CN102053044B - Method for quickly measuring viscous flow activation energy of polyolefin - Google Patents
Method for quickly measuring viscous flow activation energy of polyolefin Download PDFInfo
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- CN102053044B CN102053044B CN2009102370089A CN200910237008A CN102053044B CN 102053044 B CN102053044 B CN 102053044B CN 2009102370089 A CN2009102370089 A CN 2009102370089A CN 200910237008 A CN200910237008 A CN 200910237008A CN 102053044 B CN102053044 B CN 102053044B
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Abstract
The invention relates to a method for quickly measuring the viscous flow activation energy of polyolefin, which is used for measuring the viscous flow activation energy of polyolefin such as polyethylene, polypropylene, and the like. The method comprises the following steps of: carrying out temperature scanning at a temperature above the smelting point of polyolefin and below a decomposition temperature by using a dynamic rheometer to measure a plurality of change curves of the viscosity changed along with the temperature of the polyolefin; converting a measurement result into change curves of the apparent viscosity changed along with the temperature of a sample through a Cox-Merz rule; carrying out linear regression on the converted data by using a formula of lgeta<a>=K/T+b to obtain the values of K and b in the regression formula; and then obtaining the viscous flow activation energy of the measured sample according to a formula of Eeta=19.147*(J/mol). The method has the advantages of fewer required samples, short measurement period, high speed and high efficiency.
Description
Technical field
The present invention relates to polyolefinic analytical approach, specifically is the assay method of polyolefin viscous flow activation energy.
Background technology
At present, domestic plastics industry has all formed a cover than rounded system from starting material production, product processing and manufacturing until using, but the research of the rheological property of plastic processing but relatively lags behind, and many medium-sized and small enterprises also only dependence experience are produced.The plastic processing parameter exterior quality and the internal performance that directly has influence on product accurately be set, so the research of raw material rheological property has direct directive function to the production of plastic products.Viscous flow activation energy is an important parameter of material flowing deformation performance; It had both reflected the complexity that material flows; The more important thing is the temperature sensitivity that has reflected that viscosity of material changes; The variation directive significance important of research viscous flow activation energy to being processed with of plastic products, and that the fast measuring viscous flow activation energy just seems is extremely important.
Viscous flow activation energy is defined as in the flow process, and flow unit is used to overcome barrier potential and transits near " hole " required least energy by original position.Introduced the method for mensuration viscous flow activation energy commonly used in the document " the viscous flow activation energy research of several kinds of different PE and PP resin " (using chemical industry, 2008,37 (1)).
More than flow temperature, the AV of superpolymer and temperature relation meet the Arrhenius experimental formula:
In the formula, η
aApparent shear viscosity when (T) being temperature T, PaS; A is a constant; E
ηBe viscous flow activation energy, J/mol, R are gas law constant, 8.314; T is an absolute temperature, K.Further can get:
Make lg η
aThe relation curve of～1/T, its slope K=E
η/ 2.303R, thus viscous flow activation energy obtained.In the document under the different temperatures AV be that AV through under selected a plurality of temperature conditions, repeatedly measuring polymkeric substance obtains with the variation of shear rate.Therefore will obtain viscous flow activation energy just needs test of many times, and efficient is not high.
All mentioned the assay method of other a kind of viscous flow activation energy among CN101157738A and the US6258912B1.Through the Arrhenius formula by shifter factor (a
T) the calculating viscous flow activation energy.
Said shifter factor is to obtain when according to time-temperature superposition principle the dynamic rheological property trial curve being superposeed.In measuring process, measure the change curve with angular frequency such as storage modulus under the different temperatures, selected reference temperature T in each temperature of measuring
0, with the curve that records under each temperature reference temperature T that is added to
0The time curve on, thereby confirm the shifter factor of each temperature.The slope of through type (4) and formula (5) are calculated:
ln(a
T)＝m/T+n (4)
E
η＝|8.314m| (5)
The software for calculation that the aforementioned calculation process need is special, like Rhios V.4.4.4.And obtaining viscous flow activation energy equally need be in test of many times under the different temperatures, and efficient is not high.
This shows that these the two kinds method principles of measuring viscous flow activation energy commonly used at present all are based on the Arrhenius experimental formula, obtain required result and at first all need carry out test of many times, efficiency of measurement is not high.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing dynamic rheometer to measure the polyolefin viscous flow activation energy fast; Utilize Arrhenius experimental formula (1); Adopted the metering system that is different from prior art, and, can just can obtain viscous flow activation energy through single test through data-switching.
The method of fast measuring polyolefin viscous flow activation energy of the present invention mainly may further comprise the steps:
1) preparation dynamic rheological property specimen;
2) below the above decomposition temperature of polyolefin fusing point, carry out temperature scanning with dynamic rheometer, measure the polyolefin complex viscosity with variation of temperature;
3) be converted to AV with variation of temperature according to the Cox-Merz rule;
4) use formula
Carry out linear regression and obtain viscous flow activation energy.
The present invention also provides a kind of concrete grammar of fast measuring polyolefin viscous flow activation energy, may further comprise the steps:
1) preparation dynamic rheological property specimen;
2) dynamic rheometer is debugged to testing SBR; Load the dynamic rheological property specimen then; Set test frequency, below the above decomposition temperature of polyolefin fusing point, set the temperature range of scanning and the temperature interval of value, under the frequency of setting, carry out temperature scanning; The complex viscosity that obtains specimen is with variation of temperature data and curve, and the preservation test figure is to be analyzed;
3) be converted to AV with the variation of temperature curve according to the Cox-Merz rule;
4) use formula
Carry out linear regression and obtain viscous flow activation energy.
The temperature range of temperature scanning can be more than the fusing point of polyolefin sample in the inventive method, and the condition setting that experimentizes as required below the decomposition temperature, preferred range are above 20 ℃ to more than the fusing point 100 ℃ of fusing point.The temperature interval of measuring can be preferably per 5 ℃ and get a bit according to how much being provided with of requisite number strong point.
Because viscous flow activation energy is relevant with shear rate, generally the viscous flow activation energy of more different samples is all under same shear rate condition.The viscous flow activation energy that just can guarantee to obtain in same frequency measurement among the present invention is under identical conditions, and preferred frequency range is below the 100rad/s.
The inventive method does not limit polyolefinic form, and powder or pellet are all applicable.
The present invention does not have specific (special) requirements for the preparation process of rheometer test sample, if the specimen of preparation evenly, no bubble, surface cleaning be smooth, as obtaining, also can obtain through the method for injection moulding through the method that mould is suppressed.
The inventive method does not limit for the model of dynamic rheological property analyser, is applicable to the dynamic rheological property analyser of various models.
The inventive method is preferably under the nitrogen atmosphere carries out, and avoids specimen oxidative degradation to guarantee reliability of testing result.
The Cox-Merz rule of using in the inventive method is total to as those skilled in the art to be known; Can adopt rheological analysis software such as Rheology Advantage Data analysis to convert the specimen complex viscosity into AV with the variation of temperature curve with the variation of temperature curve; Its data conversion process also can manually be accomplished by the analyst.
Among the present invention the data linear regression obtained that the step method of viscous flow activation energy is well known to those skilled in the art, can in software commonly used such as Microsoft Excel, realize.
The inventive method is compared with art methods, has the following advantages:
1) only needs one-shot measurement just can obtain viscous flow activation energy, be specially adapted to polyolefinic viscous flow activation energy such as tygon, polypropylene and measure.
2) the present invention can obtain tens even tens data points easily through changing the temperature interval in the measuring condition, improves the degree of accuracy of result of calculation.Just need one-shot measurement and obtain a data points in the prior art, therefore method of the present invention can obtain the result of pinpoint accuracy faster, easily than prior art.
3) dynamic rheometer of the present invention's use can be under extremely low frequency; Measure down like 0.01rad/s; Compare the viscous flow activation energy that obtains more easily under the low shear rate condition with capillary rheometer; And the time that is consumed does not increase, and the viscous flow activation energy required time that prior art will obtain under the low shear rate condition will increase a lot.
4) sample size required for the present invention is few, only need a few gram samples to get final product, and the capillary rheometer measurement needs tens gram samples.
5) quick, efficient, the easy operating of this method does not need dedicated calculation software.
6) the present invention is all applicable to polyolefinic powder or pellet.
Description of drawings
Fig. 1 is the rheometer test curve of LDPE 2426H
Fig. 2 is the curve of LDPE 2426H after the conversion of Cox-Merz rule
The curve that Fig. 3 obtains for LDPE 2426H linear regression
Fig. 4 is the rheometer test curve of PP T38F
Fig. 5 is the curve of PP T38F after the conversion of Cox-Merz rule
The curve that Fig. 6 obtains for PP T38F linear regression
Embodiment
Below through embodiment and accompanying drawing the present invention is described further.
The used instrument of embodiment is:
(1) AR-G2 dynamic rheological property analyser U.S. TA company produces
Frequency range: 7.54 * 10
-7～628.3rad/s, temperature range :-150～400 ℃
(2) the big hydraulic machinery in Pu, XLB-0.25D/Q vulcanizing press Shanghai Manufacturing Co., Ltd produces
Pressure: 0～16MPa, temperature: 0～300 ℃
1) test sample preparation
In vulcanizing press, use down moulds that powdery or granular polyolefin particles are pressed into diameter 25mm at 180 ℃, thick 2mm evenly, no bubble, the smooth disk of surface cleaning.
2) testing procedure
(1) open pressurized air, regulating the flow graph inlet pressure is 30psi;
(2) open the flow graph safety lock;
(3) AR-G2 flow graph main frame start, after the instrument oneself detected and passes through, whether the inspection air bearing was normal, and can software control flow graph;
(4) sectional fixture and carry out status adjustment comprises that the gap makes zero and rotate mapping;
(5) load sample is treated to adjust anchor clamps after the sample melted;
(6) strike off unnecessary sample, spacing is set to assigned address;
(7) set experiment condition and begin test.Test condition: 150～230 ℃ of temperature ranges, get some strain 0.1%, test frequency 38.988rad/S for per 5 ℃.Wherein T38F measurement temperature range is 170～250 ℃, and other conditions are identical.
(8) the preservation test figure is to be analyzed.
3) test result, calculating
(1) will test resulting polyolefin complex viscosity and convert AV to the variation of temperature curve with the Cox-Merz rule with the variation of temperature curve;
(2) with apparent viscosity data substitution equation lg η under the different temperatures
aCarry out linear regression among the=K/T+b, obtain K and b value in the regression formula;
(3) according to formula E
η=K * 2.303R=19.147 * K (J/mol) obtains the viscous flow activation energy of institute's test sample article.
Embodiment 1:
The viscous flow activation energy of HDPE 9455F.
The viscous flow activation energy of table 1 HDPE 9455F
Comparative Examples 1:
Use German Goettfert 2000 high pressure capillary rheometers, measure the change curve of the AV of 9455F with shear rate down at 170 ℃, 190 ℃, 210 ℃, 230 ℃ respectively, it is 38.988S that test result under four temperature is chosen shear rate respectively
-1The time corresponding apparent shear viscosity, with formula lg η
a=K/T+b carries out linear regression, obtains K and b value, then according to formula E
η=19.147 * K (J/mol) obtains the viscous flow activation energy of institute's test sample article.
The viscous flow activation energy of table 2 HDPE 9455F
Embodiment 2:
The viscous flow activation energy of LDPE 2426H.
Fig. 1 is the rheometer test curve of LDPE 2426H, measures through a temperature scanning and can obtain complex viscosity value corresponding under 17 temperature; Fig. 2 is the curve of LDPE 2426H after the conversion of Cox-Merz rule, obtains 17 AV values under the temperature after the data-switching; The curve that Fig. 3 obtains for LDPE 2426H linear regression promptly carries out linear regression with the AV value under each temperature to its corresponding temperature in Microsoft Excel software, obtain the parameter in the regression formula, and calculate viscous flow activation energy, sees table 3.
The viscous flow activation energy of table 3 LDPE 2426H
Embodiment 3:
The viscous flow activation energy of LLDPE LL1201.
The viscous flow activation energy of table 4 LLDPE LL1201
Embodiment 4:
The viscous flow activation energy of mLLDPE 3527CB.
The viscous flow activation energy of table 5 mLLDPE 3527CB
Comparative Examples 2:
Use the U.S. AR-G2 of TA company dynamic rheometer; Measure of the variation of 3527CB storage modulus down at 150 ℃, 170 ℃, 190 ℃, 210 ℃ respectively with angular frequency; With TTS (time temperature equivalence) function in the Rheology Advantage Data analysis software with each temperature lower curve translation 190 ℃ of lower curves that are added to; Obtain shifter factor (seeing table 6), obtain viscous flow activation energy with the Arrhenius equation model.
The TTS result of table 6 3527CB
With Arrhenius equation model result:
E
η：34.61kJ/mol
Reference temperature: 463.1K
Reference temperature: 190.0 ℃
Standard deviation: 16.48
Termination condition: normal termination
Embodiment 5:
The viscous flow activation energy of PP T38F.
Fig. 4 is the rheometer test curve of PP T38F in the accompanying drawing, measures through a temperature scanning and can obtain complex viscosity value corresponding under 17 temperature; Fig. 5 is the curve of PP T38F after the conversion of Cox-Merz rule, obtains 17 AV values under the temperature after the data-switching; The curve that Fig. 6 obtains for PP T38F linear regression promptly carries out linear regression with the AV value under each temperature to its corresponding temperature in Microsoft Excel software, obtain the parameter in the regression formula, and calculate viscous flow activation energy, sees table 7.
The viscous flow activation energy of table 7 PPT38F
Can know that by embodiment and Comparative Examples method of the present invention can be rapidly, just obtain polyolefinic viscous flow activation energy through a flow measurement quickly, and linear regression good relationship (R square greater than 0.98).And need 4 flow measurements with prior art in the Comparative Examples 2, and just can obtain similar results with software processing.Need 4 flow measurements just can obtain the result with prior art in the Comparative Examples 1, and linear regression error big (R square is 0.9436, and less than among the embodiment 1 0.9923, data more meet resulting linear formula in the illustrative embodiment 1).
Claims (6)
1. the method for a fast measuring polyolefin viscous flow activation energy mainly may further comprise the steps:
1) preparation dynamic rheological property specimen;
2) below the above decomposition temperature of polyolefin fusing point, carry out temperature scanning with dynamic rheometer, measure the polyolefin complex viscosity with variation of temperature;
3) be converted to AV with variation of temperature according to the Cox-Merz rule;
4) carry out linear regression with formula
and obtain viscous flow activation energy.
2. the method for claim 1; It is characterized in that step 2) be specially: dynamic rheometer is debugged to testing SBR, loads the dynamic rheological property specimen then, sets test frequency; Below the above decomposition temperature of polyolefin fusing point, set the temperature range of scanning and the temperature interval of value; Under the frequency of setting, carry out temperature scanning, the complex viscosity that obtains specimen is with variation of temperature data and curve, and the preservation test figure is to be analyzed.
3. method as claimed in claim 2 is characterized in that the described temperature range condition setting that more than the fusing point of polyolefin sample, below the decomposition temperature, experimentizes as required, and how many temperature intervals is provided with according to the requisite number strong point.
4. like claim 2 or 3 described methods, it is characterized in that described temperature range is above 20 ℃ to more than the fusing point 100 ℃ an of fusing point, the temperature interval is 5 ℃.
5. method as claimed in claim 2 is characterized in that described test frequency is below the 100rad/s.
6. according to claim 1 or claim 2 method is characterized in that dynamic rheometer tests under nitrogen atmosphere.
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| GB2499990A (en) * | 2012-03-04 | 2013-09-11 | Carsten Andreas Wochnowski | Determination of the activation energy of viscous flow by the temperature dependency of electrolysis |
| CN103268924B (en) * | 2013-05-10 | 2015-09-16 | 佛山市金辉高科光电材料有限公司 | A kind of polyolefin micro porous polyolefin membrane and preparation method thereof |
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| CN105675439A (en) * | 2014-11-20 | 2016-06-15 | 中国石油天然气股份有限公司 | Detection method for rapid determination of melt index and molecular weight of fiber-type polypropylene special-purpose material |
| CN104483235A (en) * | 2014-12-05 | 2015-04-01 | 浙江万马高分子材料有限公司 | Method for detecting crosslinkable vinyl polymer chain structure for high voltage cable |
| CN109752404B (en) * | 2017-11-02 | 2021-11-23 | 中国科学院宁波材料技术与工程研究所 | System and method for testing apparent activation energy of ceramic precursor melt |
| CN110057717B (en) * | 2019-04-19 | 2021-06-11 | 深圳大学 | Method for establishing polymer melt viscous flow activation energy model based on characteristic dimension |
| CN110487673B (en) * | 2019-08-09 | 2021-10-08 | 上海化工研究院有限公司 | Method for quantitatively determining entanglement degree of ultrahigh molecular weight polyethylene resin |
| CN110595952B (en) * | 2019-09-10 | 2022-05-10 | 吴宗周 | Method for measuring and calculating viscous flow activation energy of high polymer material |
| CN111122385A (en) * | 2020-01-10 | 2020-05-08 | 吴宗周 | Method for quickly measuring and calculating viscous flow activation energy of pseudoplastic fluid |
| CN113092276A (en) * | 2021-03-10 | 2021-07-09 | 上海工程技术大学 | Method for testing accelerated creep of thermoplastic elastomer |
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