CN106270479A - A kind of attapulgite-nanometer silver composite inorganic powder and preparation method - Google Patents
A kind of attapulgite-nanometer silver composite inorganic powder and preparation method Download PDFInfo
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Abstract
The invention discloses a kind of attapulgite-nanometer silver composite inorganic powder and preparation method.In composite powder, silver is 10/100-100/100 with the mass ratio of attapulgite, and the particle diameter of nanometer silver is 3-100nm.Preparation method includes: attapulgite and water are mixed and made into attapulgite suspension by (1)；(2) silver nitrate is joined in the attapulgite suspension described in step (1), be then stirred heat treatment；(3) attapulgite suspension after step (2) processes is carried out spray drying and obtain attapulgite clay compounded powder；(4) the attapulgite clay compounded powder that step (3) prepares is carried out roasting, obtain the composite inorganic powder containing nanometer silver.Present invention process is simple, silver load capacity is big in composite powder and is firmly combined with attapulgite.
Description
Technical field
The present invention relates to composite inorganic powder field, say further, relate to a kind of with attapulgite for carrying
The composite inorganic powder containing nano silver particles of body and preparation method, this composite inorganic powder can add as antibacterial
Add agent to use.
Background technology
Due to silver have efficiently, safety, fungicidal spectrum are wide, thermostability, have no drug resistance and the advantage such as high selectivity,
For a long time, people begin to use silverware and utensil to carry out disinfection, and silver ion has high reaction activity,
The antibacterial characteristics of silver ion be generally attributed to it with mercaptan and carboxylate, phosphate, hydroxyl, imidazole radicals,
Indole, the interaction of amine disturb the normal physiological process of microorganism.But in most of actual application,
As antibacterial, silver ion is had certain limitation, and silver ion is easy to react with biological fluid and inactivate,
And antibacterial mechanisms requires certain density silver ion sustained release out；But these limitation can be passed through
Nano silver particles has been resolved.Along with emergence and the development of nanosecond science and technology, nanometer silver initially enters the day of people
Often life, has been widely used in health care and food hygiene field.
At medical field, such as anti-bacterial fibre and the antiseptic dressing of preparation, it is widely used in burn and scald, burns and plant
The aspects such as skin, nanometer silver stripping and slicing patch and adhesive bandage with nm silver fabric layer；The most antibacterial hands of antibacterial medical equipment facility of preparation
Art cutter, tweezers, conduit etc., reduce the probability of infection, and antibacterial apparatus is widely used.In life
Aspect, active carbon loading silver fiber applications is in the sterilization of drinking water, and it had both played NACF to Organic substance
Excellent absorption property, adds again the bacteriostasis and sterilization function of carbon fiber, promotes NACF at drink
With the extensive application in Water warfare.
So many researcheres are prepared nanometer silver and are used as antibacterial, the preparation of nano silver powder can be divided into thing
Reason method, chemical method and biological method.
Physical method generally includes spray pyrolysis and ion sputtering process, and the method directly can be from common simple substance
Silvery is for nano-Ag particles, and technique is simple, and purity is higher, but the highest to equipment requirements, the longest, raw
Produce cost the highest；Such as (micro-sized spherical silver powder prepared by spray pyrolysis and morphology control thereof, China such as Liu Zhihongs
Non-ferrous metal journal, the 1st phase of volume 17 in January, 2007) use spray pyrolysis to prepare argentum powder, only exist
Keeping time enough at higher than 600 DEG C, silver nitrate could completely thermally decompose and be converted into argent, and silver granuel
Footpath skewness, particle diameter is mostly at more than 500nm；It is similar to, (the Journal of Wuhan such as Zhang
University of Technology-Mater.Sci.Ed.Dec.2009) by control silver nitrate solution concentration,
Flow and the pressure of spray drying, under the furnace temperature of 720 DEG C, spray-wall interaction prepares mean diameter is 100nm
Nanometer silver.
Bioanalysis produces the catalyst mechanism of different enzyme by Institute of Micro-biology, carrys out reducing metal ion, prepares nanometer
Silver, but time-consuming long productivity is low, and particle diameter and the pattern of generation are wayward, and raw-material source is by greatly
Restriction.
Chemical method is the most popular method preparing nanometer silver at present, and it is mainly the most in the liquid phase, and it is suitable to use
Reducing agent such as boron hydride, hydrazine hydrate, sodium citrate, aminated compounds, glucose, ascorbic acid, double
Oxygen water, aldehyde compound etc. are by Ag+It is reduced into Ag0, the method that obtains nanometer silver by growth.This method prepares
Nanometer silver easily reunite, the most often need to add appropriate stabilizer such as polyvinylpyrrolidone (PVP), polyvinyl alcohol
(PVA), hydroxyethyl cellulose (HEC), dodecyl sodium sulfate, Polyethylene Glycol, polyacrylamide (PAM)
Etc. the reunion degree reducing Argent grain.
In order to improve antibacterial effect and the dispersibility of nanometer silver, generally by nano-silver loaded on different carriers,
Use as antibacterial additives.The carrier carrying silver is usually the inorganic mineral of meso-hole structure, including zeolite,
Galapectite, meerschaum, mesoporous silicon oxide, attapulgite etc..Wherein attapulgite is receiving of loose structure
Rice corpuscles, its main component is Paligorskite (attapulgite), be a kind of have chain layer structure containing Shuifu County's magnesium
Silicate clay mineral.Its framing structure is 3 D stereo shape, silicon-oxy tetrahedron and magnalium octahedron pass through
Shared summit is connected with each other and forms, and has and numerous is parallel to rod brilliant (needle-like, micro-bar-shaped or fibrous monocrystal)
The tubular nanometer level duct of direction arrangement, total is run through in duct, is equal in magnitude from Shang Kan duct, cross section
(about 0.38nm × 0.63nm) is cellular, belongs to natural monodimension nanometer material, have good absorption property and
Inexpensive, it is ideal carrier material, therefore causes the attention of scholar and research structure.As China is special
Profit CN1568703A is under conditions of surfactant and organic reducing agent exist, with attapulgite as carrier
Complex antimicrobials is formed with silver nitrate solution chemical reaction；It is similar to, Chinese patent CN1685830A, boiling
Stone powder body is immersed in silver nitrate solution so that silver ion fully adsorbs in the hole of zeolite, is then stirring
Adding hydrazine hydrate under conditions of mixing is nanometer silver silver ion reduction.
Carrying out outside the method reduced divided by directly utilizing reducing agent after above silver nitrate and carrier being mixed, China is specially
First fullerene surface is modified by profit CN103329893A with reducing agent etc., then makes modified richness
Strangle alkene and prepare fullerene loading nano silvery particle with silver nitrate reaction；Similar Chinese patent
First montmorillonite is modified by CN103461382A with sulfur-containing amino acid, then is exchanged silver ion by ion
It is supported on modified montmorillonoid interlayer, by ultraviolet irradiation, silver ion is changed into nanometer silver, obtain silver-carrying modified
Montmorillonite antibacterial agent.
Chemical reduction method prepares carrying silver antimicrobials, generally has high requirements the purity of carrier, surface nature etc.,
And also carrier solution is disperseed and regulates before adding silver nitrate solution the process of pH value.In order to subtract
Mutual reunion between few Nano silver grain, also to add considerable amount of surfactant in reduction process,
After also to fall the remaining reducing agent in the inside and surfactant by continuous eccentric cleaning, preparation process is complicated,
Manufacturing cycle is long, limits its large-scale production application.The content of nanometer silver of this type of method supported on carriers
The lowest, it is not fine for causing antibacterial antiplaque agent effect, the reducing agent remained in antibacterial and surfactant pair
Its application has a great impact.
Summary of the invention
For solving carrying silver antimicrobials produced problem in prior art, the invention provides a kind of attapulgite-receive
Rice silver composite inorganic powder and preparation method.The present inventor is found by great many of experiments, with cheap attapulgite
Soil and silver nitrate are raw material, it is not necessary to add any reducing agent, by the powder after spray-dried at 200-500 DEG C
The attapulgite clay compounded inorganic powder of the i.e. available described carrying nano silver of calcination process.Present invention process is simple,
Environmental protection.Avoid traditional attapulgite clay compounded inorganic powder preparing carrying nano silver to need first to attapulgite
Soil carries out pickling and adds chemical reducing agent in the silver nitrate suspension with attapulgite by silver nitrate reduction
For the complex process steps of elemental silver, and decrease environmental pollution.
An object of the present invention is to provide a kind of attapulgite-nanometer silver composite inorganic powder.
Wherein silver and the mass ratio of attapulgite are 10/100-100/100, preferred mass ratio for 30/100-80/100,
The particle size range of nanometer silver is 3-100nm.
Described attapulgite has in bar-shaped or filamentary structure and has the nanoscale duct of hollow, attapulgite
The brilliant diameter of rod of soil is between 30-80nm, and draw ratio is generally higher than 10；It is loaded with grain in attapulgite's surface
The nano-Ag particles of footpath 3-100nm, nano-Ag particles is spherical, and attapulgite with the mass ratio of nanometer silver is
10/100-100/100。
The two of the purpose of the present invention are to provide the preparation method of a kind of attapulgite-nanometer silver composite inorganic powder.
Including:
(1) attapulgite and water are hybridly prepared into attapulgite suspension；Described attapulgite is preferably heat
The attapulgite that activation and dispersion process, it is not necessary to acid treatment step.Described thermal activation treatment can use roasting side
Method, wherein, sintering temperature is preferably 200-450 DEG C, and roasting time is preferably 5-60min；Described attapulgite
In soil suspension, attapulgite soil mass concentration is less than 10%；The dispersion of described attapulgite processes and can adopt
Use conventional method of the prior art, such as: the dispersion of ultrasonic disperse, mechanical agitation is (such as ball milling dispersion, height
Speed dispersed with stirring etc.) etc..
(2) silver nitrate is joined in the attapulgite suspension described in step (1), be then stirred
Heat treatment；Described silver nitrate is 17/100-170/100 with the mass ratio of attapulgite, and preferred mass ratio is
50/100-135/100；Described heat treatment temperature is more than 50 DEG C, preferably 50-90 DEG C, during described heat treatment
Between be more than 1h.
(3) attapulgite suspension after step (2) processes is carried out spray drying and obtain attapulgite
Composite powder；The temperature of described spray drying is preferably 150-250 DEG C, more preferably 150-200 DEG C.
(4) the attapulgite clay compounded powder that step (3) prepares is carried out roasting, obtain answering containing nanometer silver
Close inorganic powder；Wherein, described roasting can be conventional method of roasting, such as by attapulgite clay compounded powder in
Muffle kiln roasting, described sintering temperature is 200-500 DEG C；The too high meeting of sintering temperature makes attapulgite duct collapse
Collapsing thus cause absorbability to be deteriorated, and be easily caused attapulgite reunion, temperature is too low, cannot be received
Rice silver simple substance.Described roasting time is more than 5min, preferably 5-180min；Described roasting back loading is recessed
The particle diameter of the nano silver particles on convex rod soil surface is 3-100nm.
Silver nitrate is stirred with attapulgite by the present invention at a certain temperature after mixing, need to pass through spray dried
Dry mode obtains treating the composite powder of roasting.Use other the side such as filtered and be dried by convection oven
Method, it is impossible to obtain and be spray-dried identical technique effect.It is not intended to be bound by theory, the present inventor
Think during the attapulgite clay compounded powder of nanometer silver of the preparation present invention, by attapulgite suspension and
Silver nitrate solution mixing is dissolved through heated and stirred, the carbanion that can promote in attapulgite in carbonate
And react generation Disilver carbonate absorption in attapulgite's surface with silver ion.In spray-drying process, unreacted
Silver nitrate solution and dispersed attapulgite in the solution can be further under the effect adding thermal current
React generation Disilver carbonate.Simultaneously because the flash drying effect of drying process with atomizing, unreacted nitric acid
Silver solution can be evenly distributed in attapulgite's surface the most in solid particulate form, substantially increases
The contact area of the two.Silver nitrate solid particle and attapulgite institute carbon containing during follow-up baking heat
Hydrochlorate also can react generation Disilver carbonate further, and Disilver carbonate can be decomposed into silver simple substance, finally to receive
The form of meter Yin is supported on attapulgite's surface equably.
The present invention, by attapulgite and silver nitrate solution being uniformly mixed, is then spray-dried,
Finally carry out roasting, prepare the attapulgite with attapulgite as carrier-nanometer silver composite inorganic powder.
The present invention specifically can be by the following technical solutions:
(1) attapulgite and water are mixed and made into attapulgite suspension；
(2) silver nitrate is joined in the attapulgite suspension described in step (1), be then stirred
Heat treatment；
(3) attapulgite suspension after step (2) processes is carried out spray drying and obtain attapulgite
Composite powder；
(4) attapulgite clay compounded powder step (3) prepared is in Muffle kiln roasting, obtains containing nanometer
The composite inorganic powder of silver；
Attapulgite described in step (1) is preferably thermal activation and the attapulgite of dispersion process, and described heat is lived
Change processes can use roasting method, and sintering temperature is 200-450 DEG C, roasting time 5-60min；Described concavo-convex
In rod soil suspension, the mass concentration of attapulgite is less than 10%；The decentralized approach of described attapulgite
Common method of the prior art can be used, such as: ultrasound wave dispersion, mechanical agitation are disperseed (such as ball milling
Dispersion, high-speed stirred dispersion etc.) etc..Described in step (2), silver nitrate with the mass ratio of attapulgite is
17/100-170/100；Described heat treatment temperature is 50-90 DEG C, described heat treatment time be 1h and more than.
The temperature being spray-dried described in step (3) is 150-250 DEG C, preferably 150-200 DEG C；
The described middle Muffle furnace sintering temperature of step (4) is 200-500 DEG C；Described roasting time is 5-180min；
Described roasting back loading is 3-100nm at the nano silver particles particle diameter of attapulgite's surface.
Compared with prior art, advantages of the present invention is embodied in:
Attapulgite is natural monodimension nanometer material, has the biggest specific surface area, absorption property and chemistry anti-
Answer the nano effects such as activity so that the nanometer silver formed after roasting can firmly adsorb in attapulgite's surface,
So form equally distributed nano level Argent grain in attapulgite's surface.Although by directly heating calcining
Method silver nitrate is decomposed can also obtain nanometer silver simple substance, but its decomposition temperature is high, energy consumption is high, system
Standby nano silver particles is susceptible to reunite, and particle diameter is bigger.By heated and stirred, then it is spray-dried and makes
Obtain contained carbonate inside silver nitrate and attapulgite fully to react, then less than under silver nitrate decomposition temperature
Roasting can be prepared by nanometer silver, not only avoid the environment using reducing agent or other chemical reactions to bring dirty
Dye, and the decomposition temperature of Disilver carbonate is relatively low, and roasting can generate silver simple substance at relatively low temperatures,
Silver simple substance adsorbs in attapulgite's surface uniformly with the form of nanometer silver, and this absorption is in attapulgite's surface
Nano silver active very big, can slowly release the silver ion with antibacterial effect, and nano-Ag particles
It is firmly combined with attapulgite.
Accompanying drawing explanation
The transmission electron microscope of the attapulgite-nanometer silver composite inorganic powder of Fig. 1: embodiment 10 preparation shines
Sheet.
The XRD spectra of the attapulgite-nanometer silver composite inorganic powder of Fig. 2: embodiment 10 preparation.
Detailed description of the invention
Below in conjunction with embodiment, further illustrate the present invention.
Raw materials used in embodiment being commercially available, in embodiment, attapulgite draw ratio used is more than 10, single
The diameter of rod crystalline substance is between 30-80nm.
The present invention is by using X-ray diffraction analysis (XRD) and transmission electron microscope (TEM) to institute
Attapulgite-nanometer silver composite inorganic the powder of preparation characterizes.
Attapulgite thermal activation and dispersion process as follows:
A certain amount of attapulgite is put in Muffle furnace, roasting 30min at 400 DEG C；By above-mentioned roasting
Attapulgite put in ball mill, ball milling 3h at 500 rpm；Weigh the attapulgite of a certain amount of above-mentioned process
Soil, adds and is configured to the suspension that attapulgite mass concentration is 5% after distilled water, first mechanical agitation 1h, then
Ultrasonic Treatment 30min；Then by the suspension handled well by centrifuge carry out under 12000r/min from
The heart；Finally discard the supernatant, obtain thermal activation and the attapulgite of dispersion process.
Embodiment 1
Weigh a certain amount of attapulgite (AT) processed through thermal activation and dispersion, be configured to attapulgite quality dense
Degree is the water slurry of 1%, then by silver nitrate solution (AgNO3/ AT=17/100) be added to attapulgite hang
In supernatant liquid, at 50 DEG C, magnetic agitation 1h, then attapulgite suspension is carried out at 200 DEG C spray dried
Dry, collect spray-dried prepared composite powder, finally by the composite powder that obtains in Muffle furnace at 500 DEG C
Lower roasting 30min, obtains attapulgite-nanometer silver composite inorganic powder.
The composite powder prepared after above-mentioned spray-dried prepared composite powder and roasting is carried out X respectively penetrate
Line diffraction (XRD) characterizes, and result is listed in table 1, and the particle size range of nanometer silver is 3-100nm.
Embodiment 2
In addition to after silver nitrate solution and attapulgite suspension being mixed, the temperature of magnetic agitation is adjusted to 70 DEG C,
Other processing step is same as in Example 1, and characterization result is listed in table 1, and the particle size range of nanometer silver is 3-100nm.
Embodiment 3
In addition to after silver nitrate solution and attapulgite suspension being mixed, the temperature of magnetic agitation is adjusted to 90 DEG C,
Other processing step is the most same as in Example 1 with characterizing method, and characterization result is listed in table 1, the particle diameter of nanometer silver
Scope is 3-100nm.
Comparative example 1
In addition to after silver nitrate solution and attapulgite suspension being mixed, the temperature of magnetic agitation is adjusted to room temperature,
Other processing step is the most same as in Example 1 with characterizing method, and characterization result is listed in table 1.
Composite powder and the composite powder characterization result of comparative example 1 preparation prepared by embodiment 1-3 are listed in table 1.
Table 1
From table 1 it follows that attapulgite suspension mixes with silver nitrate solution only higher than room temperature
Under the conditions of carry out, just can prepare the composite powder containing simple-substance nano silvery.
Embodiment 4
Weigh a certain amount of attapulgite processed through thermal activation and dispersion, add distilled water and be configured to attapulgite
Mass concentration is the suspension of 10%, then silver nitrate solution (AgNO3/ AT=170/100) be added to concavo-convex
In rod soil suspension, at 60 DEG C, stir 1h, then attapulgite suspension is carried out spray dried in 150 DEG C
Dry, collect spray-dried prepared composite powder, finally by the composite powder that obtains in 200 DEG C of roasting 10min,
Obtain attapulgite-nanometer silver composite inorganic powder.
The composite powder prepared after above-mentioned spray-dried prepared composite powder and roasting is carried out X-respectively penetrate
Line diffraction (XRD) characterizes, and result is listed in table 2, and the particle size range of nanometer silver is 3-100nm.
Embodiment 5
In addition to after silver nitrate solution and attapulgite suspension being mixed, the time of magnetic agitation is adjusted to 2h, its
Its processing step is the most the same as in Example 4 with characterizing method, and characterization result is listed in table 2, the particle diameter model of nanometer silver
Enclose for 3-100nm.
Comparative example 2
Except by after silver nitrate solution and attapulgite suspension mix homogeneously without heating magnetic agitation, directly
Outside spray drying, other processing step is the most the same as in Example 4 with characterizing method, and characterization result is listed in table 2.
Comparative example 3
In addition to after silver nitrate solution and attapulgite suspension being mixed, the time of magnetic agitation is adjusted to 30min,
Other processing step is the most the same as in Example 4 with characterizing method, and characterization result is listed in table 2.
Composite powder characterization result prepared by embodiment 4-5 and comparative example 2-3 is listed in table 2.
Table 2
From Table 2, it can be seen that in the case of other conditions are identical, mixing time can ensure that more than 1h
Finally prepare the composite powder containing nanometer silver.
Embodiment 6
Weigh a certain amount of attapulgite processed through thermal activation and dispersion, after adding distilled water, be configured to attapulgite
Soil mass concentration is the suspension of 5%, then silver nitrate solution (AgNO3/ AT=135/100) be added to concavo-convex
In rod soil suspension, at 90 DEG C, magnetic agitation 3h, then attapulgite suspension is sprayed in 170 DEG C
Mist is dried, and collects spray-dried prepared composite powder, finally by the composite powder that obtains in 200 DEG C of roastings
15min, obtains attapulgite-nanometer silver composite inorganic powder.
The composite powder prepared after above-mentioned spray-dried prepared composite powder and roasting is carried out X-respectively penetrate
Line diffraction (XRD) characterizes, and result is listed in table 3, and the particle size range of nanometer silver is 3-100nm.
Embodiment 7
In addition to after being spray-dried, the sintering temperature of powder is adjusted to 300 DEG C, other processing step and embodiment 6
Identical；Characterizing method is same as in Example 1, and result is listed in table 3, and the particle size range of nanometer silver is 3-100nm.
Embodiment 8
In addition to after being spray-dried, the sintering temperature of powder is adjusted to 400 DEG C, other processing step and embodiment 6
Identical；Characterizing method is same as in Example 1, and result is listed in table 3, and the particle size range of nanometer silver is 3-100nm.
Embodiment 9
In addition to after being spray-dried, the sintering temperature of powder is adjusted to 500 DEG C, other processing step and embodiment 6
Identical, characterization result is listed in table 3；Characterizing method is same as in Example 1, and result is listed in table 3, nanometer silver
Particle size range is 3-100nm.
Comparative example 4
In addition to after being spray-dried, the sintering temperature of powder is adjusted to 150 DEG C, other processing step and embodiment 6
Identical；Characterizing method is same as in Example 1, and result is listed in table 3.
Composite inorganic Powder characterization result prepared by embodiment 6-8 and comparative example 4 is listed in table 3.
Table 3
From table 3 it is observed that in the case of other conditions are identical, sintering temperature just reaches more than 200 DEG C
The nanometer silver composite powder of the present invention can be prepared.
Embodiment 10
Weigh a certain amount of attapulgite processed through thermal activation and dispersion, after adding distilled water, be configured to attapulgite
Soil mass concentration is the suspension of 3%, then silver nitrate solution (AgNO3/ AT=50/100) be added to concavo-convex
In rod soil suspension, at 70 DEG C, magnetic agitation 2h, then attapulgite suspension is carried out at 170 DEG C
It is spray-dried, collects the composite powder after being spray-dried, finally by the composite powder that obtains at 350 DEG C
Roasting 5min, obtains attapulgite-nanometer silver composite inorganic powder.
The composite powder prepared after above-mentioned spray-dried prepared composite powder and roasting is carried out transmission respectively
Ultramicroscope (TEM) characterizes (as shown in Figure 1) and X-ray diffraction (XRD) characterizes (such as Fig. 2
Shown in), result is listed in table 4, and the particle size range of nanometer silver is 3-100nm.
Embodiment 11
In addition to the roasting time of spray-dried rear powder is adjusted to 20min, other processing step and sign
Method is the most same as in Example 10, and characterization result is listed in table 4, and the particle size range of nanometer silver is 3-100nm.
Embodiment 12
In addition to the roasting time of spray-dried rear powder is adjusted to 60min, other processing step and sign
Method is the most same as in Example 10, and characterization result is listed in table 4, and the particle size range of nanometer silver is 3-100nm.
Embodiment 13
In addition to the roasting time of spray-dried rear powder is adjusted to 180min, other processing step and sign
Method is the most same as in Example 10, and characterization result is listed in table 4, and the particle size range of nanometer silver is 3-100nm.
Comparative example 5
In addition to the roasting time of spray-dried rear powder is adjusted to 2min, other processing step and sign side
Method is the most same as in Example 10, and characterization result is listed in table 4.
Composite powder characterization result prepared by embodiment 10-13 and comparative example 5 is listed in table 4.
Table 4
As can be seen from Table 4, roasting time i.e. can get the nanometer silver composite powder of the present invention more than 5min.
Embodiment 14
In addition to silver nitrate and attapulgite mass ratio are adjusted to 135:100, other processing step and sign side
Method is the most same as in Example 1, and characterization result is listed in table 5, and the particle size range of nanometer silver is 3-100nm.
Comparative example 6
Weigh a certain amount of attapulgite processed through thermal activation and dispersion, after adding distilled water, be configured to attapulgite
Soil mass concentration is the suspension of 1%, then certain density hydrochloric acid solution is joined above-mentioned attapulgite and hangs
In supernatant liquid, room temperature magnetic agitation 1h, it is ensured that carbonate contained inside attapulgite is complete by hydrochloric acid reaction,
Dense by attapulgite being configured to quality after the attapulgite deionized water eccentric cleaning after above-mentioned HCl treatment
Degree is the suspension of 1%, then by silver nitrate (AgNO3/ AT=17/100) solution is added drop-wise to attapulgite solution
In, at 50 DEG C, magnetic agitation 1h, then attapulgite suspension is spray-dried at 200 DEG C,
Collect the composite powder after being spray-dried, the composite powder roasting 30min at 500 DEG C that finally will obtain.
The composite powder prepared after above-mentioned spray-dried prepared composite powder and roasting is carried out X-respectively penetrate
Line diffraction (XRD) characterizes, and result is listed in table 5.
Comparative example 7
In addition to the sintering temperature of spray-dried rear powder is adjusted to 300 DEG C, other processing step and sign side
Method is all identical with comparative example 6, and characterization result is listed in table 5.
Composite powder characterization result prepared by embodiment 14 and comparative example 6-7 is listed in table 5.
Table 5
As can be seen from Table 5, if the attapulgite in the present invention to be carried out traditional thermal activation, dispersion
And pickling processes, it will changing the chemical composition of attapulgite, causing cannot be by the preparation method of the present invention
Prepare nanometer silver composite powder.
Embodiment 15
Weigh a certain amount of attapulgite processed through thermal activation and dispersion, after adding distilled water, be configured to attapulgite
Soil mass concentration is the suspension of 5%, then silver nitrate solution (AgNO3/ AT=135/100) be added to concavo-convex
In rod soil suspension, at 90 DEG C, magnetic agitation 3h, then attapulgite suspension is carried out at 170 DEG C
It is spray-dried, collects the composite powder after being spray-dried, finally by the composite powder that obtains at 500 DEG C
Roasting 30min.
The composite powder prepared after above-mentioned spray-dried prepared composite powder and roasting is carried out X-respectively penetrate
Line diffraction (XRD) characterizes, and result is listed in table 6, and the particle size range of nanometer silver is 3-100nm.
Comparative example 8
Except directly carrying out roasting after the attapulgite suspension after magnetic agitation being dried in the baking oven of 80 DEG C
Outward, other processing step is all identical with embodiment 15 with characterizing method, and characterization result is listed in table 6.
Comparative example 9
Except directly roasting after the attapulgite suspension after magnetic agitation is dried in the baking oven of 170 DEG C
Outside burning, other processing step is all identical with embodiment 15 with characterizing method, and characterization result is listed in table 6.
Composite powder acquired results prepared by embodiment 15 and comparative example 8-9 is listed in table 6.
Table 6
As can be seen from Table 6, without spray drying, and directly dried in an oven for mixed solution,
Preparing possibly together with substantial amounts of unconverted silver nitrate component in nanometer silver composite powder, silver nitrate is soluble in
Water, is difficult in the application be attached together with attapulgite, easily runs off, thus affects final application effect
Really.Therefore, the drying process with atomizing in the preparation method of the present invention is combined for finally preparing nanometer silver
Powder it is critical that.
Claims (9)
1. attapulgite-nanometer silver composite inorganic powder, it is characterised in that:
Silver is 10/100-100/100 with the mass ratio of attapulgite, and the particle size range of nanometer silver is 3-100nm.
2. attapulgite-nanometer silver composite inorganic powder as claimed in claim 1, it is characterised in that: silver with
The mass ratio of attapulgite is 30/100-80/100.
3. the preparation method of attapulgite-nanometer silver composite inorganic powder, it is characterised in that described method
Including:
(1) attapulgite and water are mixed and made into attapulgite suspension；Described attapulgite suspension concave
The mass concentration of convex rod soil is less than 10%；
(2) silver nitrate is joined in the attapulgite suspension described in step (1), be then stirred
Heat treatment；Described silver nitrate is 17/100-170/100 with the mass ratio of attapulgite；Described heat treatment temperature is
More than 50 DEG C, described heat treatment time is more than 1h；
(3) attapulgite suspension after step (2) processes is carried out spray drying and obtain attapulgite
Composite powder；
(4) the attapulgite clay compounded powder that step (3) prepares is carried out roasting, obtain answering containing nanometer silver
Close inorganic powder；Wherein, sintering temperature is 200-500 DEG C, and roasting time is more than 5min；Described roasting
Back loading is 3-100nm at the particle diameter of the nano silver particles of attapulgite's surface.
4. the preparation method of attapulgite-nanometer silver composite inorganic powder as claimed in claim 3, its feature
Being: in step (2), described silver nitrate is 50/100-135/100 with the mass ratio of attapulgite.
5. the preparation method of the attapulgite as described in claim 3 or 4-nanometer silver composite inorganic powder, its
Being characterised by: in step (1), described attapulgite is the attapulgite processed through thermal activation and dispersion.
6. the preparation method of attapulgite-nanometer silver composite inorganic powder as claimed in claim 5, its feature
Being: in step (1), described thermal activation uses method of roasting, and wherein, sintering temperature is 200-450 DEG C,
Roasting time is 5-60min.
7. the preparation method of the attapulgite as described in claim 3 or 4-nanometer silver composite inorganic powder, its
It is characterised by: described heat treatment temperature is 50-90 DEG C.
8. the preparation method of the attapulgite as described in claim 3 or 4-nanometer silver composite inorganic powder, its
It is characterised by:
The temperature of described spray drying is 150-250 DEG C.
9. the preparation method of the attapulgite as described in claim 3 or 4-nanometer silver composite inorganic powder, its
It is characterised by:
The roasting time of described step (4) is 5-180min.
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