CN106835124A - A kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser - Google Patents

A kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser Download PDF

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Publication number
CN106835124A
CN106835124A CN201710128280.8A CN201710128280A CN106835124A CN 106835124 A CN106835124 A CN 106835124A CN 201710128280 A CN201710128280 A CN 201710128280A CN 106835124 A CN106835124 A CN 106835124A
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laser
carbide
parts
toughened
intermetallic compound
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CN201710128280.8A
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CN106835124B (en
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魏振华
刘玉柱
刘兆环
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Tangshan City Atlas Metallurgical Equipment Manufacturing Co Ltd
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Tangshan City Atlas Metallurgical Equipment Manufacturing Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/06—Surface hardening
    • C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/38—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for roll bodies
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/10—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on titanium carbide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides

Abstract

The present invention relates to a kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser, belong to metallurgical roller technical field.Technical scheme is：Using intermetallic compound Fe3Al and ZrO2Composite, participate in laser nano intensive treatment；Using nano level base carbide as enhancing phase, nano level 60 70 parts of Ti bases carbide, 46 parts of Si bases carbide, 12 parts of W bases carbide, 12 parts of Cr base carbide；The beneficial effects of the invention are as follows：By the hot roll of laser composite intensive treatment, working surface forms obdurability strengthening layer, maintain the fatigue strength such as high temperature hardness, high abrasion, anti-oxidant, wear resistant corrosion resistant basis, increased strengthening layer toughness and tenacity, the cracking brought by fragility is improved to be inclined to, the steel transportation amount of hot roll can be significantly improved, extends the roll change cycle.

Description

A kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser
Technical field
The present invention relates to a kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser, belong to metallurgical roller skill Art field.
Background technology
Roll is the primary deformable instrument on the various bar and shape mills of steel industry.Largely using various on steel rolling production-line The roll of type, wherein hot roll are usage amount and the maximum roll of consumption.Hot roll high temperature, top load, alternating hot and cold, It is on active service under the conditions of the bad working environments such as burn into abrasion, undergoes the alternate stresses such as powerful impulsive force and pressure and act on, generation abrasion, Corrosion, crackle, peeling, in addition fracture etc. fatigue damage, cause its fail or scrap.Various rolls, particularly hot roll are steel A very big consumption in iron enterprise's production capacity, is always an important problem in iron and steel enterprise's technology and production.For The use time of hot roll can suitably be increased, improve the performance and quality of rolled-section, reduce consumption and production cost, it is existing Technology uses traditional welding repair method, can make the size of part steel and ball roll proper restoration original new product made of iron, Although not reaching former technical performance index and service life, it is also possible to which product are temporarily used as an alternative.In recent years, it is molten using laser Cover carries out intensive treatment with ceramic surface reinforcement technique to hot roll, the technical performance of hot roll and service life is recovered With raising.But, there are the following problems for the application of unlike material hot roll laser melting and coating technique：Heat after ceramic material reinforcing is steady Qualitative deficiency, microstructure toughness is relatively low in strengthening layer, and strengthening layer easily produces cracking etc. in use.
The content of the invention
It is an object of the present invention to provide a kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser, by laser The hot roll of composite intensive treatment, working surface forms obdurability strengthening layer, maintains high temperature hardness, high abrasion, antioxygen The fatigue strength such as change, wear resistant corrosion resistant basis, increased strengthening layer toughness and tenacity, improves the cracking brought by fragility and is inclined to, The steel transportation amount of hot roll can be significantly improved, extends the roll change cycle, solve problem present in background technology.
The technical scheme is that：
A kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser, comprising following processing step：
Using intermetallic compound Fe3Al and ZrO2Composite, participate in laser nano intensive treatment；So, effectively The performance such as the high intensity that has using this compound-material, high-temerature creep, heat endurance, anti-oxidant and corrosion-resistant；Meanwhile, In compound phase, the superposition of its distinctive various strengthening and toughening mechanism and the cooperative effect of additional are made full use of；For increasing Toughness and tenacity in the reinforcing of heated roll laser nano, improves the toughness reinforcing index of hardening constituent；
The composite, is intermetallic compound Fe3Al and ZrO2, micron particles shape thing is fabricated to by equal proportion share Material.
Using nano level base carbide as enhancing phase, the component mass fraction for strengthening phase is：Nano level 60-70 Part Ti bases carbide, 4-6 parts of Si bases carbide, 1-2 parts of W bases carbide, 1-2 parts of Cr base carbide；Enhancing mutually improves ceramics Material embrittlement, forms dominant complementation effect；Possesses high temperature hardness, elevated temperature strength, high high-temp stability, wear-resistant, resistance to The features such as burn into toughness reinforcing cooperates with and be not aging, has reached intermetallic compound composite material and has matched somebody with somebody with tough collaboration of ceramic material Close, obtain solution strengthening and dispersion-strengtherning and precipitation strength and toughened and strengthened effect；
Comprise the following steps that：Enhancing by mass fraction 1-2 parts of composite with 10-15 parts is mutually mixed, and composition is compound The Toughened Materials of structure, Toughened Materials are coated on hot roll work roll surface or are sent to body of roll table using coaxial powder-feeding mode in advance On face, precoating thickness is painting 0.2-0.3mm；Laser compound processing treatment is carried out using Laser Processing unit, in roller surface Toughened and strengthened layer is formed in 0.5-2.0mm depth.
The Laser Processing unit is operated using intelligent robot, laser power density 2x105w/cm2, hot spot Φ 5mm sweep Speed 60-100mm/s is retouched, laser compound processing treatment is carried out, Mass distribution is formed in roller surface 0.5-2.0mm depth Solution strengthening and the toughened and strengthened layer of precipitation strength.
By the hot roll of laser composite intensive treatment of the present invention, working surface formed by between micron particles metal The obdurability strengthening layer of the coordinated that compound composite material is collectively constituted with nanoscale reinforcing materials, contrasts prior art list Pure nano ceramic material laser reinforcing treatment, maintains the fatigue strength such as high temperature hardness, high abrasion, anti-oxidant, wear resistant corrosion resistant Basis, increased strengthening layer toughness and tenacity, improves the cracking brought by fragility and is inclined to.Hot roll can be significantly improved crosses steel Amount, extends the roll change cycle, increases the service life more than 50%.
The beneficial effects of the invention are as follows：By the hot roll of laser composite intensive treatment, working surface forms tough Property strengthening layer, maintain the fatigue strength such as high temperature hardness, high abrasion, anti-oxidant, wear resistant corrosion resistant basis, increased strengthening layer strong Tough performance, improves the cracking brought by fragility and is inclined to, and can significantly improve the steel transportation amount of hot roll, extends the roll change cycle.
Specific embodiment
Below in conjunction with by example, the invention will be further described.
A kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser, comprising following processing step：
Using intermetallic compound Fe3Al and ZrO2Composite, participate in laser nano intensive treatment；So, effectively The performance such as the high intensity that has using this compound-material, high-temerature creep, heat endurance, anti-oxidant and corrosion-resistant；Meanwhile, In compound phase, the superposition of its distinctive various strengthening and toughening mechanism and the cooperative effect of additional are made full use of；For increasing Toughness and tenacity in the reinforcing of heated roll laser nano, improves the toughness reinforcing index of hardening constituent；
The composite, is intermetallic compound Fe3Al and ZrO2, micron particles shape thing is fabricated to by equal proportion share Material.
Using nano level base carbide as enhancing phase, the component mass fraction for strengthening phase is：Nano level 60-70 Part Ti bases carbide, 4-6 parts of Si bases carbide, 1-2 parts of W bases carbide, 1-2 parts of Cr base carbide；Enhancing mutually improves ceramics Material embrittlement, forms dominant complementation effect；Possesses high temperature hardness, elevated temperature strength, high high-temp stability, wear-resistant, resistance to The features such as burn into toughness reinforcing cooperates with and be not aging, has reached intermetallic compound composite material and has matched somebody with somebody with tough collaboration of ceramic material Close, obtain solution strengthening and dispersion-strengtherning and precipitation strength and toughened and strengthened effect；
Comprise the following steps that：Enhancing by mass fraction 1-2 parts of composite with 10-15 parts is mutually mixed, and composition is compound The Toughened Materials of structure, Toughened Materials are coated on hot roll work roll surface or are sent to body of roll table using coaxial powder-feeding mode in advance On face, precoating thickness is painting 0.2-0.3mm；Laser compound processing treatment is carried out using Laser Processing unit, in roller surface Toughened and strengthened layer is formed in 0.5-2.0mm depth.
The Laser Processing unit is operated using intelligent robot, laser power density 2x105w/cm2, hot spot Φ 5mm sweep Speed 60-100mm/s is retouched, laser compound processing treatment is carried out, Mass distribution is formed in roller surface 0.5-2.0mm depth Solution strengthening and the toughened and strengthened layer of precipitation strength.
In the present embodiment, the hot roll of rolled threaded steel, material is to be manufactured containing chromium, nickel infinitely chilled ductile cast iron.Specification is Φ 370x650x1513mm, hardness of roll body are 72-74HSD.In the bad working environments bar such as high temperature, high pressure, alternating hot and cold in work Under part, the principal element that the fatigue damages such as abrasion, fire check, corrosion are hot roll service life cycle is shorts is produced.
Using present invention process, micron particles Fe3Al and ZrO2Composite is made with nanoscale Si, Ti, Cr, W base carbide For enhancing is mutually mixed, the Toughened Materials of composite construction are constituted, the technical performance index for lifting hot roll extends it Steel transportation amount and cycle service life.
First, by after new roll or cycle use by turning（Or grinding）Roll barrel surface stand-by afterwards uniformly precoats The Toughened Materials of the composite construction of 0.2-0.3mm thickness, it would however also be possible to employ coaxial powder-feeding mode.Using 3KW semiconductor lasers Processing combination and single arm type intelligent robot control operation.Laser power density 2x105w/cm2, hot spot Φ 5mm, scanning Speed 70mm/s, the toughened and strengthened layer of 0.5-2.0mm depth is processed in body surface laser reinforcing.
By the hot roll of laser treatment, used in input Rolling production.Due to using obdurability intensive treatment, compared to original Pure laser nano ceramic material intensive treatment, the cycle steel transportation amount and service life of hot roll are substantially increased, every heat Roll totality service life improves about 80%.

Claims (2)

1. a kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser, it is characterised in that comprising following technique step Suddenly：
Using intermetallic compound Fe3Al and ZrO2Composite, participate in laser nano intensive treatment；The composite, It is intermetallic compound Fe3Al and ZrO2, micron particles shape material is fabricated to by equal proportion share；
Using nano level base carbide as enhancing phase, the component mass fraction for strengthening phase is：Nano level 60-70 parts of Ti Base carbide, 4-6 part of Si bases carbide, 1-2 parts of W bases carbide, 1-2 parts of Cr base carbide；
Comprise the following steps that：Enhancing by mass fraction 1-2 parts of composite with 10-15 parts is mutually mixed, and composition is compound The Toughened Materials of structure, Toughened Materials are coated on hot roll work roll surface or are sent to body of roll table using coaxial powder-feeding mode in advance On face, precoating thickness is painting 0.2-0.3mm；Laser compound processing treatment is carried out using Laser Processing unit, in roller surface Toughened and strengthened layer is formed in 0.5-2.0mm depth.
2. a kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser according to claim 1, its feature It is：The Laser Processing unit is operated using intelligent robot, laser power density 2x105w/cm2, hot spot Φ 5mm, scanning Speed 60-100mm/s, carries out laser compound processing treatment.
CN201710128280.8A 2017-03-06 2017-03-06 A kind of toughened and strengthened technique of roller surface intermetallic compound recombination laser Active CN106835124B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107988595A (en) * 2017-11-30 2018-05-04 钢铁研究总院 Laser melting coating prepares Fe3Al/Cr3C2The method of composite coating
CN110747457A (en) * 2019-11-15 2020-02-04 唐山市兆寰冶金装备制造有限公司 Method for reinforcing railway turnout forging and pressing die based on ceramic carbon/carbon combined laser
CN110885976A (en) * 2019-11-15 2020-03-17 唐山市兆寰冶金装备制造有限公司 Laser banded nano composite strengthening process
WO2022111739A1 (en) * 2020-11-30 2022-06-02 湖南金天铝业高科技股份有限公司 Iron-aluminum alloy composite reinforced aluminum-based material, preparation method therefor and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002022918A1 (en) * 2000-09-13 2002-03-21 Chrysalis Technologies Incorporated Nanocrystalline intermetallic powders made by laser evaporation
CN103060800A (en) * 2013-01-28 2013-04-24 山东建筑大学 Material for laser cladding of titanium alloy surface and laser cladding method
CN104233288A (en) * 2014-09-15 2014-12-24 华东交通大学 Preparation method of TiCFeAl-based wear-resistant coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002022918A1 (en) * 2000-09-13 2002-03-21 Chrysalis Technologies Incorporated Nanocrystalline intermetallic powders made by laser evaporation
CN103060800A (en) * 2013-01-28 2013-04-24 山东建筑大学 Material for laser cladding of titanium alloy surface and laser cladding method
CN104233288A (en) * 2014-09-15 2014-12-24 华东交通大学 Preparation method of TiCFeAl-based wear-resistant coating

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
CHEN YAO ET AL.: "Morphological evolution of primary TiC carbide in laser clad TiC", 《TRANS.NONFERROUS MET.SOC .CHINA》 *
刘涛等: "Fe3Al/ZrO2复合材料海水腐蚀电化学行为", 《中国腐蚀与防护学报》 *
张金升等: "激光熔覆法纳米Fe3Al/Al2O3梯度涂层在钢板上的应用研究", 《涂料工业》 *
江涛等: "金属间化合物/陶瓷基复合材料的制备工艺与研究进展", 《中国陶瓷工业》 *
蒲飞等: "激光表面合金化制备Tic/Fe3Al复合涂层组织及TiC演变规律", 《中国激光》 *
龚红宇等: "Fe3Al纳米粒子增强Al2O3陶瓷的制备及性能", 《中国有色金属学报》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107988595A (en) * 2017-11-30 2018-05-04 钢铁研究总院 Laser melting coating prepares Fe3Al/Cr3C2The method of composite coating
CN110747457A (en) * 2019-11-15 2020-02-04 唐山市兆寰冶金装备制造有限公司 Method for reinforcing railway turnout forging and pressing die based on ceramic carbon/carbon combined laser
CN110885976A (en) * 2019-11-15 2020-03-17 唐山市兆寰冶金装备制造有限公司 Laser banded nano composite strengthening process
WO2022111739A1 (en) * 2020-11-30 2022-06-02 湖南金天铝业高科技股份有限公司 Iron-aluminum alloy composite reinforced aluminum-based material, preparation method therefor and application thereof

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