CN103172925A - Method for modifying polyethylene composite material by use of multiferroic nano bismuth ferrite particles - Google Patents
Method for modifying polyethylene composite material by use of multiferroic nano bismuth ferrite particles Download PDFInfo
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- CN103172925A CN103172925A CN2013101379839A CN201310137983A CN103172925A CN 103172925 A CN103172925 A CN 103172925A CN 2013101379839 A CN2013101379839 A CN 2013101379839A CN 201310137983 A CN201310137983 A CN 201310137983A CN 103172925 A CN103172925 A CN 103172925A
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- nanometer bismuth
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Abstract
The invention discloses a method for modifying a polyethylene composite material by the use of multiferroic nano bismuth ferrite particles, relates to a composite material modification method, and aims at solving the technical problem that an existing polymer insulating dielectric material has a small volume resistivity. The method comprises the following steps of: (I) preparing nano bismuth ferrite particles; (II) modifying the nano bismuth ferrite particles; and (III) adding the modified nano bismuth ferrite particles and polyethylene into a mixing machine, and mixing for 1 hour; and granulating to obtain the multiferroic nano bismuth ferrite particle-modified polyethylene composite material. According to the method disclosed by the invention, the volume resistivity of the obtained multiferroic nano bismuth ferrite particle-modified polyethylene composite material is 1.18*10<16> ohm.m. The bismuth ferrite has strong breakdown field strength and high volume resistivity after modifying polyethylene, and the aging breakdown time of an electrical tree is prolonged. The method disclosed by the invention belongs to the field of composite material modification.
Description
Technical field
The present invention relates to a kind of modified poly ethylene matrix material.
Background technology
In the power system of China, the polymer insulation dielectric substance is widely used.But the development along with high pressure and extra-high-tension cable, the working strength of cable insulation material constantly increases, be subject to again the common additive effect of voltage, heat, machinery, magnetic in operational process, aging to insulating material has produced promoter action, this will become the hidden danger of cable reliability service, be also the important source of jeopardizing safe operation of electric network simultaneously.
Polyethylene belongs to non-polar polymer, there is good dielectric characteristics, now scholars put forth effort to carry out and take polyethylene and add nanoparticle to improve the research of insulating material performance as matrix, the high performance insulating material of the research and development third generation, make the insulated compound system have special electric property, principal character is high breaking down field strength, ageing-resistant, high-k, low-loss, anti-branch.This energy-conservation, efficient, miniaturization to power equipment, reliability play important strategic importance.
Bismuth ferrite material with multiferroic matter, be one of minority single phase multi-iron material of simultaneously having at ambient temperature G type antiferromagnetism and ferroelectric property, its antiferromagnetic Neel temperature T
n=380 ℃ and ferroelectrie Curie temperature T
c=830 ℃.The characteristics of this multi-iron material maximum are the magnetoelectric effects that can produce the magnetization M be directly proportional to extra electric field E or the polarization P be directly proportional to externally-applied magnetic field H.When externally-applied magnetic field or electric field, the corresponding adjustment can occur and change in the direction of the spontaneous magnetic polarization of this class material or self power generation polarization.By it, special multiferroic matter in insulative dielectric material, reaches certain effect of improving by itself and polyethylene Application of composite.
Summary of the invention
The objective of the invention is, in order to solve the existing little technical problem of polymer insulation dielectric resistivity, provides the method for the granule modified composite polyethylene material of a kind of multiferroic nanometer bismuth ferrite.
The method of the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite is as follows:
One, nanometer bismuth ferrite particle surface modification:
The acetic acid of the coupling agent of the water of the dehydrated alcohol of 10-12 weight part, 0.5 weight part, 0.5 weight part and 0.1 weight part is blended in to sonic oscillation 4h under the condition of 40 ℃, again the nanometer bismuth ferrite particle of 2 weight parts is added, then ball milling 5-6h in planetary ball mill, again by the suspension liquid ageing after ball milling 24 hours, remove supernatant liquid, dry 24h at 90 ℃, obtain the nanometer bismuth ferrite particle after modification;
Two, by the nanometer bismuth ferrite particle after modification and dehydrated alcohol or acetone, be that the ratio of 1: 6 is placed in planetary ball mill by weight, with the revolution ball millings of 4500 rev/mins 6 hours;
Three, the preparation of composite polyethylene material: by Low Density Polyethylene 80 ℃ of dryings 12 hours, dried Low Density Polyethylene is placed in the general torque rheometer in Kazakhstan of 160 ℃, mixing 10 minutes, then the ratio that is 100: 2 according to the nanometer bismuth ferrite particle weight ratio after Low Density Polyethylene and modification through step 2 is processed adds the nanometer bismuth ferrite particle after modification mixing 1 hour, granulation, obtain the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite.
The volume specific resistance of the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite that the inventive method obtains is 1.18 * 10
16Ω m.There is higher breaking down field strength, higher volume specific resistance after the bismuth ferrite modified poly ethylene, extended electric branch aging breakdown time.AC breakdown strength has improved 14% than polyethylene matrix, and the polyethylene breaking down field strength can reach 99.11kV/mm, and unmodified matrix material breaking down field strength is 104.1kV/mm, and after modification, the matrix material breaking down field strength is 112.7kV/mm; The direct current branch has improved more than 10 times than polyethylene matrix aging breakdown time, the polyethylene electric branch can reach 8760 seconds aging breakdown time, unmodified matrix material electric branch aging breakdown time is 45000 seconds, and after modification, matrix material electric branch aging breakdown time is 90180 seconds.
The accompanying drawing explanation
Fig. 1 is the shape appearance figure of test one step 2 gained nanometer bismuth ferrite particle atomic power photo;
Fig. 2 is the phase diagram of test one step 2 gained nanometer bismuth ferrite particle atomic power photo;
Fig. 3 is the three-dimension surface of test one step 2 gained nanometer bismuth ferrite particle atomic power photo;
Fig. 4 is the shape appearance figure of the nanometer bismuth ferrite particle atomic power photo after test two step 2 gained modifications;
Fig. 5 is the phase diagram of the nanometer bismuth ferrite particle atomic power photo after test two step 2 gained modifications;
Fig. 6 is the three-dimension surface of the nanometer bismuth ferrite particle atomic power photo after test two step 2 gained modifications;
Fig. 7 is the stereoscan photograph of test one gained without the coupling agent modified granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite;
Fig. 8 is the stereoscan photographs of test two gained through the coupling agent modified granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite;
Fig. 9 is the front nanometer bismuth ferrite particle infrared spectrogram of modification in test two;
Figure 10 is the nanometer bismuth ferrite particle infrared spectrogram after modification in test two.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the method for the granule modified composite polyethylene material of present embodiment multiferroic nanometer bismuth ferrite is as follows:
One, nanometer bismuth ferrite particle surface modification:
The acetic acid of the coupling agent of the water of the dehydrated alcohol of 10-12 weight part, 0.5 weight part, 0.5 weight part and 0.1 weight part is blended in to sonic oscillation 4h under the condition of 40 ℃, again the nanometer bismuth ferrite particle of 2 weight parts is added, then ball milling 5-6h in planetary ball mill, again by the suspension liquid ageing after ball milling 24 hours, remove supernatant liquid, dry 24h at 90 ℃, obtain the nanometer bismuth ferrite particle after modification;
Two, by the nanometer bismuth ferrite particle after modification and dehydrated alcohol or acetone, be that the ratio of 1: 6 is placed in planetary ball mill by weight, with the revolution ball millings of 4500 rev/mins 6 hours;
Three, the preparation of composite polyethylene material: by Low Density Polyethylene 80 ℃ of dryings 12 hours, dried Low Density Polyethylene is placed in the general torque rheometer in Kazakhstan of 160 ℃, mixing 10 minutes, then the ratio that is 100: 2 according to the nanometer bismuth ferrite particle weight ratio after Low Density Polyethylene and modification through step 3 is processed adds the nanometer bismuth ferrite particle after modification mixing 1 hour, granulation, obtain the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite.
The preparation of nanometer bismuth ferrite particle in present embodiment: five water Bismuth trinitrates of 3 weight part nine water iron nitrates and 4 weight parts are dissolved in the distilled water of 80 weight parts, constantly stir, make salt mix (solution presents transparent red-brown), the Citric acid monohydrate Food grade that adds 1 weight part, be stirred to fully and dissolve, add again rare nitric acid that 12 weight part volumetric molar concentrations are 0.8mol/l, regulating the pH value with ammoniacal liquor is 7-8, filter, obtain precursor liquid, precursor liquid is heated in the water-bath of 80 ℃, until solution evaporate to dryness, be placed in again dry 24 hours of the convection oven of 80 ℃, under the condition that to put into the tubular type high temperature resistance furnace be 600 ℃ in calcining temperature, calcining is 2 hours, obtain nanometer BiFeO
3particle,
Embodiment two: what present embodiment was different from embodiment one is that the coupling agent described in step 1 is the 3-aminopropyl triethoxysilane, and molecular formula is C
9h
23nO
3si.Other is identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one be in step 1 in planetary ball mill ball milling 5h.Other is identical with embodiment one.
Embodiment four: present embodiment is different from embodiment one be in step 1 in planetary ball mill ball milling 6h.Other is identical with embodiment one.
Embodiment five: present embodiment is different from embodiment one is in step 1, the acetic acid of the coupling agent of the water of the dehydrated alcohol of 10 weight parts, 0.5 weight part, 0.5 weight part and 0.1 weight part to be blended in to sonic oscillation 4h under the condition of 40 ℃, then the nanometer bismuth ferrite particle of 2 weight parts is added.Other is identical with embodiment one.
Embodiment six: present embodiment is different from embodiment one is in step 1, the acetic acid of the coupling agent of the water of the dehydrated alcohol of 12 weight parts, 0.5 weight part, 0.5 weight part and 0.1 weight part to be blended in to sonic oscillation 4h under the condition of 40 ℃, then the nanometer bismuth ferrite particle of 2 weight parts is added.Other is identical with embodiment one.
Adopt following verification experimental verification effect of the present invention:
Test one: the preparation method of multiferroic nanometer bismuth ferrite particle composite polyethylene material:
One, the preparation of nanometer bismuth ferrite particle: five water Bismuth trinitrates of 3 weight part nine water iron nitrates and 4 weight parts are dissolved in the distilled water of 80 weight parts, constantly stir, make salt mix (solution presents transparent red-brown), the Citric acid monohydrate Food grade that adds 1 weight part, be stirred to fully and dissolve, add again rare nitric acid that 12 weight part volumetric molar concentrations are 0.8mol/l, regulating the pH value with ammoniacal liquor is 7, filter, obtain precursor liquid, precursor liquid is heated in the water-bath of 80 ℃, until solution evaporate to dryness, be placed in again dry 24 hours of the convection oven of 80 ℃, under the condition that to put into the tubular type high temperature resistance furnace be 600 ℃ in calcining temperature, calcining is 2 hours, obtain nanometer BiFeO
3particle,
Two, by nanometer bismuth ferrite particle and dehydrated alcohol or acetone, be that the ratio of 1: 6 is placed in planetary ball mill by weight, with the revolution ball millings of 4500 rev/mins 6 hours;
Three, the preparation of composite polyethylene material: by Low Density Polyethylene 80 ℃ of dryings 12 hours, dried Low Density Polyethylene is placed in the general torque rheometer in Kazakhstan of 160 ℃, mixing 10 minutes, then the ratio that is 100: 2 according to Low Density Polyethylene and the nanometer bismuth ferrite particle weight ratio of processing through step 3 adds nanometer bismuth ferrite particle mixing 1 hour, granulation, obtain multiferroic nanometer bismuth ferrite particle composite polyethylene material.
Under 140 ℃, multiferroic nanometer bismuth ferrite particle composite polyethylene material is pressed into to the thin slice that thickness is 120 microns left and right with vulcanizing press, two-sidedly plates the aluminium electrode that diameter is 25mm, test volume resistivity is 2.52 * 10
15Ω m.Pure poly volume specific resistance test result is 1.02 * 10
15Ω m.
Test two:
The method of the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite is as follows:
One, the preparation of nanometer bismuth ferrite particle: five water Bismuth trinitrates of 3 weight part nine water iron nitrates and 4 weight parts are dissolved in the distilled water of 80 weight parts, constantly stir, make salt mix (solution presents transparent red-brown), the Citric acid monohydrate Food grade that adds 1 weight part, be stirred to fully and dissolve, add again rare nitric acid that 12 weight part volumetric molar concentrations are 0.8mol/l, regulating the pH value with ammoniacal liquor is 8, filter, obtain precursor liquid, precursor liquid is heated in the water-bath of 80 ℃, until solution evaporate to dryness, be placed in again dry 24 hours of the convection oven of 80 ℃, under the condition that to put into the tubular type high temperature resistance furnace be 600 ℃ in calcining temperature, calcining is 2 hours, obtain nanometer BiFeO
3particle,
Two, nanometer bismuth ferrite particle surface modification:
The acetic acid of the coupling agent of the water of the dehydrated alcohol of 12 weight parts, 0.5 weight part, 0.5 weight part and 0.1 weight part is blended in to ultrasonic (ultrasonic frequency is 40KHz) vibration 4h under the condition of 40 ℃, again the nanometer bismuth ferrite particle of 2 weight parts is added, then ball milling 5-6h in planetary ball mill, again by the suspension liquid ageing after ball milling 24 hours, remove supernatant liquid, dry 24h at 90 ℃, obtain the nanometer bismuth ferrite particle after modification;
Three, by the nanometer bismuth ferrite particle after modification and dehydrated alcohol or acetone, be that the ratio of 1: 6 is placed in planetary ball mill by weight, with the revolution ball millings of 4500 rev/mins 6 hours;
Four, the preparation of composite polyethylene material: by Low Density Polyethylene 80 ℃ of dryings 12 hours, dried Low Density Polyethylene is placed in the general torque rheometer in Kazakhstan of 160 ℃, mixing 10 minutes, then the ratio that is 100: 2 according to the nanometer bismuth ferrite particle weight ratio after Low Density Polyethylene and modification through step 3 is processed adds the nanometer bismuth ferrite particle after modification mixing 1 hour, granulation, obtain the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite.
Under 140 ℃, the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite is pressed into to the thin slice that thickness is 120 microns left and right with vulcanizing press, two-sidedly plates the aluminium electrode that diameter is 25mm, test volume resistivity is 1.18 * 10
16Ω m.
Claims (6)
1. the method for the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite is characterized in that the method for the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite is as follows:
One, nanometer bismuth ferrite particle surface modification:
The acetic acid of the coupling agent of the water of the dehydrated alcohol of 10-12 weight part, 0.5 weight part, 0.5 weight part and 0.1 weight part is blended in to sonic oscillation 4h under the condition of 40 ℃, again the nanometer bismuth ferrite particle of 2 weight parts is added, then ball milling 5-6h in planetary ball mill, again by the suspension liquid ageing after ball milling 24 hours, remove supernatant liquid, dry 24h at 90 ℃, obtain the nanometer bismuth ferrite particle after modification;
Two, by the nanometer bismuth ferrite particle after modification and dehydrated alcohol or acetone, be that the ratio of 1: 6 is placed in planetary ball mill by weight, with the revolution ball millings of 4500 rev/mins 6 hours;
Three, the preparation of composite polyethylene material: by Low Density Polyethylene 80 ℃ of dryings 12 hours, dried Low Density Polyethylene is placed in the general torque rheometer in Kazakhstan of 160 ℃, mixing 10 minutes, then the ratio that is 100: 2 according to the nanometer bismuth ferrite particle weight ratio after Low Density Polyethylene and modification through step 3 is processed adds the nanometer bismuth ferrite particle after modification mixing 1 hour, granulation, obtain the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite.
2. the method for the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite according to claim 1, is characterized in that the coupling agent described in step 1 is the 3-aminopropyl triethoxysilane, and molecular formula is C
9h
23nO
3si.
3. the method for the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite according to claim 1, is characterized in that in step 1 ball milling 5h in planetary ball mill.
4. the method for the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite according to claim 1, is characterized in that in step 1 ball milling 6h in planetary ball mill.
5. the method for the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite according to claim 1, it is characterized in that in step 1 the acetic acid of the coupling agent of the water of the dehydrated alcohol of 10 weight parts, 0.5 weight part, 0.5 weight part and 0.1 weight part is blended in sonic oscillation 4h under the condition of 40 ℃, then the nanometer bismuth ferrite particle of 2 weight parts is added.
6. the method for the granule modified composite polyethylene material of multiferroic nanometer bismuth ferrite according to claim 1, it is characterized in that in step 1 the acetic acid of the coupling agent of the water of the dehydrated alcohol of 12 weight parts, 0.5 weight part, 0.5 weight part and 0.1 weight part is blended in sonic oscillation 4h under the condition of 40 ℃, then the nanometer bismuth ferrite particle of 2 weight parts is added.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945713A (en) * | 2015-06-23 | 2015-09-30 | 哈尔滨理工大学 | Preparing method for nanometer bismuth oxide and aluminum hydroxide/polyethylene flame-retardant composite material |
| CN108276645A (en) * | 2018-02-05 | 2018-07-13 | 无锡市方成彩印包装有限公司 | A kind of Green Polymer packaging film and preparation method thereof that can cause the degradation of the multiple environment factor |
| CN114906877A (en) * | 2022-04-01 | 2022-08-16 | 哈尔滨理工大学 | Preparation method of cobalt ferrite capable of being compounded with LDPE (Low-Density polyethylene) to prepare magnetic nano dielectric medium |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008118422A1 (en) * | 2007-03-26 | 2008-10-02 | The Trustees Of Columbia University In The City Of New York | Metal oxide nanocrystals: preparation and uses |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008118422A1 (en) * | 2007-03-26 | 2008-10-02 | The Trustees Of Columbia University In The City Of New York | Metal oxide nanocrystals: preparation and uses |
Non-Patent Citations (1)
| Title |
|---|
| 宋伟等: "柠檬酸溶胶－凝胶法制备BiFeO3纳米陶瓷材料", 《第十三届全国工程电介质学术会议论文集》, 31 December 2011 (2011-12-31), pages 126 - 128 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945713A (en) * | 2015-06-23 | 2015-09-30 | 哈尔滨理工大学 | Preparing method for nanometer bismuth oxide and aluminum hydroxide/polyethylene flame-retardant composite material |
| CN108276645A (en) * | 2018-02-05 | 2018-07-13 | 无锡市方成彩印包装有限公司 | A kind of Green Polymer packaging film and preparation method thereof that can cause the degradation of the multiple environment factor |
| CN114906877A (en) * | 2022-04-01 | 2022-08-16 | 哈尔滨理工大学 | Preparation method of cobalt ferrite capable of being compounded with LDPE (Low-Density polyethylene) to prepare magnetic nano dielectric medium |
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