CN102585330A - Tungsten-polymer composite material and preparation method thereof - Google Patents

Abstract

The invention discloses a tungsten-polymer composite material and a preparation method thereof. The tungsten-polymer composite material comprises the following components in percentage by weight: 20-100% of polymers, 950-1000% of tungsten powder, 0-50% of tungsten fibers, 0.5-5% of coupling agent and 0.5-10% of other auxiliaries, wherein the tungsten powder is prepared through airflow pulverization and surface modification. The tungsten powder disclosed by the invention is good in compaction and flowability and high in loading capacity. The composite material disclosed by the invention is good in physical and mechanical properties, and excellent in weathering resistance, chemical resistance and organic solvent resistance, not only can be applied to the field of ray shielding, but also can be applied to the fields of vibration isolation, weight counterbalance, heat conduction, weapons and ammunitions and the like.

Description

Ming composite material and method for preparing a polymer

FIELD

[0001] The present invention belongs to the field of materials engineering, in particular to tungsten - composite material and method for preparing polymers.

Background technique

Reactor [0002] The nuclear power plant is a huge radiation source, when the nuclear fuel and fission neutron radiation Y, activation products and fission products of the activation reaction fission reaction also yields a, 0, and Y radiation decay Therefore, nuclear power plant facility has great potential danger, it must be a radiation shield to avoid all possible accidents. Meanwhile, the disposal of nuclear waste is also crucial. Commonly referred to as nuclear waste comprises radioactive nuclear waste of low and high level radioactive nuclear waste categories, the former mainly refers to nuclear power generation during power generation of radioactive waste, waste, accounting for 99% of all nuclear waste, the latter refers to a change from the nuclear reactor core of the nuclear fuel after combustion, because of its highly radioactive, commonly known as a high radiation waste. When the above sound processing nuclear waste, but also requires the necessary radiation shielding process.

[0003] In the prior art multi-ray-shielding material is a metal of lead, the shielding effect is good, low cost and ease of processing, however, lead itself toxic, lead-containing waste gas, waste water, waste air pollution, water and crops, can endanger nearby residents, so instead of lead material applied to other fields of nuclear radiation shielding imperative.

[0004] Studies have shown that the ability of a substance to its radiation and the atomic number density of the material, the higher the atomic number, the greater the density of the material, the better the shielding properties. Tungsten atomic number of 74, a density of 19. 35g / cm3, having a good radiation shielding performance, is used to make the best choice of shielding material, but the high-melting refractory metal is tungsten, forming processing difficulties which, in the application when susceptible shape restricted. In the prior art polymer matrix to tungsten powder to prepare a high-density tungsten filler - polymer composites to solve the above problems, Patent US5001354 natural rubber latex surgical glove, and tungsten powder is prepared starting materials having radiation properties. Patent US7304105B2 tungsten powder filled elastomers of different diameters of the radiation to produce a composite material, the material has good workability and flexibility, but requires three different particle size tungsten powder with each other to increase the loading of tungsten the amount of manufacturing process is complicated. The tungsten powder used in the prior art usually by conventional ball milling techniques and the like made of tungsten powder thus obtained severe particle agglomeration, irregular shape, flowability and compactibility is poor, loading the composite material low, is not easy to uniformly in the polymer matrix dispersion, resulting in poor mechanical properties of the composite material.

SUMMARY

[0005] The object of the present invention is to overcome defects in the prior art, to provide a good physical and mechanical properties of tungsten - polymer composite material and its preparation method.

[0006] aspect of the present invention is as follows:

[0007] - Species tungsten - polymer composites, parts by weight of component comprising:

[0008] The polymers 20-100

Tungsten powder 950~1000

Tungsten fibers 0~50

Coupling 0.5~5

Other additives 0.5~IO.

[0009] The diameter of the tungsten fibers have 10~30 ii m, an aspect ratio of 50~150.

[0010] A mixture of the tungsten powder particle size is Fisher 0. 4 m~60 m or more of tungsten powder, tungsten powder.

[0011] The one or more polymers as plastic, rubber or thermoplastic elastomer.

[0012] The plastics include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamide, polyimide, polyurethane, polymethyl methacrylate, polyethylene terephthalate, acrylonitrile - styrene - butadiene copolymer of one or more.

[0013] The rubber include natural rubber, fluorine rubber, silicone rubber, nitrile rubber, ethylene propylene rubber, chloroprene rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber of one or more.

[0014] The thermoplastic elastomer of the styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, diene-based thermoplastic elastomer, a vinyl chloride-based thermoplastic elastomer, polyurethane elastomer, polyester elastomer, polyamide-based thermoplastic one or more elastomers, fluorine-based thermoplastic elastomer, a silicone-based thermoplastic elastomer.

[0015] The coupling agent is a silane coupling agent, a titanate coupling agent or a rare earth is one or more coupling agent.

The [0016] Other auxiliaries are plasticizers, one or more antioxidant, flame retardant, anti-UV agents, crosslinking agents, vulcanizing agents, vulcanization accelerators.

[0017] A process for preparing the tungsten - high molecular polymer composite material, characterized by: comprising the steps of:

[0018] (I) pulverized tungsten powder stream;

[0019] (2) the gas stream through the pulverized tungsten powder or tungsten powder and tungsten-doped fiber continuously stirred pot, and diluted with ethanol to spray the surface modification of a coupling agent;

[0020] (3) the polymers, surface-modified or a mixture of tungsten powder and tungsten powder and other additives which tungsten fibers mixed in the above parts by weight, uniform kneading prepared feed;

[0021] (4) Molding: The feed extrusion molding through an extruder, injection molding machine or by injection, or press molding by a press molding machine;

[0022] (5) Post-treatment: The resulting article cropping, chamfered.

[0023] Advantageous effects of the present invention are:

[0024] I, the composite material of the present invention the weight ratio of the components by the following composition: 20-100 polymers, 950~1000 tungsten powder, tungsten fibers 0~50, coupling agents and other 0. 5~5 0. 5 to 10 auxiliaries, compared to the prior art, in addition to having good flexibility and processing properties, the composite material of the present invention due to the high content of tungsten which has good radiation shielding properties, while the addition of tungsten fiber composite material such that the present invention has good mechanical strength and physical properties.

[0025] 2, the composite material used in the present invention is tungsten powder and pulverized to obtain surface-modified by air. Compared with the prior art, jet milling process is simple and efficient, significantly reducing the agglomeration of the tungsten powder, tungsten powder resulting regular shape, good fluidity, and further, the surface modification, so that the tungsten powder with the polymer matrix among the better binding, allowing easy in the polymer matrix uniformly dispersed, high loading, has good physical and mechanical properties of the composite material of the present invention, the tungsten powder was prepared.

[0026] 3, the composite material of the present invention, there is added a plasticizer, an antioxidant, a flame retardant, anti-UV agents, crosslinking agents, vulcanizing agent, vulcanization accelerator is one or more, it weather resistance, chemical resistance and improved resistance to organic solvents, having a wide range of applications, can be applied not only to the field of radiation shielding, isolation can also be applied, weight, thermal conductivity, ordnance ammunition art.

Detailed ways

[0027] Here will be further described and description of the invention According to a particular embodiment.

[0028] Example I

[0029] The high density tungsten - polymer ray shielding composite formulation is:

[0030]

[0031]

[0032] The tungsten - preparation of the polymer composite material, comprising the steps of:

[0033] (I) by the above-described parts by weight of tungsten powder weighed, was jet milled tungsten powder, feed pressure O. 9MPa, pulverization pressure I. IMPa.

[0034] (2) the gas stream through the pulverized-doped tungsten powder in a pot continuously stirred, and diluted with ethanol spray titanate coupling agents for surface modification;

[0035] (3) According to the above parts by weight of other materials weighed, the first styrene-based thermoplastic elastomer to a kneader, and then put into 500 parts by weight of the tungsten powder, kneading tungsten powder remaining after the appropriate time and antioxidant was added, to obtain a uniform feeding kneading the kneading temperature of 140 ° C.

[0036] (4) Molding: The feed to the extruder after the extrusion granulation 210 C, cooled to obtain strip article.

[0037] (5) Post-treatment: The resulting article cropping, chamfered.

[0038] Example 2

[0039] High density W - polymer ray shielding composite formulation is:

[0040]

[0041]

[0042] The tungsten - preparation of the polymer composite material, comprising the steps of:

[0043] (I) by the above-described parts by weight of tungsten powder weighed, was jet milled tungsten powder, a feed pressure of 0. 8MPa, pulverization pressure I. OMPa.

[0044] (2) the gas stream through the pulverized-doped tungsten powder in a pot continuously stirred, and diluted with ethanol to spray the surface-modified silane coupling agent;

[0045] (3) According to the above referred to other materials taken parts by weight of EPDM rubber was added first a kneader, and then put into 500 parts by weight of the tungsten powder at 120 ° C after appropriate curing agent in addition to the kneading time All remaining outside the material added sequentially, after kneading the material are hook, and finally vulcanizing agent is added in the open roll, the kneaded sheet was prepared by feeding the hook.

[0046] (4) Molding: The feed in the flat vulcanized rubber vulcanization 170 ° C to obtain a sheet article.

[0047] (5) Post-treatment: The resulting article cropping, chamfered.

[0048] Example 3

[0049] The high density tungsten - polymer ray shielding composite formulation is:

[0050]

[0052] The tungsten - preparation of the polymer composite material, comprising the steps of:

[0053] (I) by the above-described parts by weight of tungsten powder weighed, was jet milled tungsten powder, a feed pressure of 0. 9MPa, pulverization pressure I. OMPa.

[0054] (2) by jet milling the tungsten powder and tungsten-doped fiber continuously stirred pot, and diluted with ethanol to spray the surface-modified rare earth coupling agent;

[0055] (3) According to the above parts by weight of other materials weighed, natural rubber was added first a kneader, and a mixture of styrene and 500 parts by weight of tungsten powder and the tungsten fibers, at 80 ° C suitable kneading after the remaining time of all materials except the vulcanizing agent were added, and kneaded uniformly discharge, discharge temperature below 130 ° C. Finally, curatives were added on the open roll, the kneaded sheet was prepared by feeding the hook.

[0056] (4) Molding: The feed in the flat vulcanized rubber vulcanization 150 ° C to obtain a sheet article.

[0057] (5) Post-treatment: The resulting article cropping, chamfered.

[0058] Example 4

[0059] The high density tungsten - polymer ray shielding composite formulation is:

[0060]

[0061]

[0062] The tungsten - preparation of the polymer composite material, comprising the steps of:

[0063] (I) by the above-described parts by weight of tungsten powder weighed, was jet milled tungsten powder, feed pressure I. OMPa, pulverization pressure I. IMPa. [0064] (2) the gas stream through the pulverized-doped tungsten powder in a pot continuously stirred, and diluted with ethanol spray titanate coupling agents for surface modification;

[0065] (3) According to the above parts by weight of other materials weighed, nylon 6 was added first a kneader, and then put into 500 parts by weight of the tungsten powder, kneading tungsten powder remaining after the appropriate time and the antioxidant is added, kneading obtain a uniform feeding the kneading temperature is 230 0C o

[0066] (4) Molding: After feeding the granulated on an injection machine to obtain shaped member 240 ° C injection molding.

[0067] (5) Post-treatment: The resulting article cropping, chamfered.

[0068] Example 5

[0069] The high density tungsten - polymer ray shielding composite formulation is:

[0070]

[0071] The tungsten - preparation of the polymer composite material, comprising the steps of:

[0072] (I) by the above-described parts by weight of tungsten powder weighed, was jet milled tungsten powder, a feed pressure of 0. 9MPa, pulverization pressure 0. 9MPa.

[0073] (2) the gas stream through the pulverized-doped tungsten powder in a pot continuously stirred, and diluted with ethanol spray titanate coupling agents for surface modification;

[0074] (3) According to the above referred to other materials taken parts by weight, the silicone rubber was added first a kneader, followed by addition of 500 parts by weight of the tungsten powder, at 40 ° C after kneading appropriate time all remaining except the vulcanizing agent materials were added, and kneaded uniformly discharge, discharge temperature below 50 ° C; kneading the material allowed to cool to room temperature and then placed in an oven for 2h at 140 ° C, remove and cool naturally, in the open remill on the mill and adding a vulcanizing agent is mixed uniformly and then parked overnight, and then back to refining, to prepare a sheet feeder.

[0075] (4) Molding: The feed in the flat vulcanized rubber vulcanization 200 ° C to obtain a sheet article.

[0076] (5) Post-treatment: The resulting article cropping, chamfered.

[0077] Example 6

[0078] The high density tungsten - polymer ray shielding composite formulation is:

[0079]

[0080] The tungsten - preparation of the polymer composite material, comprising the steps of:

[0081] (I) by the above-described parts by weight of tungsten powder weighed, was jet milled tungsten powder, feed pressure 0.9MPa, pulverization pressure I. IMPa.

[0082] (2) the gas stream through the pulverized-doped tungsten powder in a pot continuously stirred, and diluted with ethanol spray titanate coupling agents for surface modification;

[0083] (3) According to the above parts by weight of other materials weighed, the first olefin-based thermoplastic elastomer to a kneader, and 500 parts by weight A cast tungsten powder described above, after a suitable kneading time remaining tungsten powder and antioxidant was added, to obtain a uniform feeding kneading, the kneading temperature is above 140 ° c.

[0084] (4) forming: After the feed to the extruder pelletizing extruder 200 C, cooled to obtain a rod-shaped article.

[0085] (5) Post-treatment: The resulting article is clipped.

[0086] Example I

[0087] High density W - polymer ray shielding composite formulation is:

[0088]

[0089] The tungsten - preparation of the polymer composite material, comprising the steps of:

[0090] (I) by the above-described parts by weight of tungsten powder weighed, was jet milled tungsten powder, feed pressure I. OMPa, pulverization pressure I. OMPa0

[0091] (2) by jet milling the tungsten powder and tungsten-doped fiber continuously stirred pot, and diluted with ethanol spray titanate coupling agents for surface modification;

[0092] (3) According to the above parts by weight of other materials weighed, first a styrene based thermoplastic elastomer is added a kneader, 500 parts by weight of the mixture was then put in the tungsten powder and tungsten fibers, after a suitable kneading time remaining antioxidant mixture of tungsten powder and tungsten fibers added, to obtain a uniform feeding kneading the kneading temperature of 140 ° C.

[0093] (4) Molding: The feed to the extruder after the extrusion granulation 210 C, cooled to obtain a tubular article.

[0094] (5) Post-treatment: The resulting article is clipped.

[0095] Example 8

[0096] High density W - polymer ray shielding composite formulation is:

[0097]

[0098] The tungsten - preparation of the polymer composite material, comprising the steps of:

[0099] (I) by the above-described parts by weight of tungsten powder weighed, was jet milled tungsten powder, feed pressure I. OMPa, pulverization pressure I. OMPa0

[0100] (2) the gas stream through the pulverized-doped tungsten powder in a pot continuously stirred, and diluted with ethanol to spray the silane coupling agent and a titanate coupling agent for surface modification;

[0101] (3) According to the above referred to the other parts by weight of the material taken, first a styrene based thermoplastic elastomer and the polypropylene was added a kneader, and then put into 500 parts by weight of the tungsten powder, kneading the tungsten powder remaining after an appropriate time and the antioxidant was added, to obtain a uniform feeding kneading the kneading temperature of 180 ° C.

[0102] (4) Molding: The feed to the extruder after the extrusion granulation 210 C, cooled to obtain strip article.

[0103] (5) Post-treatment: The resulting article cropping, chamfered.

[0104] The above are only preferred embodiments of the present invention only, modifications and equivalent so it can not limit the scope of embodiments of the present invention, i.e., under this patent specification the content and scope of the invention is made, are still to be It encompassed within the scope of the present invention.

Claims (10)

A tungsten - polymer composites, characterized by: comprising the following parts by weight of component: 20-100 tungsten powder polymer fiber 950~1000 tungsten coupling 0.5~5 0~50 other co agent 0.5~IO.

2. tungsten claim I - polymer composites, characterized in that: the tungsten fibers have a diameter of 10~30 μ m, an aspect ratio of 50~150.

3. tungsten according to claim 2 - polymer composites, characterized in that: the tungsten powder as a particle size tungsten powder Fisher O. 4 μ m~60 μ m or more of tungsten powder mixture.

The polymer is a plastic, rubber or a thermoplastic elastomer or: polymer composites, characterized in that - 4 I according to any one of claims 3 and tungsten claim several.

5. tungsten claimed in claim 4, wherein - polymer composites, characterized in that: said plastic include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyamide, polyimide, polyurethane, polymethyl methacrylate, polyethylene terephthalate, acrylonitrile - styrene - butadiene copolymer in one or more of.

6. tungsten claimed in claim 4, wherein - polymer composites, characterized in that: said rubber comprises natural rubber, fluorine rubber, silicone rubber, nitrile rubber, ethylene propylene rubber, chloroprene rubber, iso isoprene rubber, styrene-butadiene rubber, butadiene rubber of one or more.

7. tungsten claimed in claim 4, wherein - polymer composites, wherein: said thermoplastic elastomer comprises a styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, diene-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, polyurethane elastomer, polyester elastomer, polyamide-based thermoplastic elastomer, fluorine-based thermoplastic elastomer, silicone-based thermoplastic elastomer is one or more.

The coupling agent is a silane coupling agent, a titanate coupling agent or RE: polymer composites, characterized in that - 8 I according to any one of claims 3 and tungsten claim one or more coupling agents.

I as claimed in claim 9 tungsten to 3 of any one of claims - polymer composites, characterized in that: the other auxiliaries are plasticizers, anti-aging agents, flame retardants, UV one or more agents, crosslinking agents, vulcanizing agents, vulcanization accelerators.

(; (1) was jet milled tungsten powder: comprising the steps of: high molecular polymer composite material, characterized in that - A tungsten-I according to claim any of claim 3 for preparing 2) the gas stream through the pulverized tungsten powder or tungsten powder and tungsten-doped fiber continuously stirred pot, and diluted with ethanol to spray the surface-modified coupling agent; (3) the polymer, the surface modified tungsten powder or the mixture of tungsten powder and tungsten fibers and other additives in accordance with the above-described parts by weight are mixed to obtain a uniform kneaded feeding; (4) molding: the feed extrusion molding through an extruder, or by injection molding machine injection, by means of a pressure molding machine or molding press; (5) post-treatment: the resulting article cropping, chamfered.