CN101648213A - Hard alloy roll collar for finished frame of high-speed wire mill and preparation method thereof - Google Patents
Hard alloy roll collar for finished frame of high-speed wire mill and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hard alloy roll collar for the finished frame of a high-speed wire mill and a preparation method thereof. The roll collar has excellent wear resistance and thermal crack propagation resistance, WC grains are irregular polygons and have clear boundaries, the average grain fineness number of the alloy is more than 3.2mu m, the binding phase is distributed evenly and beta-phase distribution size is (1-2)mu m. In the preparation, coarse grain WC is reduced at high temperature to prepare the desired coarse grain W powder through yellow tungsten process, then the prepared coarse grain W powder is treated by air-flow multi-level elimination, W powder with the Fsss grain size of more than 90mu m is sent to perform high temperature carbonation production and the Fsss grainsize of the prepared coarse grain raw material WC; a milling method is adopted to distribute WC, binding phase, forming agent and other substances evenly, a special technology is used to reduce the milling efficiency so as to ensure the integrity of the coarse grain WC; the spray drying process is used to dry the mixture, the roll collar is pressed and the hydrogen dewaxing low pressure sinteringintegration technology is used for production.
Description
Technical field
The present invention relates to the carbide roll ring that high-speed wire mill hot rolling steel wire is used, particularly can be used for carbide roll ring of high-speed wire mill finished frame hot rolling steel wire and preparation method thereof.
Background technology
At present, carbide roll ring has been widely used for the high-speed wire mill high speed hot rolling steel wire of steel industry, can be used for pre-finish rolling, the finish rolling of high-speed wire mill and subtracts each frame of sizing.Carbide roll ring in use, the red steel drift that the groove surface of collars is advanced at utmost speed hits (the blackhead steel impulsive force when changing base is bigger), then, steel billet is extruded and attenuates elongatedly, leaves groove then, makes groove be subjected to impact extruded generation strain and elastic recovery in moment, and high temperature (750～1050 ℃) high-speed rolling, the degree of its distortion and answer and number of times are very high, therefore, require collars that very high toughness and thermal fatigue resistance, fire check performance will be arranged.Simultaneously, it is more that high-speed rolling also makes the unit interval pass through the wire rod of collars, and this just requires the roller rooved face that very high wearability will be arranged.A large amount of heat energy that wire rod rolling when distortion produces have improved the temperature when rolling again, must carry out water cooling, cooling water is all slant acidity or alkalescence generally, and have the trace tiny solids, rapidly the collars of rotation bears sometimes cold and sometimes hot alternate stress again, and this more requires collars that high heat conductivility and higher cracking resistance line, corrosion resistance will be arranged.
Development along with rolling technique, high-speed wire mill is more and more higher to the requirement in carbide roll ring quality and service life, particularly go out the finished frame (be generally high-speed wire mill last two) of final products, mill speed is the highest, general linear velocity all more than 90 meter per seconds, reaches as high as 140 meter per seconds; The roller footpath of collars is minimum, and rotating speed is also the highest; Must guarantee the rolled wire surface quality again.Therefore, require carbide roll ring both to have higher thermal conductivity and wearability, have higher toughness, thermal fatigue resistance again and resist the ability of the formation and the expansion of fire check, the service life that could improve collars.Industry technical staff knows, should select coarse-grain WC as far as possible for use for this reason, and reduces the cobalt content in the alloy, and has carried out a large amount of research.Chinese patent 97114701.9 discloses a kind of " the hot rolling collars that heat-resisting cracking and wearability improve ", the carbide roll ring feature of this invention is: WC grain is circular, average grain diameter is 3～10 μ m, maximum particle diameter does not exceed the twice of mean value, is not more than 2% less than half crystal grain of average grain diameter value in the tissue.This invention has also proposed to prepare the method for this collars: by milling with or without the injection of screening WC powder is milled into the powder of removing coarse grain and the narrow particle diameter distribution of compact grained, this WC powder with can form bonding obtained mutually expecting final composition powder, depressor and thickener under the condition of not milling, promptly do not take place under the particle diameter minimizing condition, wet-mixing becomes slip together, with the dry slip of spray drying process, suppress collars and sintering with spray-dried powders according to standard technology.Available cobalt applies WC powder before mixing.This patent adopts injection to mill and produces the WC powder that narrow particle diameter distributes, the method that adopts or do not adopt cobalt to apply WC prepares compound under the condition of not milling, the subject matter that exists in practice is: WC powder, depressor and thickener wet-mixing are together become slip, and without milling, bonding is difficult to even distribution at alloy, bond strength between bonding phase and the WC grain is not enough, must influence the quality and the quality of stability thereof of carbide roll ring, finally influence the collars serviceability.Among the embodiment that this patent provides, it is that the stainless steel steel wire of 40 meter per seconds is rolling that its collars only can be used for mill speed.In addition, the collars of this patent preparation requires harshness to the particle diameter of WC powder, and the complexity that must increase manufacturing facilities and the difficulty of technology controlling and process not only increase production cost, and product quality also is difficult to stablize.
Summary of the invention
The objective of the invention is to overcome bonding skewness in alloy that above-mentioned prior art exists, and with technological deficiencies such as the WC grain bond strength are not enough, provide a kind of WC to have more uniform internal organizational structure and bond strength mutually with bonding, higher thermal conductivity factor, the higher hardness and the carbide roll ring of wearability, it can be used to have the high-speed wire mill finished frame of maximum speed and mill speed, not only make stocking have good surface quality, and service life is longer.
For this reason, the present invention starts with from raw material and technology simultaneously, preparation coarse-grain tungsten powder and tungsten carbide powder, the mean grain size of increase hard phase WC; Adopt wet-milling to prepare tungsten carbide, bonding phase and forming agent compound, distributing homogeneity and the bond strength of strengthening the bonding phase realize objects of the present invention.Its concrete technical scheme is as follows:
This carbide roll ring that is used for the high-speed wire mill finished frame of the present invention, WC content is 85～94wt%, WC grain is the irregular polygon with clear boundary, mean grain size is 3.2～8.0 μ m, the bonding phase content is 6～15wt%, and bonding is pure cobalt mutually, or be cobalt with the nickel compoiste adhering mutually, or be cobalt, nickel and chromium compoiste adhering mutually, the bonding in the alloy is the even distribution of 1～2 μ m mutually.
Described WC mean grain size is preferably 4.0～6.0 μ m.
This carbide roll ring that is used for the high-speed wire mill finished frame of the present invention, when adopting cobalt to prepare mutually with the nickel compoiste adhering, the bonding content of middle Ni mutually is preferably 20～55wt%.
This carbide roll ring that is used for the high-speed wire mill finished frame of the present invention, at the employing cobalt, when nickel prepares mutually with the chromium compoiste adhering, the preferred bonding content of middle Ni mutually is 20～55wt%, the content of Cr is no more than 8wt%.
The present invention is the irregular polygon with clear boundary at the preparation WC grain, mean grain size is 3.2～8.0 μ m, bonding in the alloy is the preparation method of the equally distributed carbide roll ring of 1～2 μ m mutually: comprise the yellow tungsten of raw material at 900～1050 ℃ of reduction preparation coarse-grain tungsten powders, coarse-grain tungsten powder to preparation carries out the air current classifying screening, choose the Fsss granularity and carry out carbonization at 1900～2200 ℃ greater than the coarse-grain tungsten powder of 9.0 μ m, preparing the Fsss granularity is the coarse-grain raw material WC of 9～17 μ m, with coarse-grain raw material WC, bonding phase and forming agent are blended in the wet milk mills, with the compound spray-drying after milling, pressed compact, dewaxing, low pressure sintering becomes collars.
Advantage of the present invention is (to choose yellow tungsten WO from the preferred feedstock tungsten oxide
3) start with, high temperature reduction is prepared the coarse-grain tungsten powder, and choose big coarse-grain tungsten powder through air current classifying, pyrocarbon changes into coarse-grain raw material tungsten carbide powder then, again coarse-grain raw material tungsten carbide powder, bonding phase and forming agent suitably being milled to prepare in wet milk mixes, and keeps the compound of tungsten carbide coarse-grain feature again substantially.Therefore the carbide roll ring of preparation has higher hardness, hardness HRA 〉=84 (HV
3〉=870); Has toughness preferably, bending strength 〉=2480N/mm
2, fracture toughness is (18～22) MN/m
3/2(formula is adopted in the test of fracture toughness
By measuring HV Vickers hardness number and ∑ 1 is that the crack length sum at four angles is calculated), the stronger ability that mechanical stress is destroyed and crackle is expanded of resisting is arranged, satisfy the instructions for use of high-speed wire mill finished frame harshness fully.Compare with other finished product frame collars, its good heat conductivity has been postponed the generation of groove fire check and the corrosion wear of groove, has reduced the fatigue that collars produces through thermal cycle, and because its case hardness height, the surface quality of stocking is good.The groove life-span of this collars of the present invention is higher more than 2～3 times than the life-span of other trade mark carbide roll ring.
Description of drawings
Fig. 1 is the metallography microscope photo (1600X) of carbide roll ring of the present invention;
Fig. 2 is the SEM microphoto of the coarse-grain raw material tungsten carbide powder for preparing of the present invention;
Fig. 3 is a collars fracture toughness test diagram of the present invention.
The specific embodiment
Now the present invention is described in detail in conjunction with the accompanying drawings and embodiments.
The coarse-grain raw material WC that the present invention selects for use adopts yellow tungsten (WO
3) the technology preparation, yellow tungsten is carried out high temperature reduction under 900～1050 ℃ temperature, prepare required coarse-grain tungsten powder.Coarse-grain tungsten powder to preparation carries out the air current classifying screening, filter out the Fsss granularity and under 1900～2200 ℃, carry out high temperature cabonization greater than the tungsten powder of 9.0 μ m (micron), preparation go out required coarse-grain raw material WC, measure the Fsss granularity of coarse-grain raw material WC, satisfy between 9～17 μ m.The SEM photo of coarse-grain raw material WC as shown in Figure 2.The coarse-grain raw material WC that then preferred for preparation is gone out, bonding phase and forming agent (paraffin, PEG etc.) are milled at wet milk together.The purpose of milling mainly is that WC, bonding phase and forming agent etc. are evenly disperseed fully, increases WC and bonding bond strength mutually.Simultaneously, adopt conventional means to reduce grinding efficiency (method that shorten grinding time such as adopting, reduces ratio of grinding media to material) as far as possible, the effect of milling crystal grain is too attenuated with minimizing.Then, adopt the spray drying process dry pack, with spray-dried powders compacting collars base, use hydrogen dewaxing, (argon gas, 5MPa) sintering is prepared carbide roll ring to low pressure.WC grain is irregular polygon in the collars of preparation, has border clearly, and the mean grain size of WC is 3.2～8.0 μ m greater than 3.2 μ m, and the bonding in the alloy is evenly distributed mutually, is distributed as 1～2 μ m, and the metallurgical microstructrue of alloy as shown in Figure 1.Hard phase (WC) in the alloy and the bonding intensity height that combines, the fracture toughness of measurement is shown in Figure 3, test result satisfies and is (18～22) MN/m
3/2
In order to satisfy the requirement of high-speed wire mill finished frame to wearability, the present invention improves wearability by the content that improves hard phase (WC) in the alloy, and the content of hard phase (WC) is 85～94wt%, hardness of alloy value HRA 〉=84 (HV
3〉=870).
For the environment for use that satisfies different high-speed wire mills (mainly comprising milling train cooling water situation: pH value, index such as suspension in the water), and improve the serviceability of collars under high temperature (750～950 ℃), the present invention also selects the different phase structures that bond.High-speed wire mill cooling water situation is good, PH 〉=7.2, and suspension content can be selected pure cobalt binder phase for use less than 15mg/L in the water, and content is 6～15wt%; High-speed wire mill cooling water situation is relatively poor, and PH＜7.2 become slant acidity, to cobalt have a corrosiveness aggravation, can select corrosion resistant (Co+Ni) compoiste adhering phase for use, content is 6～15wt%, wherein bonding mutually in the content of Ni account for 20～55wt%; Be further to improve the high temperature serviceability of alloy material, the alloy bonding phase that optional being used in (Co+Ni) compoiste adhering adds Cr (Co+Ni+Cr) in mutually, wherein Cr is 8wt% at the high-load of bonding in mutually.
Embodiment 1:
DANIELI subtracts the sizing module, is used in last two (31#, 32#), the carbide roll ring specification: external diameter 212mm, internal diameter 120mm, height 60, mill speed 105 meter per seconds, 950 ℃ of blank outlet temperatures, rolling steel grade ER50-6, rolling specs Φ 5.5mm, cooling water pH value 7.2.
According to the preparation method of coarse-grain raw material WC of the present invention, choose yellow tungsten (WO
3) under (950～1050) ℃, carry out high temperature reduction, coarse-grain tungsten powder to preparation carries out the air current classifying screening, filter out the Fsss granularity and under 1950～2050 ℃, carry out high temperature cabonization greater than the tungsten powder of 9.0 μ m (micron), preparation go out required coarse-grain raw material WC, the Fsss granularity of measuring coarse-grain raw material WC is 12.5 μ m (micron), and the SEM photo satisfies shown in Figure 2.The pure cobalt binder phase that the carbide roll ring material that makes according to the present invention is chosen, content is respectively the WC of 92wt% and the cobalt of 8wt%, grind in wet milk with forming agent paraffin, carry out drying and granulating by spray drying process, the low pressure sintering of suppressing then, dewax, the alloy microstructure that makes satisfies shown in Figure 1, and measuring the alloy mean grain size is 4.2 μ m, hardness HRA reaches 88.0 (HV3 is 1200), bending strength 2800N/mm
2, the fracture toughness that records is 20.89MN/m
3/2
By rolling use, Steel Wire Surface is carried out strict detection, this collars list groove steel transportation amount is more than 120 (2.3 tons /), rolling tonnage is 300 a tons/groove, has satisfied the instructions for use of this high-speed wire mill.
Embodiment 2:
Last two of the root six generations milling train reducing sizing mill group of rubbing, carbide roll ring specification: external diameter 156mm, internal diameter 94mm, height 57mm, mill speed 112 meter per seconds, blank outlet temperature (780～1050) ℃, rolling steel grade SAE1008B, rolling specs Φ 5.5mm, cooling water pH value 7.2.
According to the preparation method of coarse-grain raw material WC of the present invention, choose yellow tungsten (WO
3) under (950～1050) ℃, carry out high temperature reduction, coarse-grain tungsten powder to preparation carries out the air current classifying screening, filter out the Fsss granularity and under 1950～2050 ℃, carry out high temperature cabonization greater than the tungsten powder of 9.0 μ m (micron), preparation go out required coarse-grain raw material WC, the Fsss granularity of measuring coarse-grain raw material WC is 12.5 μ m (micron), and the SEM photo satisfies shown in Figure 2.(Co+Ni+Cr) alloy bonding phase that the carbide roll ring material that makes according to the present invention is chosen, the Ni of Co, the 5.5wt% of 4.5wt% and Cr, the surplus of 0.5wt% are WC to the bonding phase content respectively, grind in wet milk with forming agent paraffin, carry out drying and granulating by spray drying process, the low pressure sintering of suppressing then, dewax, the alloy microstructure that makes satisfies shown in Figure 1 substantially, measuring the alloy mean grain size is 4.0 μ m, hardness HRA reaches 86.0 (HV3 is 1000), bending strength 2600N/mm
2, the fracture toughness that records is 19.38MN/m
3/2
By rolling use, Steel Wire Surface is carried out strict detection, the rolling tonnage of this collars list groove steel transportation amount is 500 a tons/groove, has satisfied the instructions for use of this high-speed wire mill.
Claims (5)
1, a kind of carbide roll ring that is used for the high-speed wire mill finished frame, WC content is 85～94wt%, the bonding phase content is 6～15wt%, bonding is pure cobalt mutually, or be cobalt with the nickel compoiste adhering mutually, or be cobalt, nickel and chromium compoiste adhering mutually, it is characterized in that WC grain is the irregular polygon with clear boundary, mean grain size is 3.2～8.0 μ m, and the bonding in the alloy is the even distribution of 1～2 μ m mutually.
2, carbide roll ring according to claim 1 is characterized in that described WC mean grain size is 4.0～6.0 μ m.
3, the carbide roll ring that is used for the high-speed wire mill finished frame according to claim 1 and 2 is characterized in that adopting cobalt and nickel compoiste adhering phase time, and the bonding content of middle Ni mutually is 20～55wt%.
4, the carbide roll ring that is used for the high-speed wire mill finished frame according to claim 1 and 2 is characterized in that adopting cobalt, nickel and chromium compoiste adhering phase time, and the bonding content of middle Ni mutually is 20～55wt%, and the content of Cr is no more than 8wt%.
5, the preparation method who is used for the carbide roll ring of high-speed wire mill finished frame according to claim 1, comprise coarse-grain raw material WC preparation, with coarse-grain raw material WC, bonding phase and forming agent are milled in wet milk, with the compound spray-drying after milling, pressed compact, dewaxing, low pressure sintering, it is characterized in that the yellow tungsten of raw material at 900～1050 ℃ of reduction preparation coarse-grain tungsten powders, coarse-grain tungsten powder to preparation carries out the air current classifying screening, choose the Fsss granularity and carry out carbonization greater than the coarse-grain tungsten powder of 9.0 μ m at 1900～2200 ℃, preparing the Fsss granularity is the coarse-grain raw material WC of 9～17 μ m.
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| CN101914714A (en) * | 2010-08-25 | 2010-12-15 | 株洲硬质合金集团有限公司 | Nonmagnetic hard alloy and preparation method |
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| CN102634684B (en) * | 2011-02-10 | 2015-06-24 | 厦门金鹭特种合金有限公司 | Method for preparing ultra-coarse grain cemented carbide by flexible ball milling technology |
| CN102247992A (en) * | 2011-06-17 | 2011-11-23 | 株洲硬质合金集团有限公司 | Hard alloy roll collar for two-dimensional cold-rolled ribbed steel bar |
| CN102784918A (en) * | 2012-08-23 | 2012-11-21 | 蓬莱市超硬复合材料有限公司 | Method for producing roll collars by recycling tungsten carbide from waste hard alloy roll collars |
| CN102974828B (en) * | 2012-10-12 | 2015-04-15 | 金川集团股份有限公司 | Production process of hard alloy roll collar |
| CN102974828A (en) * | 2012-10-12 | 2013-03-20 | 金川集团股份有限公司 | Production process of hard alloy roll collar |
| CN102994792A (en) * | 2012-12-10 | 2013-03-27 | 湖南世纪特种合金有限公司 | Preparation method for high-strength and high-hardness nanocrystalline tungstate-cobalt hard alloy |
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| CN103866172A (en) * | 2012-12-17 | 2014-06-18 | 北京有色金属研究总院 | Narrow-particle size distribution extra-coarse cemented carbide and preparation method thereof |
| CN103866172B (en) * | 2012-12-17 | 2016-06-15 | 北京有色金属研究总院 | A kind of super thick and stiff matter Alloy And Preparation Method of narrow particle size distribution |
| CN104388726A (en) * | 2014-12-15 | 2015-03-04 | 技锋精密刀具（马鞍山）有限公司 | Pretreatment production process for hard alloy |
| CN104388726B (en) * | 2014-12-15 | 2016-03-30 | 技锋精密刀具（马鞍山）有限公司 | A kind of pre-treatment production technique of Wimet |
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| CN109468517A (en) * | 2018-12-29 | 2019-03-15 | 株洲硬质合金集团有限公司 | A kind of preparation method and application of pile foundation engineering hard alloy |
| CN111778435A (en) * | 2020-05-28 | 2020-10-16 | 南通德元机械制造有限公司 | Hard alloy roll collar and preparation method thereof |
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| C06 | Publication | ||
| PB01 | Publication | ||
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