CN106317787B - High-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material and its preparation - Google Patents
High-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material and its preparation Download PDFInfo
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- CN106317787B CN106317787B CN201610819750.0A CN201610819750A CN106317787B CN 106317787 B CN106317787 B CN 106317787B CN 201610819750 A CN201610819750 A CN 201610819750A CN 106317787 B CN106317787 B CN 106317787B
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The present invention provides a kind of high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material and preparation method, which is prepared by weight by following components：50 100 parts of epoxy resin；10 100 parts of curing agent；100 800 parts of radiation proof function auxiliary agent；5 100 parts of fibre reinforced materials；10 150 parts of flame retarding function filler；1 50 parts of processing aid.The shielding composite that the present invention is prepared has good neutron and gamma ray shielding performance, dimensional stability and flame retardant property；In addition, the material can the long-term work in 120 200 DEG C of temperature ranges, neutron and gamma ray shielding performance stabilization.
Description
Technical field
The present invention relates to a kind of high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material and its preparations, belong to core
Factors for radiation shielding technical field.
Background technology
In the world, nuclear power industry development is swift and violent, nuclear power station, the radiation safety of nuclear reactor and protection question
It is more and more important.When using nuclear energy, be both needed to carry out effective shielding protection to neutron irradiation, according to the different-energy of neutron or
Slowing down or absorption, while also needing to carry out effective protection to secondary gamma-rays.
Currently, radiation shielding material used in the fields such as nuclear reactor, nuclear fuel factory is mostly with polyethylene, paraffin, again
Concrete and aluminium boride etc. are the composite material of base material, wherein the most widely used is loaded concrete and polyvinyl composite wood
Material.There is excellent radiation shield performance due to its boron content or protium content height, but polyvinyl shields composite wood
The heat resistance and anti-flammability of material are poor, and linear expansion coefficient is larger, poor dimensional stability.It is multiple to shielding in order to meet different occasions
The promotion that the technology of condensation material requires, effective protection neutron and gamma-rays screen can be stablized at relatively high temperatures by developing one kind
It is very necessary to cover composite material.
Invention content
In order to solve above-mentioned disadvantage and deficiency, the purpose of the present invention is to provide a kind of high-temperature-resistant epoxy resin base neutrons
With gamma ray shielding composite material.
The present invention also aims to provide above-mentioned high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material
Preparation method.
In order to achieve the above objectives, on the one hand, the present invention provides a kind of high-temperature-resistant epoxy resin base neutron and gamma-rays screens
Composite material is covered, is prepared by weight by following components：
50-100 parts of epoxy resin；
10-100 parts of curing agent；
100-800 parts of radiation proof function auxiliary agent；
5-100 parts of fibre reinforced materials；
10-150 parts of flame retarding function filler；
1-50 parts of processing aid.
Shielding composite according to the present invention, it is preferable that the epoxy resin include bisphenol A type epoxy resin,
The combination of one or more of bisphenol-A epoxy resin, novolac epoxy resin and hydrogenation novolac epoxy resin.
Shielding composite according to the present invention, it is preferable that the curing agent includes polyamide, diamino two
Benzene sulfone, diaminodiphenylmethane, diethylenetriamine, polyethylene polyamine, cyclohexylamine, m-phenylene diamine (MPD), different Fu Er ketone diamines, methyl four
The combination of one or more of hydrogen phthalic anhydride and pyromellitic acid anhydride.
Shielding composite according to the present invention, it is preferable that the radiation proof function auxiliary agent includes boron powder, carbonization
The combination of one or more of boron, boronation gadolinium, boron oxide, boron nitride, boric anhydride, lithium, gadolinium, tungsten, lead, copper, iron and its compound.
Shielding composite according to the present invention, it is preferable that the fibre reinforced materials includes glass fibre, boron fibre
The combination of one or more of dimension, aramid fiber and carbon fiber.
Shielding composite according to the present invention, it is preferable that the flame retarding function filler includes zinc borate, hydroxide
The combination of one or more of magnesium and aluminium hydroxide.
Shielding composite according to the present invention, it is preferable that the processing aid includes coupling agent, accelerating agent, increasing
The combination of one or more of tough dose and diluent.
Shielding composite according to the present invention, coupling agent used is the conventional substances that this field uses, at this
In invention specific implementation mode, the coupling agent includes the combination of one or more of KH-550, KH-560 and D-90.
Shielding composite according to the present invention, accelerating agent used is the conventional substances that this field uses, at this
In invention specific implementation mode, the accelerating agent include Tertiary amine accelerators, Imidizole accelerator and one kind in acid anhydrides accelerating agent or
Several combinations.
Shielding composite according to the present invention, toughener used is the conventional substances that this field uses, at this
In invention specific implementation mode, the toughener includes polyetherimide, polyether sulfone, polyether-ether-ketone, end carboxyl liquid butyronitrile rubber
The combination of one or more of glue, hydroxyl terminated butyl nitrile (HTBN) rubber and amino terminated liquid nitrile rubber.
Shielding composite according to the present invention, diluent used is the conventional substances that this field uses, at this
In invention specific implementation mode, the diluent includes phenyl glycidyl ether, benzyl glycidyl ether, the shrink of polypropylene glycol two
The combination of one or more of glycerin ether, polyethyleneglycol diglycidylether and C12-14 alkyl glycidyl ethers.
Tertiary amine accelerators, Imidizole accelerator and acid anhydrides accelerating agent used in the present invention are the conventional substances of this field, this
It is suitable that field technology personnel can need to select from Tertiary amine accelerators, Imidizole accelerator and acid anhydrides accelerating agent according to field operation
Specific substance, as long as being capable of the object of the invention.
Composite material according to the present invention, wherein the present invention is to coupling agent, accelerating agent, toughener and diluent
Specific dosage is not required, as long as ensureing the dosage for the processing aid that the present invention is added in 1-50 parts of ranges.
Shielding composite according to the present invention, it is preferable that when the curing agent is powder, the shielding composite wood
Material is prepared by weight by following components：
50-100 parts of epoxy resin；
10-100 parts of curing agent；
100-800 parts of radiation proof function auxiliary agent；
5-100 parts of fibre reinforced materials；
10-150 parts of flame retarding function filler；
1-50 parts of processing aid；
50-400 parts of solvent；
It is highly preferred that the solvent includes acetone or absolute ethyl alcohol.
Shielding composite according to the present invention, it is preferable that the density of the shielding composite is 1.5-5.0g/
cm3, coefficient of thermal expansion is 10 × 10-6 ℃-1-30×10-6 ℃-1, flame retardant property is UL94V-0 grades, and it is resistant to 120-200
DEG C high temperature.
The present invention provides a kind of high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite materials, are by with the following group
It point is prepared by weight：
50-100 parts of epoxy resin；
10-100 parts of curing agent；
100-800 parts of radiation proof function auxiliary agent；
5-100 parts of fibre reinforced materials；
10-150 parts of flame retarding function filler；
1-50 parts of processing aid；
Wherein, the preparation method of the high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material comprising following
Step：
(1) when the curing agent is powder：The curing agent is dissolved in solvent, obtains the solution of curing agent, then to this
Epoxy resin is slowly added in the solution of curing agent, 55-75 DEG C of progress pre-reaction 4-6h obtains pre-polymerization liquid；
Alternatively, the curing agent is slowly added in epoxy resin, it is warming up to 70-180 DEG C, pre-reaction 0.5-2h is carried out, makes
It melts and is dispersed in epoxy resin, obtains pre-polymerization liquid；
When the curing agent is liquid：The curing agent is added in epoxy resin, mixed liquor is obtained；
(2) processing aid, radiation proof function auxiliary agent, flame retarding function is sequentially added into the pre-polymerization liquid or mixed liquor again to fill out
Material and fibre reinforced materials, stir evenly, vacuum defoamation obtains composite glue solution；
(3) composite glue solution is filled up and carries out curing molding in warmed-up mold, after solidification, be cooled to room
Temperature, stripping forming obtain the high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material.
On the other hand, the present invention also provides above-mentioned high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite materials
Preparation method comprising following steps：
(1) when the curing agent is powder：The curing agent is dissolved in solvent, obtains the solution of curing agent, then to this
Epoxy resin is slowly added in the solution of curing agent, 55-75 DEG C of progress pre-reaction 4-6h obtains pre-polymerization liquid；
Alternatively, the curing agent is slowly added in epoxy resin, it is warming up to 70-180 DEG C, pre-reaction 0.5-2h is carried out, makes
It melts and is dispersed in epoxy resin, obtains pre-polymerization liquid；
When the curing agent is liquid：The curing agent is added in epoxy resin, mixed liquor is obtained；
(2) processing aid, radiation proof function auxiliary agent, flame retarding function is sequentially added into the pre-polymerization liquid or mixed liquor again to fill out
Material and fibre reinforced materials, stir evenly, vacuum defoamation obtains composite glue solution；
(3) composite glue solution is filled up and carries out curing molding in warmed-up mold, after solidification, be cooled to room
Temperature, stripping forming obtain the high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material.
Preparation method according to the present invention, solvent for use includes acetone or absolute ethyl alcohol in step (1), and dosage is
50-400 parts by weight.
Preparation method according to the present invention, it is preferable that the mold being preheated described in step (3) is to be preheated to 30-
150 DEG C of mold.
Preparation method according to the present invention, it is preferable that curing molding described in step (3) includes grasping in detail below
Make：Composite glue solution is cured into 1-4h, pressurize 0-3MPa in 70-150 DEG C first, then with the heating rate liter of 1-10 DEG C/min
Temperature, then at 120-160 DEG C solidification 1-3h, pressurize 0-15MPa, then with the heating rate of 1-10 DEG C/min heat up, finally in
160-200 DEG C of solidification 1-3h, pressurize 0-25MPa；
Alternatively, curing molding described in step (4) includes operating in detail below：The composite glue solution is cast to mold
In, in 20-80 DEG C of temperature, pressure<Cure 2-7 days under conditions of 0.1MPa.
Preparation method according to the present invention, the curing mold used in the present invention is the conventional equipment that uses of this field,
The present invention does not make specific requirement to the equipment, those skilled in the art can be needed to select according to operation suitable curing mold into
Row curing molding, as long as it can ensure that realizing the object of the invention.
Compared with prior art, the beneficial effects of the invention are as follows：
High-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material provided by the present invention not only have good
Neutron and gamma ray shielding performance, and flame retardant property, heat resistance, dimensional stability are excellent, can be widely used for accelerator,
Isotope neutron source, the radiation protection in nuclear radiation laboratory, the radiation protection of spentnuclear fuel storage tank, nuclear reactor.
The preparation process of high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material provided by the present invention is convenient for
Construction, density adjustable range is extensive, is suitable for the site operation requirement of closed casting occasion.
In addition, the high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material contain higher protium content,
Boron compound, heavy metal element, fire retardant and fibre reinforced materials make it have good heat resistance and dimensional stability, energy
Enough stablize effectively protects neutron and gamma-rays.
Description of the drawings
Fig. 1 is the high temperature resistance phenolic aldehyde epoxy resin-matrix neutron and gamma ray shielding composite material that the embodiment of the present invention 1 provides
Preparation method process flow chart；
Fig. 2 is the high temperature resistant bisphenol A type epoxy resin base neutron and gamma ray shielding composite wood that the embodiment of the present invention 2 provides
Preparation method for material process flow chart.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, in conjunction in detail below
Embodiment and Figure of description carry out following detailed description to technical scheme of the present invention, but should not be understood as to the present invention's
Can practical range restriction.
Experimental method described in following embodiments is unless otherwise specified conventional method；The number is not said 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 material preparation side
Method, process flow chart is as shown in Figure 1, from figure 1 it appears that the preparation method includes step in detail below；
(1) 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 resins Co., Ltd |
| Pyromellitic acid anhydride | 20 parts | Langfang City Bei De commerce and trade Co., Ltd |
| Acetone | 60 parts | Beijing Chemical Plant |
| Boron carbide | 33 parts | Ningan City Bohai Sea boron carbide Co., Ltd |
| Tungsten powder | 140 parts | Beijing friend is emerging to be associated with non-ferrous metal Co., Ltd |
| Magnesium hydroxide | 100 parts | Weifang Hai Lilong Mei Ye Co., Ltds |
| Glass fibre | 40 parts | Dingxing County pavilion high mountain science and technology green wood Co., Ltd |
| KH-550 | 2 parts | Nanjing Chuan Shi auxiliary chemicals Co., Ltd |
| 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；Then to
It is slowly added to novolac epoxy resin in the acetone soln of the pyromellitic acid anhydride, pre-reaction 6h is carried out in 70 DEG C, obtains pre-polymerization
Liquid；
(3) KH-550, nbr carboxyl terminal, boron carbide, tungsten powder, hydroxide are sequentially added into the pre-polymerization liquid again
Magnesium, glass fibre, stir evenly, and vacuumize de-bubbled, remove solvent, obtain composite glue solution；
(4) above-mentioned composite glue solution is cast to and is pre-heated in 100 DEG C of mold, according to 100 DEG C of heat preservation 1h, pressurize
3MPa is then heated up with 2 DEG C/min, and 150 DEG C of heat preservation 2h, pressurize 10MPa, 180 DEG C keep the temperature 2h, and pressurize 15MPa is solidified into
Type after solidification, is cooled to room temperature, stripping forming, obtains the high temperature resistance phenolic aldehyde epoxy resin-matrix neutron and gamma-rays screen
Cover composite material.
Embodiment 2
It present embodiments provides a kind of high temperature resistant bisphenol A type epoxy resin base neutron and is prepared by gamma ray shielding composite material
Method, process flow chart is as shown in Fig. 2, from figure 2 it can be seen that the preparation method includes the following steps；
(1) 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
It closes in liquid and sequentially adds benzyl glycidyl ether, phenol, amino terminated liquid nitrile rubber, boron oxide, tungsten powder, magnesium hydroxide, glass
Glass fiber, stirs evenly, and vacuum defoamation obtains composite glue solution；
(3) above-mentioned composite glue solution is cast in mold, keeps the temperature 80 DEG C, 2h, vacuum degree<0.03MPa, after curing molding,
It is cooled to room temperature, demoulding obtains the epoxy resin-matrix neutron and gamma ray shielding composite material.
Test case
1, density
According to GBT 1033.1-2008《The measurement of the non-foam plastic density of plastics》Part 1 infusion process, liquid specific gravity bottle
Infusion process specified in method and titration measures the density of each sample in embodiment 1-2.Density result see the table below 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：
According to GBT 4339-2008《The measurement of metal material thermal expansion characteristics parameter》Specified in method measure each implementation
The average linear expansion coefficient of sample prepared by example.Average linear expansion coefficient the results are shown in Table shown in 4.
Table 4
As can be seen from Table 4, the average linear expansion coefficient for the shielding composite that embodiment 1-2 is prepared is little
In 20 × 10-6℃-1, show that high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material provided by the present invention have
Good dimensional stability.
3, neutron shield performance：
It selects252Cf neutron sources are tested, average neutron energy 2.13MeV, moderating sphere and He-3Proportional counter group
At neutron detector, the neutron counting in embodiment 1 before and after prepared shielding composite is passed through according to neutron, this is calculated
Shielding rate of the shielding composite to neutron.It the results are shown in Table shown in 5.
Table 5
As can be seen from Table 5, during the shielding composite sample that the embodiment 1 that thickness is 2cm is prepared 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 is prepared
Covering composite material has good neutron shield performance.
4, gamma ray shielding performance：
It selects60Co gamma ray radiators, average energy 1.25MeV test γ dosage with PTW types spheric (ionization) chamber, according to
Gamma-rays passes through the dosage before and after the 2cm thickness shielding composites prepared in embodiment 1-2, and the shielding composite is calculated
To gamma-ray shielding rate.It the results are shown in Table shown in 6.
Table 6
| Shielding material in the present invention | Gamma-rays absorptivity (%) |
| Embodiment 1 | 28.6 |
| Embodiment 2 | 24.2 |
As can be seen from Table 6, the embodiment 1 that thickness is 2cm and the shielding composite sample that embodiment 2 is prepared
Product gamma-rays (60Co shielding rate) can reach 28.6% and 24.2% respectively, illustrate the high-temperature resistant epoxy that the present invention is prepared
Epoxy resin-based neutron and gamma ray shielding composite material have good gamma ray shielding performance.
5, flame retardant property：
According to GB/T 2408-2008《Measurement-the Horizontal Bridgman Method and normal beam technique of Plastics Combustion performance》Specified in method measure
The vertical combustion performance of 3mm samples prepared by each embodiment, the results are shown in Table shown in 7.
Table 7
| Shielding material in the present invention | UL grades |
| Embodiment 1 | V-0 |
| Embodiment 2 | V-0 |
As can be seen from Table 7, the flame retardant property for the shielding composite that 1-2 of the embodiment of the present invention is prepared can be with
Reach UL94V-0 grades, illustrates the high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material that the present invention is prepared
With good flame retardant property.
6, heat resistance：
According to GB/T 7142-2002《The Time-temperature limit after plastics prolonged heat exposure》Specified in method measure each reality
The humidity index (TI) for applying the sample that example is prepared, 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, epoxy resin-matrix neutron and gamma ray shielding that 1-2 of the embodiment of the present invention is prepared
Composite material has good high temperature resistance.Therefore, the shielding composite that the present invention is prepared can be in hot environment
It is lower to be used 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, since it contains the higher basis material of heat resistance, boron compound, heavy metal element, fire retardant and fiber reinforcement material
Material, so, it is suitable for shielding neutron and gamma-rays, and there is good dimensional stability and flame retardant property.
Specific embodiments of the present invention are described above, for understanding technical characteristic of the invention, purpose and having
Beneficial effect.The invention is not limited in the above embodiment, those skilled in the art can make within the scope of the claims
Various modifications or improvement, this is not affected the essence of the present invention.
Claims (14)
1. a kind of high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material are prepared by weight by following components
It obtains：
50-100 parts of epoxy resin；
10-100 parts of curing agent；
100-800 parts of radiation proof function auxiliary agent；
5-100 parts of fibre reinforced materials；
10-150 parts of flame retarding function filler；
1-50 parts of processing aid；
The epoxy resin includes bisphenol A type epoxy resin, bisphenol-A epoxy resin, novolac epoxy resin and hydrogenation phenol
The combination of one or more of formaldehyde epoxy resin；
The fibre reinforced materials includes the combination of one or more of glass fibre, boron fibre, aramid fiber and carbon fiber；
The flame retarding function filler includes the combination of one or more of zinc borate, magnesium hydroxide and aluminium hydroxide；
The high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material are the preparation method systems by including the following steps
For what is obtained：
(1) when the curing agent is powder：The curing agent is dissolved in solvent, obtains the solution of curing agent, then to the solidification
Epoxy resin is slowly added in the solution of agent, 55-75 DEG C of progress pre-reaction 4-6h obtains pre-polymerization liquid；
Alternatively, the curing agent is slowly added in epoxy resin, it is warming up to 70-180 DEG C, carries out pre-reaction 0.5-2h, keeps it molten
Melt and be dispersed in epoxy resin, obtains pre-polymerization liquid；
When the curing agent is liquid：The curing agent is added in epoxy resin, mixed liquor is obtained；
(2) sequentially added again into the pre-polymerization liquid or mixed liquor processing aid, radiation proof function auxiliary agent, flame retarding function filler and
Fibre reinforced materials stirs evenly, and vacuum defoamation obtains composite glue solution；
(3) composite glue solution is filled up and carries out curing molding in warmed-up mold, after solidification, be cooled to room temperature, taken off
Mold forming obtains the high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material.
2. shielding composite according to claim 1, which is characterized in that the curing agent includes polyamide, two
Aminodiphenyl sulfone, diaminodiphenylmethane, diethylenetriamine, polyethylene polyamine, cyclohexylamine, m-phenylene diamine (MPD), different Fu Er ketone diamines,
The combination of one or more of methyl tetrahydrophthalic anhydride and pyromellitic acid anhydride.
3. shielding composite according to claim 1, which is characterized in that the radiation proof function auxiliary agent include boron powder,
One or more of boron carbide, boronation gadolinium, boron oxide, boron nitride, boric anhydride, lithium, gadolinium, tungsten, lead, copper, iron and its compound
Combination.
4. shielding composite according to claim 1, which is characterized in that the processing aid includes coupling agent, promotes
The combination of one or more of agent, toughener and diluent.
5. shielding composite according to claim 4, which is characterized in that the coupling agent includes KH-550, KH-560
And the combination of one or more of D-90.
6. shielding composite according to claim 4, which is characterized in that the accelerating agent includes Tertiary amine accelerators, miaow
The combination of one or more of azoles accelerating agent and acid anhydrides accelerating agent.
7. shielding composite according to claim 4, which is characterized in that the toughener includes polyetherimide, gathers
One in ether sulfone, polyether-ether-ketone, carboxyl-terminated liguid nitrile rubber, hydroxyl terminated butyl nitrile (HTBN) rubber and amino terminated liquid nitrile rubber
Kind or several combinations.
8. shielding composite according to claim 4, which is characterized in that the diluent includes phenyl glycidyl
Ether, benzyl glycidyl ether, polypropylene glycol diglycidyl ether, polyethyleneglycol diglycidylether and C12-14 alkyl shrink sweet
The combination of one or more of oily ether.
9. shielding composite according to claim 1, which is characterized in that when the curing agent is powder, the shielding
Composite material is prepared by weight by following components：
50-100 parts of epoxy resin；
10-100 parts of curing agent；
100-800 parts of radiation proof function auxiliary agent；
5-100 parts of fibre reinforced materials；
10-150 parts of flame retarding function filler；
1-50 parts of processing aid；
50-400 parts of solvent.
10. shielding composite according to claim 9, which is characterized in that the solvent includes acetone or absolute ethyl alcohol.
11. according to claim 1-10 any one of them shielding composites, which is characterized in that the shielding composite it is close
Degree is 1.5-5.0g/cm3, coefficient of thermal expansion is 10 × 10-6℃-1-30×10-6℃-1, flame retardant property is V-0 grades of UL94, and its
The high temperature of 120-200 DEG C of tolerance.
12. the preparation side of any one of claim 1-11 the high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material
Method comprising following steps：
(1) when the curing agent is powder：The curing agent is dissolved in solvent, obtains the solution of curing agent, then to the solidification
Epoxy resin is slowly added in the solution of agent, 55-75 DEG C of progress pre-reaction 4-6h obtains pre-polymerization liquid；
Alternatively, the curing agent is slowly added in epoxy resin, it is warming up to 70-180 DEG C, carries out pre-reaction 0.5-2h, keeps it molten
Melt and be dispersed in epoxy resin, obtains pre-polymerization liquid；
When the curing agent is liquid：The curing agent is added in epoxy resin, mixed liquor is obtained；
(2) sequentially added again into the pre-polymerization liquid or mixed liquor processing aid, radiation proof function auxiliary agent, flame retarding function filler and
Fibre reinforced materials stirs evenly, and vacuum defoamation obtains composite glue solution；
(3) composite glue solution is filled up and carries out curing molding in warmed-up mold, after solidification, be cooled to room temperature, taken off
Mold forming obtains the high-temperature-resistant epoxy resin base neutron and gamma ray shielding composite material；
Alternatively, curing molding described in step (3) includes operating in detail below：The composite glue solution is cast into mold, in
20-80 DEG C of temperature, pressure<Cure 2-7 days under conditions of 0.1MPa.
13. preparation method according to claim 12, which is characterized in that the mold being preheated described in step (3) is pre-
The mold of heat to 30-150 DEG C.
14. preparation method according to claim 12, which is characterized in that curing molding includes following described in step (3)
Concrete operations：Composite glue solution is cured into 1-4h, pressurize 0-3MPa in 70-150 DEG C first, then with the heating of 1-10 DEG C/min speed
Rate heats up, and then at 120-160 DEG C of solidification 1-3h, pressurize 0-15MPa, is then heated up with the heating rate of 1-10 DEG C/min, finally
Cure 1-3h, pressurize 0-25MPa in 160-200 DEG C.
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| CN101696316B (en) * | 2009-10-28 | 2011-11-16 | 南京航空航天大学 | Method for preparing radiation protection materials |
| CN103937160B (en) * | 2014-04-04 | 2016-06-08 | 西安交通大学 | The preparation method of a kind of nuclear radiation shield 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 |
| CN104710727B (en) * | 2015-03-27 | 2017-11-17 | 中国科学院长春应用化学研究所 | Epoxy resin-matrix neutron and gamma ray shielding composite and preparation method and application |
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