CN109627673A - A kind of high radiation preventing 3D printing composite material and preparation method - Google Patents

A kind of high radiation preventing 3D printing composite material and preparation method Download PDF

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Publication number
CN109627673A
CN109627673A CN201811523007.6A CN201811523007A CN109627673A CN 109627673 A CN109627673 A CN 109627673A CN 201811523007 A CN201811523007 A CN 201811523007A CN 109627673 A CN109627673 A CN 109627673A
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CN
China
Prior art keywords
composite material
printing
abs
bismuth oxide
high radiation
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CN201811523007.6A
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Chinese (zh)
Inventor
胡静
杜相
胡忠
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Changzhou University
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Changzhou University
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Priority to CN201811523007.6A priority Critical patent/CN109627673A/en
Publication of CN109627673A publication Critical patent/CN109627673A/en
Pending legal-status Critical Current

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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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/30—Auxiliary operations or equipment
    • B29C64/386—Data acquisition or data processing for additive manufacturing
    • B29C64/393—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)

Abstract

The invention belongs to medical field of new materials, and in particular to a kind of high radiation preventing 3D printing composite material and preparation method.First using after acetone solution ABS particle, bismuth oxide powder is added, stirring mixes them thoroughly, and obtains mixture；Then mixture is put into curer and is heated to 100 DEG C acetone is made quickly to volatilize, while mixture solidifies, then is smashed solid mixt for graininess with pulverizer；Granular mixture is finally added to single screw rod filament extruder, obtains filament after squeezing out wire drawing, is used for 3D printing.New synthetic material has been made with ABS particle and bismuth oxide for the method for the present invention.The material inherits the characteristic that ABS is easy to print, while radiation resistance is significantly better than pure ABS material.

Description

A kind of high radiation preventing 3D printing composite material and preparation method
Technical field
The invention belongs to medical field of new materials, and in particular to a kind of high radiation preventing 3D printing composite material and its preparation side Method.
Background technique
In medical instruments field, X-ray is widely used in diagnosing and treating.However the radioactivity such as X-ray, gamma-rays are penetrated Line is classified as carcinogenic substance by international cancer research institute, the World Health Organization.The work clothes for being commonly used to protection X-ray now also only limits In safety devices such as apron,leads, this kind of leaded protective garment is not only heavy but also has toxicity, thus develop it is a kind of more it is light more The alternative materials of safety are imperative.
Existing 3D printing composite material type is relatively simple and more demanding to printing technology, and print temperature is not easy really It is fixed, while easily there is a phenomenon where blocking spouts in print procedure for many composite materials containing metal or other compositions, cause There is the phenomenon that bending or surface generation aperture out-of-flatness in printed product.
Summary of the invention
The present invention makes protective garment using a kind of novel synthetic material, substitutes traditional lead protective garment, reaches convenience and safety And the resultant effect that shielding property is excellent.
Realize the technical scheme is that
(1) using ABS particle and Bismuth oxide (bismuth oxide) powder as raw material；
(2) after using specific lytic agent dissolution ABS particle, bismuth oxide powder is added, stirring is mixed them thoroughly, mixed Close object；
It is 5:1 that the present invention, which dissolves ABS, acetone and ABS according to the ratio of mass ratio using Acetone (acetone),.ABS is molten Bismuth Oxide powder is added after solution can allow the two to be more fully mixed, and available mixing is filled in following process The filament divided；Acetone is to compare its cheaper with other organic solvents as the advantage of solvent, smaller containing toxicity.
Match by the 15%-25% that the dosage of Bismuth oxide is ABS and Bismuth oxide composite material gross mass 3D printing material processed；
(3) mixture is put into curer and is heated to 100 DEG C acetone is made quickly to volatilize, while mixture solidifies, then Solid mixt is smashed as graininess with pulverizer, is prepared for following extrusion；
(4) granular mixture is added to single screw rod filament extruder, obtains the lamp for being used for 3D printing after squeezing out wire drawing Silk, i.e. 3D printing composite material；
High radiation preventing 3D printing composite material made from the method for the present invention is used for 3D printing material, in particular for 3D printing High radiation preventing protective garment.
Using XYZprinting, the printer of Inc. production prints 3D material.The parameter of printer is as follows:
Printer model: DaVinci XYZ；Jet size: 0.4mm；Filament diameter: 1.65-1.80mm；Layer is high: 0.2mm；Edge thickness: 4.0mm；Packed density: 100%；Mode: 45 °；Print temperature: 230 DEG C；Bed temperature: 110 DEG C；Printing speed Degree: 50mm/sec.
The 3D materials'use X-ray of printing carries out anti-radiation test to it.
After adopting the above technical scheme, the present invention has following good effect:
New synthetic material has been made with ABS particle and metal powder Bismuth oxide in the method for the present invention.The material after The characteristic that ABS is easy to print is held, while radiation resistance is significantly better than pure ABS material.
In order that the present invention can be more clearly and readily understood, right below according to specific embodiment and in conjunction with attached drawing The present invention is described in further detail.
Detailed description of the invention
Fig. 1 is the pure ABS sample for being all 1mm thickness and the Oxide particulate composite containing 15%, 20% and 25%Bismuth Picture of the sample under X-ray；(it is followed successively by pure ABS, 15%Bismuth Oxide, 20%Bismuth Oxide from left to right, 25%Bismuth Oxide)
Fig. 2 is the composite material micrograph (scale: 20 μm) of the powder of Oxide containing 20%Bismuth；
Fig. 3 is the crosssection micrographs (scale: 250 μm) of the particulate composite of Oxide containing 20%Bismuth filament；
Fig. 4 is the composite material micrograph (scale: 30 μm) of the powder of Oxide containing 15%Bismuth；
Fig. 5 is the crosssection micrographs (scale: 250 μm) of the particulate composite of Oxide containing 15%Bismuth filament；
Fig. 6 is the composite material micrograph (scale: 15 μm) of the powder of Oxide containing 25%Bismuth；
Fig. 7 is the crosssection micrographs (scale: 200 μm) of the particulate composite of Oxide containing 25%Bismuth filament；
Fig. 8 is the LEXI sample Average Grey containing pure ABS, 15%, 20% and 25%Bismuth Oxide powder Value and thickness relationship figure (LEXI represents composite material)；
Fig. 9 is pure ABS, the LEXI sample of the Oxide powder containing 15%, 20% and 25%Bismuth shields X-ray effect With the relational graph of thickness of sample.
Specific embodiment
Embodiment 1
Novel synthetic material for radiation protection.The following steps are included:
(1) weighing obtains the ABS particle of 80g and the Bismuth Oxide powder of 20g respectively.Use 400g Acetone Solvent dissolves ABS particle, is sufficiently stirred at normal temperature, and one evening of standing obtains the ABS&Acetone solution of fruit juice shape.Weighted Bismuth Oxide powder be added in the solution, first be sufficiently stirred manually, reuse jarring machine vibration 2h.Being filled Divide mixed mixed solution to pour into 30cm × 20cm × 3cm size plate, is then placed in heating in curer and bakes an evening.
(2) it after the mixture after drying being resolved into particle with pulverizer, is added in filament extruder and is squeezed into filament (directly Diameter 1.65mm-1.80mm), the Rear temperature for making extruder during filament is 190 DEG C, and nozzle temperature is 210 DEG C, and PSI is 273。
(3) sample is printed according to designed instance model (circle of diameter 5CM different-thickness) with 3D printer.
(4) figure is obtained with X-ray (source Xray: Feinfocus FXE, voltage: 160KV, electric current: 120 μ A) irradiating sample Piece.
Fig. 1 is the pure ABS sample and new synthetic material sample picture under X-ray simultaneously for being all 1mm thickness；It can by figure It is improved (in sample pictures more with the apparent radiation resistance for seeing sample made of the file printing synthesized by new material Black representative stops amount of radiation more).Fig. 2 is the composite material of the powder of Oxide containing 20%Bismuth in digital The microscope figure (scale: 20 μm) of new synthetic material under microscope；Fig. 3 is answering for the powder of Oxide containing 20%Bismuth The cross sectional microscopy figure (scale: 250 μm) of condensation material new synthetic material filament at digital microscope；From Fig. 2,3 It can be seen that, oxide yellow bismuth is evenly distributed in the sample printed under the proportion, the phenomenon that accumulation aggregation does not occur.
Fig. 8 is the Average Grey Value obtained after software MATLAB is to the sample pictures analysis under X-ray (AGV) with the figure of thickness；(LEXI is new synthetic) AGV is average grayness, the lower anti-radiation effect of expression sample of value Better.Fig. 9 is the shielding X-ray percentage of pure ABS and LEXI and the relational graph of thickness of sample.By calculate analysis it can be concluded that The radiation resistance of new material is excellent.
Embodiment 2
(1) weighing obtains the ABS particle of 85g and the Bismuth Oxide powder of 15g respectively.Use 425g Acetone Solvent dissolves ABS particle, is sufficiently stirred at normal temperature, and one evening of standing obtains the ABS&Acetone solution of fruit juice shape.Weighted Bismuth Oxide powder be added in the solution, first be sufficiently stirred manually, reuse jarring machine vibration 2h.Being filled Divide mixed mixed solution to pour into 30cm × 20cm × 3cm size plate, is then placed in heating in curer and bakes an evening.
(2) it after the mixture after drying being resolved into particle with pulverizer, is added in filament extruder and is squeezed into filament (directly Diameter 1.65mm-1.80mm), the Rear temperature for making extruder during filament is 190 DEG C, and nozzle temperature is 210 DEG C, and PSI is 198。
(3) sample is printed according to designed instance model (circle of diameter 5CM different-thickness) with 3D printer.
(4) figure is obtained with X-ray (source Xray: Feinfocus FXE, voltage: 160KV, electric current: 120 μ A) irradiating sample Piece.
Fig. 4 is that the composite material of the powder of Oxide containing 15%Bismuth newly synthesizes material at digital microscope The microscope figure (scale: 20 μm) of material；Fig. 5 is the composite material of the powder of Oxide containing 15%Bismuth in digital The cross sectional microscopy figure (scale: 250 μm) of new synthetic material filament under microscope；It can be seen that from Fig. 4,5, the proportion is lower to beat Oxide yellow bismuth is also evenly distributed in the sample printed off, the phenomenon that accumulation aggregation does not occur.
Embodiment 3
(1) weighing obtains the ABS particle of 75g and the Bismuth Oxide powder of 25g respectively.It is molten using 375gAcetone ABS particle is dissolved in agent, is sufficiently stirred at normal temperature, and one evening of standing obtains the ABS&Acetone solution of fruit juice shape.Weighted Bismuth Oxide powder is added in the solution, is first sufficiently stirred manually, and jarring machine vibration 2h is reused.It is abundant obtaining Mixed mixed solution pours into 30cm × 20cm × 3cm size plate, is then placed in heating in curer and bakes an evening.
(2) it after the mixture after drying being resolved into particle with pulverizer, is added in filament extruder and is squeezed into filament (directly Diameter 1.65mm-1.80mm), the Rear temperature for making extruder during filament is 190 DEG C, and nozzle temperature is 210 DEG C, and PSI is 273。
(3) sample is printed according to designed instance model (circle of diameter 5CM different-thickness) with 3D printer.
(4) figure is obtained with X-ray (source Xray: Feinfocus FXE, voltage: 160KV, electric current: 120 μ A) irradiating sample Piece.
Fig. 6 is that the composite material of the powder of Oxide containing 25%Bismuth newly synthesizes material at digital microscope The microscope figure (scale: 20 μm) of material；Fig. 7 is the composite material of the powder of Oxide containing 25%Bismuth in digital The cross sectional microscopy figure (scale: 250 μm) of new synthetic material filament under microscope；It can be seen that from Fig. 6,7, the proportion is lower to beat Oxide yellow bismuth is equally evenly distributed in the sample printed off, the phenomenon that accumulation aggregation does not occur.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one The widest scope of cause.

Claims (6)

1. a kind of high radiation preventing 3D printing composite material, it is characterised in that: the composite material is by ABS particle and bismuth oxide powder It is prepared.
2. a kind of preparation method of high radiation preventing 3D printing composite material as described in claim 1, it is characterised in that: the system Steps are as follows for Preparation Method:
(1) ABS particle and bismuth oxide powder are weighed as raw material；
(2) using after acetone solution ABS particle, bismuth oxide powder is added, stirring mixes them thoroughly, and obtains mixture；
(3) mixture that step (2) obtains is put into curer and is heated to 100 DEG C acetone is made quickly to volatilize, while mixture Solidification, is then smashed solid mixt for graininess with pulverizer；
(4) granular mixture that step (3) crush is added to single screw rod filament extruder, squeezes out wire drawing acquisition and is beaten for 3D The filament of print, i.e. 3D printing composite material.
3. the preparation method of high radiation preventing 3D printing composite material as claimed in claim 2, it is characterised in that: step (2) institute The mass ratio for stating acetone and ABS is 5:1；The dosage of the bismuth oxide is the 15%- of ABS particle and bismuth oxide powder gross mass 25%.
4. a kind of application of high radiation preventing 3D printing composite material as described in claim 1, it is characterised in that: the composite wood Material is used for 3D printing.
5. the application of high radiation preventing 3D printing composite material as claimed in claim 4, it is characterised in that: use The filament of 3D printing obtained is used to print 3D material by the printer of XYZprinting, Inc. production.
6. the application of high radiation preventing 3D printing composite material as claimed in claim 5, it is characterised in that: the ginseng of the printer Number is as follows:
Jet size: 0.4mm；Filament diameter: 1.65-1.80mm；Layer is high: 0.2mm；Edge thickness: 4.0mm；Packed density: 100%；Mode: 45 °；Print temperature: 230 DEG C；Bed temperature: 110 DEG C；Print speed: 50mm/sec.
CN201811523007.6A 2018-12-13 2018-12-13 A kind of high radiation preventing 3D printing composite material and preparation method Pending CN109627673A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104163634A (en) * 2014-07-02 2014-11-26 中国电子科技集团公司第五十五研究所 A thermoplastic material used for three-dimensional printing and an application method thereof
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
CN107531935A (en) * 2015-07-23 2018-01-02 惠普发展公司，有限责任合伙企业 Three-dimensional (3D) printing structure material compositions
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
CN107955315A (en) * 2016-10-14 2018-04-24 中广核工程有限公司 A kind of 3D printing shielding material
CN108164736A (en) * 2017-11-30 2018-06-15 中国科学院兰州化学物理研究所 A kind of preparation method of the hollow hydrogel structure body of high intensity three-dimensional
CN108912585A (en) * 2018-06-29 2018-11-30 三叠打印线材有限公司 FDM3D printing new A BS material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104163634A (en) * 2014-07-02 2014-11-26 中国电子科技集团公司第五十五研究所 A thermoplastic material used for three-dimensional printing and an application method thereof
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
CN107531935A (en) * 2015-07-23 2018-01-02 惠普发展公司，有限责任合伙企业 Three-dimensional (3D) printing structure material compositions
CN107955315A (en) * 2016-10-14 2018-04-24 中广核工程有限公司 A kind of 3D printing 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
CN108164736A (en) * 2017-11-30 2018-06-15 中国科学院兰州化学物理研究所 A kind of preparation method of the hollow hydrogel structure body of high intensity three-dimensional
CN108912585A (en) * 2018-06-29 2018-11-30 三叠打印线材有限公司 FDM3D printing new A BS material and preparation method thereof

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