CN105445154B - The Particle size analysis methods of inorganic filler in cross-linked polymer - Google Patents
The Particle size analysis methods of inorganic filler in cross-linked polymer Download PDFInfo
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- CN105445154B CN105445154B CN201510981210.8A CN201510981210A CN105445154B CN 105445154 B CN105445154 B CN 105445154B CN 201510981210 A CN201510981210 A CN 201510981210A CN 105445154 B CN105445154 B CN 105445154B
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- linked polymer
- acid
- carbon black
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- 239000011256 inorganic filler Substances 0.000 title claims abstract description 67
- 229910003475 inorganic filler Inorganic materials 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 64
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 58
- 238000003921 particle size analysis Methods 0.000 title claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 54
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 238000010306 acid treatment Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000004458 analytical method Methods 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000002203 pretreatment Methods 0.000 claims abstract description 11
- 239000000284 extract Substances 0.000 claims abstract description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- 239000006229 carbon black Substances 0.000 claims description 78
- 238000012545 processing Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 24
- 239000005060 rubber Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 239000005062 Polybutadiene Substances 0.000 claims description 12
- 229920002857 polybutadiene Polymers 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 229920000459 Nitrile rubber Polymers 0.000 claims description 6
- 229920000800 acrylic rubber Polymers 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 229910000410 antimony oxide Inorganic materials 0.000 claims description 4
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229920003049 isoprene rubber Polymers 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000000691 measurement method Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 description 32
- 230000005540 biological transmission Effects 0.000 description 28
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 17
- 235000019441 ethanol Nutrition 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000005119 centrifugation Methods 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 208000028659 discharge Diseases 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 10
- 229920002943 EPDM rubber Polymers 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000012634 fragment Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000003738 black carbon Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000003851 corona treatment Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000010129 solution processing Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002525 ultrasonication Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000005622 photoelectricity Effects 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 206010015150 Erythema Diseases 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229910025794 LaB6 Inorganic materials 0.000 description 1
- 229910002254 LaCoO3 Inorganic materials 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- 229910003264 NiFe2O4 Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000321 erythema Toxicity 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DIVDFFZHCJEHGG-UHFFFAOYSA-N oxidopamine Chemical compound NCCC1=CC(O)=C(O)C=C1O DIVDFFZHCJEHGG-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
- G01N15/02—Investigating particle size or size distribution
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides the Particle size analysis methods of inorganic filler in cross-linked polymer, comprising the following steps: provides smashed cross-linked polymer；It is modified to carry out surface to smashed cross-linked polymer for pre-treatment step；Alkali treatment extracts remaining solid using the cross-linked polymer after hydroxide aqueous solution surface modification；Acid treatment step obtains inorganic filler aggregate using remaining solid described in mineral acid treatment；Dispersion and analytical procedure disperse the inorganic filler aggregate, the inorganic filler partial size after analysis dispersion in a solvent.Measurement method of the present invention has the characteristics that accurate, strong operability.
Description
Technical field
The present invention relates to a kind of methods of inorganic filler partial size in measurement polymeric system to be specifically related to a kind of survey
The method of inorganic filler partial size in the cross-linking polymer system of the difficult resolution of amount.
Background technique
Cross-linked polymer, also known as cross-linked polymer are the polymer of tridimensional network.Cross-linking method is divided into chemical crosslinking
And physical crosslinking, as the vulcanization of rubber, all crosslinking dose of solidification of thermosetting resin participate in.Cross-linking reaction refer generally to two or
More molecules are cross-linked into the figure molecule reaction of the more stable molecule of network structure as linear molecule is mutually bonded, this anti-
Line style or the macromolecular of slight branched chain type should be made to be transformed into tridimensional network, be widely used in high polymer synthesis, such as plastics, tree
In the synthesis and modifying process such as rouge, rubber.The above-mentioned material for crosslinking reaction just becomes insoluble usually after molding and does not melt
Solid, have the performances such as better intensity, heat resistance, wearability and solvent resistance.It is added in cross-linked polymer inorganic
Filler helps to improve the rigidity of polymer product, toughness, and the performance of specific gain is different because of the type of inorganic filler, and charcoal
The partial size of the inorganic fillers such as black, white carbon black also can cause more significant impact to the performance of polymeric system, it is therefore necessary to
The partial size of inorganic filler in cross-linking polymer article is measured, with preferably adjusting process, guarantees product quality.
The cross-linked polymer of three-dimensional-structure is difficult to be dissolved in organic solvent, is using high concentration nitric acid, perchloric acid or microwave
When clearing up cross-linked polymer separation inorganic filler, although can clear up by polymer, easily inorganic filler is excessively cleared up,
And its prototype structure is damaged, largely effect on the accuracy of later period grain diameter measurement.Therefore it is highly desirable to and designs one kind accurately
The method for measuring inorganic filler partial size in cross-linking polymer system of degree height, strong operability.
Summary of the invention
The object of the present invention is to provide a kind of Particle size analysis methods of inorganic filler in cross-linked polymer, including following step
It is rapid: smashed cross-linked polymer is provided；It is modified to carry out surface to smashed cross-linked polymer for pre-treatment step；Alkali process
Step extracts remaining solid using the cross-linked polymer after hydroxide aqueous solution surface modification；Acid treatment step makes
The remaining solid described in mineral acid treatment obtains inorganic filler aggregate；Dispersion and analytical procedure, disperse the nothing in a solvent
Machine filler aggregate, the inorganic filler partial size after analysis dispersion.
As a preferred technical solution of the present invention, the cross-linked polymer includes EP rubbers, butadiene-styrene rubber, butyronitrile
Rubber, isoprene rubber, butadiene rubber, acrylic rubber, phenolic resin, epoxy resin.
As a preferred technical solution of the present invention, the inorganic filler includes carbon black, white carbon black, aluminium hydroxide, hydrogen
Magnesia, antimony oxide.
As a preferred technical solution of the present invention, the partial size of the smashed cross-linked polymer is no more than 300
mm。
As a preferred technical solution of the present invention, the pre-treatment step is included at least at low-temperature plasma spraying
Reason, the aqueous solution soaking heat treatment of alcohol or alcohol, photocatalysis treatment, photoelectrocatalysis processing, treatment with ultraviolet light.
As a preferred technical solution of the present invention, the hydroxide is selected from alkali metal, alkaline earth metal hydroxide
At least one of.
As a preferred technical solution of the present invention, the alkali treatment is arranged 90~120 DEG C of heating temperature, place
The reason time 0.5~5 hour, and the mass fraction of the hydroxide aqueous solution is 20~60%.
As a preferred technical solution of the present invention, the inorganic acid is selected from perchloric acid, nitric acid, hydrochloric acid, sulfuric acid, phosphorus
At least one of acid, hydrofluoric acid.
As a preferred technical solution of the present invention, the acid treatment step is heated using ultrasound bath, if
30~60 DEG C of temperature are set, is handled the time 1~8 hour.
As a preferred technical solution of the present invention, solvent used in the dispersion and analytical procedure is included at least
Water, alcohols solvent or alcohol-water mixture.
Measurement method of the present invention has the characteristics that accurate, strong operability.
Specific embodiment
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this public affairs can be more easily to understand
Open content.Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering is non-
It is exclusive to include.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those and want
Element, but may include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Temperature, time or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this should be understood as specifically disclosing by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1~5 ", described range should be interpreted as including range " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise the range is intended to include its end
Value and all integers and score in the range.
As used herein term " by ... preparation " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
" polymer " indicates the polymerization chemical combination prepared and by the monomer of same type or different types of monomer polymerization
Object.
Now by referring to each illustrative embodiments of the invention, embodiment is hereinafter retouched in detail below
It states.Although will be of the invention in conjunction with illustrative embodiments description, it is to be understood that, this specification is not intended to limit the invention to
These illustrative embodiments.On the contrary, the present invention will not only cover these illustrative embodiments, also to cover by appended right
Various alternative forms, modification, equivalents and other embodiments in the spirit and scope of the present invention defined by it is required that.
The present invention provides a kind of Particle size analysis methods of inorganic filler in cross-linked polymer, comprising the following steps:
Smashed cross-linked polymer is provided；
It is modified to carry out surface to smashed cross-linked polymer for pre-treatment step；
Alkali treatment extracts remaining solid using the cross-linked polymer after hydroxide aqueous solution surface modification；
Acid treatment step obtains inorganic filler aggregate using remaining solid described in mineral acid treatment；
Dispersion and analytical procedure disperse the inorganic filler aggregate, the inorganic filler grain after analysis dispersion in a solvent
Diameter.
Cross-linked polymer:
Usual cross-linking reaction, which refers to, to be attached between linear macromolecule with new chemical bond, makes three-dimensional netted
Or the reaction of three-dimensional-structure.It is mainly used for the vulcanization of rubber product, the solidification of thermosetting resin and adhesive, to improve product
Integral strength performance.The polymer for crosslinking reaction would generally become insoluble insoluble solid, have better intensity, resistance to
The performances such as hot, wearability and solvent resistance, while resolution also becomes more difficult.Inorganic filler is added in cross-linked polymer
Rigidity, the toughness of polymer product are helped to improve, the type and particle size of inorganic filler, distribution all can be specific to polymer
The performance of gain generates more significant impact.
By taking carbon black as an example, same carbon black, particle size is not identical, and is in certain distribution.It is usually existing
Signified particle size carbon black is indicated according to the assembly average of particle size in electron micrograph in technology.The partial size of carbon black
Smaller, tensile strength, tearing strength, stress at definite elongation, wearability, the hardness for being added to generated vulcanizate in rubber are higher,
Resilience and elongation at break are smaller.But if partial size is too small, it can be agglomerated again between particle, group easy to form, so as to cause
Difficulties in dispersion in mixing process reduces its plasticity and tubeability.The name of carbon black can refer to ASTMD1765 5, and " rubber is used
Carbon black classification naming system ", generally the letter and number in name can embody the general configuration and particle size range of carbon black.Work as friendship
When linked polymer is rubber, in mixing process, carbon black can generate chemical bonding with partial rubber strand, and generation cannot be by
The carbon gel or bound rubber of solvent extraction.Carbon gel plays stable skeleton function in rubber cross network, mentions
It is also exacerbated while high rubber performance and clears up isolated difficulty.In addition to carbon black, other kinds of inorganic filler such as white carbon black, hydrogen
Aluminium oxide, magnesium hydroxide, antimony oxide etc. can also there is a problem of same.
So in order to accurately measure inorganic filler partial size, need using suitable processing mode, by it from cross-linked polymeric
What is be not destroyed in objects system separates.The cross-linked polymer includes EP rubbers, butadiene-styrene rubber, nitrile rubber, isoamyl
Rubber, butadiene rubber, acrylic rubber, phenolic resin, epoxy resin.The inorganic filler includes carbon black, white carbon black, hydrogen-oxygen
Change aluminium, magnesium hydroxide, antimony oxide.
It crushes:
So-called crushing just refers to the process of that material size reduces.Various types of crushing mechanisms are generallyd use, material is applied
Different mechanical forces are added to complete, such as drawing force, extruding force, impact force and shearing force.The crushing of high impact polystyrene can
To be to crush, smash, grind or shred.Crushing is also possible to Freezing smashing.Utilize refrigerant freezing or air turbine expansion type
Freezing makes rubber product be cooled to glass transition temperature hereinafter, then being crushed with beater grinder or dry pan.It is preferred that liquid nitrogen is cold
Agar is broken.
As a preferred technical solution of the present invention, after crushed, partial size is no more than the cross-linked polymer of the offer
300 mm。
Pre-treatment step:
Pre-treatment step of the present invention can carry out surface to smashed cross-linked polymer and be modified, the pretreatment step
It is rapid including at least the aqueous solution soaking heat treatment of low-temperature plasma spray treatment, alcohol or alcohol, photocatalysis treatment, photoelectrocatalysis at
Reason, treatment with ultraviolet light.It is living that present inventor has found that these pre-treatment steps can be improved smashed cross-linked polymer surface
Property, promote the progress of subsequent alkali process and acid treatment step, help to improve later period inorganic filler analyzes measurement.
Low temperature plasma contains a large amount of electronics, excited atom and molecule and free radical isoreactivity particle, these
Active particle makes material surface cause to etch, aoxidize, restore, attacking the physical and chemical reactions such as solution, crosslinking and polymerization, to realize
Modification to material surface.Since the energy of particle in low temperature plasma is generally several to tens electron-volts, it is greater than
The combination bond energy that several to more than ten electron-volt of high molecular material can be such that the associative key of organic macromolecule material is broken completely
And form new keys；But its strong energy that can be far below high-energy radiation, therefore surface plasma processing only occurs in the table of material
Face.When the smashed cross-linked polymer of corona treatment, high-energy particle bombardment polymer makes weak breaking of covalent bonds, improves
The surface energy of rubber grain, and plasma will not influence the structure of inorganic filler.
When carrying out plasma spraying processing to the smashed cross-linked polymer, preferred static treatment, i.e., by rubber like
Product are uniform, and as thin as possible spreads on specified containers, and then specified containers are put into corona treatment instrument, carry out etc.
Gas ions processing, in entire treatment process, powdered rubber is static.In the present invention, one is preferably carried out in mode,
GPT-3 type, discharge frequency is used to discharge for the low-temp low-pressure glow discharge plasma processing instrument of 13.56MHz material
Processing.GPT-3 type corona treatment instrument is that external electrode formula induction misfortune closes Radio-frequency plasma torch.
When pretreatment is low-temperature plasma processing, the preferably low-temperature plasma handles specifically operating procedure: will
The Powdey cross-linked polymer of 100mg equably, it is as thin as possible spread in the culture dish of 15cm, be placed in GPT-3 type plasma
It in body processing instrument, closes all air intake valves and vacuumizes, when being extracted into air pressure to 10Pa, carry out gas washing with oxygen, repetition is washed
Gas 2~3 is passed through the pressure that oxygen reaches certain then by adjusting air intake valve.Thermocouple vacuum gauge is closed, radio frequency function is opened
Rate source is discharged, and is discharged the regular hour under different capacity.After experiment, directly it is put into plasma vacuum is intracavitary
Air takes out sample.Wherein the power of glow discharge be 30~120W, the discharge treatment time be 1~10min, pressure be 20~
100Pa。
When pretreatment is the aqueous solution soaking heat treatment of alcohol or alcohol, the alcohol is selected from ethylene glycol, 1,2-PD, Isosorbide-5-Nitrae-
Butanediol, 1,6-HD, neopentyl glycol, Diethylene Glycol, dipropylene glycol, trimethylolpropane, in glycerine
It is at least one.
As a preferred technical solution of the present invention, the temperature for impregnating heat treatment is 90~130 °C, heat treatment
Time be 3~15 min.Heat treatment mode is microwave heating treatment, and working frequency is 2.45 GHz.
When pretreatment is photoelectrocatalysis processing, smashed cross-linked polymer is dispersed in reaction solution, is reacted molten
Liquid is that the volume ratio of water or first alcohol and water is (2~6): 8 mixed solution, using photochemical catalyst as light anode, 20mm × 100mm's
Ti net is photocathode, and interpolar applies 1.0~3.5 V of applied voltage between electrode away from being 2cm, and under hydrogen lamp irradiation, progress photoelectricity is urged
Change reaction.Entire reactor is placed in ultrasonic reactor, in the case where continual ultrasonic, carries out this photoelectrocatalysis reaction.
The processing time 1~10 hour.
The photochemical catalyst is selected from TiO2、ZnO、CdS、WO3、Fe2O3、PbS、SnO2、InO3、ZnS、SrTiO3、LaCoO3In
At least one.
Ultraviolet light is general name of the electromagnetic spectrum medium wavelength from 0.10~0.40 micron radiation, purple according to the difference of wavelength
The medium wave erythema effect that outside line can be divided into the long wave blackspot effect ultraviolet light that wavelength is 320~400nm, wavelength is 275~320nm
Answer the shortwave sterilizing ultraviolet light that ultraviolet light, wavelength are 200~275nm and the vacuum ultraviolet that wavelength is 100~200nm.When right
When cross-linked polymer carries out ultraviolet light, it can be made quickly to absorb energy, and then the fracture of chemical bond occurs.
The specific steps of ultraviolet light in the present invention are as follows: the cross-linked polymer after heating, rapid cooling to the greatest extent may be used
It thin can sprawl in a reservoir, then container is put under ultraviolet lamp and is irradiated.In the present invention, the ultraviolet lamp using tungsten lamp,
One or more of hydrogen lamp or xenon lamp, irradiation time are 1~10h.
Appropriate to the progress of smashed cross-linked polymer it can also be heated at high temperature before the pre-treatment step and rapidly cold
But it handles, makes cross-linked polymer potential energy with higher, promote the modification in its pre-treatment step.
Alkali treatment:
Alkali treatment of the present invention, be using the cross-linked polymer after hydroxide aqueous solution surface modification,
Remaining solid is extracted again.
The hydroxide is selected from least one of alkali metal, alkaline earth metal hydroxide.Hydrogen can be specifically enumerated as
Sodium oxide molybdena, potassium hydroxide, barium hydroxide.
It is preferably carried out in mode in one kind of the present invention, the alkali treatment, 90~120 DEG C of the heating temperature of setting,
0.5~5 hour time of processing, and the mass fraction of the hydroxide aqueous solution is 20~60%.
It is preferably carried out in mode in one kind of the present invention, carries out alkali treatment in polytetrafluoroethylene (PTFE) counteracting tank.Specifically
Processing method: 0.1~0.5g crosslinked polymer powder is weighed in polytetrafluoroethylene (PTFE) counteracting tank inner canister, is slowly added to hydroxide
Aqueous solution, the amount of hydroxide aqueous solution are no more than 2/3rds of inner canister volume, cover inner cover, put on stainless steel outer tank, then
It is put into thermostatic drying chamber, stands 0.5~5 hour at 100~120 DEG C, be cooled to room temperature, using centrifugation or the side filtered
Method separates remaining solid, then cleaning is washed with deionized to pH neutrality.
10~24 hours are stood at room temperature it is highly preferred that counteracting tank is put into before thermostatic drying chamber, then is carried out subsequent
Step.
Present invention applicant can clear up most of cross-linked polymer and impurity after finding hydroxide aqueous solution processing, still
Inorganic filler formed combination gelatin substance be not resolved, and if extend digestion time or increase drying box temperature, can
Cause excessively to clear up, inorganic filler structure is damaged.Furthermore the counteracting tank that will have cross-linked polymer sample at normal temperature
A period of time is stood, places into thermostatic drying chamber, relatively low heating temperature, which is arranged, can obtain identical resolution result.
Mineral acid treatment:
An important processing step in mineral acid treatment and this method of the present invention.By above-mentioned through hydrogen-oxygen
The remaining solid that the processing of compound aqueous solution obtains is mixed with inorganic acid, is arranged 30~60 DEG C of temperature, is handled the time 1~8 hour, and
And ultrasound bath is used to heat.
As a preferred technical solution of the present invention, the inorganic acid is selected from perchloric acid, nitric acid, hydrochloric acid, sulfuric acid, phosphorus
At least one of acid, hydrofluoric acid.
In an embodiment preferably of the invention, the inorganic acid is the mixed acid of nitric acid and perchloric acid, specifically
Processing method can enumerate are as follows: by 0.1~0.5 g alkali treatment obtain remaining solid be added in conical flask, be added 1
~4 g concentrated nitric acids add 0.1~0.8 g perchloric acid, and conical flask is placed in the numerical control supersonic cleaning for having been warmed up constant temperature
In device water-bath, it is arranged 30~60 °C of bath temperature, the processing of 1~8 h ultrasound bath is carried out to sample, is cooled to room temperature, uses
Centrifugation or the method filtered extract solid in mixed solution, are cleaned with deionized water to neutrality, obtain inorganic filler aggregate.
Above-mentioned acid solution processing step can further clear up hydrogen in remaining solid under relatively low treatment temperature
The substance that oxide water solution is not cleared up, especially package inorganic filler and the part cross-linked polymeric combined closely with its surface
Object.
The unexpected discovery of present inventor, successively by the pretreating surface modification, hydroxide aqueous solution
Processing, then cross-linked polymer can have been cleared up under certain treatment temperature and processing time conditions with mineral acid treatment,
And the structure of inorganic filler will not be changed.Speculate itself the possible reason is, inorganic filler is mixed with cross-linked polymer
It generally will do it the processing such as surface coupling agent is modified before molding, can preferably disperse in cross-linked polymer and performance property
Can, modified inorganic filler can be even closer in conjunction with cross-linked polymer, or even is difficult to isolated combination at one layer of Surface Creation
Glue, alkali treatment are difficult to be eliminated, and inorganic acid promotes disintegrating in conjunction with glue under ultrasonication, in addition lower temperature
The shorter processing time can't damage the structure of inorganic filler, if alkali process, which is used alone, extends the processing time
Or improve treatment temperature and will cause and clear up excessively, and acid processing, which is used alone, can equally reduce inorganic filler measurability, therefore originally
Unexpected technical results have been achieved for invention.
Dispersion and analytical procedure:
The inorganic filler aggregate that above-mentioned steps are extracted needs further dispersion steps can be only achieved also convenient for the state of measurement.
It is described to disperse the inorganic filler aggregate in a solvent in some embodiments of the present invention, it is specific to handle
Method is: taking 0.2g inorganic filler aggregate, is put into 25~50ml colorimetric cylinder, 20~40 ml dispersing agents are added, place into
In the water-bath of numerical control ultrasonic cleaner, bath temperature -5~0 DEG C is set, 1~8 hour ultrasonication is carried out to sample, is obtained
Obtain disperse black carbon suspension.
As a preferred technical solution of the present invention, the dispersing agent is selected from monohydric alcohol, ether, anion surface active
At least one of agent.
It being preferably carried out in mode the present invention is some, the mass ratio of dispersing agent preferred alcohol, ethyl alcohol and water is 10~
The alcohol-water mixture of 20:1.
Inorganic nano partial size size indicates that measuring method has electron microscope usually with average grain diameter or specific surface area
Method, low-temperature nitrogen adsorption method, macromolecules adsorption method, Iodine adsorption method etc..
The partial size test of inorganic filler in the present invention can be surveyed using any method well known by persons skilled in the art
Examination obtains, such as can be transmission electron microscope observing method, X-ray diffraction line width method, low-angle scattering of X-rays method, BET specific surface area method
And centrifugal settling method.
As a preferred technical solution of the present invention, Electron microscopy particle size carbon black is used.Preferably transmission electricity
Sub- microscope, operating method can be enumerated are as follows: the dispersion inorganic filler that above-mentioned steps obtain is observed and clapped under transmission electron microscope
According to.With sample interior atoms phase interaction occurs for transmission electron microscope by accelerating high pressure launching electronics, and after making electron beam transmissive test
With to change its energy and the direction of motion.Since different structure has different interactions, thus, so that it may according to saturating
Radio image subsection information obtained, to understand the crystal structure inside sample.It is already dispersed in solvent in view of inorganic filler,
Common transmission electron microscope powdered samples preparation method can be directly used and extract inorganic filler.
Specifically, taking out the dispersion inorganic filler suspension that above-mentioned steps obtain with capillary glass tube, it is added dropwise and is supported in carbon
On film or copper mesh, it is put into drying 10 hours in 40 DEG C of thermostatic drying chambers, or the drying in 100 DEG C or more thermostatic drying chambers
30min, or 30min is toasted under infrared lamp, as the sample for being subsequently used for transmission electron microscope observing.
Then by the photo of transmission electron microscope random shooting carbon black, with Digital Micrograph or
Image Pro-plus software carries out data processing and statistics to inorganic filler particle partial size.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
The some nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
Test process of the invention is to be commercially available raw material and common inorganic filler before cross-linked polymer is crosslinked first, is surveyed
Measure the partial size of the original inorganic filler bought；Then inorganic filler is added during preparing cross-linked polymer, is made mixed
There is the cross-linked polymer of inorganic filler；Cross-linked polymer obtained taken to processing method of the invention, carry out inorganic filler and
The separation of cross-linked polymer, the partial size of inorganic filler after measurement separation, by itself and the partial size for measuring original inorganic filler when purchase
It compares.
In addition, if the raw material being related to below is all commercially available without other explanations.
All kinds of cross-linked polymers used in the following embodiment at the time of molding in addition to being added to corresponding inorganic filler, also plus
Enter the coupling agent for modified inorganic filler, specifically can choose KH-550 or KH-560.Inorganic fill out can also be added
Before material, surface is carried out to inorganic filler using coupling agent using well known method of modifying and is modified, then is former with cross-linked polymer raw material
Expect mixed-forming.
Corona treatment instrument involved in following embodiment or comparative example is what department of physics, Central University for Nationalities developed
Discharge frequency is the low-temp low-pressure glow discharge plasma processing instrument of 13.56MHz.
Transmission electron microscope involved in following embodiment or comparative example is the JEM-2010 of Jeol Ltd.'s production
Type high-resolution-ration transmission electric-lens, highest acceleration voltage can reach 200KV, and 1,500,000 times of maximum amplification, filament is LaB6 and W lamp
Silk, lattice resolution 0.14nm, point resolution 0.23nm.
Inorganic filler partial size involved in following embodiment or comparative example use Image Pro plus software into
Row data processing and statistics.Each embodiment and comparative example shoot 20 transmission electron microscope photos, count the flat of inorganic filler accordingly
Equal partial size.
Embodiment 1
The partial size of carbon black, step in ethylene propylene diene rubber of the measurement containing 25~30nm of carbon black N375(partial size) are as follows:
(1): ethylene propylene diene rubber sample being cut into fragment or strip first, then using liquid nitrogen frozen pulverizer to it
Liquid nitrogen frozen crushing is carried out, sample particle diameter is less than or equal to 300 mm after crushing.
(2): by the powdered ethylene propylene diene rubber of the 0.1g culture dish for spreading over 15cm equably, as thin as possible, setting
It in GPT-3 type corona treatment instrument, closes all air intake valves and vacuumizes, when being extracted into air pressure to 10Pa, use oxygen
Gas washing is carried out, repeats gas washing 3 times, then by adjusting air intake valve, is passed through oxygen, pressure 100Pa.Thermocouple vacuum gauge is closed,
It opens radio frequency power source to discharge, discharge power 70W, discharge 5min.After experiment, directly to plasma vacuum chamber
It is inside put into air, takes out sample.
(3): by step (2) treated rubber powder in polytetrafluoroethylene (PTFE) counteracting tank inner canister, being slowly added to 50% hydrogen-oxygen
Change sodium solution, and capacity is no more than 2/3rds of inner canister volume, covers inner cover, puts on stainless steel outer tank, it is dry to place into constant temperature
In dry case, 0.5 hour is stood at 120 DEG C, is cooled to room temperature, solid is separated using centrifugation or the method filtered, then spend
Ion water washing is cleaned to pH neutrality, and the first remaining solid is obtained.
(4): the first remaining solid being added in conical flask, 3g concentrated nitric acid is added, adds the perchloric acid of 0.5g, will bore
Shape bottle is placed in the numerical control ultrasonic cleaner water-bath for having been warmed up constant temperature, is arranged 50 DEG C of bath temperature, and it is small to carry out 3 to sample
When ultrasound bath handle, be cooled to room temperature, using centrifugation or filter method extract mixed solution in solid, use deionization
Water is cleaned to neutrality, obtains carbon black aggregate.
(5): carbon black aggregate being put into 25ml colorimetric cylinder, 20ml ethyl alcohol is added, places into numerical control ultrasonic cleaner
Water-bath in, be arranged 0 DEG C of bath temperature, to sample carry out 8 hours ultrasonications, obtain disperse black carbon suspension.
(6): taking out disperse black carbon suspension with capillary glass tube, be added dropwise and support to be put into 40 DEG C on film or copper mesh in carbon
It is 2 hours dry in thermostatic drying chamber.
According to the 20 of shooting transmission electron microscope photos, the carbon black average grain diameter of statistics are as follows: 28.8 ± 0.5nm.
Embodiment 2
Measure the partial size of carbon black in the nitrile rubber containing carbon black N375 and N330, step are as follows:
(1): nitrile rubber sample being cut into fragment, liquid nitrogen frozen powder then is carried out to it using liquid nitrogen frozen pulverizer
Broken, sample particle diameter is less than or equal to 300 mm after crushing.
(2): it takes 0.5 g nitrile rubber powder to be placed in 10 mL ethylene glycol, is heated to 130 °C using microwave reactor,
Time is 3 min.
(3): by step (2), treated that rubber powder is placed in polytetrafluoroethylene (PTFE) inner canister, and 60% sodium hydroxide water is added
Solution covers inner cover, puts on stainless steel outer tank, places into thermostatic drying chamber, and 0.5 h is heated under 120 °C.It is cooled to room
Temperature collects solid with filtered on buchner funnel, is washed with deionized to the aobvious neutrality of pH, obtains the first remaining solid.
(4): the first remaining solid being added in conical flask, 3 g concentrated nitric acids are added, 0.5 g perchloric acid are added, by taper
Bottle is placed in the numerical control ultrasonic cleaner water-bath for having been warmed up constant temperature, is arranged 45 °C of bath temperature, and it is super to carry out 3h to sample
Sound wave water bath processing.It is cooled to room temperature, solid is collected with Buchner funnel, is washed with deionized to neutrality, obtains carbon black reunion
Body.
(5): carbon black aggregate being added in 50 mL colorimetric cylinders, the 20 mL alcohol-water mixture (quality of ethyl alcohol and water are added
Than for 10:1).It places into the water-bath of numerical control ultrasonic cleaner, is arranged 0 °C of bath temperature, 3 h of sonic oscillation obtains charcoal
Black suspension.(6): being counted using understanding measurement method same as Example 1.
According to the 20 of shooting transmission electron microscope photos, the carbon black average grain diameter of statistics are as follows: 27.4 ± 0.5 nm.
Embodiment 3
The method for measuring particle size carbon black in the butadiene-styrene rubber containing carbon black N330, step are as follows:
(1): butadiene-styrene rubber being subjected to liquid nitrogen frozen pulverization process, sample particle diameter is less than or equal to 300 mm after crushing, then
By smashed butadiene-styrene rubber and photochemical catalyst TiO2Water and methanol solution carry out photoelectrocatalysis handle 6 hours, photoelectricity is urged
The bias for changing processing is 1.0 V.
(2): mixed solution in step (1) is mixed with 40% sodium hydroxide solution, stands 1 hour at 100 DEG C, it is cooling
To room temperature, solid is separated using centrifugation or the method filtered, then cleaning is washed with deionized to pH neutrality, it is surplus to obtain first
Remaining solid.
(3): subsequent step is same as Example 1.
According to the 20 of shooting transmission electron microscope photos, the carbon black average grain diameter of statistics are as follows: 28.8 ± 0.5nm.
Embodiment 4
The method for measuring particle size carbon black in the butadiene rubber containing white carbon black, 50~60nm of original white carbon black particle size range,
Step are as follows:
(1): butadiene rubber being subjected to liquid nitrogen frozen pulverization process, sample particle diameter is less than or equal to 300 mm after crushing, then
By smashed butadiene rubber and photochemical catalyst NiFe2O4, 100ml distilled water be added in 300ml light-catalyzed reaction bottle, carry out
Hydrogen lamp irradiates 1 hour, and light source wattage is 300W.
(2): mixed solution in step (1) being mixed with 40% sodium hydroxide solution, handles 2 hours, is cooled at 90 DEG C
Room temperature separates solid using centrifugation or the method filtered, then cleaning is washed with deionized to pH neutrality, and it is remaining to obtain first
Solid.(3): the first remaining solid being added in conical flask, 2g concentrated nitric acid is added, adds the 0.02g concentrated sulfuric acid, conical flask is put
It is placed in the numerical control ultrasonic cleaner water-bath for having been warmed up constant temperature, is arranged 35 °C of bath temperature, 5h ultrasonic wave is carried out to sample
Water bath processing.It is cooled to room temperature, solid is collected with Buchner funnel, is washed with deionized to neutrality, obtains white carbon black aggregate.
Subsequent white carbon black aggregate dispersion and grain diameter measurement step are same as Example 1.
According to the 20 of shooting transmission electron microscope photos, the white carbon black average grain diameter of statistics are as follows: 55.8 ± 0.4nm.
Embodiment 5
The partial size of carbon black in the ethylene propylene diene rubber containing carbon black N375 is measured, same as Example 1, difference is step
(3):
By step (2) treated rubber powder in polytetrafluoroethylene (PTFE) counteracting tank inner canister, it is slowly added to 50% sodium hydroxide
Solution, and capacity is no more than 2/3rds of inner canister volume, covers inner cover, puts on stainless steel outer tank, room temperature stands 15 hours, then
It is put into thermostatic drying chamber, stands 0.5 hour at 80 DEG C, be cooled to room temperature, separated using centrifugation or the method filtered solid
Body, then cleaning is washed with deionized to pH neutrality, obtain the first remaining solid.
According to the 20 of shooting transmission electron microscope photos, the carbon black average grain diameter of statistics are as follows: 28.5 ± 0.5nm.
Embodiment 6
Measure the partial size of carbon black in the acrylic rubber containing carbon black N375, step are as follows:
(1): acrylic rubber sample being cut into fragment or strip first, liquid nitrogen frozen crushes, sample grain after crushing
Diameter is less than or equal to 300 mm.
(2): taking 0.5 g acrylic rubber powder to be placed in 10 mL ethylene glycol, be heated to 120 using microwave reactor
°C, the time is 5 min.
(3): by step (2), treated that rubber powder is placed in polytetrafluoroethylene (PTFE) counteracting tank inner canister, is slowly added to 20% hydrogen
Sodium hydroxide solution, and capacity is no more than 2/3rds of inner canister volume, covers inner cover, puts on stainless steel outer tank, room temperature stands 20
Hour, it places into thermostatic drying chamber, stands 3 hours at 110 DEG C, be cooled to room temperature, collect solid with filtered on buchner funnel,
It is washed with deionized to the aobvious neutrality of pH, obtains the first remaining solid.
(4): the first remaining solid being added in conical flask, 3g concentrated nitric acid is added, conical flask is placed in and is had been warmed up
In the numerical control ultrasonic cleaner water-bath of constant temperature, it is arranged 40 DEG C of bath temperature, ultrasound bath processing in 3 hours is carried out to sample,
It is cooled to room temperature, solid in mixed solution is extracted using centrifugation or the method filtered, cleaned with deionized water to neutrality, obtained
Carbon black aggregate.
(5): carbon black aggregate being put into 25ml colorimetric cylinder, 20ml ethyl alcohol is added, places into numerical control ultrasonic cleaner
Water-bath in, be arranged 0 DEG C of bath temperature, to sample carry out 3 hours ultrasonications, obtain disperse black carbon suspension.
(6): taking out disperse black carbon suspension with capillary glass tube, be added dropwise and support to be put into 40 DEG C on film or copper mesh in carbon
It is 4 hours dry in thermostatic drying chamber.
According to the 20 of shooting transmission electron microscope photos, the carbon black average grain diameter of statistics are as follows: 29.3 ± 0.5nm.
Embodiment 7
Measure the partial size of carbon black in the butadiene rubber containing carbon black N375, step are as follows:
(1): butadiene rubber sample being cut into fragment, liquid nitrogen frozen powder then is carried out to it using liquid nitrogen frozen pulverizer
Broken, sample particle diameter is less than or equal to 300 mm after crushing.
(2): taking the powdered butadiene rubber of 0.5g, be heated to 500 DEG C, then fast transfer is into liquid nitrogen coolant；
(3): will butadiene rubber is as thin as possible sprawls in a reservoir after step (2) are handled, be placed under xenon lamp and irradiate 5h；
(4): the butadiene rubber body for the crushing that step (2) obtain being placed in polytetrafluoroethylene (PTFE) inner canister, 30% hydrogen-oxygen is added
Change sodium water solution, cover inner cover, puts on stainless steel outer tank, and capacity is no more than 2/3rds of inner canister volume, room temperature stands 10
Hour, it places into thermostatic drying chamber, 5 h is heated under 120 °C.It is cooled to room temperature, collects solid with filtered on buchner funnel,
It is washed with deionized to the aobvious neutrality of pH, obtains the first remaining solid.
(5): the first remaining solid being added in conical flask, 3g concentrated nitric acid is added, conical flask is placed in and is had been warmed up
In the numerical control ultrasonic cleaner water-bath of constant temperature, it is arranged 40 °C of bath temperature, the processing of 3 h ultrasound baths is carried out to sample.It is cold
But room temperature is arrived, solid is collected with Buchner funnel, is washed with deionized to neutrality, obtains carbon black aggregate.
(6): carbon black aggregate being added in 50 mL colorimetric cylinders, 20 mL ethyl alcohol are added.Place into numerical control supersonic cleaning
In the water-bath of device, it is arranged 0 °C of bath temperature, 3 h of sonic oscillation obtains carbon black suspension.Dispersed carbon is taken out with capillary glass tube
Black suspension is added dropwise on copper mesh, is put into 40 °C of thermostatic drying chambers dry 2h, observes and take pictures under transmission electron microscope, counts
Particle size carbon black.
According to the 20 of shooting transmission electron microscope photos, the carbon black average grain diameter of statistics are as follows: 28.5 ± 0.4 nm.
Comparative example 1
The method for measuring particle size carbon black in the ethylene propylene diene rubber containing carbon black N375, comprising the following steps:
(1): ethylene propylene diene rubber sample being cut into fragment or strip first, crushes sample.
(2): the rubbery chip that step (1) obtains being placed in polytetrafluoroethylene (PTFE) counteracting tank inner canister, 2ml dioxygen is slowly added to
Water and 5ml concentrated nitric acid, cover inner cover, put on stainless steel outer tank, are put into thermostatic drying chamber, stand 5 hours at 140 DEG C, cold
But to room temperature, solid is separated using centrifugation or the method filtered, then cleaning is washed with deionized to pH neutrality, is obtained remaining
Solid.
(3): remaining solid being extracted into carbon black using common transmission electron microscope powdered samples method for making sample, that is, is taken suitable
Solid powder and ethyl alcohol are added to small beaker, carry out sonic oscillation 15min, uniform with capillary glass tube drawing powder and ethyl alcohol
Then mixed liquor drips 2~3 and drips in the mixing liquid to copper mesh, finishes to sample drying, then observed under transmission electron microscope,
Count partial size.
According to the 20 of shooting transmission electron microscope photos, it is found that the carbon black reunion under the conditions of the comparative example is more serious, and grain
Diameter has become smaller very much, thus it is speculated that is that acid resolution is excessive, counts the average grain diameter of particle are as follows: 11.6 ± 0.3nm.
Comparative example 2
The method for measuring particle size carbon black in the ethylene propylene diene rubber containing carbon black N375, with embodiment 1 the difference is that step
Suddenly there is no alkali treatment, other step holding sequences and setting are constant.
According to the 20 of shooting transmission electron microscope photos, it is found that carbon black exists still in the form of biggish macro aggregate, but also
In the presence of the macromolecular not being resolved very much.
Comparative example 3
Same as Example 6, difference is not include step (2).
According to the 20 of shooting transmission electron microscope photos, the carbon black average grain diameter of statistics are as follows: 21.8 ± 0.5 nm.
Comparative example 4
The method for measuring particle size carbon black in the butadiene-styrene rubber containing carbon black N330, step is same as Example 3, and difference exists
In:
Step (3): the first remaining solid is added in counteracting tank, and 3g concentrated nitric acid is added, adds the perchloric acid of 0.5g,
Counteracting tank is placed on 120 DEG C of heating 10min on intelligent temperature control electric heater, places into WX-8000 microwave dissolver (Shanghai Yao's instrument
Device development in science and technology Co., Ltd product) resolution, it is arranged 80 DEG C of temperature, retention time 20min is cooled to room temperature, and it is molten to extract mixing
Solid in liquid is cleaned to neutrality with deionized water, obtains remaining solid B.
According to the 20 of shooting transmission electron microscope photos, it is found that the carbon black structure under the conditions of the comparative example is destroyed, particle side
Boundary is fuzzy, it is difficult to count effective grain size.
Comparative example 5
The method for measuring particle size carbon black in the ethylene propylene diene rubber containing carbon black N375, with embodiment 1 the difference is that institute
The sequence for stating processing step is (1) → (2) → (4) → (3) → (5) → (6), i.e., first carries out inorganic acid solution processing, then carry out
Hydroxide solution processing.
According to the transmission electron microscope photo of shooting, there is also other biggish fragment molecules in photo, carbon black shape is not advised
Then, it is difficult to count effective particle size carbon black, thus it is speculated that cleared up under the conditions of the comparative example insufficient.
Comparative example 6
The method for measuring particle size carbon black in the ethylene propylene diene rubber containing carbon black N375, with embodiment 1 the difference is that step
Suddenly (4): the first remaining solid being added in conical flask, 3g concentrated nitric acid is added, adds the perchloric acid of 0.5g, conical flask is put
It is placed in the water-bath for having been warmed up constant temperature, is arranged 50 DEG C of bath temperature, stand 3 hours, be cooled to room temperature, using centrifugation or take out
The method of filter extracts solid in mixed solution, is cleaned with deionized water to neutrality, obtains remaining solid B.
According to the transmission electron microscope photo of shooting, it is found that the carbon black reunion under the conditions of the comparative example is more serious, it is effective to counting
Partial size has a significant impact.
Comparative example 7
The partial size for measuring carbon black in the nitrile rubber containing carbon black N375 and N330, with embodiment 2 the difference is that step
(3): by step (2), treated that rubber powder is placed in polytetrafluoroethylene (PTFE) counteracting tank inner canister, and it is molten to be slowly added to 50% sodium hydroxide
Liquid, and capacity is no more than 2/3rds of inner canister volume, covers inner cover, puts on stainless steel outer tank, place into thermostatic drying chamber,
2 hours are stood at 150 DEG C, is cooled to room temperature, solid is separated using centrifugation or the method filtered, then be washed with deionized
Cleaning obtains the first remaining solid to pH neutrality.
According to the transmission electron microscope photo of shooting, it is found that the carbon black structure under the conditions of the comparative example is destroyed, it is difficult to which statistics has
Imitate partial size.
Comparative example 8
The method for measuring particle size carbon black in the butadiene rubber containing white carbon black, 50~60nm of original white carbon black particle size range,
Step is same as Example 4, and difference is not include step (2),
And step (3): the first remaining solid is added in conical flask, and 2g concentrated nitric acid is added, adds the 0.02g concentrated sulfuric acid,
Conical flask is placed in the numerical control ultrasonic cleaner water-bath for having been warmed up constant temperature, be arranged 100 °C of bath temperature, to sample into
20 min water bath processing of row.It is cooled to room temperature, solid is collected with Buchner funnel, is washed with deionized to neutrality, obtains hard charcoal
Black aggregate.
According to the 20 of shooting transmission electron microscope photos, it is found that the white carbon black reunion under the conditions of the comparative example is more serious, and
Partial size has also been smaller, and counts the average grain diameter of particle are as follows: 20.6 ± 0.5nm.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.It is all
The equivalent changes and modifications that content is done according to the present invention are encompassed by the scope of the patents of the invention.
Claims (3)
1. the Particle size analysis methods of inorganic filler in cross-linked polymer, comprising the following steps:
Smashed cross-linked polymer is provided；
It is modified to carry out surface to smashed cross-linked polymer for pre-treatment step；
Alkali treatment extracts remaining solid using the cross-linked polymer after hydroxide aqueous solution surface modification；It is described
In alkali treatment, it is arranged 90~120 DEG C of heating temperature, handles the time 0.5~5 hour, and the hydroxide aqueous solution
Mass fraction is 20~60%；
Acid treatment step obtains inorganic filler aggregate using remaining solid described in mineral acid treatment；
Dispersion and analytical procedure disperse the inorganic filler aggregate, the inorganic filler partial size after analysis dispersion in a solvent；
Wherein, the partial size of the smashed cross-linked polymer is no more than 300mm；The pre-treatment step includes at least low temperature etc.
Plasma spray processing, the aqueous solution soaking heat treatment of alcohol or alcohol, photocatalysis treatment, photoelectrocatalysis processing, treatment with ultraviolet light；It is described
Hydroxide is selected from least one of alkali metal, alkaline earth metal hydroxide；The inorganic acid is selected from perchloric acid, nitric acid, salt
At least one of acid, sulfuric acid, phosphoric acid, hydrofluoric acid；The cross-linked polymer include EP rubbers, butadiene-styrene rubber, nitrile rubber,
Isoprene rubber, butadiene rubber, acrylic rubber, phenolic resin, epoxy resin；The inorganic filler include carbon black, white carbon black,
Aluminium hydroxide, magnesium hydroxide, antimony oxide.
2. the Particle size analysis methods of inorganic filler in cross-linked polymer according to claim 1, which is characterized in that the acid
Processing step is heated using ultrasound bath, is arranged 30~60 DEG C of temperature, is handled the time 1~8 hour.
3. the Particle size analysis methods of inorganic filler in cross-linked polymer according to claim 1, which is characterized in that described point
Solvent used in scattered and analytical procedure includes at least water, alcohols solvent or alcohol-water mixture.
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