CN107557781B - High-hardness corrosion-resistant alloy powder for laser cladding process and preparation method thereof - Google Patents
High-hardness corrosion-resistant alloy powder for laser cladding process and preparation method thereof Download PDFInfo
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- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
本发明属于激光熔覆技术领域，尤其涉及一种激光熔覆工艺用高硬度耐蚀合金粉末，包括以下重量百分比的金属原料，C：≦0.12％；Cr：17.5～18.5％；Ni：6～7％；B：0.8～1.0％；Si：1～1.5％；微量元素：1.1～3.4％；余量为Fe；其中，所述微量元素包括按重量百分比计的V：0.2～0.8％；Nb：0.2～0.8％；Ce：0.4～0.8％；Mo：0.2～0.6％；Hf：0.1‑1％。本发明还涉及一种上述合金粉末的制备方法。The invention belongs to the technical field of laser cladding, in particular to a high-hardness corrosion-resistant alloy powder for a laser cladding process, comprising the following metal raw materials by weight: C: ≤ 0.12%; Cr: 17.5-18.5%; Ni: 6- 7%; B: 0.8-1.0%; Si: 1-1.5%; trace elements: 1.1-3.4%; the balance is Fe; wherein, the trace elements include V by weight: 0.2-0.8%; Nb : 0.2-0.8%; Ce: 0.4-0.8%; Mo: 0.2-0.6%; Hf: 0.1-1%. The present invention also relates to a preparation method of the above alloy powder.
Description
Technical field
The invention belongs to laser melting and coating technique field more particularly to a kind of laser melting and coating process high rigidity corrosion resistant alloy powder
End further relates to a kind of preparation method of above-mentioned alloy powder.
Background technique
Laser melting and coating process refers to places the coating material selected with different adding material modes on by cladding matrix surface
Material through laser irradiation be allowed to matrix surface a thin layer simultaneously melt, and quickly solidify after formation dilution it is extremely low, with matrix at
The surface covering of metallurgical bonding, is modified matrix surface and repairs.
As laser technique is increasingly mature, laser power is constantly promoted with efficiency, and laser melting and coating process is increasingly subject to
To pay attention to, application field is also more and more, and the application of different field proposes more requirements to laser melting and coating process material therefor, such as
It is wear-resisting, anti-corrosion, anti-oxidant etc..The self-fluxing alloyed powder that traditional plasma spray technology uses, joined a large amount of B, and Si etc. promotees eutectic
The fusing point of powder body material can be greatly reduced in element, these elements, be adapted to the low efficiencies plasma spray technology such as flame-spraying,
But B, Si addition can be such that cladding layer brittleness increases.Laser melting and coating process feature is that centralized heat energy, cooling velocity are fast, according to height
Easily there is cladding crackle in B, Si powder body material, and preparing high hardness wear-resisting coatings art, there are bottlenecks.B simultaneously, Si are parents
Oxygen element is added the excessive powder body material that increases and aoxidizes, and corrosion resistance reduces, and is needing anti-oxidant, the corrosion resistant high B in field, Si
There are limitations.
In addition, laser melting coating powder body material is to purity requirement height, oxygen content should be less than 200PPM, to ensure to be formed no gas
Hole, slag inclusion fine and close layer；To ensure powder body material smooth, uniform, continual feeding molten bath, powder body material want ball-type or
Approximate ball-type, and need to have preferable Liu Dong≤14s/50g and biggish Song dress Mi Du≤4.4g/cm3。
Therefore, to solve problems of the prior art, laser melting and coating process feature is adapted to, different function coating is met
Performance requirement, be badly in need of research and development laser melting and coating process technology-specific powder body material.
Summary of the invention
The present invention be solve well-known technique present in technical problem and provide a kind of hardness is high, corrosion-resistant, oxygen content is low,
The laser melting and coating process of good fluidity high rigidity corrosion resistant alloy powder.
The technical scheme adopted by the present invention to solve the technical problems existing in the known art is that a kind of laser melting coating work
Skill is with high rigidity corrosion resistant alloy powder, the raw metal including following weight percent, C :≤0.12%；Cr:17.5~
18.5%；Ni:6~7%；B:0.8~1.0%；Si:1~1.5%；Microelement: 1.4~3.4%；Surplus is Fe；Wherein,
The microelement includes V:0.5~0.8% by weight percentage；Nb:0.2~0.8%；Ce:0.4~0.8%；Mo:
0.2~0.6%；Hf:0.1-1%.
The advantages and positive effects of the present invention are:
1, the addition of low content B, Si element improves laser melting and coating process and coating surface planarization, mentions simultaneously
High abrasion resistance, removes layer crackle.
2, the addition of microelement V, Ce, Mo can refining alloy crystal grain, increase the solid melt of Cr, and then change and improve alloy
Antiseptic property.
3, microelement Nb is carbide former, can form stable NbC, causes post-curing, and it is hard to improve matrix
Degree promotes wearability.
4, Hf can play the effect of purification alloy, solution strengthening.
5, Hf is by inhibiting high temperature crystal grain to grow up, Lai Tigao high temperature (700-800 DEG C) creep rupture strength, with the alloy for being free of Hf
Powder improves 10% or more compared to creep rupture strength.
6, Cr, Co, Mo, Hf high temperature when rich hafnium (Hf) type carbide for extremely dispersing is precipitated, such as (Cr Mo Hf)23C6,
(Co,Mo,Hf)2C6Deng can be improved high temperature anti-crack ability, improve high-temperature behavior.
7, Hf is as carbide former, thus it is possible to vary MC type carbide inhibits netted in brilliant intracorporal distributional pattern
Carbide is formed, while reducing carbide segregation.
It is a further object of the present invention to provide a kind of preparations of above-mentioned laser melting and coating process high rigidity corrosion resistant alloy powder
Method.
The technical scheme adopted by the present invention to solve the technical problems existing in the known art is that a kind of laser melting coating work
The preparation method of skill high rigidity corrosion resistant alloy powder, comprising the following steps: (1) screening and weighing of raw material: according to above-mentioned heavy
Amount percentage weighs the raw metal in addition to microelement, the raw metal dry tack free of selection, cleaning, S in raw metal
It is lower than 0.001% with the overall content of P；(2) drying roasting: carrying out drying roasting at 550-650 DEG C for weighed raw metal,
Removal absorption water and the crystallization water；(3) feed intake compacting: the raw metal after drying roasting is uniformly mixed, is put into induction furnace,
It is compacted, covers bell；(4) be rapidly heated: the raw metal of 150kg/ furnace is heated to 1580 DEG C of meltings in 30 minutes and obtains steel
Liquid；(5) precipitation desoxydation: mixing molten steel obtained above use Si, Ca progress that total weight percent is 0.5-1% independent or
Co-precipitation deoxidation, calm processing 3-6 minutes；(6) final deoxidizing: being rapidly heated immediately after calm to 1580 DEG C, and weight is added
It measures the Al that percentage is 0.05-0.1% and carries out final deoxidizing；(7) it microelement alloying: weighs and removes according to above-mentioned weight percent
Microelement, in the molten steel after microelement to be put into final deoxidizing；(8) be atomized casting ladle: molten steel is poured into and is poured by tilt induction furnace
In packet, atomization temperature is controlled at 1540 DEG C ± 15 DEG C；(9) high pressure gas is atomized: using high-pressure inert gas to the gold in casting ladle
Category liquid stream injection is allowed to atomization and is crushed, and the initial velocity that high-pressure inert gas is contacted with molten steel is not less than 1000m/s, gas initial temperature
Between -20 DEG C~+5 DEG C；(10) dry screening: hair powder product obtained is dried, is sieved, finished powder is made.
Preferably: the high pressure nitrogen that step (9) the mesohigh inert gas selects purity to be greater than 99.9999%.
The advantages and positive effects of the present invention are:
1, it is rapidly heated in fusion process, by 150kg/ furnace 45 minutes, is down to 30 minutes i.e. up to 1580 DEG C, shortens in furnace
Inspiratory duration reduces furnace internal oxidition, low with the alloy powder oxygen content for ensuring to prepare, and can form the densification of pore-free, slag inclusion
Layer.
2, microelement is put into after deoxidation of skimming, since microelement is mostly rare earth and some stronger metals of activity
Such as rare-earth yttrium and common active metal aluminium, magnesium, titanium, zirconium, tantalum, these micronutrient levels are very low, but these yuan
Element can play the role of pinning crystal boundary, refinement crystal grain inside alloy while hardening constituent can be promoted to be precipitated, and being added thereto can
To improve the performances such as the strength of materials, red hardness, but these elements are more active, such as excessive in melting initial stage addition scaling loss, institute
To need to be added in the melting most later period, avoid scaling loss excessive.
Specific embodiment
It is described in detail such as in order to further understand the content, features and effects of the present invention, the following examples are hereby given
Under:
In order to adapt to laser melting and coating process feature, meet the performance requirement of different function coating, research and development prepare laser melting coating
Technology powder material special is needed by 3 alloy design, alloy melting, powder by atomization basic steps.
One, alloy designs
According to laser melting and coating process feature, high hardness and corrosion resistance alloy powder material is designed, this material is using ferro element as base
This material, primary alloy constituent Fe, C, Cr, Ni, B, Si and microelement (V, Nb, Ce, Mo, Hf).Composition range is C
≤ 0.12%, Cr 17.5~18.5%, Ni 6~7%, B 0.8~1.0%, Si 1~1.5%, V 0.5~0.8%, Nb
0.2~0.8%, Ce 0.4~0.8%, Mo0.2~0.6%, Hf0.1-1%, remaining is Fe.
It is the main function of various elements in the alloy below.
Iron (Fe): matrix element.
Carbon (C): carbon content be the basic strengthening material of iron-based material can play, solution strengthening effect, while when quenching
It can increase hardenability, increase after quenching hardness just now, while carbon (C) can form carbide with other elements, carbide is more
It dissipates to be distributed in body and can obviously increase material wear ability, achieve the effect that post-curing.
Chromium (Cr): Cr can significantly improve intensity, hardness and wearability, but reduce plasticity and toughness simultaneously.Cr can be improved again
The inoxidizability and corrosion resistance of steel improve harden ability.
Nickel (Ni): it is obviously improved the harden ability of coating material, while increasing toughness of material, cladding layer is avoided to crack.
Boron (B): reducing powder body material fusing point, reduces molten steel surface tension, is conducive to powder by atomization.
Silicon (Si): reducing powder body material fusing point, reduces molten steel surface tension, is conducive to powder by atomization.
Vanadium (V): V is carbide former, forms stable VC, and the VC in drawing process is with small and dispersed particle folding
Out, post-curing is caused.Increase coating high-temp hardness, promotes wearability.
Niobium (Nb): Nb is carbide former, forms stable NbC, causes post-curing, improves matrix hardness, mentions
Rise wearability.
Cerium (Ce): refinement coating structure is played, while promoting strength of coating and toughness.
Molybdenum (Mo): Mo can make the crystal grain refinement of coating, improve harden ability and thermostrength, keep enough strong at high temperature
Degree and creep resisting ability (being deformed at high temperature by stress for a long time, claim creep).
Hafnium (Hf): being solid-solution in coating with solution, intensity can be improved, while hafnium can promote elevated temperature strength increase
High temperature abrasion resistance.
Two, alloy melting
(1) screening and weighing of raw material: weighing the raw metal in addition to microelement according to above-mentioned weight percent, choosing
Raw metal dry tack free, cleaning, the overall content of S and P is lower than 0.001% in raw metal；
(2) weighed raw metal drying roasting: is subjected to drying roasting, removal absorption water and crystallization at 550-650 DEG C
Water；
(3) feed intake compacting: the raw metal after drying roasting being uniformly mixed, is put into induction furnace, is compacted, covers furnace
Lid；
(4) be rapidly heated: the raw metal of 150kg/ furnace is heated to 1580 DEG C of meltings in 30 minutes and obtains molten steel；
(5) precipitation desoxydation: mixing molten steel obtained above uses total weight percent to carry out for Si, Ca of 0.5-1%
Precipitation desoxydation, calm processing 3-6 minutes alone or in combination；
(6) final deoxidizing: being rapidly heated immediately after calm to 1580 DEG C, and the Al that 0.05-0.1% is added take off eventually
Oxygen；
(7) microelement alloying: weighing according to above-mentioned weight percent except microelement, and microelement is put into end
In molten steel after deoxidation.
Three, powder by atomization
(1) be atomized casting ladle: tilt induction furnace pours into molten steel in casting ladle, and atomization temperature is controlled at 1540 DEG C ± 15 DEG C；
(2) high pressure gas is atomized: atomization is allowed to the metal liquid stream injection in casting ladle using high-pressure inert gas and is crushed, it is high
The initial velocity that pressure inert gas is contacted with molten steel is not less than 1000m/s, and gas initial temperature is between -20 DEG C~+5 DEG C；
(3) dry screening: hair powder product obtained is dried, is sieved, finished powder is made.
In order to further understand the content, features and effects of the present invention, hereby enumerating following specific embodiments specifically
It is bright as follows:
Embodiment 1:
A kind of laser melting coating powder material, the raw material including following weight percent, C 0.05%, Cr 17.8%, Ni
6%, B 0.8%, Si 1%, microelement (V 0.2%, Nb 0.2%, Ce 0.4%, Mo0.2%, Hf0.3%), remaining is
Fe。
Pulverizing process:
1) raw material screening and pretreatment: it is the raw material dry tack free of selection, clean and tidy, weigh the raw material of above-mentioned weight percent
(raw material in addition to microelement)；
2) drying roasting: raw material carries out 600 DEG C of drying roastings, removes absorption water and the crystallization water；
3) feed intake compacting: putting the raw materials into induction furnace, is compacted, covers bell；
4) it is rapidly heated, 150kg/ furnace was through 30 minutes up to 1580 DEG C；
5) precipitation desoxydation: using the deoxidation of Si, Ca co-precipitation, calm processing 6 minutes；
6) final deoxidizing: after calm, 1580 DEG C is warming up to and is kept the temperature, and 0.05-0.1%Al final deoxidizing is added；
7) microelement alloying: weighing according to above-mentioned weight percent except microelement, and microelement is put into end
In molten steel after deoxidation；
8) be atomized casting ladle: induction furnace inclination pours into molten steel in packet, and atomization temperature is controlled at 1540 DEG C ± 15 DEG C；
9) liquid nitrogen is atomized: atomization is carried out to molten metal stream using high-purity nitrogen (purity is greater than 99.9999%) and is crushed, gas
Body and molten steel contact initial velocity are not less than 1000m/s, and gas initial temperature is between -20 DEG C+5 DEG C；
10) dry screening: by obtained hair powder product drying, finished powder is made in screening.
Test result:
1, oxygen content measures:
Using U.S.'s power can TC400 row nitrogen oxygen analyzer, to obtained powder body material carry out oxygen content measurement, randomly select one
10 positions criticized in powder are tested, test result such as table 1, and oxygen content mean value is 185ppm.
1 embodiment of table, 1 oxygen content test data
2, fluidity testing:
Using Britain's Malvern ms3000 type laser particle size analyzer, oxygen content measurement is carried out to obtained powder body material, with
10 positions that machine is chosen in a collection of powder are tested, and test result such as table 2, mobility mean value reaches 13.79s/50g.
2 embodiment of table, 1 fluidity testing data
3, apparent density is tested:
Using JL-A3 type powder characteristics tester, apparent density measurement is carried out to obtained powder body material, randomly selects a batch
10 positions in powder are tested, and test result such as table 3, apparent density mean value reaches 4.44g/cm3。
3 embodiment of table, 1 apparent density test data
4, hardness test:
Laser melting coating is carried out using the powder body material, using HR-150A Rockwell hardness instrument, hardness is carried out to obtained cladding layer
It tests (HRC hardness), randomly selects at 10 points and tested, test result such as table 4, HRC hardness mean value reaches 52.5.
4 embodiment of table, 1 hardness test data
5, salt spray test:
Laser melting coating is carried out using the powder body material, using SK-160A type salt spray test chamber, carries out neutral salt spray test,
It makes ten styles to be tested, test result such as table 5, not occurring the salt spray test average time corroded is 145.7 hours
(h)。
5 embodiment of table, 1 salt spray test data
Embodiment 2:
A kind of laser melting coating powder material, the raw material including following weight percent, C 0.03%, Cr 18.5%, Ni
7%, B 0.8%, Si 1.2%, microelement (V 0.6%, Nb 0.7%, Ce 0.6%, Mo0.5%, Hf0.8%), remaining
For Fe.
Pulverizing process is the same as embodiment 1.
Test process
1, oxygen content measures:
Using U.S.'s power can TC400 row nitrogen oxygen analyzer to obtained powder body material carry out oxygen content measurement, randomly select one
10 positions criticized in powder are tested, test result such as table 6, and oxygen content mean value is 188.8ppm.
6 embodiment of table, 2 oxygen content test data
2, fluidity testing:
Using Britain's Malvern ms3000 type laser particle size analyzer, oxygen content measurement is carried out to obtained powder body material, with
10 positions that machine is chosen in a collection of powder are tested, and test result such as table 7, mobility mean value reaches 13.58s/50g.
7 embodiment of table, 2 fluidity testing data
3, apparent density is tested:
Using JL-A3 type powder characteristics tester, apparent density measurement is carried out to obtained powder body material, randomly selects a batch
10 positions in powder are tested, and test result such as table 8, apparent density mean value reaches 4.502g/cm3.
8 embodiment of table, 2 apparent density test data
8, hardness test:
Laser melting coating is carried out using the powder body material, using HR-150A Rockwell hardness instrument, hardness is carried out to obtained cladding layer
It tests (HRC hardness), randomly selects at 10 points and tested, test result such as table 9, HRC hardness mean value reaches 52.4.
9 embodiment of table, 2 hardness test data
5, salt spray test:
Laser melting coating is carried out using the powder body material, using SK-160A type salt spray test chamber, carries out neutral salt spray test,
It makes ten styles to be tested, test result such as table 10, not occurring the salt spray test average time corroded is 145.4 hours
(h)。
10 embodiment of table, 2 salt spray test data
Embodiment described above is merely to illustrate technical idea and feature of the invention, in the art its object is to make
Technical staff it will be appreciated that the contents of the present invention and implement accordingly, patent of the invention only cannot be limited with above-described embodiment
Range, i.e., same changes or modifications made by all disclosed spirit, still falls in the scope of the patents of the invention.
Claims (2)
1. a kind of laser melting and coating process preparation method of high rigidity corrosion resistant alloy powder, the alloy powder includes following weight
The raw metal of percentage, C :≤0.12%；Cr:17.5~18.5%；Ni:6~7%；B:0.8~1.0%；Si:1~
1.5%；Microelement: 1.1~3.4%；Surplus is Fe；Wherein, the microelement includes V:0.2 by weight percentage
~0.8%；Nb:0.2~0.8%；Ce:0.4~0.8%；Mo:0.2~0.6%；Hf:0.1-1%, it is characterised in that: including
Following steps,
(1) screening and weighing of raw material: weighing the raw metal in addition to microelement according to above-mentioned weight percent, selection
Raw metal dry tack free, cleaning, the overall content of S and P is lower than 0.001% in raw metal；
(2) weighed raw metal drying roasting: is subjected to drying roasting, removal absorption water and the crystallization water at 550-650 DEG C；
(3) feed intake compacting: the raw metal after drying roasting being uniformly mixed, is put into induction furnace, is compacted, covers bell；
(4) be rapidly heated: the raw metal of 150kg/ furnace is heated to 1580 DEG C of meltings in 30 minutes and obtains molten steel；
(5) precipitation desoxydation: molten steel obtained above uses total weight percent to carry out individually or join for Si, Ca of 0.5-1%
Close precipitation desoxydation, calm processing 3-6 minutes；
(6) final deoxidizing: being rapidly heated immediately after calm to 1580 DEG C, and be added Al that weight percent is 0.05-0.1% into
Row final deoxidizing；
(7) microelement alloying: microelement is weighed according to above-mentioned weight percent, after microelement is put into final deoxidizing
Molten steel in；
(8) be atomized casting ladle: tilt induction furnace pours into molten steel in casting ladle, and atomization temperature is controlled at 1540 DEG C ± 15 DEG C；
(9) high pressure gas is atomized: being allowed to atomization to the metal liquid stream injection in casting ladle using high-pressure inert gas and is crushed, high pressure is lazy
Property the initial velocity that is contacted with molten steel of gas not less than 1000m/s, gas initial temperature is between -20 DEG C~+5 DEG C；
(10) dry screening: hair powder product obtained is dried, is sieved, finished powder is made.
2. a kind of preparation method of the laser melting and coating process as described in claim 1 with high rigidity corrosion resistant alloy powder, feature
It is: the high pressure nitrogen that step (9) the mesohigh inert gas selects purity to be greater than 99.9999%.
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| CN108396317B (en) * | 2018-01-25 | 2020-03-10 | 河北五维航电科技股份有限公司 | Surfacing method of turbine blade alloy layer |
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| CN111496245B (en) * | 2020-04-30 | 2022-03-22 | 湖南瑞华新材料有限公司 | High-corrosion-resistance powder material and preparation method and application thereof |
| CN111809177B (en) * | 2020-06-23 | 2022-10-14 | 宁波中物力拓超微材料有限公司 | Laser cladding alloy powder for repairing die and preparation method thereof |
| CN111702182A (en) * | 2020-08-05 | 2020-09-25 | 矿冶科技集团有限公司 | Preparation method of low-impurity-content alloy powder for additive manufacturing |
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Denomination of invention: A high hardness and corrosion-resistant alloy powder for laser cladding process and its preparation method Granted publication date: 20190510 Pledgee: Bank of Beijing Limited by Share Ltd. Tianjin branch Pledgor: TIANJIN ZHUJIN TECHNOLOGY DEVELOPMENT Corp. Registration number: Y2025990000018 |