CN103045916B - Composite shielding material and preparation method thereof - Google Patents
Composite shielding material and preparation method thereof Download PDFInfo
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- CN103045916B CN103045916B CN201210570726.XA CN201210570726A CN103045916B CN 103045916 B CN103045916 B CN 103045916B CN 201210570726 A CN201210570726 A CN 201210570726A CN 103045916 B CN103045916 B CN 103045916B
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Abstract
The invention relates to a composite shielding material and a preparation method thereof, in particular to the composite shielding material applied to nuclear radiation places such as nuclear reactor, spent fuel assembly storage and radioactive substance storage and transportation and the like. The composite shielding material is characterized by comprising the following components in percentage by weight: 0 to 30 percent of w and compound thereof, 0 to 70 percent of B4C, 0 to 90 percent of aluminum or aluminum alloy, 0 to 8 percent of other elements and the like. The composite shielding material comprising tungsten B4C/aluminum alloy is uniform in distribution of W2B5 and B4C, high in densification degree, high in strength and toughness, and particularly applicable to the field of neutron/gamma ray shielding.
Description
Technical field
The invention belongs to composite shielding material field, particularly relate to the composite shielding material and preparation method thereof for nuclear reactor, irradiated fuel assembly storage and the nuclear radiation place such as radioactive substance storing.
Background technology
In the radiation that the fields such as nuclear reactor, irradiated fuel assembly storage produce, the shielding problem will paid attention to especially is the gamma-radiation that neutron radiation and penetration power are large, the field producing neutron radiation is general all along with gamma-radiation, in order to reduce the irradiation suffered by human body and equipment, also gamma-ray irradiation should be shielded while sub-radiation in the shield.The materials such as the paraffin that general hydrogen content is higher, polyethylene, polypropylene are excellent Moderation of the fast neutrons materials, containing the lithium fluoride of elemental lithium, lithiumbromide, lithium hydroxide be excellent thermal neutron absorbing material containing the boron oxide of boron, boric acid and norbide etc., simultaneously also fine by tungsten effect to the shielding of fast neutron, because the material of its 10cm thickness can reach 93% to the shielding rate of neutron.Good material is shielded for lead, tungsten and other heavy metals etc. to gamma-radiation.These materials and matrix material thereof have been widely used in various nuclear reactor shielding harness and have played considerable effect.
The more composite shielding material of current use is lead-boron polythene, the comprehensive shielded effect of such material is better, but be take polymkeric substance as matrix due to material, therefore its use temperature is only 80-100 DEG C, mechanical property is also poor, be generally 10MPa-20MPa, the service requirements to the neutron shield field that thermotolerance and mechanical property have higher requirements can not be met.Al-B
4c has the advantage of aluminium and norbide concurrently, and density is low, and hardness is high, thermal-neutron capture cross-section is high, cheap, good toughness, there is good mechanical mechanics property and neutron absorption performance, since the eighties in last century, be subject to the extensive attention of radio-protective researcher.But Al-B
4the anti-gamma-radiation poor-performing of C, and current Al-B
4c development concentrates on Al-B mostly
4the preparation aspect of C composite, about the research of the comprehensive shielded performance of its neutron/gamma-radiation does not almost have.Therefore, be badly in need of optimizing Al-B further
4the comprehensive shielded performance of C composite, fully to expand its application potential in nucleus screening field.
Summary of the invention
For solving above technical problem, the object of the present invention is to provide a kind of composite shielding material with neutron radiation shielding properties and gamma-radiation shielding properties, and respective components can be adopted according to neutron and gamma-rays distribution situation, its component comprises W and compound, B
4c, aluminum or aluminum alloy and other element.
Solve a kind of composite shielding material of above technical problem in the present invention, it is characterized in that: be made up of the component of following weight per-cent: the compound of W or W of 0-30%, the B of 0-70%
4the aluminum or aluminum alloy of C, 0-90%, other element of 0-8%.
The compound of described W or W is W, WO
3, W
2o
5or W
2b
5deng.
Other element described is Ti, Si, Mg, Zr, V, Cr or its compound, rare earth element.
The compound of described above-mentioned element is TiB
2, TiO
2, SiO
2, MgO, ZrO
2, V
2o
5, Cr
2o
3, Y
2o
3or La
2o
3deng.
With B
4c, aluminum or aluminum alloy are main raw, significantly improving the gamma ray shielding performance of material, adding other a small amount of element as reactive sintering agent, to improve B by adding appropriate W and compound thereof
4the wettability of C and aluminium, controls its surface reaction, the over-all propertieies such as the nuclear radiation shield performance of raising material and mechanical property.
At existing B
4on the basis of C/Al neutron shielding material, introduce W and the compound thereof with excellent gamma-radiation performance, by the shielding properties of Monte Carlo method Calculating material, optimize composite material compositions, make B
4c/Al matrix material has excellent neutron shield performance and gamma-radiation shielding properties simultaneously.
Prepare a kind of method of composite shielding material, it is characterized in that: step is as follows:
Step one, take raw material weight per-cent: the compound of W or W of 0-30%; The B of 0-70%
4c; The aluminum or aluminum alloy of 0-90%; Other element of 0-8%;
Step 2, mix each component material, load in ball grinder and carry out ball milling, inject argon gas in ball grinder as protective atmosphere, Ball-milling Time 2-25h, obtains mixed powder after ball milling;
Step 3, mixed powder adopt cold isostatic compaction after loading soft mode, and pressure is 100-270MPa, time 5-60min; The material of soft mode is PVC, and PVC is made mould and carries out cold isostatic compaction by shape per sample, size.
Step 4, base of colding pressing carry out HIP sintering, and hot isostatic pressing gas is argon gas, and temperature is 680-1200 DEG C, and pressure is 30-150MPa, and the time is 0-180min;
Step 5, namely the material after hot isostatic pressing is obtained composite shielding material after the demoulding.
Ball grinder is stainless steel jar mill, and abrading-ball is sintered carbide ball.The main component of sintered carbide ball is same containing W in WC, B4C/Al matrix material, therefore, selects Wimet can reduce the introducing of impurity element as abrading-ball.Take argon gas as gaseous media when ball milling and hot isostatic pressing, the oxidation of aluminium and other metal can be prevented.
Due to norbide and aluminium need could be good under the high temperature of about 1200 DEG C wetting, and in this temperature range, aluminium and B
4c can generate more Al on interface
4c
3brittlement phase, reduce interface bond strength, and under high temperature, molten aluminium alloy easily volatilizees, and causes waste of raw materials, also has certain harm to experimental installation.Therefore, how effectively to reduce the temperature of reaction of matrix material, generation that control inerface reaction particularly controls high-temperature brittleness phase is technological difficulties of the present invention.The present invention adopts hot isostatic pressing technique to prepare powder metallurgy B
4c/ aluminium alloy, solves B
4c and Al is difficult to the problem soaked at low temperature, greatly reduce sintering temperature (sintering temperature can be reduced to the fusing point of a little higher than Al), reduce surface reaction speed, avoid harmful phase to generate, effective control composite material interface phase structure, optimizes the mechanical property of matrix material.
The present invention meets nuclear radiation shield field to the requirement of shielding material at comprehensive shielded aspect of performance, have developed and a kind of there is good neutron radiation shielding properties and the composite shielding material of gamma-radiation shielding properties, and the composite shielding material of respective components can be adopted according to neutron and gamma-rays distribution situation.Adopt tungstenic B prepared by above-mentioned technique
4c/ aluminium alloy compound shielding material W
2b
5and B
4c is evenly distributed, and densification degree is high, and intensity and toughness well, are specially adapted to neutron/gamma shielding field.
Composite shielding material of the present invention has good neutron radiation shielding properties and gamma-radiation shielding properties, and can adopt the matrix material of respective components according to neutron and gamma-rays distribution situation.More traditional composite shielding material is compared, and to the performance that neutron radiation shielding has had, improves 5-20% or more to gamma-radiation shielding properties simultaneously.
Specific embodiment
embodiment 1
Take raw material weight per-cent WO
315%, B
4c's 15%, aluminium alloy 67%, Ti 3%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt YG8 sintered carbide ball, Ball-milling Time 24h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 250MPa, temperature 18 DEG C, time 10min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 900 DEG C, and hot isostatic pressing pressure is 120MPa, and hot isostatic pressing soaking time is 1h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 2
Take raw material weight per-cent WO
325%, B
4c's 10%, Al 60%, TiO
25%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, Ball-milling Time 24h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 200MPa, temperature 25 DEG C, time 20min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 800 DEG C, and hot isostatic pressing pressure is 80MPa, and hot isostatic pressing soaking time is 3h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 3
Take raw material weight per-cent WO
35%, B
4c's 20%, Al 72%, Cr3%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, Ball-milling Time 22h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 180MPa, temperature 20 DEG C, time 30min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 680 DEG C, and hot isostatic pressing pressure is 140MPa, and hot isostatic pressing soaking time is 1h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 4
W by weight percentage
2b
510%; B
4c's 45%; Aluminium alloy 40%; SiO
25% takes raw material.By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt YG8 sintered carbide ball, Ball-milling Time 24h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 250MPa, temperature 22 DEG C, time 5min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 800 DEG C, and hot isostatic pressing pressure is 100MPa, and hot isostatic pressing soaking time is 1h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/ aluminium alloy compound shielding material.Adopt tungstenic B prepared by above-mentioned technique
4c/ aluminium alloy compound shielding material W
2b
5and B
4c is evenly distributed, and densification degree is high, and intensity and toughness well, are specially adapted to neutron/gamma shielding field.
embodiment 5
Take raw material weight per-cent W
2b
55%, B
4c's 25%, Al 67%, rare earth 3%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, Ball-milling Time 23h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 150MPa, temperature 24 DEG C, time 40min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 700 DEG C, and hot isostatic pressing pressure is 150MPa, and hot isostatic pressing soaking time is 1.5h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 6
Take raw material weight per-cent W
2b
525%, B
4c10%'s, Al 60%, MgO5%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, Ball-milling Time 20h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 150MPa, temperature 23 DEG C, time 50min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 1100 DEG C, and hot isostatic pressing pressure is 100MPa, and hot isostatic pressing soaking time is 2.5h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 7
Take raw material weight per-cent WO
315%, B
4c's 30%, aluminium alloy 50%, Ti 5%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt YG8 sintered carbide ball, Ball-milling Time 15h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 250MPa, temperature 24 DEG C, time 60min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 900 DEG C, and hot isostatic pressing pressure is 120MPa, and hot isostatic pressing soaking time is 1h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 8
Take raw material weight per-cent W 30%, B
4c's 30%, Al 32%, TiB
28%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, Ball-milling Time 10h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 270MPa, temperature 19 DEG C, time 15min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 1000 DEG C, and hot isostatic pressing pressure is 90MPa, and hot isostatic pressing soaking time is 2h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 9
Take raw material weight per-cent W2%, B
4c's 68%, Al 23%, Zr7%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, Ball-milling Time 2h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 270MPa, temperature 22 DEG C, time 20min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 1200 DEG C, and hot isostatic pressing pressure is 30MPa, and hot isostatic pressing soaking time is 3h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 10
Take raw material weight per-cent W
2o
530%, B
4c's 50%, Al 15%, ZrO
25%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, Ball-milling Time 22h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 150MPa, temperature 23 DEG C, time 25min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 900 DEG C, and hot isostatic pressing pressure is 100MPa, and hot isostatic pressing soaking time is 2h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 11
Take raw material weight per-cent W
2o
56%, B
4c's 15%, Al 75%, V
2o
54%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, Ball-milling Time 25h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 120MPa, temperature 25 DEG C, time 30min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 850 DEG C, and hot isostatic pressing pressure is 250MPa, and hot isostatic pressing soaking time is 1h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 12
Take raw material weight per-cent W
2o
50%, B
4c's 50%, Al 45%, V5%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, with dehydrated alcohol as ball-milling medium, Ball-milling Time 25h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 120MPa.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 750 DEG C, and hot isostatic pressing pressure is 250MPa, and hot isostatic pressing soaking time is 1h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 13
Take raw material weight per-cent W 3%, B
4c's 5%, Al 90%, Cr
2o
32%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, Ball-milling Time 22h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 200MPa, temperature 22 DEG C, time 20min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 1000 DEG C, and hot isostatic pressing pressure is 90MPa, and hot isostatic pressing soaking time is 2h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material.
embodiment 14
Take raw material weight per-cent W 10%, B
4c70%'s, Al17%, Y
2o
33%; By each component material by formula mixing, load in stainless steel jar mill and carry out ball milling, adopt sintered carbide ball, Ball-milling Time 22h; Powder after ball milling loads soft mode and carries out cold isostatic compaction, and isostatic cool pressing pressure is 220MPa, temperature 25 DEG C, time 25min.Base of colding pressing loads the rear HIP sintering of jacket sealing, and hot isostatic pressing gas is argon gas, and hip temperature is 900 DEG C, and hot isostatic pressing pressure is 120MPa, and hot isostatic pressing soaking time is 2h.Tungstenic B can be prepared by after the material release after hot isostatic pressing
4c/Al composite shielding material
Performance index:
Table 1 is containing WO
3b
4the composition of C/Al matrix material and shielding properties
Table 2 is containing W
2b
5b
4the composition of C/Al or Al alloy composite and shielding properties
Table 2 is containing W, W
2o
5b
4the composition of C/Al or Al alloy composite and shielding properties
Note: the 1. thick 4cm of shielding material, diameter 100cm.
2. neutron energy is Cf-252 fission spectrum, and energy of γ ray is 661keV.
More than table is found out, the tungstenic B prepared in the present invention
4c/ aluminium alloy compound shielding material W
2b
5and B
4c is evenly distributed, and densification degree is high, and intensity and toughness well, are specially adapted to neutron/gamma shielding field.More traditional composite shielding material is compared, and to the performance that neutron radiation shielding has had, improves 5-20% or more to gamma-radiation shielding properties simultaneously.
Claims (3)
1. a composite shielding material, is characterized in that: be made up of the component of following weight per-cent: the compound of W or W of 2-30%, the B of 10-68%
4the aluminum or aluminum alloy of C, 23-72%, other component of 3-8%;
The compound of described W or W is W, WO
3, W
2o
5or W
2b
5, other component described is Ti, Si, Mg, Zr, V, Cr or its compound, rare earth element, Y
2o
3or La
2o
3; Wherein, described composite shielding material making step is as follows:
Step one, take raw material weight per-cent: the compound of W or W of 2-30%; The B of 10-68%
4c; The aluminum or aluminum alloy of 23-72%; Other component of 3-8%;
Step 2, mix each component material, load in ball grinder and carry out ball milling, inject argon gas in ball grinder as protective atmosphere, Ball-milling Time 2-25h, obtains mixed powder;
Step 3, mixed powder adopt cold isostatic compaction after loading soft mode, and pressure is 100-270MPa, time 5-60min;
Step 4, base of colding pressing carry out HIP sintering, and hot isostatic pressing gas is argon gas, and temperature is 680-1200 DEG C, and pressure is 30-150MPa, and the time is 20-180min;
Namely material after step 5, hot isostatic pressing obtains composite shielding material after the demoulding.
2. a kind of composite shielding material according to claim 1, is characterized in that: in other component described, the compound of Ti, Si, Mg, Zr, V, Cr is TiB
2, TiO
2, SiO
2, MgO, ZrO
2, V
2o
5, Cr
2o
3.
3. according to the method for a kind of composite shielding material described in claim 1, it is characterized in that: described ball grinder is stainless steel jar mill, abrading-ball is sintered carbide ball.
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