CN101025413A - Method for rapid detecting ISO 9080 grade of PVC pipe material - Google Patents
Method for rapid detecting ISO 9080 grade of PVC pipe material Download PDFInfo
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Abstract
The invention discloses a method to quickly detect polyethylene pipe material rank of ISO9080, it includes (1) detect polyethylene pipe material structure distribution in condensation state, the structure distribution in condensation state includes mass per centum content distribution of crystal phase, interface phase and amorphism phase;(2)compute the mass per centum content distribution of crystal phase, interface phase and amorphism phase;(3) bases the result of the (2)step, process the ISO9080 ratings of the polyethylene pipe material: the mass per centum content of crystal phase is 50-90%for polyethylene pipe material with PE80 rank and more than it, the mass per centum content of interface phase is 5-45%, the mass per centum content of amorphism phase is 0-15%. Compared to pipe certification authority hydrostatic test rating, This method has advantages of convenient, fast, and saving money, accelerate the new pipe material products into research development process, and with high accuracy, wide adaptation.
Description
Technical field
The present invention relates to the method for a kind of polyethylene pipe material performance evaluation and deciding grade and level, especially a kind of method of ISO9080 grade of fast detecting polyethylene pipe material.
Technical background
Since 1980, polyethylene pipe widely utilizes in fields such as water delivery and gas transmissions, and especially after the nineteen ninety-five Japan Kobe violent earthquake, the superiority of PE pipe is widely cognitive by common people.Even to this day, in the combustion gas field, no matter be reparation and renewal for new laying or old pipeline, polyethylene pipe all is one of main selection.Adopt tygon to bury ground gas pipeline reliable in quality, security of operation, easy maintenance, expense economy.
The deciding grade and level of PE tube material is the basis that the PE pipe is used.When the PE pipe is defined the level, need be according to the requirement [1] of ISO9080, under 20 ℃, 60 ℃ and 80 ℃ of these three temperature conditions, carry out the hydrostatic test more than at least 9000 hours respectively, and then carry out complicated multiple linear regression analysis, be extrapolated to the confidence lower limit σ of 20 ℃ and the hydrostatic intensity 97.5% predicted in 50 years
LCLσ
LCLPolythene material at 8.00～9.99MPa is a PE80 level tube material.Tube material only finishing above-mentioned test and obtaining under the prerequisite of corresponding grade authentication, could be used as the production Gas Pipe.Gas Pipe is the PE80 level to the minimum requirement of material grade.Now, along with the continuous development of polyethylene production technology, developed third generation polyvinyl piping materials PE100 and captured high-end polyvinyl piping materials market rapidly.Be compared to first generation PE63 level and second generation PE80 level pipe material, the PE100 resin adopts bimodal distribution, hervene copolymer technology (also having manufacturer to adopt the butylene copolymerization) more, when improving long-term hydrostatic intensity, also improved anti-slow crack growth performance, and have good processability, for raising pipe network discharge pressure, increase pipe diameter, expansion pipeline range of application have been created condition.The tubing use amount, the particularly consumption on heavy caliber pipe of PE100 rise rapidly at present.
Need when as previously mentioned, the PE pipeline being defined the level to carry out long-term hydrostatic test in internationally recognized certification authority (as Sweden Bodycote).The PE pipeline stage that this evaluation method is determined is with a high credibility, but its shortcoming is that test period is long, and the stand-by period of manufacturer is of a specified duration, and is particularly unfavorable for more high-grade tube material research and development.Therefore, a kind of tube material method of evaluating performance of quick test can be proposed, the PE tubing that is preferred for authenticating, the paces of quickening research and development have important practical significance.Reach this purpose,, reduce unnecessary expenditure to enterprise with reducing the risk of manufacturer's pipe resin greatly by authentication.
At present, tube material performance evaluation and Study on Quality Control are mainly concentrated both ways, at first be based on test and regulation and control the resinous molecular structure parameter, as: parameters such as molecular weight, molecular weight distribution, the degree of branching.The advantage of this method is deep to the essence understanding of tube material matrix resin, is easy to regulate and control in reactive end.Shortcoming is the application end away from tube material, can't estimate in the variation that all kinds of process take place tubing.Next is all kinds of short-term Mechanics Performance Testings that tubing is carried out, as the low-temperature creep performance test.Deviation was bigger when this class testing result was used for the prediction of tubing long-term behaviour.
Increasing experiment and the molecular simulation support crystallization of predicted in theory existence once, amorphous interface phase, (Polymer 2002 as the article " Evidence for a PartiallyOrdered Component in Polyethylene from Wide-angle X-ray Diffraction " of A.M.E.Baker and A.H.Windle, 42,667), the article of L.Mandelkem " The Sructure of CrystallinePolymers " (Acc.Chem.Res.1990,23,380), R.R.Eckman, P.M.Henrichs, (Macromolecules 1997 for the article of A.T.Peacock " Study of Polyethylene by Solid State NMR Relaxationand Spin Diffusion ", 30,2474), but this theory does not obtain practical application so far.
Summary of the invention
The invention provides a kind of method that detects polyethylene pipe material,, the PE tube material is carried out conveniently performance evaluation and quality control by test analysis to resin crystallization phase, interface phase, amorphous phase.
A kind of method of ISO9080 grade of fast detecting polyethylene pipe material comprises the steps:
(1) detect the polyethylene pipe material condensed state structure and distribute, described condensed state structure distribution comprises the distribution of the mass percentage content of crystallization phase, interface phase and amorphous phase;
(2) mass percentage content of calculating crystallization phase, interface phase and amorphous phase;
(3) according to the result of step (2), carry out the ISO9080 deciding grade and level of polyethylene pipe material: the mass percentage content of the crystallization phase of the polyethylene pipe material of PE80 and above grade is 50～90%, interface phase mass percentage content is 5～45%, the amorphous phase mass percentage content is 0～15%.
In the described method, when the crystallization phase mass percentage content of polyethylene pipe material is 60～80%, interface phase mass percentage content is 10～30%, when the amorphous phase mass percentage content is 1～5%, its performance is more excellent, can illustrate more accurately that in other words polyethylene pipe material has reached PE80 and above grade.
The used tygon of described polyethylene pipe material is the multipolymer of Alathon and/or ethene and C3～C12 olefin comonomer.Described C3～C12 olefin comonomer is one or more in butylene, hexene or the octene.
Described polyethylene pipe material comprises polyethylene powder, true qualities pellet, carbon black be mixed pellet, compressing tablet material, extruded stock or tubing finished product material.
Described detection polyethylene pipe material condensed state structure distributes and adopts solid state nmr technology, Raman spectroscopy, X-ray diffraction to analyze combine technology, small-angle neutron scattering technology or infrared spectrum technology with difference formula weight heat, the preferred solid state nmr technology that adopts obtains result more accurately.
The present invention forms with the condensed state of PE tube material resin and property analysis carries out the pipe performance evaluation as the basis, is characterized in:
(a) be compared to polymer molecular structure, condensed state structure, i.e. the solid powder of pipe resin, granulation material and sheet stock even tube forming material structure not only more near the actual use of tubing, and have contained each stage of its processing.Therefore the structure of this level is tested and analyzed, more effective to the evaluation and the control of pipe performance.
(b) be compared to the short-term Mechanics Performance Testing, the analysis of condensed state structure is deep into the level of molecular stuffing and motion in the solid material, more deep for the understanding of material microstructure, therefore the evaluation to performance has more accuracy.
(c) analysis of condensed state structure can be reached by multiple means of testing, even the on-line analysis of practicable production run, so range of application is more extensive.
Thus, key of the present invention be from the test of solid polyethylene condensed state structure and analyzing development to the method for PE tube material performance evaluation and even deciding grade and level.
Characteristics of the present invention are the condensed state structure of quantitatively characterizing tube material and in view of the above the tube material performance are estimated.High molecular condensed state structure is meant arrangement and the packing structure between the macromolecular chain, is also referred to as supramolecular structure.For the hemicrystalline tygon, comprise the interior transport properties of molecules of content, each phase region size and phase region of the interface phase between crystalline phase, amorphous phase and crystalline phase, the amorphous phase.High molecular chain structure (molecular structure) is the principal element of decision superpolymer fundamental property, and high molecular condensed state structure is the principal element of decision superpolymer bulk properties.The usability of polyethylene pipe material directly is decided by formed aggregated structure in molding process, on this meaning, can think, chain structure is the performance that molecular structure just affects indirectly polyethylene pipe material, and condensed state structure is only the direct factor that influences its performance.Traditional crystallization, amorphous tow phase model for the tygon condensed state structure think that the mechanical property of polyethylene pipe material and the character of its crystalline region are closely related, as what of crystalline region massfraction (crystallinity), crystalline region defective.Recent discovers that the anti-slow crack growth performance of the character of tygon amorphous phase and its tube material (SCG) has much relations.It should be noted that in addition, the crystallization of increasing experiment and molecular simulation support predicted in theory existence once, amorphous interface mutually, thereby and the tie molecule amount between the character of interface phase and polythene material crystalline region be closely related can be to the long-term mechanical property generation material impact of tube material.These all show the parsing of tygon condensed state structure, and the important information of tube material usability can be provided.
The phase content of tube material resin and phase morphology analysis can be reached by solid state nmr hydrogen spectrum and carbon spectral technology, Raman spectroscopy, small-angle x-ray diffractive technology, small-angle neutron scattering technology and wide-angle x-ray diffraction and DSC combination technology.The test philosophy of each technical basis self segments the condensed state structure of solid polyethylene, tells that the random guiding of crystallization phase, strand that sub polyethylene subchain high-sequential arranges is similar to be in the complete amorphous phase of solution state and between the interface phase between the two.This wherein, solid state nmr carbon spectrum and hydrogen spectral analysis technology can provide the complete information of phase content and phase structure, and other several analytical approachs all can only provide the information of phase content and phase region size, and therefore preferred solid state nmr technology is as the standard method of tube material deciding grade and level and high-grade tube material performance evaluation.Because the development of nuclear-magnetism on-line analysis technology and optical fiber transmission technique, solid state nmr and Raman spectroscopy all might be realized the on-line analysis to different phase, different conditions polyvinyl piping materials in the production run, therefore preferred these two kinds of technology as tube material production and process quality assessment and control at line technology.
According to this invention tube material is defined the level time institute's accepted standard, the analytical test result who is based on the PE tube material of a large amount of different brackets sums up.The sample that is adopted comprises PE63, PE80, the PE100 tube material resin that Ziegler-Natta catalyst and Cr series catalysts are produced.These resins also have from reactor powder, true qualities pellet, carbon black mixed ingredients and thus gained the compressing tablet material, melt extrude the broad form of material even final tubing finished product material.The condensed state structure analysis result of PE80 and above tube material resin thereof shows and contains the abundant interface phase (quality percentage composition 10%～30%) of quantity in this class material, and content very low (the quality percentage composition is lower than 8%) or extremely low (the quality percentage composition is lower than 4%) of amorphous phase fully.The following grade pipe material of PE80 then generally lacks this feature, can define the level to tube material in view of the above.Further, because PE80 and above grade pipe material thereof, PE100 tube material particularly, has splendid environmental stress crack resistance (ESCR), therefore the content of interface phase and the long-term mechanical property of tube material can be interrelated, be high interface phase content corresponding to better anti-stress cracking performance at a slow speed, can carry out the long-term mechanical property prediction of tube material in view of the above.When carrying out the performance evaluation of PE80 and above grade pipe material thereof, except that especially the interface phase content compares to three phase contents, need to consider the form of each phase region, comprise the motility of PE strand in phase region pattern, size and the phase region.The solid state nmr experiment can provide the complete information of these phase region forms, as: the hydrogen spectrum spectral line width in the triple-phase region is corresponding to the laterally slow Henan time of PE strand; SPIN LATTICE slow Henan timing in the triple-phase region; Measure the phase region size of triple-phase region with spin/diffusion experiment.The phase content and the phase morphology analysis result of comprehensive polyethylene pipe material can be estimated long-term and the short-term mechanical property and the part processing characteristics of PE80 and above grade polyethylene tube material, and particular content comprises:
(a) the interface phase content is high more, and the interior mutually molecular motion in interface is obstructed more, and then the anti-cracking performance at a slow speed (SCG) of tubing is good more.
(b) the similar different polyethylene pipe materials (interface phase mass content differs and is lower than 2%) of interface phase content, the high more then mechanical strength of crystallization phase (or solid phase) content is high more, and processing characteristics is relatively poor.
(c) the similar different polyethylene pipe materials of phase composition, molecular motion is obstructed more in the triple-phase region, and then long-term the and short-term mechanical property of material is good more, corresponding to more high-grade tube material.
(d) transport properties of molecules in interface phase and the amorphous phase also can be used as the criterion of sag resistant performance quality in the tube material process.That is: in different pipe resins under the similar situation of two phase contents, the spin/lattice of the phase region slow Henan time is long more, then corresponding to better sag resistant performance.
Description of drawings
The wide line hydrogen spectrum of the nuclear-magnetism of Fig. 1 PE1, two kinds of polyethylene pipe material resins of PE2;
The decomposing schematic representation of the wide line hydrogen spectrum of Fig. 2 PE1 sample nuclear-magnetism;
The Raman spectrum c h bond vibrating area decomposing schematic representation of Fig. 3 PE2 sample;
The c h bond vibrating area Raman spectrum decomposing schematic representation of Fig. 4 PE1 sample;
The complex viscosity of Fig. 5 PE1, two kinds of carbon black mixed ingredients of PE4 contrasts with the shearing frequency change curve;
Embodiment
Embodiment 1 solid state nmr hydrogen spectral analysis technology is judged the grade of different PE tube materials
The powder of two kinds of tube material resins, the three-phase of wide line hydrogen spectrum of its nuclear-magnetism and hydrogen spectrum is resolved respectively as depicted in figs. 1 and 2.The mass fraction of three-phase is provided by the integral area branch rate of corresponding model curve separately, and its result is as shown in table 1.
The wide line hydrogen spectrum of the solid state nmr of table 1 PE1, two kinds of samples of PE2 phase content analysis result
| Sample | Phase content | ||
| Crystallization phase | The interface phase | Amorphous phase | |
| PE1 PE2 | 0.84 0.97 | 0.14 0 | 0.02 0.03 |
*Resultant error is no more than 3%.
Can judge that according to the result in the table 1 PE1 sample institute respective tube material is PE80 and above rank thereof, and PE2 sample institute respective tube material rate is PE63 or inferior grade more.This conclusion conforms to manufacturer sampling information.
Embodiment 2 Raman spectrum analysis technology are judged the grade of different tube materials
During with Raman spectrum analysis solid polyethylene tubing phase structure, be based on 1200cm
-1To 1600cm
-1C h bond rocks the spectrogram swarming parsing [13] in vibration and flexural vibrations district in the zone.The content of crystallization phase, amorphous phase and interface phase is calculated by following formula respectively:
Crystallization phase content X
C=I
1416/ [0.46 (I
1295+ I
1303)]
Amorphous phase content X
a=I1303/ (I
1295+ I
1303)
Interface phase content X
i=1-X
c-X
a
Wherein I refers to compose the peak integral area, and the result provides by the computing machine swarming.
Analysis result to two kinds of tygon phase structures is as shown in table 2:
The Raman spectrum phase content analysis result of table 2 PE1, two kinds of samples of PE2
| Sample | Phase content | ||
| Crystallization phase | The interface phase | Amorphous phase | |
| PE1 PE2 | 0.61 0.80 | 0.37 0.06 | 0.02 0.14 |
*Resultant error is no more than 10%.
Given result shows that also the pairing tube material of PE1 sample reaches PE80 or above grade in the table 2, and PE2 sample institute respective tube material rate is lower.
Embodiment 3 wide-angle x-rays and dsc analysis combination technology are judged the rank of different brackets tube material
Wide-angle x-ray (WAXD) method can be analyzed the phase structure of solid superpolymer, has comprised the contribution of interface phase in the resulting crystallization phase content, and the given approximate content that is all strand high-sequential crystallization phase that waits of crystallinity of DSC technology.The crystallinity difference reaction that two kinds of method of testings are given what of solid material median surface phase content, can tell three phase compositions in the polyvinyl piping materials resin thus, as shown in table 3 to the analytical test result of PE1 and two kinds of samples of PE2:
Table 3 WAXD, the DSC phase composition analysis of technology that combine to the PE tube material
| Sample | Phase content | ||
| Crystallization phase | The interface phase | Amorphous phase | |
| PE1 PE2 | 0.65 0.81 | 0.26 0.03 | 0.09 0.16 |
The result of comparing embodiment 1,2,3 can find that different analysis test methods have nothing in common with each other to the segmentation result of tube material condensed state structure, and this test philosophy that can be interpreted as the whole bag of tricks institute foundation has nothing in common with each other.The solid state nmr technology is based on the motility difference of strand in the different phase regions; Raman spectroscopy is based on the vibration performance difference of c h bond in the different phase regions, and the heat content effect of DSC different phase regions that method is based on, the WAXD method then is the electron density difference that relies on different phase regions.But no matter be which kind of method, to the feature through three given phase compositions of the different brackets PE tube material of same treatment is identical, be to contain abundant more interface phase in the pipe resin of PE80 and above grade, and amorphous phase content is low fully, as what showed among top three embodiment.Can tentatively judge the grade of tube material in view of the above.
Embodiment 4 condensed state structure analyses are to the evaluation of different PE100 tube material performances
Two kinds of PE100 tube materials are produced by Cr series catalysts gas fluidized-bed process, ethene hervene copolymer and Ziggler-Natta catalyzer series reactor process, ethylene butene copolymerization respectively.Its tube material resin feature is as shown in table 4:
The resin properties of table 4 PE1, PE3 tube material
| Sample | M w | M w/M n | T m(℃) | X c(％DSC) |
| PE1, bimodal PE100 tube material PE3, unimodal PE100 tube material | 282162 241756 | 36.7 27.1 | 131 128 | 67％ 59％ |
Powder and true qualities pellet to these two kinds of high-end tubes materials carry out the analysis of nuclear-magnetism condensed state structure, and analytic process is with embodiment 1, and its result is as shown in table 5:
The solid state nmr hydrogen spectrum Phase Structure Analysis of table 5 PE1, PE3 tube material
| Sample | Phase composition (%) | Hydrogen spectral line width (Hz) | ||||
| Crystallization phase | The interface phase | Amorphous phase | Crystallization phase | The interface phase | Amorphous phase | |
| PE1 true qualities pellet PE3 true qualities pellet PE1 powder PE3 powder | 78.14 73.46 84.16 82.21 | 17.78 21.42 14.08 15.94 | 4.08 5.12 1.76 1.85 | 50879 47931 49227 47974 | 10646 11061 11823 12858 | 3383 3210 2359 2328 |
The spectral line width here refer to each phase region half high half-peak breadth of corresponding matched curve, this line width values is big more, shows transport properties of molecules restricted more [14] in the corresponding phase region of institute.The performance comparison of two kinds of tube materials has following characteristics: (1) all reaches the PE100 grade by authentication; (2) the more unimodal PE100 pipe of the hydrostatic time to rupture of the high temperature material of bimodal PE100 pipe material is longer; (3) the technological operation scope of unimodal ethene hervene copolymer pipe material is narrower.By the three-phase structure analysis result of solid state nmr, following explanation can be arranged respectively: all contain abundant interface phase content in (1) two kind of tube material, and amorphous phase content is relatively very low,, can both reaches the above grade of PE80 according to criterion of the present invention.(2) PE1 pipe material has higher crystallinity, and PE3 with respect to the big portion of this part crystallinity that PE1 reduced be transformed into the interface mutually in.Because at the higher lower temperature boundary face caused stress rupture of easier generation strand disentanglement mutually, hydrostatic destruction time of occurrence is more early under higher temperature to make PE3.(3) the reactor tandem process can be realized respectively tube material crystallization phase and the interface regulation and control respectively of character mutually, and the ethene hexene polymerization technique of single reactor requires the content of hexene monomer need be controlled at suitable scope.Thereby high hexene content can reduce the mechanical property variation that material crystallinity causes material, and low hexene content can not be produced the enough interface phases that meet the demands.The latter's technology adjustable extent is narrower by contrast.
The result of present embodiment also shows, introduces condensed state structure evaluation method proposed by the invention, has avoided unimodal bimodal polyethylene can both prepare the puzzlement of PE100 tube material, has disclosed the immanent structure essence that determines PE tube material short-term and long-term mechanical property.Why ethene hexene Monomodal copolymer also can reach the rank of PE100, is wherein to contain abundanter interface phase, and the interface mutually in the mutual entanglement of strand strengthen, the motion of strand is more restricted, and is as shown in table 5.
The sag resistant performance evaluation of 5 two kinds of above grade polyethylene materials of PE80 of embodiment
The carbon black mixed ingredients of two kinds of above grade polyethylene tube material of PE80 PE1, PE4 is applied to small-bore respectively and production heavy caliber pipe because of having different sag resistant performances.Both molecular weight distribution all are bimodal distribution, and carbon black content is identical with the dispersion degree grade.
The Phase Structure Analysis of table 6 PE1, two kinds of tube materials of PE4
| Sample | Phase composition (%) | Hydrogen spectral line width (Hz) | ||||
| Crystallization phase | The interface phase | Amorphous phase | Crystallization phase | The interface phase | Amorphous phase | |
| PE1 carbon black mixed ingredients PE4 carbon black mixed ingredients | 75.98 77.20 | 19.26 17.44 | 4.77 5.37 | 49890 51143 | 10706 10348 | 2904 2912 |
The hydrogen spectrum spin/lattice slow Henan time of table 7 PE1, two kinds of tube materials of PE4
| Sample | T1 (single component match) | T1 (bi-component match) | |
| PE1 carbon black mixed ingredients PE4 carbon black mixed ingredients | 758ms 794ms | 781ms 854ms | 160ms 306ms |
The sag resistant performance of PE tube material, significant for the production of heavy caliber PE tube material.Its implication is that PE tubing is resisted the caused distortion of himself weight and caved in when extruding.The rheological curve that Fig. 5 has provided PE1, two kinds of tube materials of PE4 relatively has obviously higher complex viscosity at low frequency range PE4 pipe material, as can be seen therefore to better melt strength and sag resistant performance should be arranged.Correspondingly, provided the solid state nmr Phase Structure Analysis result of two kinds of tube materials in table 6 and the table 7 respectively.The phase composition of two kinds of materials and hydrogen spectral line width difference are not obvious in the table 6, may be because both are prepared by identical polymerization technique, and belong to the above grade PE pipe of PE80 material together, and therefore wide line hydrogen analysis of spectrum result is similar.But the slow Henan of spin/lattice of further testing two kinds of materials was observed PE4 and has been had obviously higher spin/lattice slow Henan time during the time.Sag resistant performance and its spin/lattice slow Henan time that can tentatively infer tube material thus are closely related, and correspondence of slow Henan time of higher spin lattice is the sag resistant performance preferably.
Claims (7)
1, a kind of method of ISO9080 grade of fast detecting polyethylene pipe material is characterized in that comprising the steps:
(1) detect the polyethylene pipe material condensed state structure and distribute, described condensed state structure distribution comprises the distribution of the mass percentage content of crystallization phase, interface phase and amorphous phase;
(2) mass percentage content of calculating crystallization phase, interface phase and amorphous phase;
(3) according to the result of step (2), carry out the ISO9080 deciding grade and level of polyethylene pipe material: the mass percentage content of the crystallization phase of the polyethylene pipe material of PE80 and above grade is 50～90%, interface phase mass percentage content is 5～45%, the amorphous phase mass percentage content is 0～15%.
2, method according to claim 1, it is characterized in that: in the described ISO9080 grade, the crystallization phase mass percentage content of the polyethylene pipe material of PE80 and above grade is 60～80%, interface phase mass percentage content is 10～30%, the amorphous phase mass percentage content is 1～5%.
3, method according to claim 1 is characterized in that: described polyethylene pipe material comprises polyethylene powder, true qualities pellet, carbon black be mixed pellet, compressing tablet material, extruded stock or tubing finished product material.
4, method according to claim 1 is characterized in that: the used tygon of described polyethylene pipe material is the multipolymer of Alathon and/or ethene and C3～C12 olefin comonomer.
5, method according to claim 1 is characterized in that: described C3～C12 olefin comonomer is one or more in butylene, hexene or the octene.
6, method according to claim 1 is characterized in that: described detection polyethylene pipe material condensed state structure distributes and adopts solid state nmr technology, Raman spectroscopy, X-ray diffraction to analyze technology or the small-angle neutron scattering technology of combining with difference formula weight heat.
7, method according to claim 6 is characterized in that: described detection polyethylene pipe material condensed state structure distributes and adopts the solid state nmr technology.
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| CN 200710067862 CN101025413A (en) | 2007-03-30 | 2007-03-30 | Method for rapid detecting ISO 9080 grade of PVC pipe material |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102954980A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Method for rapidly detecting grade of special material for polyethylene pipe |
| CN109297997A (en) * | 2017-07-24 | 2019-02-01 | 北京化工大学 | A method of measurement polymer crystallinity, mesomorphic degree and unformed degree |
| WO2019136791A1 (en) * | 2018-01-09 | 2019-07-18 | 广州特种承压设备检测研究院 | Method for rapidly evaluating slow crack growth resistance of plastic pipe |
| CN112041670A (en) * | 2018-04-02 | 2020-12-04 | 株式会社理学 | Quantitative analysis device, analysis method, and analysis program for amorphous phase |
| CN114414612A (en) * | 2022-01-28 | 2022-04-29 | 浙江大学 | Method for quickly prejudging pressure-resistant grade of special material for polyethylene pipe |
-
2007
- 2007-03-30 CN CN 200710067862 patent/CN101025413A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102954980A (en) * | 2011-08-19 | 2013-03-06 | 中国石油天然气股份有限公司 | Method for rapidly detecting grade of special material for polyethylene pipe |
| CN102954980B (en) * | 2011-08-19 | 2015-08-19 | 中国石油天然气股份有限公司 | Method for rapidly detecting grade of special material for polyethylene pipe |
| CN109297997A (en) * | 2017-07-24 | 2019-02-01 | 北京化工大学 | A method of measurement polymer crystallinity, mesomorphic degree and unformed degree |
| CN109297997B (en) * | 2017-07-24 | 2020-09-04 | 北京化工大学 | Method for measuring crystallinity, mesomorphism and amorphous degree of polymer |
| WO2019136791A1 (en) * | 2018-01-09 | 2019-07-18 | 广州特种承压设备检测研究院 | Method for rapidly evaluating slow crack growth resistance of plastic pipe |
| CN112041670A (en) * | 2018-04-02 | 2020-12-04 | 株式会社理学 | Quantitative analysis device, analysis method, and analysis program for amorphous phase |
| CN114414612A (en) * | 2022-01-28 | 2022-04-29 | 浙江大学 | Method for quickly prejudging pressure-resistant grade of special material for polyethylene pipe |
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