CN106378459A - High-boron stainless steel neutron-absorbing material and preparation method thereof - Google Patents
High-boron stainless steel neutron-absorbing material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-boron stainless steel neutron-absorbing material and a preparation method thereof, and belongs to the field of neutron-absorbing materials. The high-boron stainless steel neutron-absorbing material comprises the following components in percentage by mass: 0.2-3% of B, 12-26% of Cr, 1.5-23% of Ni, 0.02-0.6% of C, 1-11% of Mn, 0-7% of Mo, no less than 3% of Si, no less than 0.2% of P, no less than 0.030% of S and the balance of iron. The preparation method comprises the following steps: atomization spraying for powder preparation; hot-isostatic-pressing sintering, and rolling. The prepared high-boron stainless steel has the advantages that the stainless steel density is high, the relative density is higher than 99.8%, the stainless steel structure is uniform; the room-temperature tensile strength is higher than 500 MPa, the yield strength is higher than 200 MPa and the ductility is higher than 5%. Meanwhile, the prepared high-boron stainless steel is applicable to a nuclear radiation protective shielding material, a spent fuel storage material, a reactor control material and the like, and has good economic benefit and social benefit.
Description
Technical field
The invention belongs to neutron absorber material field, it is related to a kind of high boron rustless steel neutron absorber material and its preparation side
Method.
Background technology
The fields such as nuclear power plant's bunkering screen work, fuel transport, transhipment, neutron shield need neutron absorber material, to keep away
Exempt from neutron to external radiation.Conventional neutron absorber material has lead-boron polythene, boracic polypropylene, cadmium plate, boron carbide, aluminium base carbonization
Boron and boron steel etc., boron steel is with having enough structural mechanical properties, and good neutron absorption capability.
Boron atom ordinal number is 5, and atomic weight is 10.811, has two kinds of stable isotopes：Boron 10 and boron 11, natural abundance is divided
Wei 19.78% and 80.22%；Boron 10 is more than 5 times of natural abundance boron to the absorption cross-section of neutron, is more than 20 times of graphite,
It is more than 500 times as NEUTRON PROTECTION material concrete.Boronated stainless steel as neutron absorber material, nuclear power, modern industry,
The aspect such as military equipment and advanced medical has a wide range of applications.
Effect in steel for the boron is extremely complex, and the dissolubility in steel is minimum, with various crystal defects（As crystal boundary, dislocation
With room etc.）There is strong interaction；It can form various types of being mingled with other elements such as oxygen, nitrogen, the carbon etc. in steel
Thing and precipitated phase.Thus, in the steel of different conditions, smelted due to its experience, processing, heat treatment state different, boron point
Cloth and effect are just different.In time in the steel of same boron content, due to the change of boron deregulation state, reality is to steel hardenability, toughness
Can be entirely different etc. the boron amount working.
Add micro boron in steel, the quenching degree of steel can be improved.Steel alloy with boron as main alloy element is commonly referred to as
High boron steel, typically in 0.2%-3%, Boron contents are higher for its boron weight content, absorb thermal neutron ability stronger.General boron in α-Fe and
The maxima solubility of γ-Fe is respectively 0.0081% and 0.02%, and the boron exceeding solid solubility is analysed along crystal boundary generally in the form of boron phase
Go out, in netted precipitation distribution, so that the toughness of steel is declined, this phenomenon is referred to as " boron is crisp ".Boron contents in steel are more, this precipitation
The amount of phase is more, and the quantity of precipitated phase, shape, size and distribution are closely related with the performance of steel；If being distributed in crystal boundary, and
During in continuous distribution, make the toughness severe exacerbation of high boron steel.Generally, the Boron contents in high boron steel, in 0.5-1%, are
Hypoeutectic structure, boron phase is Fe2B, and eutectic structure is along crystal boundary continuous distribution；Boron contents are that during 1.0-2.5%, Fe2B amount increases, and are in
Typical arborescent structure；For being eutectic structure during 2.5-4.0%, boride is Fe2B or Fe2 to Boron contents（C,B）.
Under traditional casting technique, high boron steel is difficult to avoid crystal grain group big and continuous net-shaped eutectic boron in process of setting
The formation of compound.High boron rustless steel, containing elements such as chromium, nickel and molybdenums, can improve solid solubility in ferrous alloy for the boron, part
Reduce the precipitation of boron phase, but boron increase of solid solubility in rustless steel is also extremely limited, and thick boron phase also occurs.
Heat and other static pressuring processes are advanced material processing and preparation technology, and its principle is the surrender of material at high temperature under high pressure
Intensity declines, and the migration velocity of atom is accelerated, and can accelerate powder consolidation densification rate, improves densification degree；Can also
Eliminate internal void and the defect of material, improve the performance of material.It is widely used in special powder sintering, such as high-speed steel, height
Temperature alloy, titanium alloy, special cermacis etc. are difficult to casting and normal pressure-sintered powder；Be also applied to Aero-Space nuclear power cast member,
The elimination internal flaw of forging rolling part and hole, improve the fields such as performance.
Content of the invention
For the defect of prior art, it is an object of the invention to provide a kind of high boron stainless steel alloy and its preparation side
Method, the method adopts the preparation of aerosolization-high temperature insostatic pressing (HIP)-hot rolling technology, preparation to meet material density high, intensity and toughness are comprehensive
Close performance high, it is to avoid the high boron of conventional cast stainless in Grain Boundary Segregation, suitable mass production.
In order to reach object above, the present invention adopts the following technical scheme that：A kind of high boron rustless steel neutron absorber material system
Preparation Method, in turn includes the following steps：
（1）The preparation of powder of stainless steel：By the ferroalloys such as ferro-boron, ferrochrome, ferronickel, ferromanganese and pure iron, proportioning enters circulation of qi promoting as requested
Atomization, and sieve, obtain the alloy powder of the even tissue under 60 mesh -300 mesh sieve；Powder stock is prepared using aerosolization, protects
Card powder purity is high, oxygen content is low, element especially boron element is evenly distributed on powder particle does not have the phenomenons such as segregation；
（2）High temperature insostatic pressing (HIP) forming step：The alloy powder of aerosolization gained is loaded jacket, pumping, sealing, then in a constant temperature
Carry out HIP sintering under degree and pressure, obtain the blank with high-compactness, almost there is no microdefect；
（3）Milling step：Upper high temperature insostatic pressing (HIP) blank is removed after jacket, carries out hot rolling, obtain board-like material.
Preferably, high boron rustless steel neutron absorber material includes boron, nickel, chromium, manganese, molybdenum, silicon, p and ses element, all with
The form of ferroalloy adds.
Using such preparation method, technological process is short, and energy consumption is low.
Preferably, described high boron rustless steel neutron absorber material Boron contents are B to any of the above-described scheme：0.2-3%.
Preferably, described high boron rustless steel neutron absorber material also includes Cr to any of the above-described scheme：12-26%, Ni：
1.5-23%, C：0.02-0.6%, Mn：1-11%, Mo：0-7%, Si：≤ 3%, P≤0.2%, S≤0.030, remaining is ferrum.
Preferably, described high boron rustless steel neutron absorber material includes B to any of the above-described scheme：2.1%, Cr：19%, Ni：
14%, C：0.08%, Mn：2%, Si：0.75, P≤0.045%, S≤0.030, remaining is ferrum.
Preferably, described high boron rustless steel neutron absorber material includes B to any of the above-described scheme：0.25%, Cr：15%, Ni：
12%, C：0.20%, Mn：1.5%, Si：2.5%, P≤0.045%, S≤0.030, remaining is ferrum.
Preferably, described high boron rustless steel neutron absorber material includes B to any of the above-described scheme：0.6%, Cr：15%, Ni：
12%, C：0.20%, Mn：1.5%, Si：2.5%, P≤0.045%, S≤0.030, remaining is ferrum.
Preferably, described ferroalloy includes B to any of the above-described scheme：1.5%, Cr：18%, Ni：15%, C：0.04%, Mn：
1.0%, Mo：6%, Si：1.0%, P≤0.045%, S≤0.030, remaining is ferrum.
Preferably, by ferro-boron, ferrochrome, ferronickel, ferromanganese and pure iron, proportioning carries out aerosol to any of the above-described scheme as requested
During change, fusion temperature exceeds 100-300 DEG C of fusing point, and protective gas is argon, and atomisation pressure is 5-40MPa.Exemplarily, melt
Temperature exceed 100 DEG C of fusing point, 150 DEG C, 200 DEG C, 250 DEG C, atomisation pressure 30MPa, 25MPa, 20MPa, 10MPa.
Preferably, the granularity that obtains is in the powder of 300-60 mesh, close after 200-500 DEG C of evacuation for any of the above-described scheme
Envelope, the described jacket of sealing is carried out hip treatment, and pressure is 80-150MPa, and temperature is 900-1200 DEG C, temperature retention time
For 1 ~ 4 hour.Temperature retention time is longer, and the blank consistency obtaining is higher, more abundant with the interface cohesion of carborundum.Exemplary
Ground, the granularity obtaining is respectively -200 mesh, -150 mesh, -100 mesh, the powder of -80 mesh, at 450 DEG C, 350 DEG C, 300 DEG C, 250 DEG C
After evacuation rear enclosed, carry out high temperature insostatic pressing (HIP) densification sintering, heat etc. in the range of 100MPa, 120MPa, 140MPa-150MPa
Static pressure temperature is 950 DEG C, 1050 DEG C, 1100 DEG C, 1150 DEG C, and temperature retention time is 1.5h, 2.0h, 2.5h, 3.5h.Temperature during evacuation
Degree is higher than more than 350 DEG C, and degassing efficiency is higher, and residual gas is less.
Preferably, high temperature insostatic pressing (HIP) forming blank relative density is more than 99.8% to any of the above-described scheme.
Any of the above-described scheme preferably, is 900-1150 degree Celsius as a kind of preferred embodiment hot-rolled temperature, becomes
Shape amount is in 20-80%.Exemplarily hot-rolled temperature be 950 DEG C, 1000 DEG C, 1050 DEG C, 1100 DEG C, deflection be 30%, 50%,
60%、80%.
Present invention simultaneously provides a kind of high boron rustless steel neutron absorber material, it adopts above high boron rustless steel neutron to inhale
The preparation method receiving material prepares.
The present invention is had the advantages that compared with prior art：
（1）A kind of high boron rustless steel of the present invention and preparation method thereof, prepares powder stock using aerosolization it is ensured that powder is pure
Degree is high, oxygen content is low, element especially boron element is evenly distributed on powder particle does not have the phenomenons such as segregation.（2）The present invention adopts
High temperature insostatic pressing (HIP) is shaped and is carried out with sintering simultaneously, and operation is simple, uniform in material, material density height, relative density reach 99.8% with
On, and boron element is evenly distributed in intra-die and is difficult in Grain Boundary Segregation.In sum, the high boron prepared using the present invention is not
Rust steel has the features such as good, the good r ray of relative density height, uniform in material, comprehensive mechanical property and neutron-absorbing performance,
Can be applicable to the fields such as nuclear power plant's bunkering screen work, fuel transport, transhipment, neutron shield, be with a wide range of applications.
Brief description
Fig. 1 is a preferred embodiment flow chart of the high boron stainless steel alloy preparation method according to the present invention.
Fig. 2 is the microstructure of a preferred embodiment of the high boron stainless steel alloy according to the present invention.
Specific embodiment
For the more clear content of the invention understanding the present invention exactly, below in conjunction with the accompanying drawings and specific embodiment is further
Illustrate.
Embodiment 1
This embodiment provide high boron rustless steel neutron absorber material composition be.B：2.1%, Cr：19%, Ni：14%, C：0.08%,
Mn：2%, Si：0.75, P≤0.045%, S≤0.030 remaining be ferrum, these elements are all added with ferroalloy form.
As shown in figure 1, the preparation of the high boron rustless steel neutron absorber material in the present embodiment in turn includes the following steps：
（1）Material powder preparation steps：Various ferroalloy compositions are melted in aerosolization, exceed 100 DEG C of fusing point, the pressure that dusts is
30MPa, receive powder crosses 200 mesh sieves, -200 mesh powder recovery rates are more than 50%；
（2）High temperature insostatic pressing (HIP) forming step：Described mixed powder is loaded jacket, vacuum suction temperature be 450 DEG C, sealing, heat etc.
Static pressure is processed, and pressing pressure is 100MPa, and temperature is 950 DEG C, and temperature retention time is 1.5 hours, obtains high temperature insostatic pressing (HIP) blank；
（3）Hot-rolled step：The blank of high temperature insostatic pressing (HIP) is carried out hot rolling, hot-rolled temperature is 950 DEG C, deflection is 30%
The microstructure of high boron rustless steel neutron absorber material manufactured in the present embodiment is as shown in Fig. 2 height manufactured in the present embodiment
In boron rustless steel, the relative density of word absorbing material is 99.8%, room temperature tensile intensity is 700MPa, yield strength is 500MPa,
Elongation percentage is 14%.
Embodiment 2
The high boron rustless steel neutron absorber material composition that this embodiment provides is B：0.25%, Cr：15%, Ni：12%, C：0.20%,
Mn：1.5%, Si：2.5%, P≤0.045%, S≤0.030 remaining be ferrum.These elements are all added with ferroalloy form.
The preparation of the high boron rustless steel neutron absorber material in the present embodiment in turn includes the following steps：
（1）Material powder preparation steps：Various ferroalloy compositions are melted in aerosolization, exceed 150 DEG C of fusing point, the pressure that dusts is
25MPa, receive powder crosses 150 mesh sieves, -150 mesh powder recovery rates are more than 50%；
（2）High temperature insostatic pressing (HIP) forming step：Described mixed powder is loaded jacket, vacuum suction temperature be 350 DEG C, sealing, heat etc.
Static pressure is processed, and pressing pressure is 120MPa, and temperature is 1050 DEG C, and temperature retention time is 2.0 hours, obtains high temperature insostatic pressing (HIP) blank；
（3）Hot-rolled step：The blank of high temperature insostatic pressing (HIP) is carried out hot rolling, hot-rolled temperature is 1000 DEG C, deflection is 50%
High boron rustless steel relative density manufactured in the present embodiment is 99.8%, and room temperature tensile intensity is 750MPa, yield strength is
600MPa, elongation percentage are 10%.
Embodiment 3
The high boron rustless steel neutron absorber material composition that this embodiment provides is B：0.6%, Cr：15%, Ni：12%, C：0.20%,
Mn：1.5%, Si：2.5%, P≤0.045%, S≤0.030 remaining be ferrum.These elements are all added with ferroalloy form.
The preparation of the high boron rustless steel neutron absorber material in the present embodiment in turn includes the following steps：
（1）Material powder preparation steps：Various ferroalloy compositions are melted in aerosolization, exceed 200 DEG C of fusing point, the pressure that dusts is
20MPa, receive powder crosses 100 mesh sieves, -100 mesh powder recovery rates are more than 55%；
（2）High temperature insostatic pressing (HIP) forming step：Described mixed powder is loaded jacket, vacuum suction temperature be 300 DEG C, sealing, heat etc.
Static pressure is processed, and pressing pressure is 140MPa, and temperature is 1100 DEG C, and temperature retention time is 2.5 hours, obtains high temperature insostatic pressing (HIP) blank；
（3）Hot-rolled step：The blank of high temperature insostatic pressing (HIP) is carried out hot rolling, hot-rolled temperature is 1050 DEG C, deflection is 60%
High boron rustless steel relative density manufactured in the present embodiment is 99.8%, and room temperature tensile intensity is 800MPa, yield strength is
700MPa, elongation percentage are 7%.
Embodiment 4
The high boron rustless steel neutron absorber material composition that this embodiment provides is B：1.5%, Cr：18%, Ni：15%, C：0.04%,
Mn：1.0%, Mo：6%, Si：1.0%, P≤0.045%, S≤0.030 remaining be ferrum.These elements are all added with ferroalloy form.
The preparation of the high boron rustless steel neutron absorber material in the present embodiment in turn includes the following steps：
（1）Material powder preparation steps：Various ferroalloy compositions are melted in aerosolization, exceed 250 DEG C of fusing point, the pressure that dusts is
10MPa, receive powder crosses 80 mesh sieves, -80 mesh powder recovery rates are more than 65%；
（2）High temperature insostatic pressing (HIP) forming step：Described mixed powder is loaded jacket, vacuum suction temperature be 250 DEG C, sealing, heat etc.
Static pressure is processed, and pressing pressure is 150MPa, and temperature is 1150 DEG C, and temperature retention time is 3.5 hours, obtains high temperature insostatic pressing (HIP) blank；
（3）Hot-rolled step：The blank of high temperature insostatic pressing (HIP) is carried out hot rolling, hot-rolled temperature is 1100 DEG C, deflection is 80%
High boron rustless steel relative density manufactured in the present embodiment is 99.8%, and room temperature tensile intensity is 850MPa, yield strength is
780MPa, elongation percentage are 6%.
Embodiment 5
The high boron rustless steel neutron absorber material composition that this embodiment provides is B：1.5%, Cr：18%, Ni：15%, C：0.04%,
Mn：1.0%, Mo：6%, Si：1.0%, P≤0.045%, S≤0.030 remaining be ferrum.These elements are all added with ferroalloy form.
The preparation of the high boron rustless steel neutron absorber material in the present embodiment in turn includes the following steps：
（1）Material powder preparation steps：Various ferroalloy compositions are melted in aerosolization, exceed 100 DEG C of fusing point, the pressure that dusts is
5MPa, receive powder crosses 60 mesh sieves, -60 mesh powder recovery rates are more than 70%；
（2）High temperature insostatic pressing (HIP) forming step：Described mixed powder is loaded jacket, vacuum suction temperature be 200 DEG C, sealing, heat etc.
Static pressure is processed, and pressing pressure is 80MPa, and temperature is 900 DEG C, and temperature retention time is 1 hour, obtains high temperature insostatic pressing (HIP) blank；
（3）Hot-rolled step：The blank of high temperature insostatic pressing (HIP) is carried out hot rolling, hot-rolled temperature is 900 DEG C, deflection is 20%.
High boron rustless steel relative density manufactured in the present embodiment is 99.8%, and room temperature tensile intensity is 900MPa, yield strength
It is 6% for 785MPa, elongation percentage.
Embodiment 6
The high boron rustless steel neutron absorber material composition that this embodiment provides is B：1.5%, Cr：18%, Ni：15%, C：0.04%,
Mn：1.0%, Mo：6%, Si：1.0%, P≤0.045%, S≤0.030 remaining be ferrum.These elements are all added with ferroalloy form.
The preparation of the high boron rustless steel neutron absorber material in the present embodiment in turn includes the following steps：
（1）Material powder preparation steps：Various ferroalloy compositions are melted in aerosolization, exceed 300 DEG C of fusing point, the pressure that dusts is
40MPa, receive powder crosses 300 mesh sieves, -300 mesh powder recovery rates are more than 65%；
（2）High temperature insostatic pressing (HIP) forming step：Described mixed powder is loaded jacket, vacuum suction temperature be 500 DEG C, sealing, heat etc.
Static pressure is processed, and pressing pressure is 150MPa, and temperature is 1200 DEG C, and temperature retention time is 4 hours, obtains high temperature insostatic pressing (HIP) blank；
（3）Hot-rolled step：The blank of high temperature insostatic pressing (HIP) is carried out hot rolling, hot-rolled temperature is 1150 DEG C, deflection is 80%.
High boron rustless steel relative density manufactured in the present embodiment is 99.8%, and room temperature tensile intensity is 820MPa, yield strength
It is 8% for 700MPa, elongation percentage.
It should be noted that various embodiments above, only in order to technical scheme to be described, is not intended to limit；Although
With reference to foregoing embodiments, the present invention is described in detail, it will be understood by those within the art that：It is still
Technical scheme described in foregoing embodiments can be modified, or wherein some or all of technical characteristic is carried out
Equivalent；And these modifications or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention technical side
The scope of case.
Claims (10)
1. a kind of preparation method of high boron rustless steel neutron absorber material, in turn includes the following steps：
（1）The preparation of powder of stainless steel：By ferro-boron, ferrochrome, ferronickel, ferromanganese and pure iron, proportioning carries out aerosolization as requested, and
Sieve, obtain the alloy powder of the even tissue under 300-60 mesh sieve；
（2）High temperature insostatic pressing (HIP) forming step：The alloy powder of aerosolization gained is loaded jacket, pumping, sealing, then in a constant temperature
Carry out HIP sintering under degree and pressure, obtain the blank with high-compactness；
（3）Milling step：Upper high temperature insostatic pressing (HIP) blank is removed after jacket, carries out hot rolling, obtain board-like material.
2. preparation method as claimed in claim 1 it is characterised in that：Described high boron rustless steel neutron absorber material include boron,
Nickel, chromium, manganese, molybdenum, silicon, p and ses element, are added in the form of ferroalloy.
3. preparation method as claimed in claim 2 it is characterised in that：Described high boron rustless steel neutron absorber material includes B：
0.2-3%.
4. preparation method as claimed in claim 3 it is characterised in that：Cr：12-26%, Ni：1.5-23%, C：0.02-0.6%,
Mn：1-11%, Mo：0-7%, Si：≤ 3%, P≤0.2%, S≤0.030, remaining is ferrum.
5. preparation method as claimed in claim 1 it is characterised in that：By ferro-boron, ferrochrome, ferronickel, ferromanganese and pure iron according to will
When asking proportioning to carry out aerosolization, fusion temperature exceeds 100-300 DEG C of fusing point, and protective gas is argon, and atomisation pressure is 5-
40MPa.
6. preparation method as claimed in claim 1 it is characterised in that：The granularity obtaining in the powder of 300-60 mesh, in 200-
500 DEG C of sealed after being vacuumized, the described jacket of sealing is carried out hip treatment.
7. preparation method as claimed in claim 6 it is characterised in that：During described hip treatment, pressure is 80-
150MPa, temperature is 900-1200 DEG C, and temperature retention time is 1 ~ 4 hour.
8. preparation method as claimed in claim 7 it is characterised in that：High temperature insostatic pressing (HIP) forming blank relative density is more than 99.8%.
9. preparation method as claimed in claim 1 it is characterised in that：Hot-rolled temperature is 900-1150 degree Celsius, and deflection exists
20-80%.
10. a kind of high boron rustless steel neutron absorber material, it adopts in the high boron rustless steel any one of claim 1-9
The preparation method of sub- absorbing material prepares.
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