CN104552970B - A kind of polymer composite fibrous preparation method and its preparation containing ultrafine metal fibers it is polymer composite fibrous - Google Patents
A kind of polymer composite fibrous preparation method and its preparation containing ultrafine metal fibers it is polymer composite fibrous Download PDFInfo
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Abstract
The present invention provides a kind of polymer composite fibrous preparation method containing ultrafine metal fibers and its prepared polymer composite fibrous.The preparation method is that the metal powder by fusing point not less than fluoropolymer resin fusing point or softening temperature is filled into fluoropolymer resin, longitudinal stretching is directly carried out when blend squeezes out by extruder and passes through extruding dies, is obtained containing the polymer composite fibrous of ultrafine metal fibers；During the preparation process, make metal powder extend in situ due to factors such as effects between polymer and metal and form ultrafine metal fibers as dispersed phase distribution in polymer fiber, to improve the performance of composite fibre.The preparation method has good applicability and lower cost.And the ultrafine metal fibers diameter contained in obtained composite fibre can be kept adjustable, even up to nanoscale by the adjusting to metal powder partial size, type of polymer etc., to make the composite fibre that there are excellent properties.
Description
Technical field
The present invention relates to a kind of polymer composite fibrous preparation methods, further, be related to it is a kind of by metal powder
The polymer composite fibrous preparation method containing ultrafine metal fibers of end and thermoplastic polymer preparation and obtained
It is polymer composite fibrous.
Background technique
Background technique
Compare natural fiber, synthetic fibers have cheap, and the low characteristics such as low with hydroscopicity of density are widely used in day
The often fields such as the textile garment class of production and living, woven bag.But the electrical insulation capability of synthetic fibers is good, resistivity is high, makes
With easy to produce static electricity in the process, harm can all be brought to industrial production and people's lives.And with high-tech development, due to
Electrostatic and Electrostatic Absorption dust are to lead to modern electronic equipment operational failure, short circuit, dropout, error code, yield rate
One of low immediate cause.There is spy to the protection of electrostatic in industries such as petroleum, chemical industry, precision machinery, coal mine, food, medicine
Different requirement.Therefore, exploitation has the fiber of superior electrical property to reduce the harm of electrostatic bring and become very urgent class
Topic.
Carbon nanotube is the nanoscale tubular structure for the similar curling graphite being made of carbon hexatomic ring.Since carbon nanotube has
There are excellent electricity and mechanical property, therefore is widely used in polymer matrix composite or composite fibre field.But due to
The high surface energy of nanoparticle itself causes carbon nanotube to have serious reuniting effect, to increase the filling of nanoparticle
Amount and cost.Meanwhile a large amount of nano-particles filled also results in difficulty to the production of fiber.How carbon nanotube use is reduced
Amount reduces production difficulty and is a problem to be solved.
It is to effectively improve fiber electrical efficiency that third component, which is added, using composite conducting conductive filler technology, drops low-carbon nano
The effective ways of pipe content.Patent CN102409421A, which is disclosed, a kind of prepares polypropylene/Nano stannic oxide/carbon nanotube
The preparation method of composite fibre.Although the technology reduces the resistivity of composite fibre, but the third component being added is similarly
Nanoparticle increases the difficulty to process raw material, and fiber surface is coarse, and feel is poor, mechanical properties decrease, and fracture of wire is easy in production
Phenomena such as.
In recent years, there is new development in domestic and international polymer/low-melting-point metal field of compound material.Low-melting-point metal is with height
The characteristics such as conductivity, the easy processing conductive filler new as one is widely used in the field of compound material of polymer.Patent
CN102021671A discloses a kind of polymer/low-melting-point metal compound wire and its manufacturing method, while patent
CN102140707A discloses a kind of skin-core composite electromagnetic shielding fiber and preparation method thereof.Above-mentioned two technologies are multiple using core-skin
The method that conjunction technology prepares polymer overmold low-melting-point metal conducting wire or fiber.But special composite spinning is needed in the technology
Machine, and increased as the sandwich layer metal specific gravity of fiber, although ensure that fiber low resistivity, need a large amount of addition gold
Belong to, increases production cost.
Summary of the invention：
In order to, containing the polymer composite fibrous of ultrafine metal fibers, be proposed with easy and low cost method preparation
The present invention.
The polymer composite fibrous preparation method containing ultrafine metal fibers that the purpose of the present invention is to provide a kind of.
The preparation method is that metal powder is filled into thermoplastic polymer resin, when blend passes through extrusion
Machine squeezes out, and by directly carrying out longitudinal stretching when extruding dies, obtains containing the polymer composite fibrous of ultrafine metal fibers；
In the drawing process for forming composite fibre by extruding dies, since the factors such as effect between polymer and metal make
Metal powder extends form ultrafine metal fibers in situ.Thus obtained polymer composite fibrous micromorphology is ultra-fine gold
Belong to fiber to be evenly distributed in the polymeric matrix of composite fibre as dispersed phase along the axial direction of composite fibre, contain to be formed
There is the polymer composite fibrous of ultrafine metal fibers.This method passes through extruder by the way that metal powder to be filled into polymer
Mouth mold directly carries out longitudinal stretching, and a step obtains polymer composite fibrous, and method is simple, easily operated.
Specifically, the polymer composite fibrous preparation method of the invention containing ultrafine metal fibers is：
Metal powder is filled into thermoplastic polymer resin, gained blend is squeezed out by extruder；From extruder
Longitudinal stretching is directly carried out to blend when die extrusion, is obtained containing the polymer composite fibrous of ultrafine metal fibers；Wherein
The fusing point of the metal powder is not less than thermoplastic polymer fusing point or softening temperature.In this way durings filling etc., substantially
It keeps metal powder not melt, thus can be convenient for making metal powder extend into fiber in situ when squeezing out and stretching.Described herein
Thermoplastic polymer fusing point or softening temperature refer to the heated temperature for starting to melt or soften of thermoplastic polymer, for crystallization
For thermoplastic polymer, this temperature is known as thermoplastic polymer fusing point, this temperature for amorphous thermoplastic's polymer
Just it is thermoplastic polymer softening temperature.
Further, the polymer composite fibrous preparation method to of the invention containing ultrafine metal fibers is described in detail such as
Under：
When wherein metal powder is filled into thermoplastic polymer resin, according to thermoplastic polymer resin and metal powder
Total volume parts calculate, wherein the volume parts of the metal powder be less than or equal to 30%vol, preferably less than or
Equal to 15%vol, more preferably less than or equal to 10%vol.
Thermoplastic polymer resin described in the method for the present invention does not have any restrictions, can be various thermoplastics in the prior art
Property fluoropolymer resin, preferably at least one of the polyvinyl alcohol of polylactic acid, polyamide, polyester, melt-processable.Wherein institute
The polyamide stated includes any kind of polyamide in the prior art, more preferable nylon 6, nylon66 fiber, nylon 11 or nylon 12.Institute
The polyester stated can be any kind of polyester in the prior art, more preferable polyethylene terephthalate（PET）Or it is poly- to benzene
Naphthalate（PTT）.For polyvinyl alcohol in the prior art due to molecular chain structure difference, can be divided into can be with melt-processed
With cannot melt-processed two parts.The polyvinyl alcohol of melt-processable of the present invention can as lead in the prior art
Cross the polyvinyl alcohol that melting processing method is processed.Thermoplastic polymer resin of the present invention is most preferably fusible adds
The polyvinyl alcohol of work.
Wherein the metal of the metal powder be fusing point in 55~500 DEG C of single component metal and metal alloy at least
One kind, fusing point are preferably 90~350 DEG C, more preferably 100~300 DEG C, most preferably 120~250 DEG C.It is of the present invention
The melting point metal of metal powder is not less than used thermoplastic polymer resin's fusing point or softening temperature, is preferably at least higher than institute
Thermoplastic polymer fusing point or 5 DEG C of softening temperature are stated, the thermoplastic polymer fusing point or softening temperature are more preferably at least higher than
10 DEG C, more preferably at least it is higher than the thermoplastic polymer fusing point or 15 DEG C of softening temperature.The single component metal be preferably gallium,
Caesium, rubidium, indium, tin, bismuth, cadmium, lead element elemental metals；The metal alloy is preferably gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead
Two or more metal alloy in element, or at least one of gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element and copper,
The metal alloy of at least one of silver, gold, iron or Zn-ef ficiency, or in gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element
The alloy that at least one of at least one and copper, silver, gold, iron or Zn-ef ficiency are formed with element silicon and/or carbon.
The temperature of the extruding dies is higher than melting point polymer or softening temperature, while being preferably up to optionally greater than metal
It is 15 DEG C of fusing point, minimum lower than being equal to 15 DEG C of melting point metal, more preferably up to it is optionally greater than 10 DEG C of melting point metal, it is minimum lower than being equal to
It is 10 DEG C of melting point metal, minimum lower than equal to 5 DEG C of melting point metal most preferably up to optionally greater than 5 DEG C of melting point metal.
There is no limit partial size is smaller, composite fibre prepared by preparation method according to the present invention for the partial size of metal powder
In the diameter of ultrafine metal fibers that contains with regard to smaller.It is preferred that the metal powder of micron-level particle size, powder diameter is less than or waits
In 500 μm, more preferably less than or equal to 200 μm, more preferably less than or equal to 100 μm, more preferably less than or equal to 80 μm.
In the preparation method, described that metal powder is filled into equipment used in fluoropolymer resin is not any
Limitation, usually using the usually used equipment of blending technology as on plastics and rubber industry.Including extruder, open mill and close
Mill.It is described that metal powder is filled into the preferred extruder of the equipment in polymer, i.e., it is same extruder with the stage of extrusion, it will
Filling blend and extrusion are preferred in completing on same extruder.If the equipment choosing that metal powder is filled into polymer is opened
Mill or mixer, then gained blend then will carry out extrusion stretching using extruder.The preferred screw extruder of extruder.
The screw extruder includes single screw extrusion machine, double screw extruder etc..
In preparation method of the present invention, described metal powder is filled into method employed in fluoropolymer resin is exactly rubber
Common blending modification method in modeling processing.Wherein the condition of the blending meets the processing conditions of usual polymer blending modification i.e.
It can.But wherein in the Blending Processes and subsequent extrusion process, each section of processing temperature of equipment setting, in addition to squeezing out the stage
Outside extruding dies part, it is preferably to not higher than the fusing point of metal, to guarantee that polymer sufficiently melts and golden in the blending process
It is substantially non-fusible to belong to powder, metal powder only in this way just can preferably be made to extend firmly from graininess into threadiness.
Longitudinal stretching is carried out in the method directly when blend passes through extruding dies to obtain containing ultra-fine gold
Belong to fiber it is polymer composite fibrous when, draw ratio（Revolving speed/blend melt extruded velocity of winding motor）It is bigger, it obtains
Composite fibre diameter it is thinner, wherein ultrafine metal fibers are also thinner and length is also longer, can additionally prevent polymer molten
The mutual welding of metal dispersion phase factor in body and cause it is final obtained by metallic fiber diameter it is too big.So working as the thermoplasticity
When the blend of polymer and metal powder is directly stretched through extruding dies, draw ratio is preferably 20-2000, more
Preferably 100-1000, most preferably 100-500.
In addition, the routine that thermoplastic polymer resin's processing can be added in right amount in material is blended helps according to processing needs
Agent, such as antioxidant, plasticizer and other processing aids etc..These common auxiliary dosages are conventional amount used, or according to reality
The requirement of situation carries out adjustment appropriate.The each components such as the polymer and metal can be passed through into metering in the blending process
The modes such as charging are added in melt blending equipment carry out melt blending simultaneously；General mixing apparatus can also be first passed through, in advance
Each component is uniformly mixed, then using rubber plastic blend equipment melt blending.The material mixing equipment is selected from
High-speed mixer in the prior art, the mechanical mixing equipments such as kneader.
Obtained polymer composite fibrous micromorphology is：In polymer and metal powder in Blending Processes and altogether
For mixed object during stretch spinning, the metal powder ultrafine metal fibers that extension generates in situ are as dispersed phase along composite fibre
Axial direction be evenly distributed in the polymeric matrix of composite fibre.
It is a further object of the present invention to provide a kind of polymer containing ultrafine metal fibers by above method preparation to answer
Condensating fiber.
Using the above polymer composite fibrous preparation method of the invention containing ultrafine metal fibers, by metal powder
The adjusting of the optimum choice and type of polymer and fiber forming process technical parameter of last partial size makes to contain in obtained composite fibre
The diameter of ultrafine metal fibers is adjustable, it might even be possible to prepare diameter in nanoscale ultrafine metal fibers dispersed phase, to make
Prepared composite fibre has excellent performance.Furthermore, it is possible to according to the composite fibre for requiring can to prepare different-diameter.
Polymer composite fibrous preparation method of the present invention containing ultrafine metal fibers can be in polymer/gold
Belong to blend preparation process in directly by the blend squeezed out in mouth mold stretching obtain it is polymer composite fibrous, in this process
In since the factors such as interaction between polymer and metal make metal powder extend in situ generate metallic fiber, preparation contains
The ultrafine metal fibers of diameter in a certain range it is polymer composite fibrous.The preparation process is simple, easy to operate, has good
Applicability and lower equipment cost.It is obtained it is polymer composite fibrous in the diameter of ultrafine metal fibers that contains can
It adjusts, by further selecting suitable metal powder partial size and type of polymer and to the adjusting of die drawing process, even
Diameter can be prepared in nanoscale ultra-fine metallic particles dispersed phase, to make prepared composite fibre that there is excellent property
Energy.Equipment used by simultaneously is simple and low energy consumption, had not only improved production efficiency in this way but also had reduced production cost.
Detailed description of the invention
Fig. 1 is 4 gained polyvinyl alcohol of the embodiment of the present invention/metal composite fiber Nano-CT（X-ray tomoscan）
Photo.Dark strokes is the ultrafine metal fibers being dispersed in composite fibre in photo.
Specific embodiment:
Below with reference to embodiment, the present invention is further illustrated.
Embodiment 1：
By the polyvinyl alcohol of melt-processable（Kuraray Corporation, trade mark CP-1000, fusing point are 174 DEG C）It is closed with tin-lead silver
Bronze（180 DEG C of fusing point, 24~45 μm of partial size, three He Dingxin hi-tech development Co., Ltd of Beijing）It is mixed in high-speed mixer
It closes uniform；Wherein the volume parts of tin-lead silver alloy are 5%vol, then through German HAAKE company PolymLab twin-screw extrusion
Machine melt blending squeezes out.Extruder temperature of each section is 140 DEG C, 170 DEG C, 170 DEG C, 175 DEG C, 175 DEG C, 180 DEG C（Machine head port mould temperature
Degree）.Blend melt is directly carried out after die extrusion draw ratio be 310 high-speed stretch and winding obtain polyvinyl alcohol/
Metal composite fiber.Observed by Nano-CT photo, the ultrafine metal fibers contained in polymers obtained composite fibre it is straight
Diameter is 0.5~10 μm, and length is 100~3000 μm.
Embodiment 2：
In addition to double screw extruder die temperature is set as 185 DEG C, remaining is same as Example 1.Pass through Nano-CT
Photo is observed, and the diameter of the ultrafine metal fibers contained in polymers obtained composite fibre is 0.5~10 μm, length 100
~5000 μm.
Embodiment 3：
Except the partial size of tin-lead silver alloy powder becomes 15~25 μm（Three He Dingxin hi-tech development Co., Ltd of Beijing）,
Polyvinyl alcohol/metal composite fiber draw ratio is outside 350, remaining condition is same as Example 1.Pass through Nano-CT photo
It observes, the diameter of the ultrafine metal fibers contained in polymers obtained composite fibre is 0.2~6 μm, and length is 30~700 μ
m。
Embodiment 4：
In addition to double screw extruder die temperature is set as 175 DEG C, remaining is same as Example 3.It is shone by Nano-CT
Piece is observed, and the diameter of the ultrafine metal fibers contained in polymers obtained composite fibre is 0.2~5 μm, and length is 30~600
μm。
Embodiment 5：
In addition to double screw extruder head temperature is set as 178 DEG C, remaining is same as Example 3.It is shone by Nano-CT
Piece is observed, and the diameter of the ultrafine metal fibers contained in polymers obtained composite fibre is 0.2~6 μm, and length is 30~600
μm。
Embodiment 6：
Except the volume fraction of tin-lead silver alloy in blend is 10%vol, polyvinyl alcohol/metal composite fiber draw ratio
Outside 155, remaining condition is same as Example 4.It is observed by Nano-CT photo, is contained in polymers obtained composite fibre
The diameter of some ultrafine metal fibers is 0.2~9 μm, and length is 20~300 μm.
Embodiment 7：
In addition to double screw extruder head temperature is set as 178 DEG C, remaining is same as Example 6.It is shone by Nano-CT
Piece observation, the diameter of the ultrafine metal fibers contained in polymers obtained composite fibre are 0.2~5 μm, length is 20~
1000μm。
Embodiment 8：
Except the partial size of tin-lead alloy for dental amalgam is 1~15 μm（Three He Dingxin hi-tech development Co., Ltd of Beijing）Outside,
Yu Jun is same as Example 4.It is observed by Nano-CT photo, the superfine metal contained in polymers obtained composite fibre is fine
The diameter of dimension is 0.2~5 μm, and length is 10~500 μm.
Embodiment 9：
Except metal alloy powder is leypewter powder（183 DEG C of fusing point, 1~15 μm of partial size, the prosperous new and high technology hair of three standing grain ancient cooking vessel of Beijing
Open up Co., Ltd）Outside, remaining is same as Example 1.It is observed by Nano-CT photo, in polymers obtained composite fibre
The diameter of the ultrafine metal fibers contained is 0.2~5 μm, and length is 10~500 μm.
Claims (26)
1. a kind of polymer composite fibrous preparation method containing ultrafine metal fibers, includes the following steps：
Metal powder is filled into thermoplastic polymer resin, gained blend is squeezed out by extruder；From extruding dies
Longitudinal stretching is directly carried out to blend when extrusion, is obtained containing the polymer composite fibrous of ultrafine metal fibers；It is wherein described
Metal powder fusing point be not less than thermoplastic polymer fusing point or softening temperature；The thermoplastic polymer resin is poly- cream
At least one of acid, polyamide, polyester, polyvinyl alcohol of melt-processable.
2. polymer composite fibrous preparation method according to claim 1, it is characterised in that：
The draw ratio when blend carries out longitudinal stretching by extruding dies is 20-2000.
3. polymer composite fibrous preparation method according to claim 2, it is characterised in that：
The draw ratio when blend carries out longitudinal stretching by extruding dies is 100-1000.
4. polymer composite fibrous preparation method according to claim 3, it is characterised in that：
The draw ratio when blend carries out longitudinal stretching by extruding dies is 100-500.
5. polymer composite fibrous preparation method according to claim 1, it is characterised in that：
Equipment when metal powder to be filled into fluoropolymer resin is selected from extruder, open mill or mixer.
6. polymer composite fibrous preparation method according to claim 5, it is characterised in that：
Equipment when metal powder to be filled into fluoropolymer resin is selected from extruder.
7. polymer composite fibrous preparation method according to claim 5, it is characterised in that：
The extruder is screw extruder.
8. polymer composite fibrous preparation method according to claim 7, it is characterised in that：
The extruder is single screw extrusion machine or double screw extruder.
9. polymer composite fibrous preparation method according to claim 1, it is characterised in that：
The thermoplastic polymer resin is nylon 6, nylon66 fiber, nylon 11, nylon 12, polyethylene terephthalate, gathers
At least one of propylene glycol ester terephthalate and the polyvinyl alcohol of melt-processable.
10. polymer composite fibrous preparation method according to claim 9, it is characterised in that：
The thermoplastic polymer resin is the polyvinyl alcohol of melt-processable.
11. polymer composite fibrous preparation method according to claim 1, it is characterised in that：
The volume parts of the metal powder are calculated as being less than according to the total volume parts of thermoplastic polymer resin and metal powder
Or it is equal to 30%vol.
12. polymer composite fibrous preparation method according to claim 11, it is characterised in that：
The volume parts of the metal powder are calculated as being less than according to the total volume parts of thermoplastic polymer resin and metal powder
Or it is equal to 15%vol.
13. polymer composite fibrous preparation method according to claim 12, it is characterised in that：
The volume parts of the metal powder are calculated as being less than according to the total volume parts of thermoplastic polymer resin and metal powder
Or it is equal to 10%vol.
14. polymer composite fibrous preparation method according to claim 1, it is characterised in that：
The metal of the metal powder is fusing point at least one of 55~500 DEG C of single component metal and metal alloy.
15. polymer composite fibrous preparation method according to claim 14, it is characterised in that：
The metal of the metal powder is fusing point at least one of 90~350 DEG C of single component metal and metal alloy.
16. polymer composite fibrous preparation method according to claim 15, it is characterised in that：
The metal of the metal powder is fusing point at least one of 100~300 DEG C of single component metal and metal alloy.
17. polymer composite fibrous preparation method according to claim 16, it is characterised in that：
The metal of the metal powder is fusing point at least one of 120~250 DEG C of single component metal and metal alloy.
18. polymer composite fibrous preparation method according to claim 14, it is characterised in that：
The single component metal is the elemental metals of gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead element；The metal alloy be gallium,
Caesium, rubidium, indium, tin, bismuth, cadmium, metal alloy two or more in lead element, or be gallium, caesium, rubidium, indium, tin, bismuth, cadmium, lead member
The metal alloy of at least one of element and at least one of copper, silver, gold, iron or Zn-ef ficiency, or for gallium, caesium, rubidium, indium,
At least one of at least one of tin, bismuth, cadmium, lead element and copper, silver, gold, iron or Zn-ef ficiency and element silicon and/or carbon member
The alloy that element is formed.
19. polymer composite fibrous preparation method according to claim 1, it is characterised in that：
The metal powder fusing point is at least above melting point polymer or 5 DEG C of softening temperature.
20. polymer composite fibrous preparation method according to claim 19, it is characterised in that：
The metal powder fusing point is at least above the melting point polymer or 10 DEG C of softening temperature.
21. polymer composite fibrous preparation method according to claim 20, it is characterised in that：
The metal powder fusing point is at least above the melting point polymer or 15 DEG C of softening temperature.
22. polymer composite fibrous preparation method according to claim 1, it is characterised in that：
The blend is squeezed out by extruder, and the temperature of the extruding dies is higher than thermoplastic polymer fusing point or softening temperature
Degree, while highest is higher than 15 DEG C of melting point metal, it is minimum to be lower than 15 DEG C of melting point metal.
23. polymer composite fibrous preparation method according to claim 22, it is characterised in that：
The temperature highest of the extruding dies is minimum to be lower than 10 DEG C of melting point metal higher than 10 DEG C of melting point metal.
24. polymer composite fibrous preparation method according to claim 23, it is characterised in that：
The temperature highest of the extruding dies is minimum to be lower than 5 DEG C of melting point metal higher than 5 DEG C of melting point metal.
25. polymer composite fibrous preparation method described according to claim 1~one of 24, it is characterised in that：
During the metal powder is filled into thermoplastic polymer resin and gained blend squeezes out, in addition to squeezing out
When extruder other outer each section of processing temperature of mouth mold be not higher than the fusing point of metal.
26. it is a kind of according to claim 1~one of 25 described in the polymer composite fibrous preparation containing ultrafine metal fibers
It is polymer composite fibrous prepared by method.
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| CN102532864A (en) * | 2010-12-07 | 2012-07-04 | 合肥杰事杰新材料股份有限公司 | Continuous long fiber reinforced thermoplastic polyurethane material and preparation method thereof |
| CN102140707A (en) * | 2010-12-21 | 2011-08-03 | 东华大学 | Skin-core composite electromagnetic shielding fiber and preparation method thereof |
| CN102021670A (en) * | 2010-12-31 | 2011-04-20 | 中国纺织科学研究院 | Conductive core-sheath compound fibre and preparation method thereof |
| CN102181133A (en) * | 2011-01-27 | 2011-09-14 | 上海锦湖日丽塑料有限公司 | Metal fiber reinforced polybutylene terephthalate (PBT) resin and preparation method thereof |
| CN102391647A (en) * | 2011-09-06 | 2012-03-28 | 四川瑞安特电子技术有限公司 | Manufacturing method of polyphenylene sulfide composite heat conduction material for light-emitting diode (LED) |
| CN102746658A (en) * | 2012-06-15 | 2012-10-24 | 苏州宇度医疗器械有限责任公司 | Preparation method of metal fiber filled nylon composite material |
| CN103088462A (en) * | 2013-01-30 | 2013-05-08 | 吉林大学 | Preparation method of polyether-ether-ketone monofilament with electromagnetic shielding function |
| CN103205110A (en) * | 2013-04-17 | 2013-07-17 | 常熟市康宝医疗器械厂 | Preparation method of environmentally-friendly polyamide alloy material modified by polypropylene |
| CN103319893A (en) * | 2013-07-11 | 2013-09-25 | 四川中物材料有限责任公司 | Preparation method of high-heat-conducting polyphenylene sulfide material and prepared material |
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