CN101200553A - Slver particles/polyvinyl alcohol composite as well as preparation method and uses thereof - Google Patents
Slver particles/polyvinyl alcohol composite as well as preparation method and uses thereof Download PDFInfo
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Abstract
The present invention pertains to the art of nano material preparation technology, in particular to a silver-nano particle/polyevinyl alcohol composite membrane as well as the preparation method and the purpose. The present invention takes polyevinyl alcohol and silver nitrate as reactants without any reducing agent, carries out rapid heating under the temperature of 110 to 250 DEG C and controls the mol ratio of silver nitrate/ polyevinyl alcohol, so as to obtain silver-nano particles of different granular diameter. The present invention has no need of reducing agent, simple preparation process, low cost and mild reaction conditions. The silver-nano particle/polyevinyl alcohol composite membrane provided by the present invention has the advantages of good transparency, large spectral absorption, indissolubility in water and excellent antiseptic activity, which can be used as antiseptic coating layer, slow-release antiseptic membrane, construction paint, special packaging material, filter plate, diffuser, etc.
Description
Technical field
The invention belongs to the nano material preparation technical field, particularly a kind of Nano silver grain/polyvinyl alcohol compound film and its production and use.
Background technology
Owing to have special chemistry and physical properties, polyvinyl alcohol has been subjected to people's attention always since finding, and at industrial widespread use (the K.A.M.Abd El-Kader that obtained, S.F.AbdelHamied.Journal of Applied Polymer Science, 2002,86,1219～1226).Soluble in water, the good biocompatibility of polyvinyl alcohol is easy to moulding and has the very high transparency, so be well suited for doing polymeric film material.The optical application of polyvinyl alcohol film mainly is its filterability to light and image, can be used as (P.K.Khanna such as contact lense, medicament slow release system and artificial skin at medical field in addition, Narendra Singh, Shobhit Charan, V.V.V.S.Subbarao, R.Gokhale, U.P.MulikMater.Chem.and Phys.93,2005,117～12).A long time ago, people just recognize anti-microbial effect (the Qifeng Wang of silver and silver salt, Huijun Yu, Ling Zhong, Junqiu Liu, Junqi Sun, andJiacong Shen.Chem.Mater.2006,18,1988～1994), the someone proposes reduce the toxicity of silver ions, the flowability in film and reduces its absorption (Haijun Yu on wound recently, XiaoyiXu, Xuesi Chen, Tiancheng Lu, Peibiao Zhang, Xiabin Jing.J.Appl.Polym.Sci., 103,2007,125～133).And Nano silver grain is compared with silver ions, and toxicity is littler, and biocompatibility is also better.
The common synthetic method of Nano silver grain has chemical reduction method, uv irradiating method, microwave exposure method, adds the gentle phase sedimentation of hot reducing method etc.Add hot reducing method and generally finish reaction under the mild conditions between 90～200 degrees centigrade.This method is dissolved in the water Silver Nitrate, with reductibility mixed with polymers such as polyvinyl alcohol, starch, and after stirring, film forming or transfer in other reaction vessel, control certain reaction temperature and time.Porel etc. (Shatabdi Porel, Shashi Singh, S.Sree Harsha, D.NarayanaRao, and T.P.Radhakrishnan.Chem.Mater.2005,17,9～12) for example.But in the ordinary course of things, polyvinyl alcohol film or fibre product can be water-soluble again, limited its application in some aspects.To add thermal reduction and carry out more than 150 degrees centigrade, silver ions is reduced by polyvinyl alcohol on the one hand, and on the other hand, polyvinyl alcohol can become water insoluble by physical crosslinking in this process.
Summary of the invention
One of purpose of the present invention provides a kind of method of in-situ preparing Nano silver grain/polyvinyl alcohol compound film, and this preparation method's technology is simple, cost is low.
Two of purpose of the present invention provides the spectrum property of Nano silver grain/polyvinyl alcohol compound film and this laminated film.
Three of purpose of the present invention provides the purposes of Nano silver grain/polyvinyl alcohol compound film.
The present invention provides the novel method of simple, the with low cost preparation Nano silver grain/polyvinyl alcohol compound film of a kind of method.Silver Nitrate and polyvinyl alcohol with cheapness are reactant, need not add reductive agent, 110～190 degrees centigrade of rapid heating, by the mol ratio of control Silver Nitrate/polyvinyl alcohol, can obtain the Nano silver grain of different-grain diameter.Through the prepared Nano silver grain/polyvinyl alcohol compound film of test, its smooth surface, thickness is 200～500 nanometers, has the higher transparency, bigger spectral absorption and good antimicrobial property especially show excellent anti-microbial property to intestinal bacteria.
The preparation method of Nano silver grain/polyvinyl alcohol compound film of the present invention may further comprise the steps:
(1). at room temperature get polyvinyl alcohol and be dissolved in the distilled water, heat and stir at 70～100 degrees centigrade and dissolved fully until polyvinyl alcohol in 15～30 minutes;
(2). silver nitrate solution is joined in the polyvinyl alcohol solution that step (1) obtains, and wherein, the molar ratio of Silver Nitrate and polyvinyl alcohol is 1/100～1/10, mixes with magnetic agitation;
(3). get step (2) and obtain mixing solutions and drip on the glass substrate and film, obtain Silver Nitrate/PVA (PVOH) FILM;
(4). Silver Nitrate/PVA (PVOH) FILM that step (3) is obtained heated 3～10 minutes at 110～250 degrees centigrade, can obtain light yellow transparent Nano silver grain/polyvinyl alcohol compound film.
In the mixed solution of Silver Nitrate and polyvinyl alcohol, can change the thickness of laminated film by the concentration that changes polyvinyl alcohol.
Described silver nitrate solution is joined in the polyvinyl alcohol solution is dropwise to add silver nitrate solution.
Described Silver Nitrate purity is not less than 99.8%.
Described polyvinyl alcohol molecular-weight average is 70000～100000, and alcoholysis degree is 70～90%.
The thickness of the smooth surface that is obtained by the inventive method, transparent Nano silver grain/polyvinyl alcohol compound film is 200～500 nanometers, and the particle diameter of Nano silver grain is 5～20 nanometers in the laminated film; Silver Nitrate/PVA (PVOH) FILM among the present invention is under 110～250 degrees centigrade, Silver Nitrate content in the high more and/or Silver Nitrate/PVA (PVOH) FILM of Heating temperature is big more, the ultraviolet-visible optical absorption intensity of the Nano silver grain/polyvinyl alcohol compound film that obtains is big more, and this moment, the transparency of film was good; At silver nitrate concentration is 100mmol/L, and the spectral absorption of the Nano silver grain/polyvinyl alcohol compound film that is obtained by Silver Nitrate/PVA (PVOH) FILM when Heating temperature is 190～250 degrees centigrade is greater than 2.0.It is water insoluble that this Silver Nitrate/PVA (PVOH) FILM is heated to the Nano silver grain/polyvinyl alcohol compound film that obtains more than 150 degrees centigrade.By improving silver nitrate concentration, the color of laminated film is deepened gradually.
Nano silver grain/polyvinyl alcohol compound film of the present invention can be as antimicrobial coating; And as the slowly-releasing antibacterial film, building coating, the extra package material also can be used as spectral filter, light polarizing film etc.This Nano silver grain/polyvinyl alcohol compound film has higher anti-microbial activity to intestinal bacteria.
Nano silver grain provided by the invention/polyvinyl alcohol compound film preparation methods and mechanism: get polyvinyl alcohol and mix with distilled water, heated and stirred, purpose are to make polyvinyl alcohol dissolve and form the solution of homogeneous fully.Dropwise add silver nitrate solution then, purpose is to make the Silver Nitrate can uniform distribution in solution, and it is too high to be unlikely to partial concn.The mixing solutions of Silver Nitrate and polyvinyl alcohol is spin-coated on the sheet glass, can obtains Silver Nitrate/PVA (PVOH) FILM.110～250 degrees centigrade of following reacting by heating 3～10 minutes, silver ions was reduced by polyvinyl alcohol in heat-processed, obtains light yellow transparent Nano silver grain/polyvinyl alcohol compound film with Silver Nitrate/PVA (PVOH) FILM.Heating temperature is higher than 150 degrees centigrade, and the laminated film of gained is water insoluble.Nano silver grain/polyvinyl alcohol compound film and pure PVA (PVOH) FILM are immersed the intestinal bacteria nutrient solution respectively, cultivated 24 hours down at 37 degrees centigrade.With suspension liquid difference dilution point plate, cultivated 12 hours down for 37 degrees centigrade, observe the bacterium colony number, investigate the anti-microbial property of composite membrane, its effect can be found out by the embodiment of the invention 4.
Method of the present invention need not reductive agent, and preparation technology is simple, and cost is low, the reaction conditions gentleness.Nano silver grain/polyvinyl alcohol compound film that the present invention makes has the transparency preferably, bigger spectral absorption, and it is insoluble in water, intestinal bacteria are shown excellent anti-microbial activity, have important use at aspects such as antimicrobial coating, slowly-releasing antibacterial film, building coating, extra package material, light polarizing film, spectral filters and be worth.
Description of drawings
Fig. 1. the stereoscan photograph and the transmission electron microscope picture of the Nano silver grain/PVA (PVOH) FILM of the embodiment of the invention 1 preparation, wherein:
Fig. 1 a is the sem photograph on Nano silver grain/PVA (PVOH) FILM surface, and illustration is the sem photograph in laminated film cross section.
Fig. 1 b is the transmission electron microscope picture of Nano silver grain/PVA (PVOH) FILM.Last illustration is the particle diameter statistical Butut of Nano silver grain, and following illustration is the electron-diffraction diagram of Nano silver grain.
Fig. 2. the uv-visible absorption spectroscopy figure and the transmission electron microscope picture of Nano silver grain/PVA (PVOH) FILM that the embodiment of the invention 3 makes, wherein:
Fig. 2 a be Silver Nitrate/PVA (PVOH) FILM respectively 110,120,130,150,170,190 degrees centigrade of following complex light spectrograms of obtaining in 5 minutes of heating; Silver nitrate concentration is 10mmol/L;
Fig. 2 b is that Silver Nitrate/PVA (PVOH) FILM is at 130 degrees centigrade of transmission electron microscope pictures that heat the Nano silver grain/PVA (PVOH) FILM that made in 5 minutes down.Illustration is the particle diameter statistical Butut of Nano silver grain.
The complex light spectrogram of Nano silver grain/PVA (PVOH) FILM that Fig. 3 embodiment of the invention 4 makes, wherein silver nitrate concentration is respectively 10,20,40,60,80,100mmol/L obtained corresponding Nano silver grain/PVA (PVOH) FILM in 5 minutes by Silver Nitrate/PVA (PVOH) FILM is heated down at 190 degrees centigrade; Illustration is the digital photograph of corresponding laminated film.
Fig. 4. the antibacterial experiment result of Nano silver grain/PVA (PVOH) FILM that the embodiment of the invention 1 makes, wherein
Left figure is the antibacterial effect of Nano silver grain/PVA (PVOH) FILM;
Right figure is the antibacterial effect of pure PVA (PVOH) FILM.
Embodiment
Embodiment 1.
The polyvinyl alcohol (molecular-weight average 100000, alcoholysis degree 88%) of getting 0.8 gram is dissolved in the 15mL distilled water, and 90 degrees centigrade of heated and stirred were dissolved cool to room temperature in 15～30 minutes fully until polyvinyl alcohol.Getting silver nitrate solution (purity is not less than 99.8%) dropwise adds in the above-mentioned polyvinyl alcohol solution, the mol ratio that makes Silver Nitrate/polyvinyl alcohol is 1/100, get 100 μ L mixing solutionss after stirring and drip on the glass substrate, spin coating is 1 minute under 3000 rev/mins rotating speed.Silver Nitrate/the PVA (PVOH) FILM of spin coating preparation was heated 5 minutes down at 190 degrees centigrade, obtain light yellow transparent Nano silver grain/polyvinyl alcohol compound film.The pattern of laminated film as shown in Figure 1a.Observations shows that the Nano silver grain/polyvinyl alcohol compound film that makes is transparent, and the surface is more smooth.Fig. 1 a illustration is the sem photograph in laminated film cross section, by measuring the cross section, estimates that the thickness of laminated film is about 400 nanometers.
The ethylene glycol monoethyl ether that takes a morsel drips on Nano silver grain/polyvinyl alcohol compound film, promotes gently thereon with glass slide, and laminated film is peeled off from glass substrate.Get the film fragments 16 μ L that are suspended in the ethylene glycol monoethyl ether, point sample is used transmission electron microscope observing afterwards in the copper mesh that is used for transmission electron microscope, and observations is shown in Fig. 1 b.Nano silver grain is circular in the laminated film, and most of particle diameter is between 5～20 nanometers.150 nanoparticles are carried out the particle diameter statistics show (Fig. 1 b illustration), median size 11 nanometers of Nano silver grain in the laminated film, standard deviation is 5.6 nanometers.Illustration is the electron diffraction analysis of Nano silver grain under Fig. 1 b, (111) of gained diffraction pattern and cubic metal silver, (200), (220), (311), (331) crystal face conforms to, and proves that the nanoparticle that generates is that silver is received crystalline substance.
The polyvinyl alcohol (molecular-weight average 100000, alcoholysis degree 88%) of getting 0.4 gram is dissolved in the 15mL distilled water, and 90 degrees centigrade of heated and stirred were dissolved cool to room temperature in 15～30 minutes fully until polyvinyl alcohol.Getting silver nitrate solution (purity is not less than 99.8%) dropwise adds in the above-mentioned polyvinyl alcohol solution, the mol ratio that makes Silver Nitrate/polyvinyl alcohol is 1/100, get 100 μ L mixing solutionss after stirring and drip on the glass substrate, spin coating is 1 minute under 3000 rev/mins rotating speed.Silver Nitrate/the PVA (PVOH) FILM of spin coating preparation was heated 5 minutes down at 190 degrees centigrade, obtain light yellow transparent Nano silver grain/polyvinyl alcohol compound film.By measuring the cross section, estimate that the thickness of laminated film is about 200 nanometers.
Embodiment 3.
Method according to embodiment 1 prepares Nano silver grain/polyvinyl alcohol compound film.Get a certain amount of polyvinyl alcohol (molecular-weight average 100000, alcoholysis degree 88%) and be dissolved in the 15mL distilled water, 90 degrees centigrade of heated and stirred were dissolved cool to room temperature in 15～30 minutes fully until polyvinyl alcohol.Get silver nitrate solution (purity is not less than 99.8%) and dropwise add in the polyvinyl alcohol solution, making the mol ratio of Silver Nitrate/polyvinyl alcohol is 1/100, gets 100 μ L mixing solutionss after stirring and drips on the glass substrate, and spin coating is 1 minute under 3000 rev/mins rotating speed.Respectively 110,120,130,150,170,190 degrees centigrade of heating 5 minutes down obtain Nano silver grain/polyvinyl alcohol compound film with the Silver Nitrate/PVA (PVOH) FILM of spin coating preparation.Along with the rising of Heating temperature, the color of the Nano silver grain/polyvinyl alcohol compound film that obtains is slightly deepened but is not obvious.The uv-visible absorption spectroscopy of Nano silver grain/polyvinyl alcohol compound film is shown in Fig. 2 a.The result shows the rising along with Heating temperature, and the optical absorption intensity of laminated film increases.Water insoluble at the Nano silver grain/polyvinyl alcohol compound film that obtains greater than 150 degrees centigrade of heating.
The ethylene glycol monoethyl ether that takes a morsel drips on Nano silver grain/polyvinyl alcohol compound film, promotes gently thereon with glass slide, and laminated film is peeled off from glass substrate.Get the film fragments 16 μ L that are suspended in the ethylene glycol monoethyl ether, point sample is used transmission electron microscope observing afterwards in the copper mesh that is used for transmission electron microscope.Observations shows that the Nano silver grain in the laminated film is spherical in shape, and along with Heating temperature raises, the Nano silver grain particle diameter that obtains increases, and size distribution broadens.
Fig. 2 b is the transmission electron microscope picture of Silver Nitrate/PVA (PVOH) FILM at 130 degrees centigrade of Nano silver grain/polyvinyl alcohol compound films that obtain after heating 5 minutes down.Fig. 2 b shows, Nano silver grain is circular in the laminated film that obtains under 130 degrees centigrade, 100 nanoparticles carried out the particle diameter statistics show (Fig. 2 b illustration) median size is in 7.5 nanometers that size distribution is narrower, and standard deviation is 1.5 nanometers.Compare with Fig. 1 b, along with Heating temperature raises, the Nano silver grain particle diameter that obtains increases as can be known, and size distribution broadens, and the result is consistent with ultraviolet-visible absorption spectroscopy.
Method according to embodiment 1 prepares Nano silver grain/polyvinyl alcohol compound film.Get a certain amount of polyvinyl alcohol (molecular-weight average 100000, alcoholysis degree 88%) and be dissolved in the 15mL distilled water, 90 degrees centigrade of heated and stirred were dissolved cool to room temperature in 15～30 minutes fully until polyvinyl alcohol.Get silver nitrate solution (purity is not less than 99.8%) and dropwise add in the polyvinyl alcohol solution, making silver nitrate concentration is 10,20,40,60,80,100mmol/L gets 100 μ L mixing solutionss and drips on the glass substrate after stirring, spin coating is 1 minute under 3000 rev/mins rotating speed.Silver Nitrate/the PVA (PVOH) FILM of spin coating preparation was heated 5 minutes down at 190 degrees centigrade, obtain Nano silver grain/polyvinyl alcohol compound film.The UV, visible light optical absorption spectra of laminated film as shown in Figure 3, the result shows the increase along with the Silver Nitrate content in the film, the ultraviolet-visible optical absorption intensity of the Nano silver grain/polyvinyl alcohol compound film that obtains is big more, at silver nitrate concentration is 100mmol/L, it is maximum that Heating temperature is that the spectral absorption of 190～250 Nano silver grain/polyvinyl alcohol compound films that obtained by Silver Nitrate/PVA (PVOH) FILM when spending reaches, and surpassed 2.0; Along with the increase of silver nitrate concentration, the color of laminated film is deepened gradually, shown in illustration among Fig. 3.
Embodiment 5.
Get the Nano silver grain/polyvinyl alcohol compound film that makes among the embodiment 1 and characterize its anti-microbial property.Detailed process is: 37 degrees centigrade of following overnight incubation, is that 1% peptone, mass concentration be 1% sodium-chlor mixing solutions dilution with mass concentration with intestinal bacteria, and making the OD value is 0.01.With a slice Nano silver grain/polyvinyl alcohol compound film as sample, a slice with the pure PVA (PVOH) FILM for preparing under the condition as reference, immerse in the intestinal bacteria nutrient solution after 1 milliliter of dilution,, obtain two parts respectively and contain colibacillary suspension liquid in 37 degrees centigrade of following shaking culture 24 hours.Get this two parts of suspension liquid 1 microlitres respectively, three (methylol) aminomethane-ethylenediamine tetraacetic acid (EDTA) buffered soln (10mmol/L three (methylol) aminomethane-hydrochloric acid with 300 microlitres, the 1mmol/L ethylenediamine tetraacetic acid (EDTA)) dilution, (mass concentration is 1% peptone to put agaropectin respectively, mass concentration is 1% sodium-chlor, and mass concentration is 1.5% agar) on, agaropectin is inverted and was cultivated 12 hours in 37 degrees centigrade, observe the difference of bacterium colony number on the agaropectin, the result as shown in Figure 4.Clearly, the bacterium colony number lacks 99.9% than the number on the reference on the sample, illustrates that Nano silver grain has the excellent antibiotic performance.Prepared Nano silver grain/polyvinyl alcohol compound film can be used for antimicrobial coating.
Claims (10)
1. the preparation method of a Nano silver grain/polyvinyl alcohol compound film, this method may further comprise the steps:
(1). at room temperature get polyvinyl alcohol and be dissolved in the distilled water, heating and stirring are dissolved fully until polyvinyl alcohol;
(2). silver nitrate solution is joined in the polyvinyl alcohol solution that step (1) obtains, and wherein, the molar ratio of Silver Nitrate and polyvinyl alcohol is 1/100～1/10, and magnetic agitation mixes;
(3). get step (2) and obtain mixing solutions and drip on the glass substrate and film, obtain Silver Nitrate/PVA (PVOH) FILM;
(4). Silver Nitrate/PVA (PVOH) FILM that step (3) is obtained obtains transparent Nano silver grain/polyvinyl alcohol compound film 110～250 degrees centigrade of heating.
2. method according to claim 1 is characterized in that: described Silver Nitrate/PVA (PVOH) FILM that step (3) is obtained is 3～10 minutes 110～250 degrees centigrade of heat-up times.
3. method according to claim 1 is characterized in that: described silver nitrate solution is joined in the polyvinyl alcohol solution is dropwise to add silver nitrate solution.
4. method according to claim 1 is characterized in that: in the mixed solution of Silver Nitrate and polyvinyl alcohol, can change the thickness of laminated film by the concentration that changes polyvinyl alcohol.
5. according to claim 1,2,3 or 4 described methods, it is characterized in that: described polyvinyl alcohol molecular weight is 70000～100000, and alcoholysis degree is 70～90%; Described Silver Nitrate purity is not less than 99.8%.
6. Nano silver grain/polyvinyl alcohol compound film that obtains by each described method of claim 1～5, it is characterized in that: by transparent Nano silver grain/polyvinyl alcohol compound film smooth surface that Silver Nitrate/the PVA (PVOH) FILM heating obtains, the thickness of laminated film is 200～500 nanometers; The particle diameter of Nano silver grain is 5～20 nanometers in the laminated film; Silver Nitrate content in the high more and/or Silver Nitrate/PVA (PVOH) FILM of Heating temperature is big more, and the ultraviolet-visible optical absorption intensity of the Nano silver grain/polyvinyl alcohol compound film that obtains is big more.
7. laminated film according to claim 6, it is characterized in that: at silver nitrate concentration is 100mmol/L, and the spectral absorption of the Nano silver grain/polyvinyl alcohol compound film that is obtained by Silver Nitrate/PVA (PVOH) FILM when Heating temperature is 190～250 degrees centigrade is greater than 2.0.
8. laminated film according to claim 6 is characterized in that: described Silver Nitrate/PVA (PVOH) FILM is water insoluble at the Nano silver grain/polyvinyl alcohol compound film that obtains greater than 150 degrees centigrade of heating.
9. purposes according to the described laminated film of claim 6～8, it is characterized in that: described Nano silver grain/polyvinyl alcohol compound film can be as antimicrobial coating; And as the slowly-releasing antibacterial film, building coating, extra package material, spectral filter, light polarizing film.
10. purposes according to the described laminated film of claim 6～8, it is characterized in that: described Nano silver grain/polyvinyl alcohol compound film has anti-microbial property to intestinal bacteria.
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