CN106317787A - High-temperature-resistant epoxy resin-based neutron and gamma-ray shielding composite material and preparation method thereof - Google Patents
High-temperature-resistant epoxy resin-based neutron and gamma-ray shielding composite material and preparation method thereof Download PDFInfo
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- CN106317787A CN106317787A CN201610819750.0A CN201610819750A CN106317787A CN 106317787 A CN106317787 A CN 106317787A CN 201610819750 A CN201610819750 A CN 201610819750A CN 106317787 A CN106317787 A CN 106317787A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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- 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
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
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- 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
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/22—Component parts, details or accessories; Auxiliary operations
- B29C39/44—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
- G21F1/10—Organic substances; Dispersions in organic carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- General Engineering & Computer Science (AREA)
- High Energy & Nuclear Physics (AREA)
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Abstract
The invention provides a high-temperature-resistant epoxy resin-based neutron and gamma-ray shielding composite material and a preparation method thereof. The high-temperature-resistant epoxy resin-based neutron and gamma-ray shielding composite material is prepared from, by weight, 50-100 parts of epoxy resin, 10-100 parts of curing agent, 100-800 parts of radiation-resistant functional auxiliary, 5-100 parts of fiber reinforced material, 10-150 parts of flame retardant functional filler and 1-50 parts of processing aid. The high-temperature-resistant epoxy resin-based neutron and gamma-ray shielding composite material has excellent neutron and gamma-ray shielding performance, dimensional stability and flame retardation and keeps stable neutron and gamma-ray shielding performance when working within 120-200 DEG C for a long time.
Description
Technical field
The present invention relates to a kind of high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite and preparation thereof, belong to core
Factors for radiation shielding technical field.
Background technology
In the world, nuclear power industry development is swift and violent, and nuclear power station, the radiation safety of nuclear reactor and protection question are also
More and more important.When utilizing nuclear energy, be both needed to neutron irradiation is carried out effective shielding protection, according to the different-energy of neutron or
Slowing down or absorption, the most also need effectively to protect secondary gamma-rays.
At present, the radiation shielding material that the place such as nuclear reactor, nuclear fuel factory uses mostly is with polyethylene, paraffin, weight
The composite that concrete and aluminium boride etc. are base material, the most the most widely used is loaded concrete and polyvinyl composite wood
Material.Due to its Boron contents or protium content height, there is excellent radiation shield performance, but polyvinyl shielding composite wood
Thermostability and the anti-flammability of material are poor, and linear expansion coefficient is relatively big, poor dimensional stability.Multiple to shielding in order to meet different occasion
The lifting that the technology of condensation material requires, develops one and can stablize effectively protection neutron and gamma-rays screen at relatively high temperatures
Cover composite the most necessary.
Summary of the invention
In order to solve above-mentioned shortcoming and defect, it is an object of the invention to provide a kind of high-temperature-resistant epoxy resin base neutron
With gamma ray shielding composite.
The present invention also aims to provide above-mentioned high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite
Preparation method.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of high-temperature-resistant epoxy resin base neutron and gamma-rays screen
Covering composite, it is prepared by weight by following components:
Epoxy resin 50-100 part；
Firming agent 10-100 part；
Radiation proof function auxiliary agent 100-800 part；
Fibre reinforced materials 5-100 part；
Anti-flaming function filler 10-150 part；
Processing aid 1-50 part.
According to shielding composite of the present invention, it is preferable that described epoxy resin include bisphenol A type epoxy resin,
The combination of one or more in bisphenol-A epoxy resin, novolac epoxy resin and hydrogenation novolac epoxy resin.
According to shielding composite of the present invention, it is preferable that described firming agent includes polyamide, diaminourea two
Benzene sulfone, MDA, diethylenetriamine, polyethylene polyamine, cyclohexylamine, m-diaminobenzene., different Fu Er ketone diamidogen, methyl four
The combination of one or more in hydrogen phthalic anhydride and pyromellitic acid anhydride.
According to shielding composite of the present invention, it is preferable that described radiation proof function auxiliary agent includes boron powder, carbonization
The combination of one or more in boron, boronation gadolinium, boron oxide, boron nitride, boric anhydride, lithium, gadolinium, tungsten, lead, copper, ferrum and compound thereof.
According to shielding composite of the present invention, it is preferable that described fibre reinforced materials includes that glass fibre, boron are fine
The combination of one or more in dimension, aramid fiber and carbon fiber.
According to shielding composite of the present invention, it is preferable that described anti-flaming function filler includes Firebrake ZB, hydroxide
The combination of one or more in magnesium and aluminium hydroxide.
According to shielding composite of the present invention, it is preferable that described processing aid includes coupling agent, accelerator, increasing
The combination of one or more in tough dose and diluent.
According to shielding composite of the present invention, coupling agent used is the conventional substances that this area uses, at this
In invention detailed description of the invention, described coupling agent includes the combination of one or more in KH-550, KH-560 and D-90.
According to shielding composite of the present invention, accelerator used is the conventional substances that this area uses, at this
In invention detailed description of the invention, described accelerator include the one in Tertiary amine accelerators, Imidizole accelerator and anhydride accelerator or
Several combinations.
According to shielding composite of the present invention, toughener used is the conventional substances that this area uses, at this
In invention detailed description of the invention, described toughener includes Polyetherimide, polyether sulfone, polyether-ether-ketone, end carboxyl nitrile (HTBN) rubber
The combination of one or more in glue, hydroxyl terminated butyl nitrile (HTBN) rubber and amino terminated liquid nitrile rubber.
According to shielding composite of the present invention, diluent used is the conventional substances that this area uses, at this
In invention detailed description of the invention, described diluent includes phenyl glycidyl ether, benzyl glycidyl ether, polypropylene glycol two shrink
The combination of one or more in glycerin ether, polyethyleneglycol diglycidylether and C12-14 alkyl glycidyl ether.
Tertiary amine accelerators, Imidizole accelerator and anhydride accelerator used by the present invention is the conventional substances of this area, this
Skilled person can need to select properly from Tertiary amine accelerators, Imidizole accelerator and anhydride accelerator according to field operation
Concrete material, as long as can the object of the invention.
According to composite of the present invention, wherein, the present invention is to coupling agent, accelerator, toughener and diluent
Concrete consumption is not required, as long as ensureing that the consumption of the processing aid that the present invention added is in the range of 1-50 part.
According to shielding composite of the present invention, it is preferable that when described firming agent is powder body, this shielding composite wood
Material is prepared by weight by following components:
Epoxy resin 50-100 part；
Firming agent 10-100 part；
Radiation proof function auxiliary agent 100-800 part；
Fibre reinforced materials 5-100 part；
Anti-flaming function filler 10-150 part；
Processing aid 1-50 part；
Solvent 50-400 part；
It is highly preferred that described solvent includes acetone or dehydrated alcohol.
According to shielding composite of the present invention, it is preferable that the density of this shielding composite is 1.5-5.0g/
cm3, thermal coefficient of expansion is 10 × 10-6 ℃-1-30×10-6 ℃-1, fire resistance is UL94V-0 level, and its tolerance 120-200
DEG C high temperature.
The invention provides a kind of high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite, it is by following group
Point prepare by weight:
Epoxy resin 50-100 part；
Firming agent 10-100 part；
Radiation proof function auxiliary agent 100-800 part；
Fibre reinforced materials 5-100 part；
Anti-flaming function filler 10-150 part；
Processing aid 1-50 part；
Wherein, this high-temperature-resistant epoxy resin base neutron and preparation method of gamma ray shielding composite, it includes following
Step:
(1) when described firming agent is powder body: be dissolved in solvent by this firming agent, the solution of firming agent is obtained, then to this
Being slowly added to epoxy resin in the solution of firming agent, 55-75 DEG C carries out pre-reaction 4-6h, obtains pre-polymerization liquid；
Or, this firming agent is slowly added in epoxy resin, is warming up to 70-180 DEG C, carry out pre-reaction 0.5-2h, make
It melts and is dispersed in epoxy resin, obtains pre-polymerization liquid；
When described firming agent is liquid: this firming agent is added in epoxy resin, obtains mixed liquor；
(2) be sequentially added into processing aid again in described pre-polymerization liquid or mixed liquor, radiation proof function auxiliary agent, anti-flaming function are filled out
Material and fibre reinforced materials, stir, and vacuum defoamation obtains composite glue solution；
(3) described composite glue solution is filled up warmed-up mould carries out curing molding, after solidification terminates, be cooled to room
Temperature, stripping forming, obtain described high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite.
On the other hand, present invention also offers above-mentioned high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite
Preparation method, it comprises the following steps:
(1) when described firming agent is powder body: be dissolved in solvent by this firming agent, the solution of firming agent is obtained, then to this
Being slowly added to epoxy resin in the solution of firming agent, 55-75 DEG C carries out pre-reaction 4-6h, obtains pre-polymerization liquid；
Or, this firming agent is slowly added in epoxy resin, is warming up to 70-180 DEG C, carry out pre-reaction 0.5-2h, make
It melts and is dispersed in epoxy resin, obtains pre-polymerization liquid；
When described firming agent is liquid: this firming agent is added in epoxy resin, obtains mixed liquor；
(2) be sequentially added into processing aid again in described pre-polymerization liquid or mixed liquor, radiation proof function auxiliary agent, anti-flaming function are filled out
Material and fibre reinforced materials, stir, and vacuum defoamation obtains composite glue solution；
(3) described composite glue solution is filled up warmed-up mould carries out curing molding, after solidification terminates, be cooled to room
Temperature, stripping forming, obtain described high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite.
According to preparation method of the present invention, in step (1), solvent for use includes acetone or dehydrated alcohol, and its consumption is
50-400 weight portion.
According to preparation method of the present invention, it is preferable that mould warmed-up described in step (3) is for being preheated to 30-
The mould of 150 DEG C.
According to preparation method of the present invention, it is preferable that described in step (3), curing molding includes grasping in detail below
Make: first composite glue solution is solidified 1-4h, pressurize 0-3MPa in 70-150 DEG C, then with the heating rate liter of 1-10 DEG C/min
Temperature, then at 120-160 DEG C of solidification 1-3h, pressurize 0-15MPa, heats up with the heating rate of 1-10 DEG C/min subsequently, finally in
160-200 DEG C of solidification 1-3h, pressurize 0-25MPa；
Or, described in step (4), curing molding includes operating in detail below: cast described composite glue solution to mould
In, in temperature 20-80 DEG C, pressure < solidifies 2-7 days under conditions of 0.1MPa.
According to preparation method of the present invention, the curing mold used by the present invention is the conventional equipment that this area uses,
This equipment is not made specific requirement by the present invention, and those skilled in the art can need to select suitable curing mold to enter according to operation
Row curing molding, as long as guaranteeing to realize the object of the invention.
Compared with prior art, the invention has the beneficial effects as follows:
High-temperature-resistant epoxy resin base neutron provided by the present invention and gamma ray shielding composite not only have good
Neutron and gamma ray shielding performance, and fire resistance, heat resistance, dimensional stability are excellent, can be widely used for accelerator,
Isotope neutron source, the radiation protection of radioprotective laboratory, spentnuclear fuel storage tank, the radiation protection of nuclear reactor.
The preparation technology of high-temperature-resistant epoxy resin base neutron provided by the present invention and gamma ray shielding composite is easy to
Construction, density adjustable range is extensive, it is adaptable to the site operation requirement of airtight casting occasion.
Additionally, this high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite contain higher protium content,
Boron compound, heavy metal element, fire retardant and fibre reinforced materials so that it is there is good thermostability and dimensional stability, energy
Enough stable protection neutron and gamma-rays effectively.
Accompanying drawing explanation
High temperature resistance phenolic aldehyde epoxy resin-matrix neutron that Fig. 1 provides for the embodiment of the present invention 1 and gamma ray shielding composite
Preparation method process chart；
High temperature resistant bisphenol A type epoxy resin base neutron that Fig. 2 provides for the embodiment of the present invention 2 and gamma ray shielding composite wood
Preparation method for material process chart.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, in conjunction with in detail below
Technical scheme is carried out described further below by embodiment and Figure of description, but it is not intended that to the present invention's
Can the restriction of practical range.
Experimental technique described in following embodiment, if no special instructions, is conventional method；Described number is said the most especially
Bright is mass fraction.
Embodiment 1
Present embodiments provide a kind of high temperature resistance phenolic aldehyde epoxy resin-matrix neutron and gamma ray shielding composite preparation side
Method, its process chart is as it is shown in figure 1, from figure 1 it appears that this preparation method includes step in detail below；
(1) this shielding composite is prepared by weight by following components (as shown in table 1):
Table 1
| Material name | Mass fraction | Production firm |
| Novolac epoxy resin F44 | 80 parts | Jinan Yi Sheng resin company limited |
| Pyromellitic acid anhydride | 20 parts | Langfang City Bei De commerce and trade company limited |
| Acetone | 60 parts | Beijing Chemical Plant |
| Boron carbide | 33 parts | The Bohai Sea, Ningan City boron carbide company limited |
| Tungsten powder | 140 parts | Beijing friend is emerging is associated with non-ferrous metal company limited |
| Magnesium hydroxide | 100 parts | Weifang Hai Lilong Mei Ye company limited |
| Glass fibre | 40 parts | High mountain, pavilion, Dingxing County science and technology green wood company limited |
| KH-550 | 2 parts | Nanjing Chuan Shi auxiliary chemicals company limited |
| Nbr carboxyl terminal | 15 parts | Zibo Qilong Chemical Industry Co., Ltd. |
(2) first pyromellitic acid anhydride is dissolved in acetone, obtains the acetone soln of pyromellitic acid anhydride；With backward
The acetone soln of this pyromellitic acid anhydride is slowly added to novolac epoxy resin, carries out pre-reaction 6h in 70 DEG C, obtain pre-polymerization
Liquid；
(3) in described pre-polymerization liquid, it is sequentially added into KH-550, nbr carboxyl terminal, boron carbide, tungsten powder, hydroxide again
Magnesium, glass fibre, stir, evacuation de-bubbled, except solvent, obtains composite glue solution；
(4) it is cast to above-mentioned composite glue solution be pre-heated in the mould of 100 DEG C, according to 100 DEG C of insulation 1h, pressurize
3MPa, heats up with 2 DEG C/min subsequently, 150 DEG C of insulations 2h, pressurize 10MPa, and 180 DEG C of insulations 2h, pressurize 15MPa are solidified into
Type, after solidification terminates, is cooled to room temperature, stripping forming, obtains described high temperature resistance phenolic aldehyde epoxy resin-matrix neutron and gamma-rays screen
Cover composite.
Embodiment 2
Present embodiments provide a kind of high temperature resistant bisphenol A type epoxy resin base neutron and be prepared by gamma ray shielding composite
Method, its process chart is as in figure 2 it is shown, from figure 2 it can be seen that this preparation method comprises the following steps；
(1) this shielding composite is prepared by weight by following components (as shown in table 2):
Table 2
(2) first polyamide 6 50 is slowly added in bisphenol A type epoxy resin E51, is uniformly mixing to obtain mixed liquor.Mixed
Close in liquid and be sequentially added into benzyl glycidyl ether, phenol, amino terminated liquid nitrile rubber, boron oxide, tungsten powder, magnesium hydroxide, glass
Glass fiber, stirs, and vacuum defoamation obtains composite glue solution；
(3) above-mentioned composite glue solution is cast in mould, is incubated 80 DEG C, 2h, vacuum < 0.03MPa, after curing molding,
Being cooled to room temperature, the demoulding obtains described epoxy resin-matrix neutron and gamma ray shielding composite.
Test case
1, density
According to GBT 1033.1-2008 " mensuration of the non-foam plastic density of plastics " part 1 infusion process, liquid specific gravity bottle
The density of each sample during the infusion process of regulation measures embodiment 1-2 in method and titrimetry.Density result see table shown in 3.
Table 3
| Shielding material in the present invention | Density (g/cm3) |
| Embodiment 1 | 2.65 |
| Embodiment 2 | 2.00 |
2, hot expansibility:
Each enforcement is measured according to the method for regulation in GBT 4339-2008 " mensuration of metal material thermal expansion characteristics parameter "
The average coefficient of linear expansion of sample prepared by example.The results are shown in Table shown in 4 of average coefficient of linear expansion.
Table 4
As can be seen from Table 4, the average coefficient of linear expansion of this shielding composite that embodiment 1-2 prepares is little
In 20 × 10-6℃-1, show that high-temperature-resistant epoxy resin base neutron provided by the present invention and gamma ray shielding composite have
Good dimensional stability.
3, neutron shield performance:
Select252Cf neutron source is tested, and average neutron energy is 2.13MeV, moderating sphere and He-3Proportional counter group
Become neutron detector, according to neutron through the neutron counting before and after shielding composite prepared in embodiment 1, calculate this
The shielding composite shielding rate to neutron.The results are shown in Table shown in 5.
Table 5
As can be seen from Table 5, thickness is during the shielding composite sample that this embodiment 1 of 2cm prepares can make
Component252Fast neutron (1MeV) shielding rate of Cf (2.13MeV) is 57%, and the shielding rate of intermediate neutron (1-100keV) is 66%,
The shielding rate of slow neutron (1eV) is 79%, shows high-temperature-resistant epoxy resin base neutron and gamma-rays screen that the present invention prepares
Cover composite and there is good neutron shield performance.
4, gamma ray shielding performance:
Select60Co gamma ray radiator, its average energy is 1.25MeV, tests γ dosage with PTW type spheric (ionization) chamber, according to
Gamma-rays, through the dosage before and after the 2cm thickness shielding composite of preparation in embodiment 1-2, calculates this shielding composite
To gamma-ray shielding rate.The results are shown in Table shown in 6.
Table 6
| Shielding material in the present invention | Gamma-rays absorbance (%) |
| Embodiment 1 | 28.6 |
| Embodiment 2 | 24.2 |
As can be seen from Table 6, this shielding composite sample that thickness is the embodiment 1 of 2cm and embodiment 2 prepares
Product gamma-rays (60Co) shielding rate can reach 28.6% and 24.2% respectively, and the high-temperature resistant epoxy that the present invention prepares is described
Epoxy resin-based neutron and gamma ray shielding composite have good gamma ray shielding performance.
5, fire resistance:
Measure according to the method for regulation in GB/T 2408-2008 " mensuration-Horizontal Bridgman Method of Plastics Combustion performance and normal beam technique "
The vertical combustion performance of 3mm sample prepared by each embodiment, the results are shown in Table shown in 7.
Table 7
| Shielding material in the present invention | UL grade |
| Embodiment 1 | V-0 |
| Embodiment 2 | V-0 |
As can be seen from Table 7, the fire resistance of the shielding composite that embodiment of the present invention 1-2 prepares is the most permissible
Reach UL94V-0 level, this high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite that the present invention prepares are described
There is good fire resistance.
6, heat resistance:
Each reality is measured according to the method for regulation in GB/T 7142-2002 " the Time-temperature limit after plastics prolonged heat exposure "
Execute the thermal index (TI) of the sample that example prepares, the results are shown in Table shown in 8.
Table 8
| Shielding material in the present invention | TI(℃) |
| Embodiment 1 | 150 |
| Embodiment 2 | 120 |
As can be seen from Table 8, this epoxy resin-matrix neutron and gamma ray shielding that embodiment of the present invention 1-2 prepares
Composite has good resistance to elevated temperatures.Therefore, this shielding composite that the present invention prepares can be in hot environment
Lower use as radiation protection material.
As above the content being explained in detail, high-temperature-resistant epoxy resin base neutron provided by the present invention and gamma ray shielding are multiple
Condensation material, owing to it contains the higher matrix material of thermostability, boron compound, heavy metal element, fire retardant and fiber reinforcement material
Material, so, it is suitable for shielding neutron and gamma-rays, and has good dimensional stability and fire resistance.
Above the specific embodiment of the present invention is described, for understanding the technical characteristic of the present invention, purpose and having
Benefit effect.The invention is not limited in above-mentioned embodiment, those skilled in the art can make within the scope of the claims
Various deformation or improvement, this has no effect on the flesh and blood of the present invention.
Claims (10)
1. high-temperature-resistant epoxy resin base neutron and a gamma ray shielding composite, it is to be prepared by weight by following components
Obtain:
Epoxy resin 50-100 part；
Firming agent 10-100 part；
Radiation proof function auxiliary agent 100-800 part；
Fibre reinforced materials 5-100 part；
Anti-flaming function filler 10-150 part；
Processing aid 1-50 part.
Shielding composite the most according to claim 1, it is characterised in that described epoxy resin includes bisphenol type epoxy
The combination of one or more in resin, bisphenol-A epoxy resin, novolac epoxy resin and hydrogenation novolac epoxy resin.
Shielding composite the most according to claim 1, it is characterised in that described firming agent include polyamide, two
ADP sulfone, MDA, diethylenetriamine, polyethylene polyamine, cyclohexylamine, m-diaminobenzene., different Fu Er ketone diamidogen,
The combination of one or more in methyl tetrahydrophthalic anhydride and pyromellitic acid anhydride.
Shielding composite the most according to claim 1, it is characterised in that described radiation proof function auxiliary agent include boron powder,
One or more in boron carbide, boronation gadolinium, boron oxide, boron nitride, boric anhydride, lithium, gadolinium, tungsten, lead, copper, ferrum and compound thereof
Combination.
Shielding composite the most according to claim 1, it is characterised in that described fibre reinforced materials includes glass fibers
The combination of one or more in dimension, boron fibre, aramid fiber and carbon fiber.
Shielding composite the most according to claim 1, it is characterised in that described anti-flaming function filler include Firebrake ZB,
The combination of one or more in magnesium hydroxide and aluminium hydroxide.
Shielding composite the most according to claim 1, it is characterised in that described processing aid includes coupling agent, promotion
The combination of one or more in agent, toughener and diluent；
Preferably, described coupling agent includes the combination of one or more in KH-550, KH-560 and D-90；
It is further preferred that described accelerator includes one or more in Tertiary amine accelerators, Imidizole accelerator and anhydride accelerator
Combination；
It is further preferred that described toughener includes Polyetherimide, polyether sulfone, polyether-ether-ketone, carboxyl end of the liquid acrylonitrile-butadiene rubber, end hydroxyl
The combination of one or more in base LNBR and amino terminated liquid nitrile rubber；
It is further preferred that described diluent includes phenyl glycidyl ether, benzyl glycidyl ether, polypropylene glycol diglycidyl
The combination of one or more in ether, polyethyleneglycol diglycidylether and C12-14 alkyl glycidyl ether.
8., according to the shielding composite described in right 1, it is characterised in that when described firming agent is powder body, this shielding is combined
Material is prepared by weight by following components:
Epoxy resin 50-100 part；
Firming agent 10-100 part；
Radiation proof function auxiliary agent 100-800 part；
Fibre reinforced materials 5-100 part；
Anti-flaming function filler 10-150 part；
Processing aid 1-50 part；
Solvent 50-400 part；
The most described solvent includes acetone or dehydrated alcohol.
9. according to the shielding composite described in any one of claim 1-8, it is characterised in that the density of this shielding composite
For 1.5-5.0g/cm3, thermal coefficient of expansion is 10 × 10-6℃-1-30×10-6℃-1, fire resistance is UL94V-0 level, and it is resistance to
By the high temperature of 120-200 DEG C.
10. high-temperature-resistant epoxy resin base neutron and the preparation side of gamma ray shielding composite described in any one of claim 1-9
Method, it comprises the following steps:
(1) when described firming agent is powder body: be dissolved in solvent by this firming agent, the solution of firming agent is obtained, then to this solidification
Being slowly added to epoxy resin in the solution of agent, 55-75 DEG C carries out pre-reaction 4-6h, obtains pre-polymerization liquid；
Or, this firming agent is slowly added in epoxy resin, is warming up to 70-180 DEG C, carry out pre-reaction 0.5-2h so that it is be molten
Melt and be dispersed in epoxy resin, obtaining pre-polymerization liquid；
When described firming agent is liquid: this firming agent is added in epoxy resin, obtains mixed liquor；
(2) be sequentially added in described pre-polymerization liquid or mixed liquor again processing aid, radiation proof function auxiliary agent, anti-flaming function filler and
Fibre reinforced materials, stirs, and vacuum defoamation obtains composite glue solution；
(3) described composite glue solution is filled up warmed-up mould carries out curing molding, after solidification terminates, be cooled to room temperature, de-
Mold forming, obtains described high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite；
Preferably, warmed-up described in step (3) mould is to be preheated to the mould of 30-150 DEG C；
It is further preferred that curing molding includes operating in detail below described in step (3): first that composite glue solution is solid in 70-150 DEG C
Change 1-4h, pressurize 0-3MPa, then heat up with the heating rate of 1-10 DEG C/min, then at 120-160 DEG C of solidification 1-3h, pressurize 0-
15MPa, heats up with the heating rate of 1-10 DEG C/min subsequently, finally solidifies 1-3h, pressurize 0-25MPa in 160-200 DEG C；
Or, described in step (4), curing molding includes operating in detail below: described composite glue solution cast to mould, in
Temperature 20-80 DEG C, pressure < solidifies 2-7 days under conditions of 0.1MPa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696316A (en) * | 2009-10-28 | 2010-04-21 | 南京航空航天大学 | Method for preparing radiation protection materials |
| CN103937160A (en) * | 2014-04-04 | 2014-07-23 | 西安交通大学 | Method for preparing nuclear radiation screening material |
| CN104710727A (en) * | 2015-03-27 | 2015-06-17 | 中国科学院长春应用化学研究所 | Epoxy resin based neutron and gamma ray shielding composite material, as well as preparation method and application thereof |
| CN105702308A (en) * | 2014-11-26 | 2016-06-22 | 天津市煜辉机械加工有限公司 | An epoxy resin based radiation protection material |
-
2016
- 2016-09-13 CN CN201610819750.0A patent/CN106317787B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696316A (en) * | 2009-10-28 | 2010-04-21 | 南京航空航天大学 | Method for preparing radiation protection materials |
| CN103937160A (en) * | 2014-04-04 | 2014-07-23 | 西安交通大学 | Method for preparing nuclear radiation screening material |
| CN105702308A (en) * | 2014-11-26 | 2016-06-22 | 天津市煜辉机械加工有限公司 | An epoxy resin based radiation protection material |
| CN104710727A (en) * | 2015-03-27 | 2015-06-17 | 中国科学院长春应用化学研究所 | Epoxy resin based neutron and gamma ray shielding composite material, as well as preparation method and application thereof |
Cited By (25)
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| CN106867200B (en) * | 2017-02-27 | 2018-12-28 | 东北大学 | A kind of gamma ray shielding material and preparation method thereof |
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Address after: 401 gate a, 201, No. a 10 Jiuxianqiao North Road, Chaoyang District, Beijing 100015 Patentee after: Beijing Ray Application Research Center Co.,Ltd. Address before: 401 gate a, 201, No. a 10 Jiuxianqiao North Road, Chaoyang District, Beijing 100015 Patentee before: BEIJING RADIATION APPLICATION RESEARCH CENTER |