CN103627089A - Method for preparing carbon nanotube/expanded graphite/polypropylene conductive composite material - Google Patents
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- B29C2945/00—Indexing scheme relating to injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould
- B29C2945/76—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2948/00—Indexing scheme relating to extrusion moulding
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- B29C2948/92504—Controlled parameter
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Abstract
The invention relates to a method for preparing a carbon nanotube/expanded graphite/polypropylene conductive composite material. The method comprises the following steps: uniformly mixing carbon nanotube, expanded graphite and polypropylene resin, extrusion molding the mixture to obtain a composite material, and then, adjusting four injection process parameters of melt temperature, dwell pressure, injection pressure and injection speed to perfect the conductivity of PP/CNTs/EG injection molding products. The method can not only be used for perfecting the alignment problem of the carbon nanotube in polypropylene base volume, but also serving as a mutual contact connecting point of the carbon nanotube to improve the conductivity, solving the easy orientation and hard dispersion problems of CNTs in the injection molding process and increasing the contact of the carbon nanotube and the expanded graphite to form a good conductive network; and the expanded graphite is added and the injection molding process is adjusted to perfect the low conductivity problem of the polypropylene/carbon nanotube in the injection molding process and simply and effectively expand the application range of the polypropylene nano composite material in the field of electric conduction.
Description
Technical field
The present invention relates to a kind of preparation method of conducing composite material, particularly the preparation method of a kind of carbon nanotube/expanded graphite/polypropylene conductive matrix material.
Background technology
Polypropylene (PP) is a kind of thermoplastic synthetic resin of excellent property, is the lightest general-purpose plastics, and it is widely used in each large field with good over-all properties.Along with the development of modification technology, various high-performance proprietary materials continue to bring out, and wherein, utilizing carbon nanotube (CNTs) reinforced polypropylene compound material to improve its product conductivity becomes one of focus of current expansion general-purpose plastics Application Areas.
Carbon nanotube has the advantages such as high length-to-diameter ratio, good heat conductivity, density are light have been caused widely and has paid close attention to.Its excellent conductivity particularly, becomes carbon nanotube to prepare the ideal filler of conductive polymer nanometer composite material.In recent years, the research of preparing Polymer/carbon Nanotubes Composites by melting mixing compression molding has obtained positive progress, but only has seldom some people to select research injection moulding to prepare conducting polymer composite material.Injection moulding is used injection moulding machine and injection molding that raw materials for plastics production are become to plastics, is one of topmost processing molding method of thermoplastics, is also the main method of production polymer conducting material.Than other forming methods, injection molding cycle is short, can be mass, but during Polymer/carbon Nanotubes Composites injection moulding, carbon nanotube dispersed is poor, tend to occur obvious orientation, make cannot mutually overlap between carbon nanotube, its conductivity is well below other forming methods, as compression molding.Thereby the carbon nanotube orientation causing in injection moulding process has seriously limited its development in conductive articles field.
For how improving the conductivity of polymer conducting material when the injection moulding, caused people's concern.The conductivity that processing parameter in change injection moulding improves Polymer/carbon Nanotubes Composites is a research direction in recent years.Under different Shooting Techniques, carbon nanotube there will be different deployment conditions in polymeric matrix, forms different conductive networks, thereby improves the conductivity of end article.In addition, expanded graphite (EG) not only has the premium properties of natural flake graphite, also has quality light, and electrical and thermal conductivity is good, and the excellent specific properties such as easy-formation make it also be subject to extensive concern.Expanded graphite adds in carbon nanotube/polypropylene matrix, not only can mutually overlap formation conductive path, and as the tie point of conductive network, the chance that CNT-CNT is in contact with one another is increased greatly, thereby significantly improve the conductivity of Polypropylene/Carbon Nanotube Composites.
Summary of the invention
In view of above problem, the invention provides the preparation method of a kind of carbon nanotube/expanded graphite/polypropylene conductive polymkeric substance, and introduce expanded graphite and change the forming method that Shooting Technique prepares the carbon nanotube/expanded graphite/polypropylene composite material of excellent conductive performance.
The present invention proposes the preparation method of a kind of carbon nanotube/expanded graphite/polypropylene conductive matrix material, utilize intercalation configuration and the excellent conductive performance of expanded graphite, expanded graphite not only can occupy effective volume, increase the interconnective chance of CNTs, and can be used as the tie point of CNTs conductive network, form good conductive path.The change that is accompanied by Shooting Technique is adjusted melt flow in injection moulding machine, and then improves the orientation problem of carbon nanotube in polypropylene matrix, and makes the increase that contacts of expanded graphite and carbon nanotube, obtains good CNTs-EG conductive network; Expanded graphite is mixed with carbon nanotube/polypropylene composite materials, be extruded into after particle, further change Shooting Technique, obtain the carbon nanotube/expanded graphite/polypropylene injection molding product of excellent conductive performance.Concrete technical scheme is as follows:
A preparation method for carbon nanotube/expanded graphite/polypropylene conductive matrix material, comprises the steps:
(1) take 1～10g expansible black lead powder and be placed in 700～850 ℃ of retort furnace high temperature puffing 30～60s, obtain expanded graphite (EG);
(2) acrylic resin, carbon nanotube/polypropylene master batch are mixed with oxidation inhibitor, then with step (1) in the expanded graphite of gained by extruding-out process, undertaken compoundly, by following weight percent content, take material:
Acrylic resin: 72.0～90.0%;
Expanded graphite: 0.1～1%;
Carbon nanotube/polypropylene master batch: 8～25%;
Oxidation inhibitor: 0.15～0.25%;
Wherein, expanded graphite, oxidation inhibitor, acrylic resin and carbon nanotube/polypropylene master batch together add from main feeding, extruder screw rotating speed is 120～600 revs/min, and temperature is 190～220 ℃, can obtain carbon nanotube/expanded graphite/polypropylene composite material;
(3) carbon nanotube/expanded graphite/polypropylene composite material step (2) being obtained is placed in the dry 4～8h of baking oven of 80～120 ℃, then adds and in injection moulding machine, carries out injection moulding; Take melt temperature, dwell pressure, injection pressure, injection speed obtains 16 experiment conditions as injection technological parameter carries out orthogonal experiment, therefrom determines optimum injection molding technique condition.
Expansible black lead described in step (1) is 80 order crystalline flake graphites, and the expanding volume of described expanded graphite is 137.5ml/g.
Described in step (2), the weight percent of carbon nanotube/polypropylene master batch is configured to: multi-walled carbon nano-tubes 20～25%, polypropylene agglomerate 75～80%; The fusing point of described carbon nanotube/polypropylene master batch is 160～170 ℃.
Described in step (2), oxidation inhibitor is the compound system of Hinered phenols antioxidant and phosphite ester kind antioxidant.
Expanded graphite described in step (3) directly adds after evenly mixing with carbon nanotube/polypropylene master batch.
The variation range of Shooting Technique parameter described in step (4) is respectively: melt temperature is 200～240 ℃, and dwell pressure is 50～120bar, and injection pressure is 50～150MPa, and injection speed is 15～75mm/s.
After intercalation configuration high temperature puffing due to expansible black lead, obtain quasiflake graphite, there is good electrical and thermal conductivity performance, therefore, with expansible black lead, prepare expanded graphite.
Beneficial effect of the present invention: the adjustment of introducing expanded graphite and carrying out Shooting Technique improves the conductivity of polypropylene/expanded graphite/carbon nano tube compound material, and its method is simple, carries out special processing without other equipment; And operation is very easy to add expanded graphite, after evenly mixing with polypropylene and carbon nanotube/polypropylene master batch, directly add pelletizing in forcing machine; Expanded graphite adds in carbon nanotube/polypropylene matrix, not only can mutually overlap formation conductive path, and as the tie point of conductive network, the chance that CNT-CNT is in contact with one another is increased greatly, thereby significantly improve the conductivity of Polypropylene/Carbon Nanotube Composites, the preparation method of above-mentioned carbon nanotube/expanded graphite/polypropylene conductive matrix material is achieved.
The explanation of accompanying drawing/table
Fig. 1 is the surface resistivity recording under comparative example 1 and 2 different Shooting Techniques.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, is necessary to be pointed out that at this following examples are that the invention will be further described, rather than limits the scope of the invention by any way.
Step (1): add 1.34g expansible black lead stand-by in crucible.Retort furnace is warming up to after 800 ℃, and expansible black lead is placed in one, and high temperature puffing 45s obtains expanded graphite;
Step (2): acrylic resin, carbon nanotube/polypropylene master batch are mixed with oxidation inhibitor, then with step (1) in the expanded graphite of gained by extruding-out process, undertaken compoundly, by following weight percent content, take material:
Acrylic resin: 74.7%;
Expanded graphite: 0.1%;
Carbon nanotube/polypropylene master batch: 25%;
Oxidation inhibitor: 0.2%;
Step (3): above-mentioned material is extruded and granulation through twin screw extruder, wherein expanded graphite, oxidation inhibitor, acrylic resin and carbon nanotube/polypropylene master batch together add from main feeding, extruder screw rotating speed is 180 revs/min, temperature is 200 ℃, can obtain carbon nanotube/expanded graphite/polypropylene composite material;
Step (4): by the above-mentioned particle dry 4h in 80 ℃ of baking ovens that extrudes, then enter and carry out injection moulding in injection moulding machine.Take melt temperature, dwell pressure, injection pressure, injection speed obtains 16 experiment conditions as injection technological parameter carries out orthogonal experiment, therefrom determines optimum injection molding technique condition, to carry out the improvement of conductivity.
In above-mentioned 16 experiment conditions, the most representative, surface resistivity differs 4 Shooting Technique conditions maximum and symmetry between two and is respectively experiment condition 3,5,10 and 13.
3. melt temperature: 200 ℃, dwell pressure: 50bar, injection pressure: 150MPa and injection speed: 75mm/s;
5. melt temperature: 200 ℃, dwell pressure: 120bar, injection pressure: 50MPa and injection speed: 15mm/s;
10. melt temperature: 240 ℃, dwell pressure: 120bar, injection pressure: 50MPa and injection speed: 15mm/s;
13. melt temperatures: 240 ℃, dwell pressure: 50bar, injection pressure: 150MPa and injection speed: 75mm/s.
Step (1): add 2.68g expansible black lead stand-by in crucible.Retort furnace is warming up to after 800 ℃, and expansible black lead is placed in one, and high temperature puffing 45s obtains expanded graphite;
Step (2): acrylic resin, carbon nanotube/polypropylene master batch are mixed with oxidation inhibitor, then with step (1) in the expanded graphite of gained by extruding-out process, undertaken compoundly, by following weight percent content, take material:
Acrylic resin: 74.6%;
Expanded graphite: 0.2%;
Carbon nanotube/polypropylene master batch: 25%;
Oxidation inhibitor: 0.2%;
Step (3): above-mentioned material is extruded and granulation through twin screw extruder, wherein expanded graphite, oxidation inhibitor, acrylic resin and carbon nanotube/polypropylene master batch together add from main feeding, extruder screw rotating speed is 180 revs/min, temperature is 200 ℃, can obtain carbon nanotube/expanded graphite/polypropylene composite material;
Step (4): by the above-mentioned particle dry 4h in 80 ℃ of baking ovens that extrudes, then enter and carry out injection moulding in injection moulding machine.Take melt temperature, dwell pressure, injection pressure, injection speed obtains 16 experiment conditions as injection technological parameter carries out orthogonal experiment, therefrom determines optimum injection molding technique condition, to carry out the improvement of conductivity.
Wherein 4 Shooting Technique conditions are identical with four conditions the most representative in embodiment 1.
Step (1): add 6.71g expansible black lead stand-by in crucible.Retort furnace is warming up to after 800 ℃, and expansible black lead is placed in one, and high temperature puffing 45s obtains expanded graphite;
Step (2): acrylic resin, carbon nanotube/polypropylene master batch are mixed with oxidation inhibitor, then with step (1) in the expanded graphite of gained by extruding-out process, undertaken compoundly, by following weight percent content, take material:
Acrylic resin: 74.3%;
Expanded graphite: 0.5%;
Carbon nano-tube/nylon master batch: 25%;
Oxidation inhibitor: 0.2%;
Step (3): above-mentioned material is extruded and granulation through twin screw extruder, wherein expanded graphite, oxidation inhibitor, acrylic resin and carbon nanotube/polypropylene master batch together add from main feeding, extruder screw rotating speed is 180 revs/min, temperature is 200 ℃, can obtain carbon nanotube/expanded graphite/polypropylene composite material;
Step (4): by the above-mentioned particle dry 4h in 80 ℃ of baking ovens that extrudes, then enter and carry out injection moulding in injection moulding machine.Take melt temperature, dwell pressure, injection pressure, injection speed obtains 16 experiment conditions as injection technological parameter carries out orthogonal experiment, therefrom determines optimum injection molding technique condition, to carry out the improvement of conductivity.
Wherein 4 Shooting Technique conditions are identical with four conditions the most representative in embodiment 1.
Step (1): add 13.42g expansible black lead stand-by in crucible.Retort furnace is warming up to after 800 ℃, and expansible black lead is placed in one, and high temperature puffing 45s obtains expanded graphite;
Step (2): acrylic resin, carbon nanotube/polypropylene master batch are mixed with oxidation inhibitor, then with step (1) in the expanded graphite of gained by extruding-out process, undertaken compoundly, by following weight percent content, take material:
Acrylic resin: 73.8%;
Expanded graphite: 1.0%;
Carbon nano-tube/nylon master batch: 25%;
Oxidation inhibitor: 0.2%;
Step (3): above-mentioned material is extruded and granulation through twin screw extruder, wherein expanded graphite, oxidation inhibitor, acrylic resin and carbon nanotube/polypropylene master batch together add from main feeding, extruder screw rotating speed is 180 revs/min, temperature is 200 ℃, can obtain carbon nanotube/expanded graphite/polypropylene composite material;
Step (4): by the above-mentioned particle dry 4h in 80 ℃ of baking ovens that extrudes, then enter and carry out injection moulding in injection moulding machine.Take melt temperature, dwell pressure, injection pressure, injection speed obtains 16 experiment conditions as injection technological parameter carries out orthogonal experiment, therefrom determines optimum injection molding technique condition, to carry out the improvement of conductivity.
Wherein 4 Shooting Technique conditions are identical with four conditions the most representative in embodiment 1.
Comparative example 1
Acrylic resin, carbon nanotube/polypropylene master batch are mixed with oxidation inhibitor, after twin screw extruder technique is compound, extrude pelletizing, obtain PP/2.5wt%CNTs matrix material, and obtain carbon nanotube/polypropylene injection-molded item according to the adjustment that the injecting condition of table 1 carries out Shooting Technique.
Step (1): take material by following weight percent content:
Acrylic resin: 87.3%;
Carbon nanotube/polypropylene master batch: 12.5%;
Oxidation inhibitor: 0.2%;
Step (2): above-mentioned material is extruded and granulation through twin screw extruder, wherein acrylic resin, oxidation inhibitor are added by main feeding after mixing with carbon nanotube/polypropylene master batch, extruder screw rotating speed is 180 revs/min, and temperature is 195 ℃, obtains carbon nanotube/polypropylene composite materials;
Step (3): by the above-mentioned particle dry 4h in 80 ℃ of baking ovens that extrudes, then enter and carry out injection moulding in injection moulding machine.Change melt temperature, dwell pressure, injection pressure and 4 processing parameters of injection speed in injection moulding, to carry out the improvement of conductivity, 16 experiment conditions of gained are as shown in table 1.
Comparative example 2
Acrylic resin, carbon nanotube/polypropylene master batch are mixed with oxidation inhibitor, after twin screw extruder technique is compound, extrude pelletizing, obtain PP/5wt%CNTs matrix material, and obtain carbon nanotube/polypropylene injection-molded item according to the adjustment that the injecting condition of table 1 carries out Shooting Technique.
Step (1): take material by following weight percent content:
Acrylic resin: 74.8%;
Carbon nanotube/polypropylene master batch: 25%;
Oxidation inhibitor: 0.2%;
Step (2): above-mentioned material is extruded and granulation through twin screw extruder, wherein acrylic resin is added by main feeding after mixing with carbon nanotube/polypropylene, extruder screw rotating speed is 180 revs/min, and temperature is 195 ℃, obtains carbon nanotube/polypropylene composite materials;
Step (3): by the above-mentioned particle dry 4h in 80 ℃ of baking ovens that extrudes, then enter and carry out injection moulding in injection moulding machine.Change melt temperature, dwell pressure, injection pressure and 4 processing parameters of injection speed in injection moulding, to carry out the improvement of conductivity.Wherein 16 experiment conditions are as shown in table 1.
The polypropylene conductive matrix material of comparative example 2 and embodiment 1～4 preparation all contains 25% carbon nanotube/polypropylene master batch.In comparative example 1, contain 12.5% carbon nanotube/polypropylene master batch.Embodiment 1～4 and comparative example 1～2 are carried out to the test of surface resistivity, and its test result is in Table 2.
From the measurement result to embodiment 1～4 and comparative example 1～2, conductivity is along with considerable change appears in the change of each embodiment Shooting Technique condition, after adding expanded graphite, electroconductibility further improves, yet in comparative example 1, change not impact of Shooting Technique, prove that change Shooting Technique is effective just now for the CNTs of certain content; When content of carbon nanotubes reaches 5wt%, during comparative example 2, change Shooting Technique very remarkable for the impact of conductivity.By above-described embodiment and comparative example, finally determine that optimum Shooting Technique is injecting condition 10, its surface resistivity is minimum.
16 experiment conditions of 4 Shooting Technique parameter quadrature gained of table 1
Table 2 the performance test results
Claims (6)
1. a preparation method for carbon nanotube/expanded graphite/polypropylene conductive matrix material, is characterized in that, comprises the steps:
(1) take 1～10g expansible black lead powder and be placed in 700～850 ℃ of retort furnace high temperature puffing 30～60s, obtain expanded graphite;
(2) acrylic resin, carbon nanotube/polypropylene master batch are mixed with oxidation inhibitor, then with step (1) in the expanded graphite of gained by extruding-out process, undertaken compoundly, by following weight percent content, take material:
Acrylic resin: 72.0～90.0%;
Expanded graphite: 0.1～1%;
Carbon nanotube/polypropylene master batch: 8～25%;
Oxidation inhibitor: 0.15～0.25%;
Wherein, expanded graphite, oxidation inhibitor, acrylic resin and carbon nanotube/polypropylene master batch together add from main feeding, extruder screw rotating speed is 120～600 revs/min, and temperature is 190～220 ℃, can obtain carbon nanotube/expanded graphite/polypropylene composite material;
(3) carbon nanotube/expanded graphite/polypropylene composite material step (2) being obtained is placed in the dry 4～8h of baking oven of 80～120 ℃, then adds and in injection moulding machine, carries out injection moulding; Take melt temperature, dwell pressure, injection pressure, injection speed obtains 16 experiment conditions as injection technological parameter carries out orthogonal experiment, therefrom determines optimum injection molding technique condition.
2. preparation method according to claim 1, is characterized in that, expansible black lead described in step (1) is 80 order crystalline flake graphites, and the expanding volume of described expanded graphite is 137.5ml/g.
3. preparation method according to claim 1, is characterized in that, described in step (2), the weight percent of carbon nanotube/polypropylene master batch is configured to: multi-walled carbon nano-tubes 20～25%, polypropylene agglomerate 75～80%; The fusing point of described carbon nanotube/polypropylene master batch is 160～170 ℃.
4. preparation method according to claim 1, is characterized in that, described in step (3), oxidation inhibitor is the compound system of Hinered phenols antioxidant and phosphite ester kind antioxidant.
5. preparation method according to claim 1, is characterized in that, expanded graphite described in step (3) directly adds after evenly mixing with carbon nanotube/polypropylene master batch.
6. preparation method according to claim 1, it is characterized in that, the variation range of Shooting Technique parameter described in step (4) respectively: melt temperature is 200～240 ℃, and dwell pressure is 50～120bar, injection pressure is 50～150MPa, and injection speed is 15～75mm/s.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384965A (en) * | 2015-11-30 | 2016-03-09 | 广东轻工职业技术学院 | Carbon nano tube/ expanded graphite combined padding and preparing method thereof as well as heat conducting high polymer material containing combined padding and preparing method of heat conducting high polymer material |
| CN108407135A (en) * | 2018-02-11 | 2018-08-17 | 华南理工大学 | The method and its application of polypropylene/exfoliated-graphite composite are prepared using water auxiliary molten mixing extrusion |
| CN108948511A (en) * | 2017-05-29 | 2018-12-07 | 镇江瑞德新材料科技研发有限公司 | A kind of preparation method of PP/KPEG/MWNTs heat-conductive composite material |
| CN110041898A (en) * | 2019-05-23 | 2019-07-23 | 江苏碳元绿色建筑科技有限公司 | A kind of nano material in-situ enhancing porous graphite material and its preparation method and application |
| CN113150014A (en) * | 2021-03-11 | 2021-07-23 | 广州工程技术职业学院 | Europium complex, polypropylene composite material and preparation method thereof |
| CN113956498A (en) * | 2021-11-15 | 2022-01-21 | 成都先进金属材料产业技术研究院股份有限公司 | Polyolefin-based conductive plastic for all-vanadium redox flow battery and preparation method thereof |
| CN115569966A (en) * | 2022-11-03 | 2023-01-06 | 山东金利特新材料有限责任公司 | Recycling method of waste filter element |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115558A (en) * | 2010-12-29 | 2011-07-06 | 四川大学 | High-conductivity polymer carbon nanotube composite material and micro-processing method thereof |
-
2013
- 2013-12-19 CN CN201310703867.9A patent/CN103627089B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115558A (en) * | 2010-12-29 | 2011-07-06 | 四川大学 | High-conductivity polymer carbon nanotube composite material and micro-processing method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 叶子，葛亚宁，李修平，李志超，邹华维，梁梅: "聚丙烯/膨胀石墨/碳纳米管复合材料电性能、微观结构", 《塑料工业》 * |
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|---|---|---|---|---|
| CN105384965A (en) * | 2015-11-30 | 2016-03-09 | 广东轻工职业技术学院 | Carbon nano tube/ expanded graphite combined padding and preparing method thereof as well as heat conducting high polymer material containing combined padding and preparing method of heat conducting high polymer material |
| CN105384965B (en) * | 2015-11-30 | 2019-01-01 | 广东轻工职业技术学院 | Carbon nanotube/expanded graphite composite filling and the heat-conducting polymer material containing composite filling |
| CN108948511A (en) * | 2017-05-29 | 2018-12-07 | 镇江瑞德新材料科技研发有限公司 | A kind of preparation method of PP/KPEG/MWNTs heat-conductive composite material |
| CN108407135A (en) * | 2018-02-11 | 2018-08-17 | 华南理工大学 | The method and its application of polypropylene/exfoliated-graphite composite are prepared using water auxiliary molten mixing extrusion |
| CN108407135B (en) * | 2018-02-11 | 2019-10-18 | 华南理工大学 | Polypropylene/exfoliated-graphite composite method and its application are prepared using water auxiliary molten mixing extrusion |
| CN110041898A (en) * | 2019-05-23 | 2019-07-23 | 江苏碳元绿色建筑科技有限公司 | A kind of nano material in-situ enhancing porous graphite material and its preparation method and application |
| CN113150014A (en) * | 2021-03-11 | 2021-07-23 | 广州工程技术职业学院 | Europium complex, polypropylene composite material and preparation method thereof |
| CN113956498A (en) * | 2021-11-15 | 2022-01-21 | 成都先进金属材料产业技术研究院股份有限公司 | Polyolefin-based conductive plastic for all-vanadium redox flow battery and preparation method thereof |
| CN115569966A (en) * | 2022-11-03 | 2023-01-06 | 山东金利特新材料有限责任公司 | Recycling method of waste filter element |
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