Method for determining optimal degree of vulcanization and optimal content of constituent ingredient of composition for vulcanization in real time by impedance measurement and analysis

a technology of impedance measurement and analysis, applied in the direction of resistance/reactance/impedence, instruments, material impedance, etc., can solve the problems of deteriorating the mechanical properties of the polymer composition, affecting the vulcanization rate, and the need for expensive rheometer equipment, etc., to optimize the properties of the vulcanized sample, and improve the vulcanization rate. rp rapid slowdown

Inactive Publication Date: 2005-08-02
KOREA KUMHO PETROCHEMICAL CO LTD
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  • Claims
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Benefits of technology

[0008]It is therefore an object of the present invention to solve the problems with the prior art and to provide an optimal method for controlling vulcanization in real time through impedance measurement and analysis of a polymer, thereby accurately evaluating the internal properties of the vulcanized polymer sample over time in the vulcanization process.
[0010]To achieve the above objects of the present invention, there is provided a method for evaluating the crosslink degree of a vulcanized sample in real time during a vulcanization process or diagnosing the electrical properties of the sample after the completion of the vulcanization process, and then determining an optimal vulcanization time and an optimal content of each constituent gradient of a composition for vulcanization that optimize the properties of the composition according to the vulcanization conditions, thereby improving the properties of the vulcanized sample prepared from a polymer by vulcanization at a high temperature. In the present invention, the whole frequency range (10 kHz to 1 Hz) of the measured impedance spectrum is taken into consideration in the analysis process. Also, the present invention approximates the impedance spectrum to a physically adequate equivalent circuit model of a vulcanized sample and thereby determines the physical properties of the vulcanized sample as capacitance and resistance components representing the microscopic internal characteristics of the sample in the level of molecule. Especially, the resistance component can be obtained by approximation to the resistance of carbon black itself and the resistance component of the polymer material. The resistance component greatly depends on the constituent ingredients of the composition for vulcanization used in the vulcanization process, the crosslinking method used for vulcanization, the temperature, and the crosslink degree. These internal resistance characteristics of the vulcanized sample can be used alone or in combination as the final criteria for the properties of the vulcanized sample and, accordingly, suitably applied for the purpose of accurately evaluating the internal properties of the vulcanized sample over time or of the sample completely vulcanized.
[0012]More specifically, the present invention includes fitting impedance data measured in the frequency range of 10 kHz to 1 Hz using an adequate analysis software according to a method disclosed in U.S. patent application Ser. No. 09 / 476,452; determining a polymer resistance Rp (i.e., a value obtained by subtracting a real part of the impedance measurement at a maximum frequency from a real part of the impedance measurement at a minimum frequency, or the magnitude of a real part of the semicircle in a Nyquist diagram) among various resistance parameters; determining, as an optimal end point of vulcanization, a time point at which the increasing rate of the polymer resistance Rp rapidly slows down; and determining the optimal content of each constituent ingredient of the composition for vulcanization when the polymer resistance Rp of the sample completely vulcanized is at its minimum. Compared with the conventional methods for evaluating vulcanization through torque variations and tensile test, the present invention is more efficient to optimize the properties of the vulcanized sample. The present invention is also a non-destructive testing method that takes a very short time of about one minute in the measurement and evaluation for securing excellent properties of the vulcanized sample and an accurate end point of vulcanization, relative to the conventional methods such as rheometer method or tensile testing method.

Problems solved by technology

On the other hand, the method of increasing the vulcanization temperature is effective in reducing the required vulcanization time but changes the crosslinking structure or the crosslink degree depending on the thermal stability of the used polymer or vulcanization system, thus deteriorating the mechanical properties of the polymer composition.
In the rheometer method, however, it is necessary to use very expensive rheometer equipment and to keep clean the surface of the oscillating disc being in contact with the vulcanized composition in every vulcanization reactor and the surface of the inner wall of the reactor for the sake of precisely measuring the torque variations of the sample over time.
When the shelf time after mixing the composition for vulcanization used for the vulcanization process and all the temperature variations of samples controlled in the vulcanization process are not constant, a considerable error on the vulcanization rate may occur in the rheometer method that measures the macroscopic properties of the sample.
This requires a little over-vulcanization in determining the end point of the vulcanization process, thus increasing the required vulcanization time, and the over-vulcanization inevitably causes a slight deterioration of the properties in the part of the sample.
The orientation speed of dipoles to the frequency applied is generally limited because the hardness of the polymer increases with the progress of the vulcanization process.
However, the evaluation method using a single high frequency (e.g., 9 kHz) in consideration of fast dynamics in the sample during the vulcanization process is unsatisfactory in accurately predicting all the internal characteristics and properties (including slow dynamics) of the vulcanized sample.
But the tensile test requires a number of samples and takes a long time for measurement (See.
Besides, the methods for measuring the properties of a vulcanized sample may include exothermic test, tearing energy measurement, repulsive elasticity test, durability test, BFG cutting and chipping characteristic test, all of which still require a long time for measurement of the properties (See.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

examples 1 , 2 and 3

EXAMPLES 1, 2 and 3

[0018]The samples used in measuring the variations of the properties of rubber during the crosslinking process were prepared with the compositions as listed in Table 1 according to a known method prior to the crosslinking process. The synthetic rubber as used in the test was styrene butadiene rubber (SBR) supplied from Korea Kumho Petrochemical Co., Ltd. The samples in Examples 1, 2 and 3 were different from one another in the content of sulfur and vulcanization accelerating agent in the rubber composition for vulcanization.

[0019]

TABLE 1Example123SampleS1S2S3Synthetic rubber137.5137.5137.5Carbon black68.7568.7568.75Zinc oxide3.03.03.0Stearic acid1.01.01.0Sulfur1.02.03.0Vulcanization accelerating agent1.02.03.0

examples 4 , 5 and 6

EXAMPLES 4, 5 and 6

[0020]The samples used in measuring the properties of the rubber after the completion of vulcanization were prepared with the compositions as listed in Table 2 according to a known method prior to the crosslinking process. Then, the vulcanization time was varied depending on the content of sulfur and vulcanization accelerating agent in the rubber composition for vulcanization. The vulcanization time based on the content was measured using a known rheometer method. The synthetic rubber as used in the test was SBR supplied from Korea Kumho Petrochemical Co., Ltd. The samples in Examples 4, 5 and 6 were different from one another in the content of sulfur and vulcanization accelerating agent in the rubber composition for vulcanization and the vulcanization time.

[0021]

TABLE 2Example123SampleS1-1S2-1S3-1Synthetic rubber137.5137.5137.5Carbon black68.7568.7568.75Zinc oxide3.03.03.0Stearic acid1.01.01.0Sulfur1.02.03.0Vulcanization accelerating agent1.02.03.0Vulcanization t...

example 7

[0022]Now, a specific example of measuring the variations of the properties of the rubber during the crosslinking process will be described in detail. The following description will be given to the real-time property measurement for samples S1, S2 and S3 of Examples 1, 2 and 3, respectively, which are different from one another in the content of sulfur and vulcanization accelerating agent in the rubber composition for vulcanization.

[0023](a) The measurement of impedance was performed to evaluate the crosslink degree of the vulcanized samples in real time during the vulcanization process. The impedance spectrum was measured in an adequate frequency range (10 kHz to 1 Hz) for determining the parameters of an equivalent circuit model used in the spectrum analysis. A battery diagnosis system (Powergraphy™, model name: BPS 1000FL) supplied from Korea Kumho Petrochemical Co., Ltd. was used in the impedance measurement. For the real-time impedance measurement during vulcanization at a high...

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Abstract

The present invention relates to a method for evaluating the crosslink degree of a vulcanized sample in real time during a vulcanization process or diagnosing the electrical properties of the sample after the completion of the vulcanization process, and then determining an optimal vulcanization time and an optimal content of each constituent gradient of a composition for vulcanization that optimize the properties of the composition according to the vulcanization conditions, for the sake of improving the properties of the vulcanized sample prepared from a polymer by vulcanization at a high temperature.The method for determining an optimal vulcanization time and an optimal content of each constituent gradient of a composition for vulcanization that optimize the properties of the composition according to the vulcanization conditions includes: (a) measuring an impedance spectrum in a specific frequency range in the individual vulcanization condition; (b) approximating the measured impedance spectrum to an equivalent circuit model consisting of resistance and capacitance components; (c) determining a polymer resistance Rp (i.e., a value obtained by subtracting a real part of the impedance measurement at a maximum frequency from a real part of the impedance measurement at a minimum frequency, or the magnitude of a real part of the semicircle in a Nyquist diagram) from the determined parameters; (d) determining, as an optimal end point of vulcanization, a time point at which the increasing rate of the polymer resistance Rp rapidly slows down; and (e) determining the optimal content of each constituent ingredient of the composition for vulcanization when the polymer resistance Rp of the sample completely vulcanized is at its minimum.

Description

BACKGROUND OF THE INVENTION[0001]1.The Field of the Invention[0002]This invention relates to a method for evaluating the crosslink degree of a vulcanized sample in real time during a vulcanization process or diagnosing the electrical properties of the sample after the completion of the vulcanization process, and then determining an optimal vulcanization time and an optimal content of each constituent gradient of a composition for vulcanization that optimize the properties of the composition according to the vulcanization conditions, thereby improving the properties of the vulcanized sample prepared from a polymer by vulcanization at a high temperature.[0003]2. Related Prior Art[0004]The polymer vulcanization process takes a most time in the manufacture of polymer products in the rubber industry relating to general polymer materials such as tires. Thus steady and persistent efforts have been made to increase the vulcanization rate so as to shorten the required time of the vulcanizati...

Claims

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Application Information

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Patent Type & Authority Patents(United States)
IPC IPC(8): C08J3/24G01N27/02G01N33/44B29C35/02B29K21/00B29K105/24C08L21/00
CPCC08J3/248G01N27/026G01N33/445C08J2321/00C08J2325/10G01N27/02
Inventor JANG, JEE-HWANSUNG, HYUN-KYUNGBAIK, HUN-JONGLEE, HO-SULL
Owner KOREA KUMHO PETROCHEMICAL CO LTD
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