CN1196924C - Method for semiquantitative characterization of carbon nanotube suspension stability - Google Patents
Method for semiquantitative characterization of carbon nanotube suspension stability Download PDFInfo
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- CN1196924C CN1196924C CN 03116185 CN03116185A CN1196924C CN 1196924 C CN1196924 C CN 1196924C CN 03116185 CN03116185 CN 03116185 CN 03116185 A CN03116185 A CN 03116185A CN 1196924 C CN1196924 C CN 1196924C
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Abstract
The present invention provides a semiquantitative characterization method of carbon nanotube suspension stability. In the method, the visible ultraviolet spectrophotometric method is mainly used as the testing method, the rule of the linear change of the absorbance of a carbon nanotube suspension with the concentration at a certain fixed wavelength is adopted, and through the absorbance change of the upper layer solution of the carbon nanotube suspension every 0.5 hour, the curve of the change of the concentration of the carbon nanotube suspension with time is calculated in a semiquantitative mode, wherein the determined wavelength of the concentration of the carbon nanotube suspension in an aqueous medium is 253 nm, and the concentration range of the standard operation curve is from 0.10 to 0.20gL<-1>; the determined wavelength in an ethanol medium is 257 nm, and the concentration range of the standard operation curve is from 0.08 to 0.25gL<-1>. With the characterization method, the limitation that the traditional settling volume characterization method is not suitable for carbon tube suspension characterization can be solved; simultaneously, the accuracy of the stability characterization method is increased, and the requirement of semiquantification is achieved.
Description
Technical field
The present invention carries out the method that sxemiquantitative exactly characterizes to the stability of carbon nano tube suspension, belongs to the dispersion technology field.
Background technology
Carbon nano-tube is since 1991 are found by Iijima, become the monodimension nanometer material that has application potential with its high aspect ratio and superpower mechanical property, it is used and has related to many-sides such as nano electron device, catalyst support, electrode material, hydrogen storage material and compound substance.The superpower mechanical property of carbon nano-tube can greatly improve the intensity and the toughness of compound substance; Conductivity that unique conduction and photoelectric properties can be improved polymeric material and the novel opto-electrical polymers compound substance of preparation; Its unique texture can prepare the one-dimensional nano-composite material of metal or metal oxide filling.The research of carbon nano tube compound material has become a very important field.Recently, at epoxy resin, pitch adds carbon nano-tube in the materials such as polymethylmethacrylate (PMMA) and aluminium oxide, wishes to improve the mechanical property of material.But add in the experiment of epoxy resin at the carbon pipe, the researcher finds that this composite material strength does not significantly strengthen, and this is mainly owing to interaction (L.S.Schadler et al. weak between carbon nano-tube and polymeric matrix, Appl.Phys.Lett., 1998, vol.73, p3842-3847).The researcher also finds to use hot-press method that the carbon pipe is added in the aluminium oxide, can not improve the physical strength of alumina compound equally effectively, they think that this mainly is because carbon nano-tube is easy to form big aggregate (T.Kuzumaki et al., J.Mater.Res., 1998, vol.13, p2445-2449).Therefore, how to improve the dispersive property of carbon nano-tube, eliminate big reunion, strengthen the interaction between carbon nano-tube and polymkeric substance and ceramic substrate, just become the important prerequisite condition of preparation carbon nano tube compound material, be significant.
Improve the carbon nano-tube dispersive property how, strengthen on the Study of Interaction between carbon nano-tube and polymkeric substance and ceramic substrate, the researcher has proposed some approach, for example utilize spreading agent to prepare finely dispersed stable carbon nano tube suspension (B.Vigolo et al., Science., 2000, vol.290, p1331-1334); The carbon tube-surface is carried out chemical treatment, so that group (the M.S.P.Shaffer et al. of chemical reaction can take place on the carbon tube-surface band, Carbon., 1998, vol.36, p1603-1612) and utilize chemical reaction to prepare carbon pipe-polymer composite body (X.Gong et al., Chem.Mater., 2000, vol.12, method such as p1049-1052).Dispersing Nano carbon tubes in solution, spreading agent and carbon nano tube surface interact, and improve the quantity of electric charge on surface on the one hand, thereby improve the electrostatic repulsion forces between the carbon pipe; On the other hand, increase the steric hindrance between the carbon nano-tube, hinder close mutually between the carbon pipe, promptly by the effect of static steric hindrance stable mechanism.The adding of spreading agent can improve the homogeneity and the stability of carbon nano tube suspension effectively, but how to characterize accurately and effectively for the raising of this stability, and not seeing yet so far has bibliographical information.
In general, important measuring of ceramic powder stability of suspension is settling volume, promptly prepares the oxide slurry of certain solid content, places graduated cylinder, observes settling volume over time.But this method and the stability that is not suitable for carbon nano tube suspension characterize.Because the carbon nano tube suspension color is a black, when sedimentation takes place, be difficult to distinguish the variation of its settling volume.Traditional settling volume method can not characterize the sxemiquantitative variation of stability exactly simultaneously, has limited applying of this method to a certain extent.Up to now, still there is not the report that sxemiquantitative exactly characterizes carbon nano tube suspension stability.
Summary of the invention
The object of the present invention is to provide a kind of sxemiquantitative exactly to characterize in water and the ethanol medium, add the method for different spreading agents front and back carbon nano tube suspension stability.
The present invention is means of testing with the ultraviolet-visible spectrophotometry, at first determine in water or ethanol medium, the standard working curve that adds different spreading agents front and back carbon nano tube suspension, and then, calculate carbon nano tube suspension upper solution concentration curve over time by the pairing concentration value of absorbance in the standard working curve.
Fig. 1 is the standard working curve that adds spreading agent front and back carbon nano tube suspension in the aqueous medium.As seen, in aqueous medium, carbon nano-tube has a maximum absorption band in ultraviolet-visible spectrum, and wavelength is 253nm, is 0.10-0.20gL in carbon pipe concentration
-1In the scope, can obtain linear well carbon nano-tube standard working curve.In ethanol medium, the carbon pipe also has a maximum absorption band in ultraviolet-visible spectrum equally, and wavelength is 257nm.The concentration range of standard working curve is 0.08-0.25gL
-1
The concrete implementation method of the present invention is the 0.200g carbon nano-tube is joined 100mL water respectively and to contain in the 100mL aqueous solution of 0.008-0.400g spreading agent, after the ultrasonic dispersion, suspending liquid is poured in the letter of 50ml amount, every 0.5 hour, the careful upper strata 1ml clear liquid of drawing, diluting 10 times, is that the 253nm place measures its absorbance at wavelength.Selected spreading agent is surfactant-based, includes lauryl sodium sulfate, sodium dodecylsulphonate, tween 100 (Triton X-100) etc.; Polymer class includes polyethyleneimine (PEI), polyacrylic acid (PAA) etc.; Tiron (Tiron).The absorbance of surveying read its concentration value according to the standard working curve that adds before and after the spreading agent respectively, having or not spreading agent to exist under the situation thereby draw, carbon nano tube suspension concentration is curve over time, as shown in Figure 2.In ethanol medium, the 0.500g carbon nano-tube is joined in the 50mL ethanolic solution that contains the 0.025-0.250g spreading agent, selected spreading agent is polyurethane (disperbyk-2150), after the ultrasonic dispersion, suspending liquid is poured in the 50mL graduated cylinder, every 0.5 hour, carefully draws upper solution concentration 1mL, diluting 10 times, is that the 257nm place measures its absorbance at wavelength.The absorbance of surveying according to the standard working curve that adds the carbon nano-tube ethanolic solution behind the spreading agent among Fig. 4, thereby draw carbon nano-tube ethanolic solution concentration curve over time after spreading agent adds, see Fig. 5.
Growth in time, the carbon nano tube suspension concentration change must be more little, and then the stability of suspending liquid is high more.As seen from Figure 3, for the carbon nano tube suspension of no spreading agent, rapid subsidence takes place promptly at short notice, arrive 500 hours, suspension concentration descends 50%, and presents the continuation downward trend.Carbon nano tube suspension behind the adding spreading agent, rear suspension liquid concentration only descended 15% in 500 hours, and no longer descended, and formed stable carbon nano tube suspension.Light micrograph shows: the serious agglomeration of carbon nano-tube in liquid phase medium obviously eliminated in the adding of spreading agent, improved the dispersiveness of carbon nano tube suspension, as shown in Figure 3.Show that thus the adding of spreading agent can be prepared finely dispersed stable carbon nano tube suspension.
The invention provides a kind of method that characterizes carbon nano tube suspension stability, this characterizing method can carry out the ground of sxemiquantitative exactly to the stability of suspending liquid and characterize, and be applicable in water, ethanol medium the carbon nano tube suspension before and after different spreading agents add.The ultraviolet-visible pectrophotometer means of testing that is adopted has solved the limitation that traditional settling volume method is unsuitable for carbon pipe solution.Used the computing method of standard working curve simultaneously, made and accurately to draw carbon pipe solution concentration quantitatively over time.
Provided by the invention in water, ethanol medium, the outstanding feature that adds the carbon nano tube suspension stability characterization method of different spreading agents is:
1. accurately sxemiquantitative ground characterizes carbon nano tube suspension concentration over time.
2. be applicable in water, the ethanol medium, add the sign of the carbon nano tube suspension stability of different spreading agents front and back.
Description of drawings
Fig. 1 is the standard working curve of carbon nano tube suspension before and after spreading agent adds in the aqueous medium.Horizontal ordinate is an absorbance, and ordinate is a carbon nano tube suspension concentration, the gL of unit
-1The standard working curve of carbon nano tube suspension when ■ is no spreading agent, ▲ be the standard working curve that adds behind the spreading agent.
Fig. 2 is that spreading agent adds front and back carbon nano tube suspension concentration curve over time in the aqueous medium.Horizontal ordinate is the time, and unit hour, ordinate are carbon nano tube suspension concentration, the gL of unit
-1Carbon nano tube suspension concentration curve over time when ■ is no spreading agent, ▲ be to add the latter two relations of spreading agent.
Fig. 3 is the light micrograph of carbon nano tube suspension before and after the adding spreading agent that is obtained for embodiment 2.The light micrograph of carbon nano tube suspension when a is no spreading agent, b are the light micrographs that adds behind the spreading agent.
Fig. 4 is the standard working curve that spreading agent adds the back carbon nano tube suspension in the ethanol medium.Horizontal ordinate is an absorbance, and ordinate is a carbon nano tube suspension concentration, the gL of unit
-1
Fig. 5 is that spreading agent adds back carbon nano tube suspension concentration curve over time in the ethanol medium.Horizontal ordinate is the time, and unit hour, ordinate are carbon nano tube suspension concentration, the gL of unit
-1
Embodiment
Further specify the method provided by the invention of utilizing below by embodiment, accurately be characterized in the different medium to sxemiquantitative, add the stability of the carbon nano tube suspension of different spreading agents front and back, but limit the present invention absolutely not.
Embodiment 1
0.012g, 0.014g, 0.018g carbon nano-tube are added respectively in the 100ml water, ultrasonic dispersion scans on ultraviolet-visible pectrophotometer, determines at wavelength to be that the 253nm place measures its absorbance, thereby the standard working curve of carbon nano-tube aqueous solutions is seen curve 1 among Fig. 1 when drawing no spreading agent.The 0.200g carbon nano-tube is added in the 100mL water, ultrasonic dispersion, suspending liquid places the 50mL graduated cylinder, every 0.5 hour, draws the 1mL upper solution, be diluted to 10mL, at wavelength is that the 253nm place measures its absorbance, and the establishing criteria working curve calculates concentration value, thereby carbon nano tube suspension concentration curve is over time seen curve 1 among Fig. 2 when obtaining not having spreading agent.
0.010g, 0.018g, 0.020g carbon nano-tube are added and contain in the 100mL aqueous solution of 0.010g spreading agent (lauryl sodium sulfate), ultrasonic dispersion, on ultraviolet-visible pectrophotometer, scan, determine at wavelength to be that the 253nm place measures its absorbance, preparation simultaneously contains the 100mL aqueous solution of 0.010g spreading agent as reference liquid, thereby obtain adding the standard working curve of carbon nano tube suspension after the spreading agent lauryl sodium sulfate, see curve 2 among Fig. 1.The adding of 0.200g carbon nano-tube is contained in the 100mL aqueous solution of 0.010g spreading agent, and ultrasonic dispersion places the 50mL graduated cylinder, every 0.5 hour, draws the 1mL upper solution, dilutes 10 times, is that the 253nm place measures its absorbance at wavelength, is 1.00gL with concentration simultaneously
-1Aqueous dispersant be reference, and contrast contains the carbon nano tube suspension standard working curve of spreading agent, draws spreading agent and adds back carbon nano tube suspension concentration curve over time, sees curve 2 among Fig. 2.Stability when as can be seen, the carbon nano tube suspension behind the adding spreading agent does not have spreading agent has had large increase.Fig. 4 is the optical microscopy map of the carbon nano tube suspension before and after the adding spreading agent.The serious agglomeration of carbon nano-tube in liquid phase medium water obviously eliminated in the adding of spreading agent, can obtain finely dispersed stable carbon nano tube suspension.
Embodiment 3
Preparation 20mL concentration range is 0.08-0.25gL
-1The carbon nano-tube ethanolic solution that contains 0.034g spreading agent polyurethane (disperbyk-2150), ultrasonic dispersion, on ultraviolet-visible pectrophotometer, scan, determine at wavelength to be that the 257nm place measures its absorbance, the spreading agent ethanolic solution for preparing same concentrations simultaneously is as reference liquid, thereby obtains adding the standard working curve of carbon nano-tube ethanolic solution behind the spreading agent, as Fig. 4.The adding of 0.500g carbon nano-tube is contained in the 50mL ethanolic solution of 0.087g spreading agent, ultrasonic dispersion, place the 50mL graduated cylinder, every 0.5 hour, its absorbance of sampling and measuring, spreading agent ethanolic solution with same concentrations is a reference, adds back carbon nano-tube ethanolic solution concentration curve over time thereby draw spreading agent, sees Fig. 5.
Claims (10)
1, a kind of sxemiquantitative characterizes the method for carbon nano tube suspension stability, it is characterized in that with the ultraviolet-visible spectrophotometry being means of testing, at first determine in water or ethanol medium, the standard working curve that adds spreading agent front and back carbon nano tube suspension, after the working curve that settles the standard, add the time dependent absorbance of spreading agent front and back carbon nano tube suspension upper solution by measuring, and then by the concentration value of absorbance correspondence in the standard working curve, calculate carbon nano tube suspension upper solution concentration curve over time, described standard working curve is carbon nano tube suspension concentration and absorbance relation curve.
2, characterize the method for carbon nano tube suspension stability by the described sxemiquantitative of claim 1, it is characterized in that in aqueous medium, the carbon nano tube suspension upper solution is at the absorbance at wavelength 253nm place behind the adding spreading agent, be that dispersant solution with same concentrations is a reference, to eliminate the influence of spreading agent to solution absorbance.
3, characterize the method for carbon nano tube suspension stability by the described sxemiquantitative of claim 2, it is characterized in that absorbance was to draw supernatant liquor every 0.5 hour, 10 times of mensuration of dilution.
4, characterize the method for carbon nano tube suspension stability by the described sxemiquantitative of claim 1, it is characterized in that in ethanol medium, the carbon nano tube suspension upper solution is at the absorbance at wavelength 257nm place behind the adding spreading agent, be that dispersant solution with same concentrations is a reference, to eliminate the influence of spreading agent to solution absorbance.
5, characterize the method for carbon nano tube suspension stability by the described sxemiquantitative of claim 4, it is characterized in that absorbance was to draw supernatant liquor every 0.5 hour, 10 times of mensuration of dilution.
6, characterize the method for carbon nano tube suspension stability by the described sxemiquantitative of claim 1, it is characterized in that in aqueous medium the carbon nano tube suspension concentration of standard working curve is 0.10～0.20gL
-1In ethanol medium, the carbon nano tube suspension concentration range of standard working curve is 0.08～0.25gL
-1
7, characterize the method for carbon nano tube suspension stability by claim 1,2 described sxemiquantitative, it is characterized in that at the spreading agent described in the aqueous medium being a kind of in surfactant-based lauryl sodium sulfate, sodium dodecylsulphonate or the tween 100.
8, characterize the method for carbon nano tube suspension stability by claim 1,2 described sxemiquantitative, it is characterized in that at the spreading agent described in the aqueous medium being a kind of in the polyethyleneimine of polymer class or the polyacrylic acid.
9, characterize the method for carbon nano tube suspension stability by claim 1,2 described sxemiquantitative, it is characterized in that at the spreading agent described in the aqueous medium be tiron.
10, characterize the method for carbon nano tube suspension stability by claim 1,4 described sxemiquantitative, it is characterized in that at the spreading agent described in the ethanol medium be polyurethane.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102169102A (en) * | 2011-01-13 | 2011-08-31 | 福州大学 | Method for monitoring and analyzing concentration of nano-carbon material electrophoretic deposition liquid |
| CN106841529A (en) * | 2017-03-10 | 2017-06-13 | 南京信息工程大学 | A kind of method for determining carbon nanotubes aqueous dispersion concentration |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169102A (en) * | 2011-01-13 | 2011-08-31 | 福州大学 | Method for monitoring and analyzing concentration of nano-carbon material electrophoretic deposition liquid |
| CN102169102B (en) * | 2011-01-13 | 2014-10-01 | 福州大学 | Method for monitoring and analyzing concentration of nano-carbon material electrophoretic deposition liquid |
| CN106841529A (en) * | 2017-03-10 | 2017-06-13 | 南京信息工程大学 | A kind of method for determining carbon nanotubes aqueous dispersion concentration |
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