CN1540039A - Nickel base alloy composite conductor roll and manufacturing method - Google Patents
Nickel base alloy composite conductor roll and manufacturing method Download PDFInfo
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- CN1540039A CN1540039A CNA2003101083380A CN200310108338A CN1540039A CN 1540039 A CN1540039 A CN 1540039A CN A2003101083380 A CNA2003101083380 A CN A2003101083380A CN 200310108338 A CN200310108338 A CN 200310108338A CN 1540039 A CN1540039 A CN 1540039A
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Abstract
A composite electric conducting roller made of Ni-base alloy for the electroplater is composed of roller axle and sleeve barrel which consists of internal sleeve made of high-strength low-alloy steel and external sleeve made of multi-element Ni-base alloy. Said external sleeve contains Cr, Mo, Nb, Ta, Nb+Ta, Al, Mg, Y, Na, N, Ti, C, Si, Mn, Fe and Ni and is prepared through smelting in electric furnace and centrifugal casting under action of magnetic field. Its advantage is high strength, toughness, and abrasion and corrosion resistance.
Description
Technical field: the present invention relates to conductive rollers and preparation method thereof, particularly be used for the nickel-base alloy composite conducting roller and the manufacture method thereof of all kinds of plating units.
Background technology: development of modern industry is more and more stricter to the steel sheet performance demands, and specifically, it not only will have the favorable mechanical performance, also good corrosion resisting property will be arranged.For anti-corrosion and decoration, also need good coating performance sometimes.Consider from material itself as single, any material that possesses good corrosion resisting property and mechanical property simultaneously, the cost height is difficult to be widely used.Coated layer steel plate great advantage is to have good solidity to corrosion, and generally than high several times to tens times of common cold-rolled carbon steel plate atmospheric corrosion resistance, in addition, their great majority have good formability and japanning, and what have also has good decorate properties.Therefore, all greatly developing the coated layer steel plate both at home and abroad, some national coated layer steel plate output has accounted for 50% of cold-reduced sheet output, accounts for 10% of output of steel.Electrogalvanizing steel plate is a principal item in the coated layer product, and world's electro-galvanizing capacity of equipment increases to 1,567 ten thousand t in 1992 from 1,150 ten thousand t in 1988, has surpassed 2,000 ten thousand t at present.The production of electrolytic galvanized sheet has entered a brand-new stage at present through 30 years of development.Since the eighties in 20th century, developing of automobile industry increases considerably the demand of electrolytic galvanized sheet, and kind and quality have been proposed more and harsher requirement.Adapt with this requirement, built up both at home and abroad a collection of new electro-galvanizing production line in recent years in succession,, mainly show the raising of unit speed and the raising of electroplating current density also having obtained major progress aspect the exploitation of the improvement of production technique and new variety.Along with the raising of unit speed and electroplating current density, unit output improves, and thickness of coating improves, and the coating kind increases, and the solidity to corrosion of electrogalvanizing steel plate also improves.Conductive rollers is the key part on the electro-galvanizing unit, in electroplating process in order to conduct powerful cathodic current.Under the conductive rollers in plating tank and the acting in conjunction of positive plate, with the zine ion in the plating bath in the plating tank at the surface of steel plate uniform deposition, wherein conductive rollers plays the plating cathodic process, conductive rollers requires to have low resistance, high conductivity is good, wear resistance and solidity to corrosion, the conductive rollers quality not only influences the quality of electrogalvanizing steel plate, also the operating rate of electro-galvanizing unit and the production cost of electrogalvanizing steel plate are had a significant effect, therefore, development of new conductive rollers material and manufacturing process thereof are electrogalvanizing steel plate manufacturing difficult problems anxious to be solved.
The improvement of conductive rollers material and manufacturing process both at home and abroad shows that mainly the copper conductive rollers replaces with rotary casting stainless steel conductive rollers and nickel-base alloy conductive rollers, has obviously improved wear resistance and solidity to corrosion.In recent years, on rotary casting nickel-base alloy conductive rollers basis, cold rolling Hastelloy hot charging composite conducting roller manufacturing technology and hot isostatic pressing nickel-base alloy conductive rollers manufacturing technology have been developed.The copper conductive rollers has excellent electroconductibility, but hardness is low, wears no resistance.The stainless steel conductive rollers replaces the copper conductive rollers, have solidity to corrosion preferably, but matrix is single austenite, and hardness is lower, and wear resistance is still on the low side, and under high electric current, solidity to corrosion also is difficult to satisfy service requirements.Among Japanese Patent Publication 63-33536 and the Japanese Patent Publication 63-33537, two kinds of polynary Cr-Ni alloy conductive rolls that contain 40%～55%Cr and alloying elements such as an amount of Mo, Nb, N, Ta, Ti and Al have been reported, they have high rigidity and high anti-corrosion, has good wear resistance, but because chromium is to form TCP phase (mainly being the σ phase) element, chromium content in these two kinds of conductive rollers is too high, causes plasticity and toughness low, is prone to cracking in casting and the use.Among the Japanese Patent JP01219134A, reported a kind of composition of nickel-base alloy conductive rollers, wherein contain 10～25%Cr, 7～12%Mo, 1～5%Nb, 0.4～5.0%Ti, 0.5～2.0%Al, also contain 5～15%Co, have good solidity to corrosion and wear resistance, but the cobalt metal that contains more costliness in the alloy, therefore, production cost is too high.Among the Chinese patent CN1116247, reported a kind of rotary casting stainless corrosion-resistant alloy conductive rolle rsleeve manufacture method, the stainless corrosion-resistant alloy composition is C, Si, Mn, Cr, Al, Ti, Fe, Ni, rare earth, Nb, Co, V, Nb wherein, Co, V contain one or more at least.The solidity to corrosion of this conductive rollers and wear resistance are better than the stainless steel conductive rollers, but are lower than the nickel-base alloy conductive rollers.Replace the rotary casting nickel-base alloy with cold rolling Hastelloy, overcome the rotary casting microstructure segregation, organized thick, inherent defects such as casting is mingled with, pore and crackle, the conductive rollers performance is further improved.Replace centrifugal casting technique with hot isostatic pressing technique and make the nickel-base alloy conductive rollers, have segregation-free, organize tiny, distributed components, characteristics such as dense structure.Main at present two hang-ups that exist of cold rolling Hastelloy hot charging composite conducting roller, first Hastelloy steel plate is too thick, the roll bending processing difficulties, therefore, and conductive rollers working lining thin thickness, work-ing life is short; It two is domestic equipment and technology of not making generous cold rolling Hastelloy plate, all from external high price import, causes conductive rollers production cost height.Also exist the low deficiency of weld seam solidity to corrosion difference and mechanical property.The use heat isostatic pressing technology replaces centrifugal casting technique and makes the nickel-base alloy conductive rollers, and the hot isostatic pressing equipment is complicated, and China does not also make the equipment and the technology of the nickel-base alloy cover that diameter is big, length is long at present.At present, China's conductive rollers mainly adopts rotary casting nickel-base alloy conductive rollers, rotary casting nickel-base alloy conductive rollers exist organize thick, column crystal obviously, deficiency such as poorly conductive, solidity to corrosion and wear resistance be low.Conductive rolle rsleeve adopts single nickel-base alloy manufacturing, exist that resistance is big, poorly conductive and the low deficiency of intensity, for overcoming these deficiencies, generally adopt the measure that strengthens the conductive rolle rsleeve wall thickness, but nickel-base alloy cost height, adopt the measure that strengthens the conductive rolle rsleeve wall thickness will significantly increase conductive rollers nickel-base alloy sleeve weight, improve production cost.Reported a kind of composite conducting roller manufacture method in the United States Patent (USP) 3860099, the overcoat of conductive rolle rsleeve adopts solidity to corrosion and the good nickel-base alloy manufacturing of wear resistance, interior cover adopts carbon steel manufacturing cheaply, interior cover and overcoat directly are combined with each other by hot charging, but contact surface resistance is big, reduces the conductivity of conductive rollers.
Summary of the invention: the technical issues that need to address of the present invention are, reduce the cost of conductive rollers, are guaranteeing under its electroconductibility, solidity to corrosion and the wear resistance prerequisite, prolong conductive rollers work-ing life.The invention provides a kind of chemical composition and manufacture method thereof of nickel-base alloy composite conducting roller.Thinking of the present invention is to adopt a kind of polynary nickel-base alloy to make the overcoat (working lining) of conductive rollers, and adopts centrifugal casting.Interior cover (inoperative layer) adopts high-strength low-alloy steel, and interior overcoat adopts hot-assembling method to be combined with each other, and is reduction conductive rollers resistance, raising conductive rollers conductivity, and overcoat compound tense in the conductive rollers, composite surface has added layer of copper.Its principal feature is to add an amount of Y, Mg, Na, N and Ti in nickel-base alloy, makes its structure refinement, helps increasing substantially of nickel-base alloy mechanical property, causes the raising of nickel-base alloy conductive rollers use properties the most at last.In addition, easily produce defectives such as segregation, thick column crystal, adopted to add electromagnetic field in the rotary casting in order to overcome common rotary casting conductive rollers, but refinement foundry goods tissue, eliminating thick column crystal, obtain tiny equiax crystal, is very favorable to wear resistance and the solidity to corrosion that improves conductive rollers.Adopt the speed change centrifugal casting technique in the centrifugal casting process, promptly periodically-varied mold speed of rotation makes the crystallization forward position obtain suitable tangential acceleration, can refinement conductive rollers body of roll tissue, improve its obdurability and solidity to corrosion.Adopt high temperature solid solution to handle simultaneously, can make conductive rollers tissue and composition more even, wear resistance and solidity to corrosion further improve.
The present invention realizes by following measure:
The present invention is a kind of nickel-base alloy composite conducting roller, the conductive rolle rsleeve hot charging is on roll shaft, conductive rolle rsleeve comprises cover in conductive rollers overcoat and the conductive rollers, the overcoat of conductive rollers is polynary nickel-base alloy, interior cover is high-strength low-alloy steel, interior overcoat adopts hot-assembling method to be combined with each other, and has all added layer of copper on the contact surface of the contact surface of roll shaft and roller shell and interior cover and overcoat.
The chemical composition of conductive rollers overcoat of the present invention is (weight %):
Cr:15.0～25.0, Mo:6.0～15.0, Nb or Ta one or both: 3.0～8.0, Al:0.5～5.0, Mg:0.003～0.020, Y:0.03～0.15, Na:0.03～0.15, N:0.05～0.15, Ti:0.08～0.50, C＜0.1, Si＜1.5, Mn＜1.5, Fe＜8.0.
All the other are Ni and inevitable trace impurity.
Conductive rollers electrosmelting of the present invention, its manufacturing technology steps is:
1. the chemical composition weight percent by the conductive rollers overcoat melts chromium metal, metal molybdenum, metal niobium, metal tantalum and nickel plate Hybrid Heating.
2. the stokehold is adjusted to branch and temperature is risen to 1580～1680 ℃ after qualified, adds aluminium deoxidation and alloying, then comes out of the stove.
3. the alterant and the ferrotianium that will contain magnesium, yttrium, sodium, nitrogen by the chemical composition weight percent of conductive rollers overcoat is crushed to the fritter of granularity less than 15mm, after oven dry below 300 ℃, place the casting ladle bottom, with the method that pours in the bag metal liquid is carried out composite inoculating and handle.
4. conductive rollers is applied mechanically centre spinning method production outward, casting mold wall thickness 40～160mm, 100～280 ℃ of preheating temperatures, and under this temperature at casting mold inner surface lining last layer refractory paint, paint thickness 0.8～6.0mm.Be installed on the whizzer to be cast after the mould drying.Mold temperature is 80～260 ℃ during cast.The metal liquid pouring temperature is 1460～1560 ℃.In nickel-base alloy cast and the process of setting, add electromagnetic field in casting mold, the magnetic induction density of electromagnetic field is 0.03T～0.25T.In rotational casting nickel-base alloy process of setting, under solid-liquid phase metal coexisting state, adopt the speed change centrifugal casting technique, make crystallization forward position melt produce tangential acceleration, tangential acceleration is 0.05m/s
2～0.25m/s
2
5. carry out solution treatment after the roughing of conductive rollers overcoat, solid solution treatment process is that conductive rollers is heated to 1020～1250 ℃ with stove, insulation 1～6h, cooling fast then.Carry out temper after the solid solution, temper technology is that conductive rollers is heated to 500～700 ℃ with stove, insulation 3～10h, the cold or air cooling of stove.
6. cover adopts high-strength low-alloy steel in the conductive rollers, by casting, forging, extruding or roll bending machine-shaping.Adopt plating or spraying method coating layer of copper at contact surface, thickness 0.05～0.50mm, conductive rollers overcoat and interior cover adopt hot-assembling method to be combined with each other, and shrink range is 0.050.25mm.
7. the conductive rollers roll shaft adopts the stainless steel manufacturing, also can adopt steel surface to coat the manufacturing of stainless steel plate method, and conductive rollers roll shaft and conductive rolle rsleeve adopt hot-assembling method compound, and shrink range is 0.05～0.25mm.Before compound, conductive rollers roll shaft and sleeve contact surface adopt and electroplate or spraying method coating layer of copper, thickness 0.05～0.50mm.Conductive rollers roll shaft and external carbon brush contact site adopt and electroplate or spraying method coating layer of copper, thickness 0.05～0.50mm.
The major cause of selecting for use nickel-base alloy to make the conductive rollers working lining is that nickel-base alloy has excellent corrosion resisting property.In the common nickel-base alloy, add alloying elements such as Cr, Mo, Nb, Ta and Al usually.The conductive rollers performance is by the metallographic structure decision, and certain tissue depends on chemical ingredients and thermal treatment process, and chemical ingredients of the present invention is to determine like this:
Cr:Cr is the solution strengthening element, can form erosion-resisting Cr again simultaneously
2O
3Protective layer, Cr
2O
3Oxide compound has densification, low cationvacancy, prevent atoms metal to harmful elements such as surface diffusion and oxygen, sulphur to the metal internal diffusion, prevent the continuation corrosion of alloy effectively, in order to improve the alloy corrosion resistance, chromium content should be controlled at more than 15%.But the chromium in the nickel-base alloy is again to form TCP phase (mainly being the σ phase) element, reduces the plasticity and the toughness of nickel-base alloy, takes all factors into consideration, and its content is controlled at 15.0%～25.0%.
Mo:Mo is strong solution strengthening element in nickel-base alloy, and its effect mainly is to form sosoloid, improves the intensity and the wear resistance of nickel-base alloy, Mo content is low excessively, and strengthening effect is not obvious, the Mo too high levels, because metal M o fusing point height, the alloy smelting difficulty, in addition, metal M o price height, add-on is too much, cause the nickel-base alloy cost obviously to increase, take all factors into consideration, Mo content is controlled at 6.0%～15.0%.
Al:Al forms γ ' (Ni in nickel-base alloy
3Al) phase distributes by γ ' disperse in matrix, thus reinforced alloys, the intensity and the wear resistance of raising nickel-base alloy, Al can also enter matrix and make matrix strengthening, and simultaneously, Al forms Al at alloy surface
2O
3Very fine and close oxide compound, the corrosion resistance that improves the nickel-base alloy conductive rollers is played good action, Al content is lower than at 0.5% o'clock, strengthen and improve the corrosion resistance DeGrain, but Al density is little, too high levels causes that easily composition profiles is inhomogeneous, takes all factors into consideration Al content is controlled at 0.5%～5.0%.
Nb and Ta:Nb, Ta mainly enter γ ', it is the principal element of reinforcement and stable γ ', Nb, Ta add-on are low excessively, strengthening effect to nickel-base alloy is not obvious, but add-on is too much, owing to Nb, Ta fusing point height, price height in addition, cause alloy melting difficulty and production cost obviously to increase, take all factors into consideration Nb or one or both content of Ta are controlled at 3.0%～8.0%.
Ti: the purpose that adds Ti is for the refinement alloy structure, improves its intensity and toughness, and Ti still is the main mutually forming element of γ ', distribute by γ ' disperse in matrix, thereby reinforced alloys, the intensity and the wear resistance of raising nickel-base alloy, Ti content is controlled at 0.08%～0.50%.
Alloying element chromium in C:C and the nickel-base alloy, titanium etc. form carbide, thereby reduced the alloying level of nickel-base alloy, and the carbide of chromium forms the resistance to corrosion that has reduced nickel-base alloy, the existence of too much TiC or Ti (CN) can cause metallurgical imperfection, therefore the carbon content in the nickel-base alloy conductive rollers is controlled at below 0.1%.
Fe:Fe reduces the solidity to corrosion of nickel-base alloy, and its content is controlled at below 8.0%.
Si:Si main solid solution in nickel-base alloy impels the matrix embrittlement in matrix, and the result of matrix embrittlement causes cracking occurring in the conductive rollers use and peeling off, and therefore Si content is limited in below 1.5%.
Mn:Mn has the tendency that makes the nickel-base alloy grain coarsening, reduces the intensity and the solidity to corrosion of conductive rollers, therefore Mn content is limited in below 1.5%.
Na:Na can reduce the Tc of nickel-base alloy, help alloy cold excessively at liquidus line, and the crystallization condensate depression of alloy increases, nucleation rate is increased greatly, therefore, Na increases the primary austenite nucleus, and primary austenite refinement, the refinement of primary austenite cause the intensity of nickel-base alloy and toughness to improve, also help and improve the nickel-base alloy solidity to corrosion, the Na add-on is very few, and is little to the performance impact of nickel-base alloy, and the Na add-on is too much, cause that The amount of inclusions increases in the alloy, reduce the nickel-base alloy mechanical property, take all factors into consideration, Na content is controlled at 0.03%～0.15%.
N: the major cause that adds N in the nickel-base alloy be before the crystallization N easily with liquid metal in Ti and the TiN and the AlN of Al reaction generation high-melting-point and high rigidity, impel alloy junction Jingjing nuclear to increase, cause the alloy structure refinement, help improving the obdurability of nickel-base alloy, TN that the high rigidity disperse distributes and the existence of AlN also help the wear resistance of improving nickel-base alloy.But add-on is too much, cause TiN and AlN thick, and quantity is too much, reduces the obdurability of nickel-base alloy on the contrary, also reduces the solidity to corrosion of nickel-base alloy simultaneously significantly, therefore its content is controlled at 0.05%～0.15%.
Mg: the major cause that adds Mg in the nickel-base alloy alloy is that it and sulphur have very strong avidity, forms sulfide, thereby reduces the deleterious effect of sulphur.Mg is again that a strong segregation is in the element of crystal boundary and phase boundary simultaneously, when Mg content is suitable, crystal boundary can obtain the carbide that the fine particle shape distributes, thereby improves the intensity and the plasticity of nickel-base alloy greatly, but Mg content is lower than 0.003%, DeGrain, and Mg content surpasses at 0.020% o'clock, and the carbide of the continuous distribution of bulk appears in crystal boundary, causes the intensity of nickel-base alloy and plasticity to reduce, during the Mg too high levels, even Ni-Ni appears
2Mg eutectic (1095 ℃ of fusing points), therefore the hot workability of deterioration nickel-base alloy, is controlled at 0.003%～0.02% with Mg content.
Y: rare earth adds the effect that has desulfurization, degasification in the nickel-base alloy, thermodynamic condition and application practice according to the re inclusion generation, the avidity of rare earth element and oxygen and sulphur is significantly greater than manganese and aluminium etc., rare earth element easily and oxygen, sulphur react, generate globular RE
2O
2S, RE
2S
3Deng re inclusion, improve the brittle rupture that nickel-base alloy produces along crystal boundary significantly.Therefore, after the rotten processing of rare earth, The amount of inclusions obviously reduces, and inclusion is tending towards nodularization and is evenly distributed in the alloy, and the toughness of alloy is improved, and a large amount of dimples will occur on the impact fracture.But excessive rare earth adds affiliation causes re inclusion to be broken chain distribution, diminishes the plasticity and the toughness of alloy on the contrary.In addition, rare earth has bigger atomic radius, and solubleness is very little in nickel.Owing to have very big electronegativity, so their chemical property is very active, can form a series of very stable compounds in nickel-base alloy, becomes the non-spontaneous crystallization core, thereby plays the effect of crystal grain thinning.In addition, rare earth is a surface active element, can increase crystallization nuclei and produce speed, stops grain growing.The refinement of crystal grain helps that alloy is moulded, toughness improves.Along with the increase of content of rare earth, grain refining is obvious more, and this is relevant with the intensity of activation that rare earth element can increase the austenite grain boundary migration.And in the crystallisation process, because rare earth element is at matrix and other partition ratio little (＜0.02%) in mutually, its surfactivity increases greatly, often is adsorbed on the crystal growth edge.Select the result of absorption, the crystal of growing up and alloy liquid interface form one deck adsorbent thin film obstruction crystal required atomic diffusion of growing up, and have reduced the crystal tendency of growing up, the refinement alloy structure.Add rare earth in the nickel-base alloy, can also improve the adhesivity of oxide film and alloy substrate, reduce oxide film and alloy substrate at the interface because Cr
3+The hole that forms to external migration, the solidity to corrosion of raising nickel-base alloy conductive rollers.The side effect that adds rare earth is to bring to be mingled with, and in order to give full play to the beneficial effect of rare earth, overcomes its side effect, replaces cerium base light rare earths commonly used with yttrium-base heavy rare earth.Yttrium-base heavy rare earth can obtain the less deoxidation of density, desulfurization product, is beneficial to its come-up.The deoxidation of cerium mischmetal, desulfurization product are with Ce
2O
2The S meter, its density is 6.00g/cm
3, the deoxidation of yttrium rare earth, desulfurization product are with Y
2O
2The S meter, density is 4.25g/cm
3, ascent rate V in centrifuge field is by Stokes formula calculating inclusion:
In the formula: V-inclusion floating speed, m/s; D-inclusion diameter, m; ρ
1The density of-metal liquid, N/m
3ρ
2The density of-inclusion, N/m
3The circular frequency of ω-casting mold rotation, rad/s; The rotation radius of arbitrfary point in the r-liquid metal, m; The kinetic viscosity of η-liquid, Ns/m
2As seen the latter's ascent rate increases 1 times than the former, and this is to use the yttrium rare earth to obtain clean tissue to the few major reason of alloy pollution.Add-on 0.03%～0.15% of Y o'clock, effect is better.
Inevitably trace impurity is to bring in the raw material, and P and S are wherein arranged, and all is harmful elements, and for the intensity, toughness and the solidity to corrosion that guarantee conductive rollers, we are controlled at P content below 0.05%, and S content is controlled at below 0.05%.
In the common rotary casting nickel-base alloy sleeve tissue, outer wall is the very thin thin equiax crystal of one deck, is to account for the most column crystal of the thickness of pipe then, and inwall is thicker equiax crystal.Thin equiaxed grain structure has excellent obdurability and wear resistance, also has good solidity to corrosion, thus the nickel-base alloy conductive rollers to obtain tiny equiaxed grain structure be very favorable to improving conductive rollers work-ing life.Usually the measure of crystal grain thinning, as reducing pouring temperature, improving mold radiating condition, mechanical vibration and add coccoid chill, these methods are effective to die casting, but rotational casting is difficult to obtain gratifying effect.Add electromagnetic field during rotary casting nickel-base alloy sleeve, the gravity segregation that both can suppress element, because the tangential component of electromagnetic force has reduced the circumferential movement speed of metal melt, thereby slowed down the radial motion of cluster group, meanwhile, under electromagnetic field effect, metal melt flows very violent, the nucleus that brushes down from the die wall upper punch and from the dendrite corrode, the nucleus that fractures increase, the more cores that can grow up are arranged, cause austenite tiny like this, become tiny equiax crystal by thick column crystal.But magnetic induction density is too small, and electromagnetic force is little, can not suppress elements segregation.Owing near the increase of the metal melt gravitation multiple solid-liquid interface forward position along with magnetic induction density descends, magnetic induction density is excessive, the A/W coefficient of metal melt will be lower than the necessary gravity coefficient of acquisition sound casting, and it is loose to cause the conductive rollers working lining to produce.The magnetic induction density of electromagnetic field is controlled at 0.03T～0.25T, both can eliminate the element segregation of rotary casting nickel-base alloy conductive rollers, can guarantee that also the nickel-base alloy conductive rollers obtains fine and close tissue under the rotary casting condition, can also obtain tiny equiaxed grain structure simultaneously.
In rotational casting nickel-base alloy process of setting, under solid-liquid phase metal coexisting state, improve the casting mold rotating speed with certain rule, make crystallization forward position melt produce acceleration dendrite is produced tangential force, can make dendrite fracture, come off, form nucleus, thereby can reach the effect of crystal grain thinning.In addition, under speed change rotary casting condition, melt is flowed relatively strengthen, the turbulent region enlarges, and has reduced the solidified front thermograde, and make solidified front diffusion boundary layer attenuate, concentration gradient increases, and the constitutional supercooling degree increases in the two-phase region thereby make, and everything all is that condition has been created in the equiax crystal growth, therefore after adopting the speed change centrifugal casting technique, rotary casting nickel-base alloy conductive rollers tissue thinning effect is remarkable.Adopt the speed change centrifugal casting technique, crystallization forward position melt produces tangential acceleration less than 0.05m/s
2The time, the conductive rollers tissue thinning effect is not obvious, and crystallization forward position melt produces tangential acceleration greater than 0.25m/s
2The time, the metal liquid turbulent flow in the casting mold is serious, and gas in the nickel-base alloy and inclusion are difficult for assembling to inwall, easily remain in the conductive rollers, have a strong impact on the use of conductive rollers, adopt the speed change centrifugal casting technique, crystallization forward position melt produces tangential acceleration and is controlled at 0.05m/s
2～0.25m/s
2The time, both can obtain the equiaxed grain structure of tiny densification, also can obtain pore and be mingled with few nickel-base alloy conductive rolle rsleeve.
The performance of alloy material also has direct relation with thermal treatment process, and it is worked out according to being:
Common rotary casting nickel-base alloy sleeve in the natural cooling process, because speed of cooling is slower, is prone to more precipitate pockety in the austenite after casting, reduce the solidity to corrosion of conductive rollers.With conductive rolle rsleeve reaustenitizing at high temperature, cooling fast can obtain the good austenite structure of solidity to corrosion then.The solid solution Heating temperature is lower than 1020 ℃, austenitizing time is oversize, the solid solution Heating temperature is higher than 1250 ℃, austenite structure is thick, reduce the solidity to corrosion and the obdurability of conductive rollers, carry out solution treatment at 1020～1250 ℃, cooling fast can obtain to organize austenite structure tiny, that performance is good behind insulation 1～6h.After the conductive rolle rsleeve solution treatment, because cooling is too fast, sleeve stress is big, after 500～700 ℃ of temper, can eliminate stress, and stabilizing tissue improves the conductive rollers performance.Tempering temperature is lower than 500 ℃, and stress relieving is insufficient, and tempering temperature is higher than 700 ℃, will produce more precipitate in the austenite, and the intensity and the solidity to corrosion of reduction conductive rollers are grown up in the precipitated phase gathering.
Metal current telescopic complex method mainly contains casting composite algorithm and hot charging composite algorithm, the casting composite algorithm has characteristics such as technology is easy, composite bed bonding strength height, but need two to overlap independently melting unit, and during the sleeve high-temperature heat treatment, composite bed is easy to crack, the tissue of interior cover low alloy steel is easily thick, causes intensity and toughness to descend significantly.When selecting the hot charging composite algorithm for use, the control of composite bed is very important, improves shrink range, although can reduce the contact resistance of conductive rollers, but shrink range is excessive, bush outer sleeve is excessive because of internal stress, easily crack, and shrink range is too big, the Heating temperature of bush outer sleeve requires high during hot charging, but Heating temperature is too high, easily produces precipitate in the nickel-base alloy, reduces the conductive rollers solidity to corrosion.When shrink range was 0.05～0.25mm, overcoat can good combination in the sleeve.In order to reduce the contact resistance of overcoat in the sleeve, with electroplating or spraying method applies the copper of a layer thickness 0.05～0.50mm, can reduce contact resistance at contact surface, improve the conductivity of conductive rollers.
The conductive rollers roll shaft uses under corrosive environment, directly adopts the stainless steel manufacturing, has solidity to corrosion preferably.Adopt steel surface to coat the manufacturing of stainless steel plate method, also can obtain high solidity to corrosion.Conductive rollers roll shaft and conductive rolle rsleeve adopt hot-assembling method compound, easy and simple to handle, shrink range is 0.05～0.25mm, and at the copper of conductive rollers roll shaft and sleeve contact surface applied thickness 0.05～0.50mm, can guarantee conductive rollers roll shaft and sleeve in conjunction with closely and contact resistance little.
Nickel-base alloy composite conducting roller of the present invention compared with prior art has following characteristics:
1. by adjusting the nickel-base alloy chemical ingredients, add trace elements such as magnesium, yttrium, sodium, nitrogen and titanium simultaneously and carry out the composite inoculating processing, but refinement nickel-base alloy tissue improves mechanical property, solidity to corrosion and wear resistance.Nickel-base alloy conductive rollers of the present invention and common nickel-base alloy conductive rollers performance comparison see Table 1.
Table 1 nickel-base alloy conductive rollers of the present invention and common nickel-base alloy conductive rollers performance comparison
Conductive rollers material hardness σ
bUnit elongation α
kThe wear resistance etching extent
(Hs) MPa ％ J/cm
2 mm
2.mm
-3?g.m
-2.h
-1
Nickel-base alloy 32.1 of the present invention～36.0 780～840 53～59 65～71 150～180 1.06～1.41
Common nickel-base alloy 30.8 763 50.5 62.2 133.7 1.58
Add electromagnetic field during rotary casting nickel-base alloy conductive rollers 2. of the present invention, the gravity segregation that can suppress element, because the tangential component of electromagnetic force has reduced the circumferential movement speed of metal melt, thereby slowed down the radial motion of cluster group, in addition, under electromagnetic field effect, metal melt flows very violent, the nucleus that brushes down from the die wall upper punch and from the dendrite corrode, the nucleus that fractures increases, the more cores that can grow up are arranged, cause austenite tiny like this, become tiny equiax crystal, can obviously improve the obdurability of nickel-base alloy conductive rollers by thick column crystal, wear resistance and solidity to corrosion.
3. the present invention under solid-liquid phase metal coexisting state, adopts speed change rotary casting mode in rotational casting nickel-base alloy process of setting, make crystallization forward position melt produce acceleration dendrite is produced tangential force, can make dendrite fracture, come off, form nucleus, thereby can reach the effect of crystal grain thinning.In addition, under speed change rotary casting condition, melt is flowed relatively strengthen, the turbulent region enlarges, reduced the solidified front thermograde, and make solidified front diffusion boundary layer attenuate, and concentration gradient increases, the constitutional supercooling degree increases in the two-phase region thereby make, everything all is that condition has been created in the equiax crystal growth, therefore after adopting the speed change centrifugal casting technique, rotary casting nickel-base alloy conductive rollers tissue thinning effect is remarkable, helps improving obdurability, wear resistance and the solidity to corrosion of nickel-base alloy conductive rollers.
4. nickel-base alloy conductive rolle rsleeve employing nickel-base alloy of the present invention and Hi-Stren steel are compound, complex method adopts hot charging compound, apply the copper of a layer thickness 0.05～0.50mm with plating or spraying method at contact surface, can reduce contact resistance, improve the conductivity of conductive rollers, make nickel-base alloy composite conducting roller with the present invention and can save production cost more than 25% than common monolithic conductive roller.
5. it is simple, easy to operate to make nickel-base alloy composite conducting roller production technique with the present invention, and conductive rollers body of roll tissue is tiny equiax crystal austenite structure, has excellent obdurability, wear resistance and solidity to corrosion.Nickel-base alloy composite conducting roller of the present invention has good result of use, be applied on the zinc-plated unit of broadband continuous electric, the galvanized sheet output of nickel-base alloy composite conducting roller of the present invention is 16600～17830t/mm, and the galvanized sheet output of common nickel-base alloy conductive rollers is 12500t/mm.Use conductive rollers of the present invention to reduce and change the conductive rollers time, improve the operating rate of electro-galvanizing unit, reduce the electrogalvanizing steel plate production cost, have good economic benefits.
Description of drawings:
Accompanying drawing is the present invention's electricity roll structure synoptic diagram
Among the figure: 1-roll shaft, cover in the 2-sleeve, 3-, 4-overcoat, 5-inner room copper layer, 6-shaft room copper layer, 7-axial plane copper layer.
Embodiment: the invention will be further described below in conjunction with embodiment:
Embodiment 1:
Conductive rollers roll shaft 1 adopts 35
#Forged steel is made, and in order to improve its solidity to corrosion, the exsertion part of roll shaft coats with the stainless steel plate of thickness 3mm.Conductive rolle rsleeve 2 is made up of interior cover 3 and overcoat 4, and interior cover 3 adopts the 16Mn weldless steel tube to process, and overcoat 4 adopts the centre spinning method manufacturing.Between interior cover 3 and the overcoat 4, adopting electro-plating method to apply thickness is the inner room copper layer 5 of 0.13mm, and the shrink range of overcoat and interior cover is 0.11mm.Between conductive rollers roll shaft 1 and the conductive rolle rsleeve 2, adopting electro-plating method to apply thickness is the shaft room copper layer 6 of 0.16mm, and the shrink range of roll shaft 1 and sleeve 2 is 0.14mm.Conductive rollers roll shaft and external carbon brush contact site adopt electro-plating method coating axial plane copper layer 7, thickness 0.20mm.
The manufacturing process of overcoat 4 is as follows:
1, batching: the consumption of various materials, by total amount 100% (weight %)
Metallic nickel 60.1, chromium metal 18.5,
Metal molybdenum 10.0, metal niobium 3.8,
Metallic aluminium 2.0, ferrotianium 1.2,
Sodium-containing material 1.2, nitrided ferro-chromium 1.5,
Magnesium-nickel alloy 1.2, Yttrium base rare earth 0.5.
2, melting: with 500 kilograms of medium-frequency induction furnace meltings
1. 300.5 kilograms of metallic nickels, 50 kilograms of metal molybdenum, 92.5 kilograms of chromium metals and 19 kilograms of metal niobium are mixed in the stove of packing into and melt;
Add 10 kilograms of aluminium when 2. temperature rises to 1620 ℃ and carry out deoxidation and alloying, promptly carve molten metal in casting ladle, be placed with granularity in the casting ladle in advance less than 15mm, and close and 2.5 kilograms of Yttrium base rare earths through 230 ℃ of 6 kilograms of sodium-containing materials of drying, 6 kilograms of ferrotianiums, 7.5 kilograms of nitrided ferro-chromiums, 6 kilograms of magnesium nickel;
3. adopt the cast iron casting mold during rotary casting of nickel-base alloy sleeve, casting mold wall thickness 130mm, 200 ℃ of casting mold preheating temperatures, and under this temperature at casting mold inner surface lining last layer refractory paint, paint thickness 1.5mm.Be installed on the whizzer to be cast after the mould drying.Mold temperature is 180 ℃ during cast.The metal liquid pouring temperature is 1530 ℃.In nickel-base alloy cast and the process of setting, add electromagnetic field in casting mold, the magnetic induction density of electromagnetic field is 0.08T.In rotational casting nickel-base alloy process of setting, under solid-liquid phase metal coexisting state, adopt the speed change centrifugal casting technique, make crystallization forward position melt produce tangential acceleration, tangential acceleration is 0.11m/s
2；
4. the solid solution treatment process of sleeve 4 is to be heated to 1150 ℃ with stove, insulation 3h, cooling fast then.Carry out temper after the solid solution, temper technology is to be heated to 650 ℃ with stove, insulation 6h, and stove is cold.Carry out chemical analysis, its composition following (weight %): 0.03C, 9.83Mo, 18.63Cr, 3.66Nb, 0.95Al from sleeve 4 samplings, 0.009Mg, 0.07Na, 0.12N, 0.31Ti, 0.07Y, 0.53Si, 0.67Mn, 3.29Fe, 0.013S, 0.036P, all the other are Ni.On the conductive rolle rsleeve entity, cut sample, the hardness of testing conductive roller and mechanical property, the result is as follows: hardness 33.7Hs, tensile strength 827MPa, unit elongation 56.2%, impelling strength 68.6J/cm
2The resistance of also having tested conductive rollers simultaneously is 0.045m Ω.
Get the nickel-base alloy composite conducting roller of the present invention use of installing, the result is as follows: working conditions is that speed is the zinc-plated unit of continuous electric of 80m/min, 6 of coating bath quantity, electric current 44KA, conductive rollers diameter 350mm, roll surface length 1800mm.Use conductive rollers of the present invention to produce electrolytic galvanized sheet output and be 17250t/mm, it is 12500t/mm that common nickel-base alloy conductive rollers is produced electrolytic galvanized sheet output.
Embodiment 2:
Conductive rollers roll shaft 1 adopts the manufacturing of 1Cr18Ni9Ti forging.Conductive rolle rsleeve 2 is made up of interior cover 3 and overcoat 4, and interior cover 3 adopts the seamless steel plate roll bending of 16Mn welding processing to form, and overcoat 4 adopts the centre spinning method manufacturing.Between interior cover 3 and the overcoat 4, adopting electro-plating method to apply thickness is the inner room copper layer 5 of 0.15mm, and the shrink range of overcoat and interior cover is 0.13mm.Between conductive rollers roll shaft 1 and the conductive rolle rsleeve 2, adopting electro-plating method to apply thickness is the shaft room copper layer 6 of 0.15mm, and the shrink range of roll shaft 1 and sleeve 2 is 0.15mm.Conductive rollers roll shaft and external carbon brush contact site adopt electro-plating method coating axial plane copper layer 7, thickness 0.18mm.
The manufacturing process of overcoat 4 is as follows:
1, batching: the consumption of various materials, by total amount 100% (weight %)
Metallic nickel 57.2, chromium metal 20,
Metal molybdenum 8.0, metal niobium 2.0,
Metal tantalum 3.5, metallic aluminium 3.8,
Sodium-containing material 1.0, nitrided ferro-chromium 1.1,
Magnesium-nickel alloy 1.5, ferrotianium 1.0,
Yttrium base rare earth 0.9.
2, melting: with 500 kilograms of medium-frequency induction furnace meltings
1. 286 kilograms of metallic nickels, 40 kilograms of metal molybdenum, 100 kilograms of chromium metals, 10 kilograms of metal niobium and 17.5 kilograms of metal tantalum are mixed in the stove of packing into and melt;
Add 19 kilograms of aluminium when 2. temperature rises to 1650 ℃ and carry out deoxidation and alloying, promptly carve molten metal in casting ladle, be placed with granularity in the casting ladle in advance less than 15mm, and close and 4.5 kilograms of Yttrium base rare earths through 230 ℃ of 5 kilograms of sodium-containing materials of drying, 5 kilograms of ferrotianiums, 5.5 kilograms of nitrided ferro-chromiums, 7.5 kilograms of magnesium nickel;
3. adopt the cast iron casting mold during rotary casting of nickel-base alloy sleeve, casting mold wall thickness 100mm, 130 ℃ of casting mold preheating temperatures, and under this temperature at casting mold inner surface lining last layer refractory paint, paint thickness 1.4mm.Be installed on the whizzer to be cast after the mould drying.Mold temperature is 130 ℃ during cast.The metal liquid pouring temperature is 1500 ℃.In nickel-base alloy cast and the process of setting, add electromagnetic field in casting mold, the magnetic induction density of electromagnetic field is 0.16T.In rotational casting nickel-base alloy process of setting, under solid-liquid phase metal coexisting state, adopt the speed change centrifugal casting technique, make crystallization forward position melt produce tangential acceleration, tangential acceleration is 0.18m/s
2
4. the solid solution treatment process of sleeve 4 is to be heated to 1100 ℃ with stove, insulation 2h, cooling fast then.Carry out temper after the solid solution, temper technology is to be heated to 600 ℃ with stove, insulation 4h, and stove is cold.Carry out chemical analysis, its composition following (weight %): 0.04C, 7.88Mo, 20.14Cr, 1.97Nb, 3.46Ta from sleeve 4 samplings, 1.91Al, 0.011Mg, 0.06Na, 0.09N, 0.15Ti, 0.11Y, 0.58Si, 0.66Mn, 3.54Fe, 0.012S, 0.032P, all the other are Ni.On the conductive rolle rsleeve entity, cut sample, the hardness of testing conductive roller and mechanical property, the result is as follows: hardness 32.9Hs, tensile strength 814MPa, unit elongation 57.5%, impelling strength 70.3J/cm
2The resistance of also having tested conductive rollers simultaneously is 0.048m Ω.
Get the nickel-base alloy composite conducting roller of the present invention use of installing, the result is as follows: working conditions is that speed is the zinc-plated unit of continuous electric of 80m/min, 6 of coating bath quantity, electric current 4.4KA, conductive rollers diameter 350mm, roll surface length 1800mm.Use conductive rollers of the present invention to produce electrolytic galvanized sheet output and be 17130t/mm, it is 12500t/mm that common nickel-base alloy conductive rollers is produced electrolytic galvanized sheet output.
Claims (8)
1, a kind of nickel-base alloy composite conducting roller that is used for all kinds of plating units, the conductive rolle rsleeve hot charging is compounded on the roll shaft, conductive rolle rsleeve comprises cover in conductive rollers overcoat and the conductive rollers, the overcoat that it is characterized in that conductive rollers is polynary nickel-base alloy, interior cover is high-strength low-alloy steel, interior overcoat adopts hot-assembling method to be combined with each other, and has all added layer of copper on the contact surface of the contact surface of roll shaft and roller shell and interior cover and overcoat.
2, nickel-base alloy composite conducting roller according to claim 1 is characterized in that roll shaft and sleeve hot charging compound shrink range are 0.05～0.25mm, and interior cover and overcoat hot charging compound shrink range are 0.05～0.25mm.
3, nickel-base alloy composite conducting roller according to claim 1 and 2 is characterized in that the thickness of copper layer between the contact surface Upper shaft sleeve of roll shaft and roller is 0.05～0.50mm, and the thickness of inner room copper layer is 0.05～0.50mm on the contact surface of interior cover and overcoat.
4, nickel-base alloy composite conducting roller according to claim 1 is characterized in that the roller overcoat adopts polynary nickel-base alloy, and its chemical ingredients is (weight %):
Cr:15.0～25.0, Mo:6.0～15.0, Nb:0～8.0, Ta:0～8.0, Nb+Ta:3.0～8.0, Al:0.5～5.0, Mg:0.003～0.020, Y:0.03～0.15, Na:0.03～0.15, N:0.05～0.15, Ti:0.08～0.50, C＜0.1, Si＜1.5, Mn＜1.5, Fe＜8.0, surplus is Ni and inevitable trace impurity.
5, claim 1 and 4 described nickel-base alloy composite conducting roller manufacture method is characterized in that the electric furnace production of roller overcoat, and its processing step is:
1. the chemical composition weight percent by the conductive rollers overcoat melts chromium metal, metal molybdenum, metal niobium, metal tantalum and nickel plate Hybrid Heating;
2. the stokehold is adjusted to branch and temperature is risen to 1580～1680 ℃ after qualified, adds aluminium deoxidation and alloying, then comes out of the stove;
3. the alterant and the ferrotianium that will contain magnesium, yttrium, sodium, nitrogen by the chemical composition weight percent of conductive rollers overcoat is crushed to the fritter of granularity less than 15mm, after oven dry below 300 ℃, place the casting ladle bottom, with the method that pours in the bag metal liquid is carried out composite inoculating and handle;
4. conductive rollers is applied mechanically centre spinning method production outward, casting mold wall thickness 40～160mm, 100～280 ℃ of preheating temperatures, and under this temperature at casting mold inner surface lining last layer refractory paint, paint thickness 0.8～6.0mm, be installed on the whizzer to be castly after the mould drying, mold temperature is 80～260 ℃ during cast, and the metal liquid pouring temperature is 1460～1560 ℃:
5. carry out solution treatment after the roughing of conductive rollers overcoat, solid solution treatment process is that conductive rollers is heated to 1020～1250 ℃ with stove, insulation 1～6h, cooling fast then, carry out temper after the solid solution, temper technology is that conductive rollers is heated to 500～700 ℃ with stove, insulation 3～10h, the cold or air cooling of stove.
6, nickel-base alloy composite conducting roller manufacture method according to claim 5 is characterized in that adding electromagnetic field in cast of roller overcoat and the process of setting in casting mold, and the magnetic induction density of electromagnetic field is 0.03T～0.25T.
7, according to claim 5 or 6 described nickel-base alloy composite conducting roller manufacture method, it is characterized in that roller is enclosed within the rotational casting process of setting outward, under solid-liquid phase metal coexisting state, adopt the speed change centrifugal casting technique, make crystallization forward position melt produce tangential acceleration, tangential acceleration is 0.05m/s
2～0.25m/s
2
8, nickel-base alloy composite conducting roller manufacture method according to claim 5 is characterized in that conductive rollers roll shaft and external carbon brush contact site, adopts and electroplates or spraying method coating one deck axial plane copper layer, thickness 0.05～0.50mm.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102009325A (en) * | 2010-11-07 | 2011-04-13 | 上海交通大学 | Method for improving corrosion resistance of weld joint of hastelloy conductive roller |
| CN101797678B (en) * | 2010-01-14 | 2012-05-09 | 上海志卓机械制造有限公司 | Cathode roll and titanium sleeve processing and assembly process |
| CN103060867A (en) * | 2012-12-27 | 2013-04-24 | 上海交通大学 | Method for preparing the working layer of a conductive roller |
| CN103071964A (en) * | 2012-11-29 | 2013-05-01 | 湖南力神新材料科技有限公司 | Manufacturing method for compound metal pipe |
| CN109563560A (en) * | 2016-08-12 | 2019-04-02 | 奥钢联中厚板有限公司 | Method for producing rolling cladding sheet |
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2003
- 2003-11-03 CN CN 200310108338 patent/CN1239753C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101797678B (en) * | 2010-01-14 | 2012-05-09 | 上海志卓机械制造有限公司 | Cathode roll and titanium sleeve processing and assembly process |
| CN102009325A (en) * | 2010-11-07 | 2011-04-13 | 上海交通大学 | Method for improving corrosion resistance of weld joint of hastelloy conductive roller |
| CN102009325B (en) * | 2010-11-07 | 2012-07-25 | 上海交通大学 | Method for improving corrosion resistance of weld joint of hastelloy conductive roller |
| CN103071964A (en) * | 2012-11-29 | 2013-05-01 | 湖南力神新材料科技有限公司 | Manufacturing method for compound metal pipe |
| CN103060867A (en) * | 2012-12-27 | 2013-04-24 | 上海交通大学 | Method for preparing the working layer of a conductive roller |
| CN103060867B (en) * | 2012-12-27 | 2015-08-19 | 上海交通大学 | The preparation method of conductive rollers working lining |
| CN109563560A (en) * | 2016-08-12 | 2019-04-02 | 奥钢联中厚板有限公司 | Method for producing rolling cladding sheet |
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