CN109251328A - A kind of tungsten for 3D printing/PEEK radiation protection composite wire and preparation method thereof - Google Patents

A kind of tungsten for 3D printing/PEEK radiation protection composite wire and preparation method thereof Download PDF

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Publication number
CN109251328A
CN109251328A CN201810868684.5A CN201810868684A CN109251328A CN 109251328 A CN109251328 A CN 109251328A CN 201810868684 A CN201810868684 A CN 201810868684A CN 109251328 A CN109251328 A CN 109251328A
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CN
China
Prior art keywords
peek
tungsten
printing
radiation protection
composite wire
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CN201810868684.5A
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Chinese (zh)
Inventor
杨永强
付凡
李阳
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South China University of Technology SCUT
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South China University of Technology SCUT
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Priority to CN201810868684.5A priority Critical patent/CN109251328A/en
Publication of CN109251328A publication Critical patent/CN109251328A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/16Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2461/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2461/04Condensation polymers of aldehydes or ketones with phenols only
    • C08J2461/16Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/08Metals
    • C08K2003/0887Tungsten
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The invention discloses a kind of tungsten for 3D printing/PEEK radiation protection composite wires and preparation method thereof;Raw material: 100 parts of tungsten powder, 40~50 parts of PEEK material are weighed according to mass fraction ratio;0.25~0.75 part of plasticizer, 0.125~0.75 part of titanate coupling agent;The present invention realizes the preparation of the dedicated tungsten of 3D printing/PEEK composite wire by melting stirring, double-screw extruding pelletizing, single screw rod extrusion of wire, the smooth cooling wire rod of wire rod planisher, coiling apparatus volume bundle, and application field is mainly nuclear power field;Tungsten of the present invention/PEEK composite wire application advantage, is the composite material specially developed for 3D printing technique and nuclear power radiation protection field related application, and PEEK material has excellent radiation resistance, superpower mechanical performance compared with other high molecular materials.The radiation protection composite material breakthrough of zero in 3D printing field is realized, also the initiative 3D printing technique that advances is in the application of manufacture nuclear power radiation shield part field.

Description

A kind of tungsten for 3D printing/PEEK radiation protection composite wire and preparation method thereof
Technical field
The present invention relates to compound 3D printing wire rod more particularly to a kind of tungsten for 3D printing/PEEK radiation protection are compound Wire rod and preparation method thereof.
Background technique
In the increasingly developed society of nuclear energy, the demand to radiation shielding material is also more and more.In various rays to people In the extent of injury of body, gamma-rays and neutron occupy first place.Nuclear radiation shield design main task be exactly shield gamma-rays and Neutron.Wherein gamma-ray shielding material generally selects high atomic number material and common architectural material, including iron, tungsten, lead, poor Uranium, concrete, brick, ionized water etc..Currently, common shielding material is mostly metal.But there are many disadvantages for metal: meeting Secondary bremstrahlen is generated, hardness is poor, and large-sized shield member structural behaviour is poor, and mechanical strength is relatively low, while lead sheet Body is source of heavy metal pollution, it is likely that heavy metal poisoning is caused in use, using being restricted.
Tungsten has high density and atomic number, has many advantages, centering as ideal radiation proof material Son is very good with gamma ray shielding effect, and asepsis environment-protecting, and furthermore tungsten material will not generate secondary electron radiation, therefore become The direction of radiation shielding material research and development.In radiation protection application aspect, if nuclear power generating equipment components go wrong, more Change that the period is longer, thus the time for causing nuclear power generating equipment stalling to wait is also too long, and increasing material manufacturing technique can be realized to zero The rapid prototyping manufacturing of part can greatly shorten nuclear power generating equipment rundown time.Tungsten is high-melting-point refractory metal, high with intensity, The features such as plasticity is poor, poor toughness, it is difficult to be directly used in increasing material manufacturing molding.
Summary of the invention
The shortcomings that it is an object of the invention to overcome the above-mentioned prior art and deficiency, provide a kind of tungsten for 3D printing/ PEEK radiation protection composite wire and preparation method thereof.
The present invention is achieved through the following technical solutions:
A kind of preparation method of the tungsten for 3D printing/PEEK radiation protection composite wire, includes the following steps:
Step 1: raw material is weighed according to mass fraction ratio comprising following components: 100 parts of tungsten powder, 40~50 parts PEEK material;0.25~0.75 part of plasticizer, 0.125~0.75 part of titanate coupling agent;
Step 2: mixing pours into each component raw material in step 1 in autoclave, opens autoclave, makes It starts to stir, and is passed through inert gas shielding, and autoclave material temperature is heated to 360 DEG C~400 DEG C;
Step 3: insulated and stirred carries out heat preservation 50~60 minutes to autoclave, is sufficiently stirred simultaneously, makes PEEK material Material becomes molten condition completely, and is uniformly mixed each component raw material;
Step 4: 360 DEG C~400 DEG C at a temperature of, by each component be uniformly mixed molten state mixing material be added to Double screw extruder obtains tungsten/PEEK mixing material master batch;
Step 5: tungsten/PEEK mixing material master batch that double screw extruder is manufactured is sent to single screw extrusion machine, obtains To tungsten/PEEK composite wire.
Tungsten/PEEK composite wire that single screw extrusion machine in step 5 squeezes out is sent into coil winder and carries out volume bundle.
Tungsten powder described in step 1 is nano-tungsten powder.
The present invention compared with the existing technology, have following advantages and effects
The invention proposes a kind of novel radiation protection composite materials, and it is compound to realize radiation protection in 3D printing field The material breakthrough of zero, also the initiative 3D printing technique that advances is in the application of manufacture nuclear power radiation shield part field.Tungsten tool There are high density and high atomic number, is the ideal material in terms of a kind of radiation shield applied to nuclear power, tungsten is to neutron and gamma-rays Shield effectiveness is very good, and asepsis environment-protecting, and furthermore tungsten material will not generate secondary electron radiation, and therefore, it has become nuclear power radiation The direction of shielding material research and development.
The present invention proposes according to the performance requirement of tungsten, the performance of PEEK material and 3D printing raw material and passes through melting Stirring, double-screw extruding pelletizing, single screw rod extrusion of wire, coiling apparatus volume are tied to realize the tungsten for 3D printing/PEEK radiation Protect the preparation process of composite wire;At the same time, preparation of the present invention also for other metals and nonmetallic composite provides Thinking and method are used for reference.
Tungsten of the present invention/PEEK composite wire application advantage is for 3D printing technique and nuclear power radiation protection field phase Close the composite material specially developed of application, PEEK material is with other high molecular materials compared with excellent radiation resistance, superpower Mechanical performance.By means of 3D printing technique, the timely reparation and replacement, shortening that can be realized nuclear power field related components are set Standby rundown time.
Detailed description of the invention
Fig. 1 is tungsten of the present invention/PEEK radiation protection composite wire preparation technology flow chart.
Specific embodiment
The present invention is more specifically described in detail combined with specific embodiments below.
As shown in Figure 1.Equipment used in preparation process of the present invention is existing equipment;In figure: argon bottle 1, reaction kettle 2, double screw extruder 3, single screw extrusion machine 4, wire rod planisher 5, coil winder 6;
Agitating device in reaction kettle 2, external argon bottle 1;Reaction kettle 2 is connect with 3 feed inlet of double screw extruder, argon Gas cylinder 1 is that reaction kettle 2 provides inert gas shielding;
3 discharge port of double screw extruder is connect with 4 feed inlet of single screw extrusion machine, the connection of 4 extrusion of single screw extrusion machine Wire rod planisher 5;
Wire rod planisher 5 is smooth to wire rod progress by roll shaft, is built-in with temperature sensor and cooler;Temperature sensing Device detects wire temperature, and cooler is cooled down when wire temperature is higher than setting value.
The present invention is used for tungsten/PEEK radiation protection composite wire preparation method of 3D printing, can be real as follows It is existing:
Step 1: raw material is weighed according to mass fraction ratio comprising following components: the tungsten powder of 100 parts (1000g), 40~ 50 parts (400~500g) of PEEK material;The plasticizer of 0.25~0.75 part (2.5~7.5g), 0.125~0.75 part (1.25 ~7.5g) titanate coupling agent;
Tungsten powder is nano-tungsten powder, and trade mark YFM08-N50, for particle diameter distribution between 15~53 microns, exterior appearance is greyish black Color, grain shape are spherical or subsphaeroidal;PEEK material be PEEK 1000P (powder), 340 DEG C of melting temperature, toughness, anti-impact It is prominent to hit performance;Plasticizer is DEHP, and DEHP is one kind of phthalic acid ester, good mixing property, plasticizing efficiency height;Coupling agent For titanate coupling agent, improve the dispersibility and adhesion of mixing material;
Step 2: mixing pours into each component raw material in step 1 in autoclave, opens autoclave, makes It starts to stir, and is passed through inert gas shielding, and autoclave material temperature is heated to 360 DEG C~400 DEG C;
Step 3: insulated and stirred carries out heat preservation 50~60 minutes to autoclave, is sufficiently stirred simultaneously, makes PEEK material Material becomes molten condition completely, and is uniformly mixed each component raw material;
Step 4: 360 DEG C~400 DEG C at a temperature of, by each component be uniformly mixed molten state mixing material be added to Double screw extruder obtains tungsten/PEEK mixing material master batch;
Step 5: tungsten/PEEK mixing material master batch that double screw extruder is manufactured is sent to single screw extrusion machine, obtains To tungsten/PEEK composite wire;
Tungsten/PEEK composite wire that single screw extrusion machine squeezes out is sent into coil winder again and carries out volume bundle.
As described above, the present invention can be better realized.
Embodiment of the present invention are not limited by the above embodiments, other are any without departing from Spirit Essence of the invention With changes, modifications, substitutions, combinations, simplifications made under principle, equivalent substitute mode should be, be included in of the invention Within protection scope.

Claims (4)

1. a kind of tungsten for 3D printing/PEEK radiation protection composite wire preparation method, it is characterised in that including walking as follows It is rapid:
Step 1: raw material is weighed according to mass fraction ratio comprising following components: 100 parts of tungsten powder, 40~50 parts of PEEK material Material;0.25~0.75 part of plasticizer, 0.125~0.75 part of titanate coupling agent;
Step 2: mixing;Each component raw material in step 1 is poured into autoclave, autoclave is opened, opens it Begin to stir, and be passed through inert gas shielding, autoclave material temperature is heated to 360 DEG C~400 DEG C;
Step 3: insulated and stirred;Heat preservation is carried out 50~60 minutes to autoclave, is sufficiently stirred simultaneously, keeps PEEK material complete Become molten condition entirely, and is uniformly mixed each component raw material;
Step 4: 360 DEG C~400 DEG C at a temperature of, the molten state mixing material that each component is uniformly mixed is added to double spiral shells Bar extruder obtains tungsten/PEEK mixing material master batch;
Step 5: by double screw extruder manufacture tungsten/PEEK mixing material master batch, be sent into single screw extrusion machine, obtain tungsten/ PEEK composite wire.
2. being used for tungsten/PEEK radiation protection composite wire preparation method of 3D printing according to claim 1, feature exists In: tungsten/PEEK composite wire that single screw extrusion machine in step 5 squeezes out is sent into coil winder and carries out volume bundle.
3. being used for tungsten/PEEK radiation protection composite wire preparation method of 3D printing according to claim 2, feature exists In: tungsten powder described in step 1 is nano-tungsten powder.
4. a kind of tungsten/PEEK radiation protection composite wire, it is characterised in that be made using preparation method described in claim 3.
CN201810868684.5A 2018-08-02 2018-08-02 A kind of tungsten for 3D printing/PEEK radiation protection composite wire and preparation method thereof Pending CN109251328A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110666167A (en) * 2019-09-11 2020-01-10 中广核研究院有限公司 Selective laser sintering 3D printing shielding material and preparation method thereof, shielding piece and manufacturing method thereof
CN111659881A (en) * 2020-06-29 2020-09-15 青岛聚鑫园钨业有限公司 Tungsten-based radiation protection composite material for additive manufacturing and preparation method thereof

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CN106147111A (en) * 2015-04-09 2016-11-23 广州新诗达电子科技有限公司 A kind of method manufacturing the radiation shield composite that 3D prints
KR20170093315A (en) * 2016-02-04 2017-08-16 서강대학교산학협력단 Composition for Manufacturing Radiation Shielding material
CN107603117A (en) * 2017-09-18 2018-01-19 广州飞胜高分子材料有限公司 A kind of 3D printing composite for shielding nuclear radiation and preparation method and application

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110666167A (en) * 2019-09-11 2020-01-10 中广核研究院有限公司 Selective laser sintering 3D printing shielding material and preparation method thereof, shielding piece and manufacturing method thereof
CN110666167B (en) * 2019-09-11 2022-03-18 中广核研究院有限公司 Selective laser sintering 3D printing shielding material and preparation method thereof, shielding piece and manufacturing method thereof
CN111659881A (en) * 2020-06-29 2020-09-15 青岛聚鑫园钨业有限公司 Tungsten-based radiation protection composite material for additive manufacturing and preparation method thereof
CN111659881B (en) * 2020-06-29 2022-03-18 青岛聚鑫园钨业有限公司 Tungsten-based radiation protection composite material for additive manufacturing and preparation method thereof

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