http://www.chemistrymag.org/cji/2001/035020pe.htm

  May 1, 2001  Vol.3 No.5 P.20 Copyright cij17logo.gif (917 bytes)


The study of the mechanism of Ec in polyelectrolyte ER system

Pang Wenmin, Wang Jianli, Fan Chenggao, Zhu Qingren
(Structure Research Laboratory, USTC, Hefei, Anhui 230026
, China )

Received Nov. 9, 2000; Supported by the National Natural Science Foundation of China (No.29874031)

Abstract For a better understandng of the mechanism of Ec (threshold field) in ER fluids, a new testing method, Saturated Electric Field (SEF) was designed. The exist of Ec1 and Ec2 is clearly proved and explained. Furthermore, the fitness of two well-known model for ER in different ER systems is defined. The computer simulation also gave out two order parameter j1 = 1.5 and j2 = 4.5, which correspond well to Ec1 and Ec2, respectively.
Keywords Electrorheological Fluid (ERF), Polyelectrolytes, Threshold Field

For the potential value in both theory and applications, Electrorhological (ER) fluids, especially polymer based systems, have recently attracted increasing attention[1,2]. Although the mechanism of ER was explained pretty well, further detail studies are still needed to reach a better understanding.
    For example, the exist of threshold fields (E
c1, Ec2) is well-known[3,4]. The classic method that Ec1 and Ec2 come from is, adding a certain electric field(usually DC field) directly to the system first, testing the value of yield stress(t s), then switching to another field and testing the t s, and so on. From so-got E vs t s curve, Ec1 and Ec2 can be observed sometimes, and sometimes not. From the classic ER model, Particle Chain Model(PCM)[5], we know t s µ E2 and no Ec can be induced from it. On the other side, R. Tao pointed out, the total energy(H) of the particle in ER fluid should be, H=K+U, which K is Brown thermadynamic energy and U is dipolarization enery. He also used j as the order parameter of ER system, which indicates the relative valuse of  K and U. After simple calculation, Tao got Ec1µ j 11/2, Ec2µ j 21/2. j 1, j 2 are two phase transition points, when j < j 1, the system is in liquid state,j > j 2, solid state and when j 1< j < j 2, the system is in a transition state like the "nematic state" in liquid crystallines. We named this model "Phase Transition Model" (PTM). So, some questions come naturally: why do the ER systems sometimes show Ec and sometimes not? Which model is right in the case of Ec, PCM or PTM? How to quantatively explain the mechanism of Ec?
    In the present paper, we afford a new testing mothod named Saturated Electric Field (SEF) in addition to the classic method mentioned above. The only different between the two methods is, the first thing before each test of E vs t s is to add an extremely high elctric field (5kV/mm here) to the ER fluid to make sure the system is "saturated" by the electric field, quit the field after 1 minute, and then add the proposed electric field to test the t s, just the same in classic method. From the advantage of the new method (SEF) as well as computer simulation, we can give the answer for above questions.

1. EXPERIMENTAL
Preparation of ER fluids. The polyelectrolyte selected as dispered phase is polystyrene-CH2COONa(trade name: G751) which was bought from Shanghai Chemical Company. The particle size is 50-70µm. This was dried uder vacuum at 110°C for 24 hours and then immediately dispersed into silicone oil in weight percent of 12.5%.
    Apparatuses. As reported in our early paper[6], an effective parall-plate static yield stress testing apparatus, which made by ourselves, is used.

03502001.jpg (12353 bytes)
Fig 1
Optical micrograph under E=0.6kV/mm (100×)
  
   Fig 2
Optical micrograph under E=1.0kV/mm (100×)

Fig 3
Optical micrograph under E=2.5kV/mm (100×)

  
   Fig 4
Optical micrograph under E=5.0kV/mm (100×)


Fig 5
Optical micrograph under after 3 days


2. RESULTS AND DISCUSSIONS
2.1 Structure relexation of the ER fluid
 
Fig. 1-4 are the pictures of the ER fluid under a series of increased eclectric field (0-5 kV/mm) at room temperature by optical microscope, showing the development of the electric-field-induced structure in the ER system. Two critical points, Ec1 (0.6 kV/mm) and Ec2 (2.5 kV/mm), were found during the process. When E>Ec1, the ER system began to form column structure in some degree(Fig. 3). These single columns changed slightly with the increased field but reformed and adjusted rapidly and formed a high order structure when E reached E
c2, as shown in Fig. 4. After that, the structure didn't change up to E = 5 kV/mm.
    Once formed, the high order structure was very stable even without electric field at all for a long time(>3days, Fig. 5). So, this kind of ER system is considered having strong relaxation in its geometry structure. And this unique character affords the basement for the new testing method SEF.
2.2 Quantitative study of Ec
We tested the relationship of E vs t s using the classic method. The results were shown by the "
§" curves in Fig. 6. The range of electric field is 0-5 kV/mm. Two threshold fields were observed, Ec1 (0.6 kV/mm) and Ec2 (2.5 kV/mm).
    Under the same condition, we switched to the new method SEF also showed the results in Fig. 6 ("." curve). The saturated field is 5 kV/mm. Obvisouly, the curve is pretty smooth and no any critic point, and this curve is basically similar to the theoretical one.

    To make it more clearer, the difference between the two methods were shown in Fig. 7 [ Dts=ts(SEF) -ts(classic)]. From Fig. 7, when Ec1<E<Ec2, the range Dts of is between 24 - 51 Pa and its average is about 36 Pa (Considering the corresponding range of E (~ 2 kV/mm), the change of Dts is very small). We noticed that this average value is almost equal to the value of ts(classic) under Ec1(35 Pa). When E>Ec2, Dts= 0, which means no difference between the two methods at that time.
    Why Ec1 and Ec2 appeared in "classic method" while not in "SEF" for the same ER system? In "SEF", when the saturated field (5 kV/mm) added, as proved above, the system formed a high order structure and especially, very stable(strong relaxation). Then when the field was changed to the proposed value, the system could keep the same high order and stable structure. In another word, the system had finished a phase transition (or proximately) before the testing. So, the electric energy received by the system could be completely used to induce the "fixed" dipoles in stead of "waste" a part of it to overcome the Brown random moving of particles as in the classic method. Under this condition, we can conclude that the ER effect and electric field have a simple one to one relationship in SEF. Thus the factor of K in R. Tao's equation can be omitted and a single continuous function was got, in which no position for Ec1 and Ec2 like in "PCM" model.
    Now the reason that Ec appeared in "classic method" becomes clear: when E<E
c1, the electric energy is relatively small compared to the thermal energy and can not induced any order structure and no any ER effect observed as a result. When Ec1<E<Ec2, the electric energy increased but only in the same level with the thermal energy, the degree of the induced structure is pretty low and far from perfect. There are lots of "voids" in the catenarian (or column) structure. So the electric energy added could be only partly changed into the "useful" dipolarization energy, and efficiency of the induced ER effect is lower than that of "SEF", in which the efficiency is near 100%. The lost part of the efficiency is believed to be dispersed in the void areas, in which Brown thermal random moving dominates, so the difference ER effect for the two methods, can properly reflect how much the thermal energy affects the ER effect. On the other hand, if we reexam the curve of E vs t s in the range of Ec1 - Ec2 in classic method from this point, the ER effect totally comes from order parts and those voids contribute nothing, we can guess this part of line in Fig. 6 is also obey the same rule as the other part(E>Ec2) or the whole line for SEF and only different in a factor, for example, t s µ AE2 , but this prediction needs a further detail study to be proved. When E>Ec2, electric energy is the dominant one and the high order structure formed, and the difference of the two methods disappeared naturally.

Fig 6 ts-E relationship curves by two methode
03502007.gif (4524 bytes)
     Fig 7 The relationship curve of Dts-E

Predictably, the relationship of circuit density I and electric field E has the similar trend under the two testing methods. The results showed it was and consistent with the above analysis. (Fig. 8)

03500208.gif (2430 bytes)
Fig
The relationship curve of Dt-E

    The order geometry structure (chain structure) is the bridge for electric energy to induce ER effect. And the structure more perfect, the higher efficiency of the energy is. Additionally, the structure itself doesn't increase the viscosity of the system, which is shown by the results under zero field in two testing methods.
    The dash line in Fig. 6 is theoretical calculation from PCM model. Under relatively low field (E<E
c2), the results from SEF fitted PCM better than those from classic method. But this does not mean that the PTM model is wrong. The consideration of thermal factor K by R. Tao et al is reasonable and necessary. Indeed, it is the competetion between k and other factor, electric U, that causes the exist of Ec1 and Ec2. The two models are both backed by some experimental results. Which one is really right? Or what's their application and limitation? Here we try to give some explanations.
(1) They are both reasonable under specific conditions.
(2) To match an experimental result to one theroy is determined by the comprehensive effect of several factors, such as testing method, range of electric field and the relaxation of ER system, etc.
(3) When the system has strong relaxation, as shown in the present paper, the effect of testing method and range of electric field is listed in Table 1.

Table 1. Effect of some factors in strong realaxion ER system

Range of Electric field

Classic method

SEF method

E < Ec1

2

1

Ec1 < E < Ec2

2

1

E > Ec2

1

1

* 1 "Particle Chain Mode"; 2 "Phase Transition Model"

    From the table, when the experimental results are got by classic method, they are not fitted or explained by only one model, and the range of electric field need to be considered to chose a model. When the results are from SEF method, it is possible and necessary to use PCM model. Of course, this does not mean that PCM is better than PTM, because the system here has strong relaxation. And the advantage of SEF method can be only shown in this kind of condition (many polymer-based ER system but not all).
(4) When the system has small or no relaxatin, like inorganic ER system or some polymer-based ER system, testing method and range of electric field has the following effect (Table 2).

Table 2. Effect of some factors in weak realaxion ER system

Range of Electric field

Classic method

SEF method

E < Ec1

2

2

Ec1 < E < Ec2

2

2

E > Ec2

2

2

* 1 "Particle Chain Model"; 2 "Phase Transition Model"

The result has no any surprise. When the realxtion of the system is very small, it is impossible to make the system form a high order structure before test in SEF method, so no difference indeed between SEF and classic method. In a word, PTM model is good for these systems( weak relaxation, some inorganic system).

2.3 Computer Simulation    
We used Monta Carlo method to simulate the ER fluid based on R. Tao's phase transition model. Here we only give out some results about E
c1 and Ec2.
    When
j, the order parameter which indicate the relative value between electric energy and thermal energy, increased from 1 to 5 step by step. We found,
    When
j <1.5, no any struture in the system.
    When
j =1.5 or higher but smaller than 4.5, single chain structure appeared.
    When
j=4.5 or higher, multi-chain struture appeared.
j =1.5 and j =4.5 are two phase transition points and correspond to E
c1 and Ec2, respectively.

3. CONCLUSION
Based on the strong relaxation character of our polyelectrolyte ER system, we study the mechanism of Ec from a new point by designing the "Saturated Electric Field" method. The exist of E
c1 and Ec2 is just because the no structure or not perfect structure in ER system under certain conditions. The structure void causes the ER effect is lower than expected value ( by PCM model) in the field range of Ec1 - Ec2. And this was proved by the successful elimination of Ec1 and Ec2 in the strong relaxtion system tested by SEF. We also made it clear that the applicatin and limitation of two well known models (PCM and PTM) the relationship between our new SEF method and the classic method, which is also probablely useful in ER application in addition to the theoretical value.

REFERENCES
[1
] Block H, Kelly J P. J. Phys Rev. D, 1988, 21: 1661.
[2
] Treasurer U, Radzilowski, Filisko F E. J. Rheol., 1991, 35 (6): 1051.
[3
] Tao R. Phys. Rev., 1993, E47: 423.
[4
] Tao R. Int. J. Mod. Phys., 1992, B6: 2635.
[5
] Flisiko F E. J. Rheol., 1990, 34: 539.
[6
] Zhu Q R, Su J, Hong K L et al. Functional Polymer, 1997, 10: 1.

 


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