# Patent

## Title
Polyaniline/carbon black composite and preparation method thereof

## Abstract

A polyaniline/carbon black composite and a preparation method thereof are disclosed The polyaniline/carbon black composite is formed by polyaniline covering carbon black and is with core-shell structure while the polyaniline/carbon black composite contains 10 ̃30 wt. % of carbon black. The preparation method of polyaniline/carbon black composite includes the steps of: disperse carbon black into solution to form carbon black solution, add aniline into the carbon black solution to form a first solution; dissolve ammonium persulfate into acid aqueous solution to form a second solution; add the second solution to the first solution, after reaction, through filtering and grinding to produce polyaniline/carbon black composite.

## Background
RELATED APPLICATIONS
This application is a Divisional patent application of co-pending application Ser. No. 11/976,932, filed on 30 Oct. 2007. The entire disclosure of the prior application Ser. No. 11/976,932, from which an oath or declaration is supplied, is considered a part of the disclosure of the accompanying Divisional application and is hereby incorporated by reference.


BACKGROUND OF THE INVENTION
The present invention relates to a polyaniline/carbon black composite and a preparation method thereof, especially to a polyaniline/carbon black composite and a preparation method thereof that are applied to dielectric material with microwave absorption or conductive coatings with corrosion resistance.
The research and development of conductive coatings have been over a half-century. Working as conductive layer, electromagnetic wave shielding layer and antistatic coating, the conductive coatings have broad perspective and increasing market demands. The membrane surface of the conductive coating has higher resistance, charge generated thereon is not dissipated effectively so that static charges tend to accumulate thereon. This leads to certain limitations on applications of some respects such as dust proofing and bacteria resistance in medicine, protection from electric shock in medical operations, static protection for preventing static ignition and explosion in mine environment and petrochemistry, dust-proofing for protection of integrated circuit, and fiber accumulation in spinning industry. The conductive coating is special coating or meeting various requirements. The conductive coating is coating with conductor and semiconductor properties and the conductivity is above 10−10 S/cm, being applied to various fields such as electronic and electric appliance industry, printed circuit board, switches, marine antifouling coatings, electrothermal material, and electromagnetic wave shielding, and surface protection.
While using carbon series as filler in preparation of conductive coating, carbon black (mainly high conductive furnace carbon black and acetylene carbon black), graphite and carbon fiber are mixed together. In literatures, graphite as conductive filler is added with epoxy resin and it is found that the conductivity is dramatically improved when amount of the graphite is over 50 wt. %. However, addition of graphite results in poor physical and mechanical properties and poor processability. This leads to limits on usefulness of the conductive coating.
The conductive, corrosion resistant and microwave absorbing polyaniline has features of light weight, good plasticity, easy raw materials acquisition, easy synthesis and high stability. Thus polyaniline together with high conductive, corrosion resistant and microwave absorbing nano-scale carbon black form a polyaniline/carbon black composite material. The polyaniline/carbon black distributed in substrate (epoxy resin, organic silicone) can overcome defects of poor physical property, poor mechanical property and poor processability caused by large amount of graphite being added. Moreover, the present invention has features of high conductivity, corrosion protection and high microwave absorption without adding large amount of carbon black. Thus weight of conventional conductive coating is reduced so as to facilitate the applications of material in conductive elements, corrosion protection or microwave absorbing elements.
SUMMARY OF THE INVENTION
Therefore it is a primary object of the present invention to provide a polyaniline/carbon black composite and a preparation method thereof that improve conductivity of polyaniline by nanoscale carbon black.
It is another object of the present invention to provide a polyaniline/carbon black composite and a preparation method thereof that the composite material is used as additive in conductive and corrosion resistant coating.
It is a further object of the present invention to provide a polyaniline/carbon black composite and a preparation method thereof that the composite is used as additive in microwave absorbing material.
It is a further object of the present invention to provide a polyaniline/carbon black composite and a preparation method thereof that overcome shortcomings of conductive coatings caused by large amount of graphite being added such as reduced physical property, poor mechanical property and poor processability.
In order to achieve objects, the present invention provides a polyaniline/carbon black composite and a preparation method thereof. The polyaniline/carbon black composite is formed by polyaniline covering carbon black and is with core-shell structure while the polyaniline/carbon black composite contains 10 ̃30 wt. % of carbon black. The preparation method of polyaniline/carbon black composite includes the steps of: disperse carbon black into solution to form carbon black solution, add aniline into the carbon black solution to form a first solution; dissolve ammonium persulfate into acid aqueous solution to form a second solution; add the second solution to the first solution, after reaction, through filtering and grinding to produce polyaniline/carbon black composite.



BRIEF DESCRIPTION OF THE DRAWINGS
The structure and the technical means adopted by the present invention to achieve the above and other objects can be best understood by referring to the following detailed description of the preferred embodiments and the accompanying drawings, wherein
FIG. 1 is a flow char showing steps of preparing polyaniline/carbon black composite according to the present invention;
FIG. 2 is infrared spectra of polyaniline/carbon black (PANI/CB) composite material containing different weight ratio of carbon black according to the present invention;
FIG. 3 is UV-Vis spectra of PANI/CB composite with various weight of carbon black according to the present invention;
FIG. 4 is XRD (X-ray Diffraction) pattern of polyaniline/carbon black composite with various weight of carbon black according to the present invention;
FIG. 5 is EPR spectroscopy of polyaniline/carbon black composite with various amount of carbon black according to the present invention;
FIG. 6 is a scanning electron microscope (SEM) image of nano-scale carbon black (CB) according to the present invention;
FIG. 7A is another SEM image of nano-scale carbon black (CB) according to the present invention;
FIG. 7B is a SEM image of PANI/CB(30) according to the present invention;
FIG. 7C is a SEM image of PANI/CB(20) according to the present invention;
FIG. 7D is a SEM image of PANI/CB(10) according to the present invention;
FIG. 8A is a TEM figure of CB according to the present invention;
FIG. 8B is a TEM image of PANI/CB(30) according to the present invention;
FIG. 8C is a TEM image of PANI/CB(20) according to the present invention;
FIG. 8D is a TEM image of PANI/CB(10) according to the present invention;
FIG. 9 is return loss of carbon black/epoxy nanocomposite material and epoxy composite material containing polyaniline/carbon black with various weight of carbon black with frequency from 2 to 18 GHz;
FIG. 10 is return loss of carbon black/epoxy nanocomposite material and epoxy composite material containing polyaniline/carbon black with various weight of carbon black with frequency from 18 to 40 GHz;
FIG. 11A are photomicrographs of 2024-T3 aluminum alloy sheet, 2024-T3 aluminum alloy sheets coated with Ormosil and different Ormosil-PANI/CB taken by a metallurgical microscope;
FIG. 11B are photomicrographs of 2024-T3 aluminum alloy sheet, 2024-T3 aluminum alloy sheets coated with Ormosil and different Ormosil-PANI/CB taken by a metallurgical microscope after being tested by the salt spray test for 7 days;
FIG. 11C are photomicrographs of 6061-T6 aluminum alloy sheet, 2024-T3 aluminum alloy sheets coated with Ormosil and different Ormosil-PANI/CB taken by a metallurgical microscope;
FIG. 11D are photomicrographs of 6061-T6 aluminum alloy sheet, 2024-T3 aluminum alloy sheets coated with Ormosil and different Ormosil-PANI/CB taken by a metallurgical microscope after being tested by the salt spray test for 7 days.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The polyaniline/carbon black composite is formed by polyaniline covering carbon black and is with core-shell structure while the polyaniline/carbon black composite contains 10 ̃30 wt. % of carbon black.
The particle diameter of the carbon black particle is 10-80 nm and the particle diameter of the polyaniline/carbon black core-shell particle ranges from 50 to 250 nm (from observation of Transmission electron microscopy (TEM)). The preferable weight percent of carbon black in the polyaniline/carbon black composite is 20 wt. %.
Refer to FIG. 1, a preparation method of polyaniline/carbon black composite according to the present invention includes the steps of:
S1 disperse carbon black into solution to form carbon black solution;
S2 add aniline into the carbon black solution to form a first solution;
S3 dissolve ammonium persulfate into acid aqueous solution to form a second solution;
S4 add the second solution to the first solution for reaction, then through filtering and grinding to produce polyaniline/carbon black composite.
In the step S1, the solution is mixture of a dispersing agent, ethanol solution and acid. The step S1 further includes a step of ultrasound vibration. The step S2 includes a step of distill and purifying the aniline. In the step S3, the acid aqueous solution is hydrochloric acid solution. In the step S4, reaction time after adding the second solution to the first solution is 1 ̃5 hours while 2 hours are optimum. In the step S3, between filtering and grinding, an acid rinsing step is further included. Hydrochloric acid is used in acid rinsing step and the filtering step is a step of vacuum filtration.
Embodiment of a Preparation Method of Polyaniline/Carbon Black (PANI/CB) Composite
(1) Add carbon black (CB; Degussa PHG-1P) into a dispersing agent (US, GE QF-DT-7100S) and 50 ml ethanol solution, then add 100 ml HCl (hydrogen chloride) (2M) into the mixture solution; after ultrasound vibration for an hour, nanoscale carbon black solution is produced.

(2) Before being used, aniline is purified by second distillation and then the purified aniline is added into above mixture solution. Keep solution temperature at 0 to 5 Celsius degrees and stir the solution for an hour to form a first solution.

(3) Dissolve ammonium persulfate into 25 ml HCl (2M) to form a second solution and slowly drop the second solution into the first solution in step (2) and stir the solution well for 2 hours.

(4) After vacuum filtration, use HCl (2M) acid rinsing at room temperature. Then a sample is produced after vacuum filtration. After being heated for drying and grinded, powder of PANI/CB nanocomposite (with core-shell structure) is obtained.

Preparation Method of Epoxy Composite Material Containing Polyaniline/Carbon Black

(1) Add 15 g powder of PANI/CB composite with core-shell structure and epoxy rein into a beaker and stir the mixture well by a DC-stirrer.

(2) Pour the mixture of step (1) into a steel mold with length, width and thickness of 15 cm, 15 cm and 0.2 cm while top and bottom sides of the steel mold are clipped by steel plates.

(3) Being hot pressed by a heat compression molding machine under pressure of 35 kg.F/cm2 at 80 □ for 2 hours, a microwave absorbing piece made from epoxy nanocomposite material containing polyaniline/carbon black is produced.

Preparation Method of Ormosil-PANI/CB Composite Material

    (1) Add precursors having tetraethoxysilane (TEOS), tetrapropoxide zirconateand (TPOZ) and glycidoxypropyltrimethoxysilane (GPTMS) in a molecular ratio of 1:1:4 into nitric acid aqueous solution (1.45 ml nitric acid in 36 ml deionized water). Then various amount (respectively 10%, 20% and 30% of weight of the TEOS+TPOZ+GPTMS mixture solution) of PANI/CB is add into above mixture solution and stir the solution for 5 days.
    (2) Then add tetraethylenepentamine (TEPA) into the final solution in step (1) and stir well for 4 hours to get sol-like organic siloxane nanocomposite material containing polyaniline/carbon black.


Samples of organic siloxane composite material containing polyaniline/carbon black. respectively are labeled in Ormosil-PANI/CB(10)-10, Ormosil-PANI/CB(10)-20, Ormosil-PANI/CB(10)-30, Ormosil-PANI/CB(20)-10, Ormosil-PANI/CB (20)-20, Ormosil-PANI/CB(20)-30, Ormosil-PANI/CB(30)-10, Ormosil-PANI/CB(30)-20 and Ormosil-PANI/CB(30)-30, wherein PANI/CB represents polyaniline/carbon black, (10) represents amount of carbon black is 10 wt % of the polyaniline/carbon black, −10 represents amount of PANI/CB is 10 wt % of organic siloxane composite material containing polyaniline/carbon black. The rest is referred as similar way above mentioned.
Preparation Method of Aluminum Alloy with Organic Siloxane Composite Material Containing Polyaniline/Carbon Black and Powder Of Organic Siloxane Composite Material Containing Polyaniline/Carbon Black
(1) Use water sander and #200 sandpaper to polish surface of aluminum alloy piece ((AA-2024-T3(Al—Cu—Mg) and (AA-6061-T6 (Al—Mn—Si))).
(2) Alkaline cleaning (5% sodium hydroxide solution) and acid rinsing (50% nitric acid aqueous solution) the aluminum alloy piece for 1 minute respectively (for removing grease).
(3) Water rinsing the aluminum alloy piece for 30 seconds.
(4) Dry the aluminum alloy piece at room temperature for 4 hours.
(5) By spin-coating, the sol-like organic siloxane composite material containing polyaniline/carbon black is coated on a 2.5×5×0.1 cm aluminum alloy piece and totally for 3 layers.
(6) Keep the coated aluminum alloy piece and rest solution static at room temperature for 2 days, then dried at 60° C. for 24 hours. After being dried, the test piece is tested by a salt spray test.
(7) Or the sol-like organic siloxane composite material containing polyaniline/carbon black is dried at 60° C. for 24 hours to get powder of organic siloxane composite material containing polyaniline/carbon black (in network structure) for performing spectral analysis.

Fourier Transform Infrared (FT-IR) Analysis

By means of Fourier Transform Infrared Spectrophotometer, it is proved that polyaniline is distributed in conductive carbon black. Refer to FIG. 2, (a) represents a spectral curve of polyaniline, (b) represents a curve of PANI/CB(10)-nano-scale carbon black is 10% of total weight of polyaniline/carbon black, (c) represents a curve of PANI/CB(20) which means nano-scale carbon black is 20% of total weight of polyaniline/carbon black, and (d) represents a curve of PANI/CB(30) which means nano-scale carbon black is 30% of total weight of polyaniline/carbon black. Refer to curve (a), there is a vibration absorption peak of N-H of polyaniline at 3460 cm−1 while two absorption peaks near 1552 and 1466 cm−1 are respectively of quinoid ring (Q) and benzenoid ring (B) of polyaniline. The C-N stretching vibration peaks at 1386 and 1240 cm−1 are of a Q-B-Q unit and a B-B-B unit. From to, intensity of absorption peak increases along with delocalized degrees and conductivity of the main chain. Thus absorption peak between 950-1110 cm−1 is considered as characteristic peak in determining whether polyaniline is with conductivity or not and is called “electronic like band”. From curve (b) to curve (d) in FIG. 2, above characteristic peak is observed. Thus it is proved that polyaniline exists in conductive carbon black.
UV-Vis Spectra Analysis
Add PANI/CB composite into deionized water and apply ultrasonic vibration by a ultrasonic vibration device for 10 minutes to make composites disperse inside the deionized water. Then measure the solution by UV-Vis Spectrophotometer. Refer to FIG. 3, UV-Vis spectra of PANI/CB composite with various weight of carbon black is disclosed. Curve (a) is spectrum of nano-scale carbon black, curve (b) is spectrum of PANI/CB(30), curve (c) is spectrum of PANI/CB(20), curve (d) is spectrum of PANI/CB(15), curve (e) is spectrum of PANI/CB(10), curve (f) is spectrum of PANI/CB(5), and curve (g) is spectrum of PANI. It is observed in FIG. 3 that there is no absorption peak of carbon black between 300 ̃800 nm. This is resulted from no conjugate electron pair of carbon black. While in liquid-phase UV-visible spectroscopy, there are three absorption peaks for PANI/CB core-shell composite. One peak at about 350 nm is absorption peak of π-π* transition of benzenoid ring. The second shoulder-like peak is about at 450 nm and absorption after 600 nm keeps extending towards higher wavelength. Such absorption is caused by transition of cation-radical and polaron-bipolaron of main chain of polyaniline. That means quinoid ring (Q) and benzenoid ring (B) of polyaniline being doped by protic acid (such as HCl) so that electron ionization occurs and further results in conjugation between quinoid ring (Q) and benzenoid ring (B). Thus electrons have high mobility This means PANI/CB composite is in the form of emeraldine salt which is a conducting (electron transfer) form. Furthermore, absorption peak near 450 nm shifts to lower wavelength area along with increasing amount of carbon black being added. This means oxidized unit of the composite increases along with the increasing amount of carbon black being added. This may be due to electron transfer force generated between the carbon black and the segments of polyaniline. This can also explain why conductivity of  PANI/CB composite increases. Moreover, carbon black itself has no absorption in UV-visible spectroscopy. Thus along with increasing amount of carbon black being added, absorption peaks of PANI/CB composite near 350 nm and 450 nm are getting weaker. However, the characteristic absorption peaks still exist and this means polyaniline is electrically conductive emeraldine salt form.
X-Ray Diffraction Analysis
Refer to FIG. 4, it shows XRD (X-ray Diffraction) pattern of polyaniline/carbon black composite with various weight of carbon black. Curve (a) is pattern of polyaniline (PANI), curve (b) is spectrum of PANI/CB(5), curve (c) is spectrum of PANI/CB(10), curve (d) is spectrum of PANI/CB(15), curve (e) is spectrum of PANI/CB(20), curve (f) is spectrum of PANI/CB(30), and curve (g) is spectrum of carbon black (CB). As to the curve of carbon black, a broad absorption peak appears at 2θ=24.3° and this means carbon black is in amorphous structure. This can be compared with TEM (transmission electron microscopy) figure of carbon black described later. Moreover, absorption peaks of PANI/CB occur at 2θ=10°, 15°, 21°, 25°, so does the pattern of the curve of aniline. These are all characteristic absorption peaks of aniline. It will be seen from this that addition of carbon black doesn't not change crystal form of aniline. Yet along with increasing ratio of carbon black in aniline, each absorption peak of aniline becomes weaker and this means the amount of carbon black is over maximum amount of carbon black that aniline covers. Conversely, aniline is covered by carbon black. Similar result is shown by a SEM figure of PANI/CB described later. Once absorption peak of PANI/CB composite at 2θ=25° is higher than the peak at 2θ=21°, it is highly doped and is conducting emeraldine salt form.
Electron Paramagnetic Resonance (EPR) and Conductivity Analysis
By means of electron paramagnetic resonance, free electron in aniline and interaction between aniline and carbon black are discussed. Refer to FIG. 5, it is EPR spectroscopy of polyaniline/carbon black composite with various amount of carbon black. All data in spectra is analyzed by Lorentzian function—a distribution function. The line width (ΔHpp), values of g factor, values of spin concentration, and spin-spin relaxation times (T2) are shown in list 1. Because carbon black has no free electron so that there is no absorption in EPR spectroscopy while other PANI/CB composite has similar pattern to EPR spectra of PANI.
By an equation (1), value of g factor of each sample is calculated and listed in list 1.

g=gs−(ΔH/H0)gs  (1)

wherein gs is g value of reference material-DPPHm ΔH is difference of spectrum half-width (full width half height) between reference material and sample to be measured.

The g value of six carbons on pure aniline is about 2.0031 and the g value of one nitrogen is about 2.0054. Thus the arithmetic average of g value is about 2.0054. The g value of PANI/CB composite ranges from 2.0043 to 2.0050. That means free electrons of polyaniline in the composite are nearer to N—H bond and polyaniline in the composite is between Emeraldine salt form and Emeraldine base form. Along with increasing amount of carbon black being added, g value tends to increase. This means free electrons of polyaniline are localized near area around N—H bond by carbon black while this will not affect conductivity of composites. Refer to values of conductivity of PANI/CB composite in list 2, the higher ratio the carbon black is, the higher conductivity the PANI/CB composite has. This may be due to bridging effect of carbon black that compensates reduced conducting ability caused by transformation of polyaniline.










List 1: EPR parameters of PANI/CB composite at room temperature











sample
ΔHpp(G)
g value
Ns(Spins/g)
T2(sec)














PANI
1.073
2.0044
4.01 × 107 
3.05 × 10−8


PANI/CB(5)
5.164
2.0046
3.78 × 109 
6.34 × 10−9


PANI/CB(10)
6.336
2.0043
1.68 × 1010
5.17 × 10−9


PANI/CB(15)
6.922
2.0046
3.78 × 1010
4.73 × 10−9


PANI/CB(20)
7.508
2.0047
7.70 × 1011
4.36 × 10−9


PANI/CB(30)
10.988
2.0050
1.36 × 1012
2.98 × 10−9









Peak-to-Peak Linewidth, ΔHpp 

As to solid samples, the following factors may have effect on the half-width thereof: (1) movement narrowing and fine splitting (2) interaction between unpaired electrons (including various types of transporting, fixing and movement) (3) exchange narrowing. It is learned from list 1 that Linewidth of each composite at room temperature is larger (5.164→10.988 G) along with increasing amount of carbon black being added (PANI/CB(5)→PANI/CB(30)). And it's larger than line width of aniline (1.073 G). This means an interactive force exists between polyaniline and carbon black. Linewidth variance is under influence of interactions between electron spinning and surroundings, spinning motion or structural rearrangement of copolymer. Thus the linewidth of PANI/CB(30) is maximum due to large interaction between polyaniline and carbon black. This indirectly indicates that polyaniline and carbon black are doped with each other evenly so that interactive force is proportional to the amount of carbon black being added.
Spin Concentration; Ns 
Area under EPR spectrum is about equal to (ΔHpp)2×h while h is height. Under the same conditions, use DPPH as reference material, number of unpaired spin electrons in the system is learned from area size. Refer to the list 1, electron spin concentration (Ns) of each composite from largest to smallest is PANI/CB(30)>PANI/CB(20)>PANI/CB(15)>PANI/CB(10)>PANI/CB(5)>PANI. Spin concentration of PANI/CB(30) is largest and this means this sample has more spin electrons than others and it is expected that PANI/CB(30) should have highest conductivity. Moreover, spin electrons of PANI is only 1/34000 of spin electrons of PANI/CB(30). It follows that addition of carbon black is helpful to generating spin electrons of polyaniline. The amount of carbon black being added is also related to the number of spin electrons generated. Along with increasing ratio of carbon black, spin concentration also increases and it is expected conductivity also becomes higher.
Spin-Spin Relaxation Time; T2 
A spin relaxation process is that an electron turns from high-energy state to low-energy state by electron transfer induction of similar electrons while a spin-spin relaxation is caused by energy difference between excited electron and electrons nearby and the spin-spin relaxation time (T2) is determined by linewidth in accordance with equation (2):




  
    
      
        
          
            1
            
              T
              2
            
          
          =
          
            
              g
              ⁢
              
                
              
              ⁢
              βΔ
              ⁢
              
                
              
              ⁢
              
                H
                
                  1
                  /
                  2
                
              
            
            η
          
        
        ,
        
          
            Δ
            ⁢
            
              
            
            ⁢
            
              H
              
                1
                /
                2
              
            
          
          =
          
            
              3
            
            ⁢
            Δ
            ⁢
            
              
            
            ⁢
            
              H
              pp
            
          
        
      
    
    
      
        (
        2
        )
      
    
  




wherein β is Bohr magneton (9.274×10−21 erg gauss−1), ΔH1/2 is Full Width Half Height of absorption peak (gauss), and η is a constant (1.054×10−27 ergs).

Through the list 1, it is found that T2 value of different PANI/CB composites with various amount of carbon black reduces from 6.34×10−9 sec to 2.98×10−9 sec (PANI/CB(5)→PANI/CB(30)) while PANI itself has highest T value (3.05×10−8 s). T2 value is affected by different electronic environment. Due to different ratio of PANI/CB, various electronic environments are available. Therefore, it is indicated that spin-spin relaxation time is inversely proportional to linewidth and is reduced along with increasing of carbon black.
Conductivity
Polyaniline is a (quasi-one-dimensional conductive polymer. After protonation, polyaniline turns from insulating states into conducting states. In the present invention, polyaniline is doped with protonic acid such as hydrochloric acid so as to produce polyaniline in emeraldine salt form. The emeraldine salt of polyaniline is polymerized in the presence of carbon black to produce conductive composite material. Measure resistance of the composite material and calculate conductivity by an equation (3).

σ=(1/R)×(h/A)  (3)

wherein conductivity has the unit of siemens per centimeter S/cm, R is resistance (Ω), h and A are respectively thickness (cm) and area (cm2) of a test piece.

Refer to list 2, it is found that conductivity of composites from largest to smallest is: CB>PANI/CB(30)>PANI/CB(20)>PANI/CB(15)>PANI/CB(10)>PANI/CB(5)>PANI. This is consistent with electron spin concentration (Ns). It follows that the larger the electron spin concentration is, the higher the conductivity is. Along with increasing ratio of carbon black, bridging effect is increased so that conductivity of composite is getting higher.
After the composite being added into organic modified organic modified siloxane (Ormosil), the conductivity is reduced to 1%. This is due to that siloxane (Ormosil) is not conductive and addition of conductive polymer makes the siloxane have conductivity above 10−3 S/cm. According to the list 3, when PANI/CB composite is added into Ormosil, conductivity of mixtures increases along with ratio of carbon black in the composite or the amount of PANI/CB composite being added. Within the ratio ranging from 10-30%, non-conductive Ormosil is turned into another form with conductivity above 10−3 S/cm.










List 2 Values of conductivity of PANI/CB at room temperature










sample
value of conductivity(S/cm)







PANI
0.19969



CB
1.22301



PANI/CB(5)
0.20569



PANI/CB(10)
0.33878



PANI/CB(15)
0.47329



PANI/CB(20)
0.63226



PANI/CB(30)
0.84523




















List 3 Values of conductivity of Ormosil-PANI/CB


at room temperature










sample
value of conductivity(S/cm)







Ormosil-PANI/CB(10)-10
0.002419



Ormosil-PANI/CB(20)-10
0.004635



Ormosil-PANI/CB(30)-10
0.007530



Ormosil-PANI/CB(10)-20
0.002593



Ormosil-PANI/CB(20)-20
0.005157



Ormosil-PANI/CB(30)-20
0.006077



Ormosil-PANI/CB(10)-30
0.003816



Ormosil-PANI/CB(20)-30
0.005652



Ormosil-PANI/CB(30)-30
0.008980










Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) Analysis

Refer to FIG. 6, it is a scanning electron microscope (SEM) image of carbon black and average diameter of its particle is from 10 to 80 nm. Although there are some clusters formed by aggregation of part of particles, it is proved that the carbon black is in nano-scale. Refer from FIG. 7A to FIG. 7D, respectively are SEM images of CB, PANI/CB(30), PANI/CB(20) and PANI/CB(10). The length of scale on bottom of each figure is 1 μm. In FIG. 7D, it is found that polyaniline covers the carbon black evenly. Yet along with increasing amount of carbon black being added, carbon black exposed outside polyaniline is getting more, as shown in FIG. 7B. Thus it is supposed that after addition of 20% of carbon black, there is over-saturation. From FIG. 7A to FIG. 7D, threadlike polyaniline is observed. This may be caused by connection of conductive channels and further a conductive network is formed. This leads to higher conductivity of composites.
Refer from FIG. 8A to FIG. 8D, respectively are TEM figures of CB, PANI/CB(30), PANI/CB(20) and PANI/CB(10). The length of scale on bottom of each figure is 0.5 μm. It is observed that either distribution of carbon black or covering of polyaniline is quite ideal and there is no mass. Thus an evenly conductive network is formed so that conductivity of the composite is increased. In FIG. 8D, the darker area is carbon black while the lighter area is polyaniline. This figure shows that the polyaniline covers the carbon black. Yet from FIG. 8A to FIG. 8C, along with increasing amount of carbon black being added, carbon black distributed outside polyaniline is getting more. This result can be compared with SEM images in FIG. 7A to FIG. 7C. Therefore, observe the microstructure, structure and distribution of PANI/CB(20) are most perfect and it has adequate conductivity without decreasing mechanical property and processability.
Microwave Absorbing Property Analysis of PANI/CB
Add powder of CB, PANI/CB(10), PANI/CB(20) and PANI/CB(30) composite into epoxy resin in weight ratio of 3/7 and the mixture is made into 15 cm×15 cm test pieces with thickness of 0.2 cm for performing microwave absorbing tests with frequency ranging 2-18 GHz and 18-40 GHz. Refer to FIG. 9, return loss of nanocomposite material with frequency from 2 to 18 GHz is disclosed, curve (a) is epoxy/CB nanocomposite material, curve (b) is epoxy/PANI/CB(10) nanocomposite material, curve (c) is epoxy/PANI/CB(20) nanocomposite material, and curve (d) is epoxy/PANI/CB(30) nanocomposite material. The values of relative dB and the peak are in list 4. The return loss of epoxy/PANI/CB(30) nanocomposite material is −40 dB and the peak is at 11.4 GHz while when dB is −10, the linewidth is about 3.1 GHz (10-13.1 GHz). The return loss of epoxy/PANI/CB(20) nanocomposite material is −16 dB and the peak is at 12 GHz while when dB is −10, the linewidth is about 2.5 GHz (10.7-13.2 GHz). The peak of epoxy/PANI/CB(10) nanocomposite material is at 15 GHz and the return loss is −6.8 while the peak of epoxy/CB is at 11 GHz and the return loss is −10. It is found from above curves that epoxy/PANI/CB(30) and epoxy/PANI/CB(20) nanocomposite materials achieve over 90% absorption of low frequency radar wave. The possible reason that the two nanocomposite material has better absorption effect of low frequency radar wave than pure epoxy/carbon black nanocomposite material is due to electromagnetic effect generated by surface polarization between polyaniline and carbon black. The absorption effect of epoxy/PANI/CB(10) nanocomposite material is not as good as the above two nanocomposite materials. The results show that with frequency ranging from 2 to 18 GHz, the epoxy/PANI/CB(30) nanocomposite material has best absorption effect and it is supposed that this is due to more amount of carbon black in the test piece. Thus it follows that when there is more amount of carbon black in the composite material, the absorption effect thereof at low frequency is more obvious.










List 4 microwave absorption parameters at low frequency of epoxy


nanocomposite material containing polyaniline/carbon black












Epoxy nanocomposite
Epoxy nanocomposite
Epoxy nanocomposite
Epoxy nanocomposite



material containing
material containing
material containing
material containing



CB
PANI/CB(10)
PANI/CB(20)
PANI/CB(30)

















peak
11.0 GHz
15.2 GHz
11.9
GHz
11.4
GHz


frequency


maximum
10.9 dB 
6.8 dB 
16
dB
40
dB


return loss


dB = −10
none
none
10.7~13.2
GHz
10~13.1
GHz


linewidth









Refer to FIG. 10, return loss of nanocomposite material with frequency from 18 to 40 GHz is disclosed, curve (a) is epoxy/CB nanocomposite material, curve (b) is epoxy/PANI/CB(10) nanocomposite material, curve (c) is epoxy/PANI/CB(20) nanocomposite material, and curve (d) is epoxy/PANI/CB(30) nanocomposite material. The values of relative dB and the peak are in list 5. The return loss of epoxy/PANI/CB(30) nanocomposite material is −11.2 dB and the peak is at 28 GHz while when dB is −10, the linewidth is about 3 GHz (26.7-29.6 GHz). The return loss of epoxy/PANI/CB(20) nanocomposite material is −16.2 dB and the peak is at 35 GHz while when dB is −10, the linewidth is about 6.5 GHz (31.9-38.4 GHz). The peak of epoxy/PANI/CB(10) nanocomposite material is at 38 GHz but it's not obvious while the peak of epoxy/CB is at 38 GHz and the return loss is −7.2. The results show that within frequency ranging from 18 to 40 GHz, the epoxy/PANI/CB(20) has best absorption effect. In summary, the epoxy/PANI/CB(30) and epoxy/PANI/CB(20) nanocomposite materials achieve over 90% absorption no matter at low frequency range or high frequency range. Moreover, the absorption effect of them is better than that of the epoxy/CB nanocomposite material. Therefore, such nanocomposite materials have wide prospects of application and research values.










List 5 microwave absorption parameters at high frequency of epoxy


nanocomposite material containing polyaniline/carbon black












Epoxy nanocomposite
Epoxy nanocomposite
Epoxy nanocomposite
Epoxy nanocomposite



material containing
material containing
material containing
material containing



CB
PANI/CB(10)
PANI/CB(20)
PANI/CB(30)

















peak
37.9 GHz
38 GHz
35.0
GHz
28
GHz


frequency


maximum
7.2 dB
none
16.2
dB
11.2
dB


return loss


dB = −10
none
none
32~38.4
GHz
26.7~29.6
GHz


linewidth









Salt Spray Test

6061-T6 and 2024-T3 aluminum alloy sheets coated with organic siloxane nanocomposite material containing polyaniline/carbon black coatings are set into a salt spray testing chamber while testing procedure and testing parameters are standardized under standard of ASTM B117. Use a 300× metallurgical microscope to observe surfaces of test sheets at 24-hour intervals. According to military specification MIL-C-81706/5541, number of rust spot within 100 mm2 test area should be no more than two. Moreover, chemical conversion coatings basically should be resistant to salt spray corrosion for at least 168 hours.
Refer to FIG. 11A, (a), (b), (c), (d) and (e) are photomicrographs of 2024-T3-0D aluminum alloy sheet, 2024-T3 aluminum alloy sheets coated with Ormosil-0D, Ormosil-PANI/CB(20)-10-0D, Ormosil-PANI/CB(20)-20-0D and Ormosil-PANI/CB(20)-30-0D taken by a metallurgical microscope. In FIG. 1B, (a), (b), (c), (d) and (e) are photomicrographs of 2024-T3-7D aluminum alloy sheet, 2024-T3-7D aluminum alloy sheets coated with Ormosil-7D, Ormosil-PANI/CB(20)-10-7D, Ormosil-PANI/CB(20)-20-7D and Ormosil-PANI/CB(20)-30-7D taken with a metallurgical microscope. With reference of FIG. 11C, (a), (b), (c), (d) and (e) are photomicrographs of 6061-T6-0D aluminum alloy sheet, 6061-T6 aluminum alloy sheets coated with Ormosil-0D, Ormosil-PANI/CB(20)-10-0D, Ormosil-PANI/CB(20)-20-0D and Ormosil-PANI/CB(20)-30-0D taken with a metallurgical microscope. In FIG. 11D, (a), (b), (c), (d) and (e) are photomicrographs of 6061-T6-0D aluminum alloy sheet, 6061-T6-0D aluminum alloy sheets coated with Ormosil-7D, Ormosil-PANI/CB(20)-10-7D, Ormosil-PANI/CB(20)-20-7D and Ormosil-PANI/CB(20)-30-7D taken with a metallurgical microscope. The 0D and 7D represent test period in a unit of day
After the salt spray test, a metallurgical microscope is used to observe corrosion on surface of aluminum alloy. After 7 days of test period, both 6061-T6 and 2024-T3 blank aluminum alloy sheets (without coating) have quite large rusted area while aluminum alloy sheets coated with organic siloxane (Ormosil) has only small area of rust. Taking PANI/CB(20) as an example, refer from FIG. 11A to FIG. 11D, aluminum alloy sheet coated with Ormosil-PANI/CB has compact structure on surface so that there is no corrosion after 7-day test period of salt spray test. But along with increasing amount of PANI/CB(20) being added, small part of the Ormosil-PANI/CB(20) attached on surface thereof begins to feel. The more amount of PANI/CB(20) is added, the more obvious the peeling is. It follows that adhesion of the carbon black in hybrid to the alloy sheet is not strong enough. After observations, it is found that change of ratio of aniline to carbon black has no obvious effect on results of the salt spray test. Results of observations by the metallurgical microscope are similar to those of Ormosil-PANI/CB(20). Moreover, corrosion resistance of Ormosil-PANI/CB hybrid coating on the 6061-T6 alloy sheet is better than that on the 2024-T3 alloy sheet.
In summary, polyaniline/carbon black composite of the present invention increases conductivity of polyaniline and is applied to corrosion resistant conductive coatings and microwave absorption dielectric material.
Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details, and representative devices shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

## Claims

1. A preparation method of polyaniline/carbon black composite comprising the steps of:
dispersing carbon black into a solution to form a carbon black solution;
adding aniline into the carbon black solution to form a first solution;
dissolving ammonium persulfate into an acid aqueous solution to form a second solution; and
adding the second solution to the first solution for reaction, and then through filtering and grinding to produce polyaniline/carbon black composite;
wherein the polyaniline/carbon composite has a core-shell structure; and
the weight of the carbon black is 20-30% of the total weight of the polyaniline/carbon black composite.

2. The method as claimed in claim 1, wherein in the step of dispersing carbon black into solution to form carbon black solution, the solution is mixture of a dispersing agent, ethanol solution and acid.

3. The method as claimed in claim 1, wherein the step of dispersing carbon black into solution to form carbon black solution further comprising a step of ultrasound vibration.

4. The method as claimed in claim 1, wherein in the step of dissolving ammonium persulfate into acid aqueous solution to form a second solution, the acid aqueous solution is hydrochloric acid solution.

5. The method as claimed in claim 1, wherein reaction time of the step of adding the second solution to the first solution for reaction, and then through filtering and grinding to produce polyaniline/carbon black composite ranges from 1 to 5 hours.

6. The method as claimed in claim 5, wherein optimum reaction time is 2 hours.

7. The method as claimed in claim 1, wherein in the step of adding the second solution to the first solution for reaction, and then through filtering and grinding to produce polyaniline/carbon black composite, an acid rinsing step is further included between filtering and grinding.

8. The method as claimed in claim 7, wherein hydrochloric acid is used in the acid rinsing step.