CN109251519A - A kind of conductive carbon fibre thermoplastic composite material and preparation method - Google Patents
A kind of conductive carbon fibre thermoplastic composite material and preparation method Download PDFInfo
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- CN109251519A CN109251519A CN201810967448.9A CN201810967448A CN109251519A CN 109251519 A CN109251519 A CN 109251519A CN 201810967448 A CN201810967448 A CN 201810967448A CN 109251519 A CN109251519 A CN 109251519A
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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
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- C08K3/08—Metals
- C08K2003/0812—Aluminium
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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
- C08K2201/001—Conductive additives
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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
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/004—Additives being defined by their length
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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
- C08K2201/011—Nanostructured additives
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2207/20—Recycled plastic
Abstract
The present invention relates to a kind of conductive carbon fibre thermoplastic composite materials, it is characterised in that: composed of the following components by weight percentage: PA6 30-50%；Carbon fiber 20-30%；Recycle Waste Composite Material 20-30%；Reinforcing agent 0.1-0.5%；Coupling agent 0.3-1.5%；Heat stabilizer 0.1-1%；Antioxidant 0.1-0.3%；Fire retardant 0.2-5%；Conducting particles 6-9%；Zinc stearate 1-3%；The invention has the benefit that being added in composite material using the waste material that automobile recycles, cost is reduced, and meet environmental requirement；It joined conducting particles in base-material, make composite material that there is preferable conductive effect.
Description
Technical field
The present invention relates to new-energy automobile field of material technology, and in particular to a kind of conductive carbon fibre thermoplastic composite wood
Material and preparation method thereof.
Background technique
Carbon fibre composite is an important branch in composite material, since it has excellent performance, this material in recent years
The purposes and yield of material gradually expand.For a long time, carbon fibre reinforced composite is counted as a kind of material of valuableness, price
About ten times of glass fibre reinforced composion are served only for the sophisticated technologies industry such as military project, aerospace.In recent years, carbon fiber is every
Year is increased with 50% or more speed, wherein there are two the development that key factor has pushed carbon fibre composite, first is that above-mentioned
Deepening continuously for material understanding, makes its performance be gradually improved, can reach the performance that many other materials hardly match, it is promoted to make
Dosage constantly rises.Second is that the continuous reduction of cost effectiveness, this be mainly attributed to Industry of Carbon Fiber can provide the fiber of high quality with
And fiber/matrix melting technology is constantly progressive.The large-scale production of carbon fiber, makes its Quality advance and price declines, and adds
The progress of work technology make again be added composite material in carbon fiber dimensional ratio constantly rise, at present up to volume ratio 60% with
On.
Carbon fibre composite development is like a raging fire, breaks with tremendous force, mostly applies thermosetting in space flight and aviation and national defense industry
Property composite material, however same with thermosetting compound material is at high cost, and molding cycle is long, and greatest problem is difficult to recycle, and pollutes environment
Consequence is serious.By being dedicated to base-material research and development for many years, successively select PC, PEEK, PPS, PI, PA, PET, PP as the examination of base-material
It tests.From the experiment, it was found that PA is a kind of particularly important thermoplastic web.Though PA itself is the engineering plastics haveing excellent performance, inhale
Moist big, product size stability is poor, and intensity and hardness are also nothing like metal, in order to overcome these disadvantages, using carbon fiber
Or the fiber of other kinds is enhanced to improve its performance.It has developed rapidly in recent years with fibre reinforced PA material, because of PA
It is all the material that engineering plastics field is had excellent performance with carbon fiber, the compound synthesis of the two embodies respective advantage, intensity and just
Property it is more much higher than non-reinforced nylon, creep is small, and dimensional accuracy is good, and thermal stability significantly improves, and wear-resisting, damping and amortization is excellent, with
Fiberglass reinforced, which is compared, better performance.But it is poor to exist on electric conductivity with regard to the carbon fibre composite that PA is base-material at present
Different, conductivity is not high, and therefore, the present invention has made improvement in response to this.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art,
A kind of conductive carbon fibre thermoplastic composite material and preparation method is provided.
To achieve the above object, the present invention provides the following technical scheme that a kind of conductive carbon fibre thermoplastic composite wood
Material, which is characterized in that composed of the following components by weight percentage:
PA6 30-50%
Carbon fiber 20-30%
Recycle Waste Composite Material 20-30%
Reinforcing agent 0.1-0.5%
Coupling agent 0.3-1.5%
Heat stabilizer 0.1-1%
Antioxidant 0.1-0.3%
Fire retardant 0.2-5%
Conducting particles 6-9%
Zinc stearate 1-3%
The conducting particles includes carbon nanotube and the dilute coating nano aluminium particle of graphite oxide；
The carbon nanotube and the weight ratio of the dilute coating nano aluminium particle of the graphite oxide are 1:2；
The PA6 partial size is no more than 22 μm.
A kind of above-mentioned conductive carbon fibre thermoplastic composite material can be further arranged to: the reinforcing agent is maleic acid
Acid anhydride grafted high density polyethylene.
A kind of above-mentioned conductive carbon fibre thermoplastic composite material can be further arranged to: the coupling agent is γ-ammonia
Propyl-triethoxysilicane.
A kind of above-mentioned conductive Carbon fibe thermoplastic composite material can be further arranged to: the heat stabilizer is organic
Zinc type thermal stabilizing agent.
A kind of above-mentioned conductive Carbon fibe thermoplastic composite material can be further arranged to: the antioxidant is phosphorous acid
Esters antioxidant.
A kind of above-mentioned conductive Carbon fibe thermoplastic composite material can be further arranged to: the fire retardant is compound three
Poly cyanamid cyanurate.
A kind of above-mentioned conductive Carbon fibe thermoplastic composite material can be further arranged to: the length of the carbon nanotube
For 40-150nm.
A kind of above-mentioned conductive carbon fibre thermoplastic composite material can be further arranged to: the nanometer alumina particles it is straight
Diameter is 31-41nm.
A kind of preparation method of conductive carbon fibre thermoplastic composite material, comprising the following steps:
1) by carbon fiber and PA6 by the abundant drying for standby of dryer, drying time is 6-8 hours, and the material after making drying contains
Water is less than 0.01wt%；
2) the PA6 thermoplastic scrapped is met into material recovery and is cleaned by cleaning machine, the waste material after cleaning is passed through into sorting
Machine is sorted and is granulated the waste material after sorting by pelletizer spare；
3) it will be stirred in nanometer alumina particles under vacuum conditions 100-150 degree Celsius range, be passed through the hydrogen of 30-55 pa pressure,
The graphite gas for passing through 60-110 pa simultaneously, cooling down after 48-54 hours, it is standby that the dilute coating nano aluminium particle of graphite oxide is made
With；
4) by the mixed PA6 in step 1, the Waste Composite Material in step 2, the nanometer alumina particles in step 3, carbon nanometer
Pipe, reinforcing agent, heat stabilizer, coupling agent, antioxidant, fire retardant hybrid reaction；
5) screw-type extruder hopper is added in the mixture after hybrid reaction in step 4, high-speed stirred simultaneously passes through carbon fiber
Extruder feed opening be added, extruding pelletization to get arrive conductive carbon fibre thermoplastic composite material.
The invention has the benefit that being added in composite material using the waste material that automobile recycles, cost is reduced, and meet
Environmental requirement；It joined conducting particles in base-material, make composite material that there is preferable conductive effect.
Below with reference to embodiment, invention is further described in detail.
Specific embodiment
It is composed of the following components by weight percentage the present invention provides a kind of conductive carbon fibre thermoplastic composite material:
PA6 30-50%
Carbon fiber 20-30%
Recycle Waste Composite Material 20-30%
Reinforcing agent 0.1-0.5%
Coupling agent 0.3-1.5%
Heat stabilizer 0.1-1%
Antioxidant 0.1-0.3%
Fire retardant 0.2-5%
Conducting particles 6-9%
Zinc stearate 1-3%
The conducting particles includes carbon nanotube and the dilute coating nano aluminium particle of graphite oxide；
The carbon nanotube and the weight ratio of the dilute coating nano aluminium particle of the graphite oxide are 1:2；
The PA6 partial size is no more than 22 μm.
The reinforcing agent is maleic anhydride grafted high density polyethylene.
The coupling agent is gamma-aminopropyl-triethoxy-silane.
The heat stabilizer is organic zinc type thermal stabilizing agent.
The antioxidant is phosphite ester antioxidant.
The fire retardant is compound melamine cyanurate.
The length of the carbon nanotube is 40-150nm.
The diameter of the nanometer alumina particles is 31-41nm.
A kind of preparation method of conductive carbon fibre thermoplastic composite material, comprising the following steps:
1) by carbon fiber and PA6 by the abundant drying for standby of dryer, drying time is 6-8 hours, and the material after making drying contains
Water is less than 0.01wt%；
2) the PA6 thermoplastic scrapped is met into material recovery and is cleaned by cleaning machine, the waste material after cleaning is passed through into sorting
Machine is sorted and is granulated the waste material after sorting by pelletizer spare；
3) it will be stirred in nanometer alumina particles under vacuum conditions 100-150 degree Celsius range, be passed through the hydrogen of 30-55 pa pressure,
The graphite gas for passing through 60-110 pa simultaneously, cooling down after 48-54 hours, it is standby that the dilute coating nano aluminium particle of graphite oxide is made
With；
4) by the mixed PA6 in step 1, the Waste Composite Material in step 2, the nanometer alumina particles in step 3, carbon nanometer
Pipe, reinforcing agent, heat stabilizer, coupling agent, antioxidant, fire retardant hybrid reaction；
5) screw-type extruder hopper is added in the mixture after hybrid reaction in step 4, high-speed stirred simultaneously passes through carbon fiber
Extruder feed opening be added, extruding pelletization to get arrive conductive carbon fibre thermoplastic composite material.
It in above scheme, is added in composite material using the waste material of recycling, reduces cost and meet environmental requirements, in base
It joined conducting particles in material, so that composite material has preferable conductive effect, conducting particles of the invention is carbon nanotube
With the dilute coating nano aluminium particle of graphite oxide, since graphene oxide coats alumina particles so that the dilute outer diameter of graphite oxide becomes larger,
And due to being added to antioxidant, and a nanometer alumina particles oxidation can be prevented.
Below by three groups of embodiments, the present invention will be further described:
Embodiment one:
1) PA6 of 30% carbon fiber and 30% is passed through into the abundant drying for standby of dryer, drying time is 6 hours, after making drying
Material moisture be less than 0.01wt%；
2) scrap 30% PA6 thermoplastic composite is recycled and is cleaned by cleaning machine, the waste material after cleaning is passed through into baking
Waste material after go-no-go is granulated by pelletizer spare by the drying of dry machine by the waste material after drying by separating machine go-no-go；
3) it will be stirred in nanometer alumina particles under vacuum conditions 70 degree Celsius ranges, be passed through the hydrogen of 30 pa pressure, be passed through simultaneously
The graphite gas of 50 pas, by 24 hours, then cooling down, it is spare that the dilute coating nano aluminium particle of graphite oxide is made.
4) by 6% nanometer of alumina particles in the mixed PA6 in step 1, the Waste Composite Material in step 2, step 3
And carbon nanotube, 0.5% maleic anhydride grafted high density polyethylene, 1.2% gamma-aminopropyl-triethoxy-silane, 1% organic zinc class
Heat stabilizer, 0.3% antioxidant, 2% compound melamine cyanurate reaction；
5) screw extruder hopper, high-speed stirred is added in the mixture after hybrid reaction in step 4, and carbon fiber is passed through and is squeezed
Machine adds fine mouth to be added out, and extruding pelletization is to get arriving conductive carbon fibre thermoplastic composite.
Embodiment two:
1) PA6 of 20% carbon fiber and 40% is passed through into the abundant drying for standby of dryer, drying time is 6 hours, after making drying
Material moisture be less than 0.01wt%；
2) scrap 30% PA6 thermoplastic composite is recycled and is cleaned by cleaning machine, the waste material after cleaning is passed through into baking
Waste material after go-no-go is granulated by pelletizer spare by the drying of dry machine by the waste material after drying by separating machine go-no-go；
3) it will be stirred in nanometer alumina particles under vacuum conditions 70 degree Celsius ranges, be passed through the hydrogen of 30 pa pressure, be passed through simultaneously
The graphite gas of 50 pas, by 24 hours, then cooling down, it is spare that the dilute coating nano aluminium particle of graphite oxide is made.
4) by 7% nanometer of alumina particles in the mixed PA6 in step 1, the Waste Composite Material in step 2, step 3
And carbon nanotube, 0.1% maleic anhydride grafted high density polyethylene, 0.6% gamma-aminopropyl-triethoxy-silane, 1% organic zinc class
Heat stabilizer, 0.3% antioxidant, 1% compound melamine cyanurate reaction；
5) screw extruder hopper, high-speed stirred is added in the mixture after hybrid reaction in step 4, and carbon fiber is passed through and is squeezed
Machine adds fine mouth to be added out, and extruding pelletization is to get arriving conductive carbon fibre thermoplastic composite.
Embodiment three:
1) PA6 of 25% carbon fiber and 40% is passed through into the abundant drying for standby of dryer, drying time is 6 hours, after making drying
Material moisture be less than 0.01wt%；
2) scrap 25% PA6 thermoplastic composite is recycled and is cleaned by cleaning machine, the waste material after cleaning is passed through into baking
Waste material after go-no-go is granulated by pelletizer spare by the drying of dry machine by the waste material after drying by separating machine go-no-go；
3) it will be stirred in nanometer alumina particles under vacuum conditions 70 degree Celsius ranges, be passed through the hydrogen of 30 pa pressure, be passed through simultaneously
The graphite gas of 50 pas, by 24 hours, then cooling down, it is spare that the dilute coating nano aluminium particle of graphite oxide is made.
4) by 9% nanometer of alumina particles in the mixed PA6 in step 1, the Waste Composite Material in step 2, step 3
And carbon nanotube, 0.1% maleic anhydride grafted high density polyethylene, 0.3% gamma-aminopropyl-triethoxy-silane, 0.1% organic zinc
Type thermal stabilizing agent, 0.3% antioxidant, 0.2% compound melamine cyanurate reaction；
5) screw extruder hopper, high-speed stirred is added in the mixture after hybrid reaction in step 4, and carbon fiber is passed through and is squeezed
Machine adds fine mouth to be added out, and extruding pelletization is to get arriving conductive carbon fibre thermoplastic composite.
Embodiment 1-3 formula and material property are shown in Table 1:
| Embodiment one | Embodiment two | Embodiment three | |
| PA6 | 30 | 40 | 40 |
| Carbon fiber | 30 | 20 | 25 |
| The composite material scrapped | 30 | 30 | 25 |
| Conducting particles | 6 | 7 | 9 |
| Maleic anhydride grafted high density polyethylene | 0.5 | 0.1 | 0.1 |
| Gamma-aminopropyl-triethoxy-silane | 1.2 | 0.6 | 0.3 |
| Organic zinc type thermal stabilizing agent | 1 | 1 | 0.1 |
| Phosphite ester antioxidant | 0.3 | 0.3 | 0.3 |
| Compound melamine cyanurate | 2 | 1 | 0.2 |
| Interlaminar fracture toughness/(kj/m2) | 1.1-2.0 | 1.2-1.5 | 0.8-1.0 |
| Tensile strength/MPa | 3087 | 3057 | 2890 |
| Tensile modulus of elasticity/GPa | 152 | 150 | 131 |
| Bending strength/MPa | 1580 | 1572 | 1480 |
| Bending elastic modulus/GPa | 142 | 137 | 114 |
| Conductivity (S/cm) | 6500 | 6500 | 6500 |
| Notch impact strength | 10.1 | 9.8 | 8.7 |
Claims (9)
1. a kind of conductive carbon fibre thermoplastic composite material, which is characterized in that composed of the following components by weight percentage:
PA6 30-50%
Carbon fiber 20-30%
Recycle Waste Composite Material 20-30%
Reinforcing agent 0.1-0.5%
Coupling agent 0.3-1.5%
Heat stabilizer 0.1-1%
Antioxidant 0.1-0.3%
Fire retardant 0.2-5%
Conducting particles 6-9%
Zinc stearate 1-3%
The conducting particles includes carbon nanotube and the dilute coating nano aluminium particle of graphite oxide；
The carbon nanotube and the weight ratio of the dilute coating nano aluminium particle of the graphite oxide are 1:2；
The PA6 partial size is no more than 22 μm.
2. a kind of conductive carbon fibre thermoplastic composite material according to claim 1, it is characterised in that: the reinforcing agent
For maleic anhydride grafted high density polyethylene.
3. a kind of conductive carbon fibre thermoplastic composite material according to claim 1, it is characterised in that: the coupling agent
For gamma-aminopropyl-triethoxy-silane.
4. a kind of conductive carbon fibre thermoplastic composite material according to claim 1, it is characterised in that: the thermostabilization
Agent is organic zinc type thermal stabilizing agent.
5. a kind of conductive carbon fibre thermoplastic composite material according to claim 1, it is characterised in that: the antioxidant
For phosphite ester antioxidant.
6. a kind of conductive carbon fibre thermoplastic composite material according to claim 1, it is characterised in that: the fire retardant
For compound melamine cyanurate.
7. a kind of conductive carbon fibre thermoplastic composite material according to claim 1, it is characterised in that: the carbon nanometer
The length of pipe is 40-150nm.
8. a kind of conductive carbon fibre thermoplastic composite material according to claim 1, it is characterised in that: the nano aluminum
The diameter of particle is 31-41nm.
9. a kind of preparation method of conductive carbon fibre thermoplastic composite material, it is characterised in that: the following steps are included:
1) by carbon fiber and PA6 by the abundant drying for standby of dryer, drying time is 6-8 hours, and the material after making drying contains
Water is less than 0.01wt%；
2) the PA6 thermoplastic scrapped is met into material recovery and is cleaned by cleaning machine, the waste material after cleaning is passed through into sorting
Machine is sorted and is granulated the waste material after sorting by pelletizer spare；
3) it will be stirred in nanometer alumina particles under vacuum conditions 100-150 degree Celsius range, be passed through the hydrogen of 30-55 pa pressure,
The graphite gas for passing through 60-110 pa simultaneously, cooling down after 48-54 hours, it is standby that the dilute coating nano aluminium particle of graphite oxide is made
With；
4) by the mixed PA6 in step 1, the Waste Composite Material in step 2, the nanometer alumina particles in step 3, carbon nanometer
Pipe, reinforcing agent, heat stabilizer, coupling agent, antioxidant, fire retardant hybrid reaction；
5) screw-type extruder hopper is added in the mixture after hybrid reaction in step 4, high-speed stirred simultaneously passes through carbon fiber
Extruder feed opening be added, extruding pelletization to get arrive conductive carbon fibre thermoplastic composite material.
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| CN201810967448.9A CN109251519A (en) | 2018-08-23 | 2018-08-23 | A kind of conductive carbon fibre thermoplastic composite material and preparation method |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875779A (en) * | 2009-12-21 | 2010-11-03 | 扬州大学 | Polyamide/nano expanded graphite/carbon fiber high-strength conducting composite material and preparation method thereof |
| CN102108204A (en) * | 2009-12-24 | 2011-06-29 | 合肥杰事杰新材料有限公司 | Plastic case material for breaker and preparation method thereof |
| US20130190472A1 (en) * | 2007-06-28 | 2013-07-25 | William Marsh Rice University | Polyamide composites having flexible spacers |
| CN103450668A (en) * | 2013-08-07 | 2013-12-18 | 上海日之升新技术发展有限公司 | High-strength carbon fiber reinforced halogen-free flame-retardant PA6 (Polyamide) composite material and preparation method thereof |
| CN104231587A (en) * | 2014-08-27 | 2014-12-24 | 上海日之升新技术发展有限公司 | Thermoplastic composite material for electromagnetic shielding housings and preparation method thereof |
-
2018
- 2018-08-23 CN CN201810967448.9A patent/CN109251519A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130190472A1 (en) * | 2007-06-28 | 2013-07-25 | William Marsh Rice University | Polyamide composites having flexible spacers |
| CN101875779A (en) * | 2009-12-21 | 2010-11-03 | 扬州大学 | Polyamide/nano expanded graphite/carbon fiber high-strength conducting composite material and preparation method thereof |
| CN102108204A (en) * | 2009-12-24 | 2011-06-29 | 合肥杰事杰新材料有限公司 | Plastic case material for breaker and preparation method thereof |
| CN103450668A (en) * | 2013-08-07 | 2013-12-18 | 上海日之升新技术发展有限公司 | High-strength carbon fiber reinforced halogen-free flame-retardant PA6 (Polyamide) composite material and preparation method thereof |
| CN104231587A (en) * | 2014-08-27 | 2014-12-24 | 上海日之升新技术发展有限公司 | Thermoplastic composite material for electromagnetic shielding housings and preparation method thereof |
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