CN104558777B - Preparation method of natural graphite/polymer electromagnetic shielding composite - Google Patents
Preparation method of natural graphite/polymer electromagnetic shielding composite Download PDFInfo
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- CN104558777B CN104558777B CN201510017126.4A CN201510017126A CN104558777B CN 104558777 B CN104558777 B CN 104558777B CN 201510017126 A CN201510017126 A CN 201510017126A CN 104558777 B CN104558777 B CN 104558777B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
Abstract
The invention discloses a preparation method of a natural graphite/polymer electromagnetic shielding composite. The natural graphite/polymer electromagnetic shielding composite is prepared from the following main raw materials in percentage by weight: 85-99.9 percent of ultrahigh molecular weight polyethylene UHMWPE and 15-0.1 percent of natural graphene NG. The preparation process comprises the following steps: (1) drying the raw materials; (2) preparing an NG/UHMWPE conductive composite particle; and (3) compression moulding. According to the preparation method disclosed by the invention, with NG with low cost as an electromagnetic functional filler, an isolation structure is constructed by utilizing selective distribution of the NG on the surface of a polymer particle, and a composite with high electromagnetic shielding effectiveness is obtained under low NG content. The natural graphite/polymer electromagnetic shielding composite is simple in preparation process, only needs mechanical blending and compression moulding without needing high intensity ultrasonic equipment and an organic solvent, is green and environmentally friendly and is low in production cost and easy in mass production.
Description
Technical field
The present invention relates to conducting polymer composite material field, divide particularly to native graphite (hereinafter referred to as ng)/superelevation
The preparation method of sub- weight northylen (hereinafter referred to as uhmwpe) electromagnetic shielding composite material.
Background technology
With widely using of business, military, scientific electronic instrument and communication apparatus, electromagnetic interference (emi) problem is increasingly
Seriously.In order to prevent this harm, the research and development of electromagnetic shielding material have become academia and the important class of industrial quarters more concern
Topic.Compared with conventional metals shielding material, conducting polymer composite material (cpcs) has light weight, easy processing, chemically-resistant because of it
The advantages of burn into low cost, structure and electrical property are significantly adjustable, it has also become the novel electromagnetic shielding material of great application prospect at present
Material (He Hezhi, etc. plastics industry 2008,36,1-5；Zhang Dongsheng, etc. material Leader 2009,23,13-19；Xu Qintao, etc. work
Engineering plastics application 2010,38,82-85；j.m.thomassin,et al.materials science and
engineering:r:reports 2013,74,211-232.).In recent years, Chinese scholars are directed to carbon system conductive nano filler
(as carbon nano-fiber cnf, CNT cnt, Graphene gns etc.) filling cpcs has carried out numerous studies (m.s.cao, et
al.carbon 2010,48,788-796；y.huang,et al,carbon 2007,45,1614-1621；h.pang,et
al.carbon 2011,49,1980-1988；z.chen,et al.advanced materials 2013,25,1296-
1300；H.b.zhang, et al.acs applied materials＆interfaces 2011,3,918-924), find this
Class material has very low conductive excess effusion value, and its electrical conductivity can be issued to anti-quiet in very low conductive filler content (0.5wt%)
Electric level (10-6s/m).However, material to be made reaches minimum level of conductivity (1s/m) and certain electromagnetism needed for electromagnetic shielding
Shield effectiveness emi se (20db), conductive filler content needed for it often higher (j.j.liang, et al.carbon, 2009,
47,922-925).Now then need to realize by introducing high-energy ultrasonic or shear by high speed melt in a large amount of organic solvents
Conductive nano filler dispersed, this will necessarily bring sharply increasing and environmental protection sex chromosome mosaicism of materials processing cost, receive simultaneously
The high cost of rice conductive filler also can make material cost increase it is difficult to realize industrialization.
Micron order ng as one kind of carbon conductive filler, its abundance, compare above-mentioned carbon system conductive nano filler valency
Lattice are much lower, and up to 10 under its electrical conductivity room temperature3S/cm, is applied in cpcs have unique advantage.Ng powder often passes through
Rule melt mixing methods (torque blending, twin-screw extrusion etc.) are easily dispersed, but need also exist for very high loading and can be only achieved
Certain effectiveness.As krueger etc. is prepared for ng/ nylon 66 conductive composite material by melt-blending process, find
Ng volume content is that when 25%, composite emi se is only 12db (q.j.krueger, et al.advances polymer
technology 2003,22,96-111.).Panwar etc. is premixed by Mechanical Method, and subsequent melt molding prepares ng/ polyethylene
Conducing composite material, ng volume content is that when 18.7%, composite emi se can improve to 33db.However, high-load ng's adds
The shortcomings of enter equally can make the processability of composite to be deteriorated, and cause material mechanical performance to deteriorate.
Compared with the cpcs of conventional melt blending method preparation, isolation structure cpcs energy under identical conductive filler content
Enough obtain higher electrical conductivity, its reason be in isolation structure cpcs conductive filler selective distribution in polymeric matrix particle
Between interface rather than be randomly distributed in inside polymeric matrix, the valid density of conductive filler significantly improves (h.pang, et
al.materials letter 2012,79,96-99.).Yoonessi etc. passes through melting mixing and the preparation of emulsion mixed method
Random distribution and isolation structure Graphene/polycarbonate composite material, find that Graphene weight content is isolation structure when 4%
The electrical conductivity of composite is 2.2 times of random distribution structural material.The more excellent electrical conductivity of isolation structure cpcs make its
Also the having broad application prospects of electromagnetic shielding material field.Gelves etc. is prepared for copper nano-wire/polystyrene isolation junction
Structure cpcs, finds that composite emi se can reach 38db (g.a.gelves, et when copper nano-wire weight content is 13%
al.journal of materials chemistry 2011,21,829-836.).In the patent applied in our prior, lead to
Cross in-situ heat method of reducing and be prepared for Graphene/uhmwpe isolation structure composite, Graphene weight content is material when 0.5%
Material emi se is up to 21db.For the patent consulted at present and document, in isolation structure cpcs, conductive filler is mostly using receiving
Meter level conductive filler, and generally relatively low using content, so the effectiveness limited (emi se is relatively low) obtaining, mainly
Led to by the high cost of nano conducting powderses and scattering problem.The content improving nanoparticle further easily causes group
Poly-, limit the structure improving conductive network.Additionally, the dispersion of nanoparticle generally requires to use complexity, high energy consumption, high cost
Means, the such as dispersion of cnt need to use high-energy ultrasonic equipment and substantial amounts of organic solvent, and the dispersion of gns removes to use and surpasses
Outside acoustic equipment and organic solvent, also need to use high temperature thermal reduction or poisonous chemical reducing agent, be not appropriate for heavy industrialization
Produce.
The ng being related in the present invention directly mixed by high speed machine with uhmwpe isolation structure cpcs and compressing i.e.
Can prepare, without using high power applications aid dispersion and any organic solvent in production process, technique is easy to grasp, green ring
Protect, low production cost, easily realize producing in enormous quantities.As conductive filler, ng abundance, cheap, by high speed machine
Tool mixing can form uniform conductive coating on uhmwpe surface, and as polymeric matrix, uhmwpe has high strand
Tangle, the gel state in melting process can effectively prevent ng to its internal diffusion, therefore can successfully prepare high conductance
Rate and the electromagnetic shielding composite material of emi se.
With the patent of isolation structure cpcs and few about electromagnetic shielding at present, and successfully ng is used for isolation structure cpcs
The middle excellent capability of electromagnetic shielding of material of realizing even more has no report.Do not find and mixed by high speed machine and be pressed into yet
The patent documentation of ng/ polymeter as electromagnetic shielding composite prepared by type.
Content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, seeks a kind of ng/ polymeter as electromagnetic shielding composite wood
The preparation method of material, and be allowed to simple with preparation process, technique is easy to grasp, need not any high power applications and organic solvent,
Low production cost, easily realizes the feature produced in enormous quantities, and the good electrical property under low ng content of the composite that produces
And capability of electromagnetic shielding.
The present invention is realized by following means.
1st, the preparation method of a kind of native graphite/polymeter as electromagnetic shielding composite, primary raw material presses following weight hundred
Divide than composition:
Ultra-high molecular weight polyethylene uhmwpe 85～99.9%
Native graphite ng 15～0.1%
Its preparation method is by the steps:
(1) raw material drying: ng is dried in an oven, until moisture weight content is less than 0.01%；
(2) ng/uhmwpe conductive composite particle preparation: dried ng in step (1) is directly led to uhmwpe particle
Cross high speed mechanical mixture, obtain ng/uhmwpe conductive composite particle；Mixing rate 23,000rpm, incorporation time 3min, mixing
60 DEG C of process keeping temperature.
(3) compressing: ng/uhmwpe conductive composite particle prepared by step (2) preheats at 180～200 DEG C, when
Between 5 minutes；Then hot pressing under the pressure of 10mpa, 5 minutes time；Finally under the pressure of 10mpa, it is cooled to room temperature, obtain
Target product.
Two kinds of component: ng and uhmwpe are included using the composite that the method for the invention obtains.Ng is as conductive phase
There is provided electrical property and capability of electromagnetic shielding, uhmwpe provides mechanical strength as matrix material.Advantages of the present invention major embodiment
In the following aspects:
1) the conductive filler ng abundance that the present invention uses, matrix much lower compared to conductive nano filler price
Uhmwpe particle is marketable material, easily realizes producing in enormous quantities.
2) present invention directly utilizes high speed machine mixing to can achieve the uniform cladding in matrix uhmwpe particle surface for the ng,
The composite with high emi se can be obtained by routine is compressing afterwards.Preparation process is simple, and technique is easy to grasp,
And any high power applications (as ultrasound wave biochemical instruments, ball mill etc.) and toxic solvent, environmental protection need not be used.Therefore, this is special
Profit easily implements the investment it is not necessary to high；
3) in the present invention, ng is selectively distributed in the interface formation conductive network of uhmwpe particle region, forms isolation junction
Structure, prepared composite has higher compared with ng/ composite conducting polymer material prepared by conventional melt mixed method
Electrical conductivity and emi se.
Brief description is as follows:
Fig. 1 is for ng/uhmwpe electromagnetic shielding composite material sample preparation schematic diagram.
Fig. 2 is uniformly wrapped on compound particle scanning electron microscope diagram (a) on uhmwpe surface and the ng/ of preparation for ng
Uhmwpe composite brittle failure Surface scan electron microscope picture (b).
Fig. 3 is the optical microscope of ng/uhmwpe composite under different ng contents, and ng content is respectively 0.1vol%
(a), 0.3vol% (b) and 0.5vol% (c).
Fig. 4 is the relation curve with ng content for the electrical conductivity of ng/uhmwpe composite.
Fig. 5 is relation curve (the frequency model of ng/uhmwpe composite electromagnet shield effect and frequency under different ng contents
Enclose 8.2～12.4ghz).
Specific embodiment
Specific embodiment is given below to be described further to technical scheme, but what deserves to be explained is with
, it is not intended that limiting the scope of the invention, the person skilled in the art in this field is according in foregoing invention for lower embodiment
Hold, the present invention is made with the improvement of some non-intrinsically safes and adjustment still falls within protection scope of the present invention.
The preparation technology flow process of sample of the present invention is as shown in fig. 1.Wherein the weight average molecular weight of uhmwpe is 550～600
Ten thousand, density is 0.945g/cm3；Ng is powder, and density is 2.2g/cm3, its lateral dimension be 20 μm
Embodiment 1-13
Processing step adopts:
(1) raw material drying: commercially available ng powder is dried in an oven, until moisture weight content is less than 0.01%；
(2) ng/uhmwpe conductive composite particle preparation: by direct for ng powder dried in step (1) and uhmwpe grain
Son measures (Ju Ti Pei Fang is shown in Table 1) by a certain percentage of the weight, is mixed by high speed machine, obtains ng/uhmwpe conductive compound
Particle；Mixing rate 23,000rpm, incorporation time 3min, 60 DEG C of mixed process keeping temperature.
(3) compressing: the ng/uhmwpe conductive composite particle that step (2) is obtained preheats (tool at 180～200 DEG C
The hot-forming temperature of body is shown in Table 1), 5 minutes time；Then hot pressing under the pressure of 10mpa, 5 minutes time；Finally exist
It is cooled to room temperature under the pressure of 10mpa, obtain target product.
Comparative example
Without ng in comparative example, its formula is shown in Table 1, and processing step is consistent with embodiment, and compressing temperature is 200
℃.
The formula of table 1 embodiment 1～13 and comparative example and compressing temperature
| Embodiment | Ng/ weight fraction (%) | Uhmwpe particle/weight fraction (%) | Compressing temperature (DEG C) |
| 1 | 0.1 | 99.9 | 180 |
| 2 | 0.3 | 99.7 | 180 |
| 3 | 0.5 | 99.5 | 180 |
| 4 | 1 | 99 | 180 |
| 5 | 2 | 98 | 180 |
| 6 | 4 | 96 | 180 |
| 7 | 8 | 92 | 180 |
| 9 | 15 | 85 | 180 |
| 10 | 8 | 92 | 190 |
| 11 | 15 | 85 | 190 |
| 12 | 8 | 92 | 200 |
| 13 | 15 | 85 | 200 |
| Comparative example | 0 | 100 | 200 |
Microscopic pattern: in order to evaluate ng/uhmwpe electromagnetic shielding composite material preparation feasibility and composite in ng
The form of conductive network and distribution, the present invention utilizes scanning electron microscope to ng cladding uhmwpe compound particle (Fig. 2 a)
And ng/uhmwpe composite brittle failure face (Fig. 2 b) of preparation is characterized, find that ng is uniformly wrapped on uhmwpe particle surface,
In the composite of compressing acquisition, uhmwpe particle is deformed into polyhedron, and ng is preferentially distributed in its interface zone and forms conduction
Network.(Fig. 3 a-c) is further analyzed to the conductive network of composite using optical microscope it can be seen that composite wood
In material, with ng, conductive network refers to that content increase is gradually perfect, has just defined substantially when ng mass content is only 0.3%
Isolation structure conductive network, when ng mass content increases to 0.5%, conductive path thickness substantially increases, and isolation structure is more
Perfect.
Electric property: in order to investigate the ng/uhmwpe electromagnetic shielding composite material electrical property of preparation, using keithley
4200scs resistance instrument (keithley, the U.S.) and rst-8 type four-point probe (Guangzhou four probe science and technology, China) are to difference
Under ng mass content, the electrical conductivity of composite is tested, and result is as shown in Figure 4.It can be seen that the conduction of composite exceedes
Oozing value is 0.27wt%, and when ng mass content is 8% and 15%, the electrical conductivity of material is respectively 1.9 and 3.9s/m, reaches
The requirement to electrical conductivity for the electromagnetic shielding material.
Capability of electromagnetic shielding: in order to investigate the ng/uhmwpe electromagnetic shielding composite material of preparation to shielding electromagnetic waves
Can, using n5230 type agilent vector network analyzer (agilent, the U.S.) to composite in 8.2～12.4ghz frequency
In the range of emi se be tested, result is as shown in Figure 5.It can be seen that composite emi se changes with the increase of frequency
Very little, illustrative material has good shielding stability in wavelength band.And increase with ng content, material emi se gradually carries
Height, when ng mass content is only 2%, material emi se just can reach 19.3db, basic close to electromagnetic shielding material use
Require (20db)；But when ng content is increased to 8% and 15%, material emi se respectively reaches 36.6db and 51.6db, can expire
The multi-field greatly electromagnetic wave shielding of foot requires.
Using the method for the invention preparation ng/uhmwpe electromagnetic shielding conductive composite because its have uniqueness every
From structure, high emi se can be obtained under low ng content.Material preparation process simple it is only necessary to mechanical blending and being pressed into
Type, need not any high power applications and organic solvent, low production cost, easily implement it is easy to industrial production operation.
Claims (5)
1. the preparation method of a kind of native graphite/polymeter as electromagnetic shielding composite, primary raw material is as following weight percent
Constitute:
Ultra-high molecular weight polyethylene uhmwpe 85～99.9%
Native graphite ng 15～0.1%
Its preparation method is by the steps:
(1) raw material drying: ng is dried in an oven, until moisture weight content is less than 0.01%；
(2) ng/uhmwpe conductive composite particle preparation: directly and uhmwpe particle passes through height by dried ng in step (1)
Fast mechanical mixture, obtains ng/uhmwpe conductive composite particle；Mixing rate 23,000rpm, incorporation time 3min, mixed process
60 DEG C of keeping temperature；
(3) compressing: ng/uhmwpe conductive composite particle prepared by step (2) preheats at 180～200 DEG C, the time 5
Minute；Then hot pressing under the pressure of 10mpa, 5 minutes time；Finally under the pressure of 10mpa, it is cooled to room temperature, obtain target
Product.
2. according to claim 1 native graphite/polymeter as electromagnetic shielding composite preparation method it is characterised in that
150 μm of the mean diameter of uhmwpe particle, weight average molecular weight is 550～6,000,000, and density is 0.945g/cm3.
3. according to claim 1 native graphite/polymeter as electromagnetic shielding composite preparation method it is characterised in that
Ng is powder, and density is 2.2g/cm3, its lateral dimension be 20 μm.
4. according to claim 1 native graphite/polymeter as electromagnetic shielding composite preparation method it is characterised in that
In described step (2), the uniform cladding on uhmwpe surface for the ng is realized by high speed machine mixing.
5. according to claim 1 native graphite/polymeter as electromagnetic shielding composite preparation method it is characterised in that
In described step (3), compressing reservation ng, in the form of uhmwpe particle surface, obtains the electromagnetic shielding with isolation structure
Composite.
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| CN110105761A (en) * | 2019-05-20 | 2019-08-09 | 四川大学 | Graphene/polyphenylene sulfide electromagnetic shielding composite material and preparation method thereof |
| CN113278218B (en) * | 2020-02-20 | 2022-06-24 | 中国科学院化学研究所 | Conductive composite material with isolation structure and preparation method thereof |
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