that solid particulate that particle diameter is not more than 100nm is dispersed in and forms stable, dispersion system uniformly in the water;
(2) according to the chemical constitution of target composite particles with as the solid matter content of the colloid of raw material or dispersion liquid two kinds, some kinds of colloids or dispersion liquid more than three kinds or three kinds are mixed according to a certain percentage, and pH=2～11 of adjusting mixed dispersion liquid, form stable colloid mixture, mixed dispersion liquid or colloid and the mixture of dispersion liquid, the general designation mixed dispersion liquid;
(3) above-mentioned mixed dispersion liquid is packed into container low temperature resistant, anti-dilatational strain, place low temperature environment freezing, freeze to be ice shape solid up to integral body, should ice the shape solid then shifts out low temperature environment together with container and thaws, after treating to thaw fully, present solid-liquid separation effect in the container, the sedimental form of solid particulate that solid matter can be differentiated appearance profile with size at 0.1～3mm, naked eyes is deposited on the bottom of container, and container top is the clarifying water of water white transparency of separating out;
(4) above-mentioned solid particulate settling is leached, and take out after making the water stirring and washing, dry in moisture eliminator, just obtain by the mixed uniformly composite particles of nano particle different types of nano-solid granulometric composition, different.
2. the method for preparing the solid composite particles according to claim 1 is characterized in that: described colloid or the solid matter in the dispersion liquid as raw material can be the metal oxide that is insoluble in water.
3. according to the method for preparing the solid composite particles described in the claim 2, it is characterized in that: the described metal oxide that is insoluble in water is silicon-dioxide, aluminium sesquioxide, titanium dioxide, ferric oxide, Z 250, zirconium dioxide, tindioxide.
4. the method for preparing the solid composite particles according to claim 1 is characterized in that: described colloid or the solid matter in the dispersion liquid as raw material can be metal simple-substance or the non-metal simple-substance that is insoluble in water.
5. the method for preparing the solid composite particles according to claim 4 is characterized in that: described metal simple-substance and the non-metal simple-substance that is insoluble in water is gold and silver, palladium, platinum, rhodium, iridium, ruthenium, carbon.
6. the method for preparing the solid composite particles according to claim 1 is characterized in that: described colloid or the solid matter in the dispersion liquid as raw material can be the metal carbonate that is insoluble in water.
7. the method for preparing the solid composite particles according to claim 6 is characterized in that: the described metal carbonate that is insoluble in water is magnesiumcarbonate, lime carbonate, barium carbonate, Strontium carbonate powder.
8. the method for preparing the solid composite particles according to claim 1 is characterized in that: described colloid or the solid matter in the dispersion liquid as raw material can be the oxide compound of rare earth element.
9. the method for preparing the solid composite particles according to claim 8 is characterized in that: described rare earth element is cerium, yttrium, lanthanum, dysprosium, praseodymium, neodymium, europium, gadolinium, erbium, ytterbium.
10. the method for preparing the solid composite particles according to claim 1 is characterized in that: described sulfide, selenide or the sulfoselenide that can be metallic element as the colloid or the solid matter in the dispersion liquid of raw material.
11. the method for preparing the solid composite particles according to claim 10 is characterized in that: the sulfide of described metallic element, selenide or sulfoselenide are Cadmium Sulfide, zinc sulphide, lead sulfide, cadmium selenide, cadmium sulfoselenide.
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| CN104368369A (en) * | 2014-10-09 | 2015-02-25 | 济南大学 | Preparation method of silver phosphate-cadmium sulfide composite visible light photocatalyst |
| CN111504759A (en) * | 2020-04-24 | 2020-08-07 | 大庆油田有限责任公司 | Method and device for dissolving consolidated and deposited fine particles, control method and control device |
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Application publication date: 20110427 |