CN1566396A - Method for enhanced treatment of ductile iron surface - Google Patents
Method for enhanced treatment of ductile iron surface Download PDFInfo
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- CN1566396A CN1566396A CN 03129633 CN03129633A CN1566396A CN 1566396 A CN1566396 A CN 1566396A CN 03129633 CN03129633 CN 03129633 CN 03129633 A CN03129633 A CN 03129633A CN 1566396 A CN1566396 A CN 1566396A
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Abstract
The invention relates to a method for enhanced treatment of ductile iron surface which comprises preheating, nitrogenization, oxygenizing, rinsing, drying and gumming.
Description
Technical field
The present invention relates to the surface treatment of metallic substance, be specifically related to magnesium iron salt bath method for surface hardening.
Background technology
QPQ is the abbreviation of Quench--Polish--Quench, it is a kind of new metal salt bath surface reinforcement modifying technology, and this technology has wide practical use in industries such as automobile, motorcycle, engineering machinery, light industry machinery, instrument, firearms, tool and moulds.The QPQ Combined Processing is actually the compound of nitriding (carbonitriding) and oxidation operation, and its agent technology is nitriding, by the salt bath nitriding change of technique.
In existing magnesium iron nitridation technique, processing modes such as gas nitriding, salt bath tufftride, gas soft nitriding are arranged usually.
Gas nitriding is to carry out in ammonia dissolving atmosphere, and the nitrogen-atoms that utilizes ammonia to decompose generation infiltrates the magnesium iron workpiece surface, produces the nitride hardened layer.Magnesium iron gas nitriding temperature is generally two sections nitrogenize of 510～570, is incubated 40～80 hours, and nitride layer is generally 0.4～0.8mm deeply, can bear ground finish.But its production cycle is oversize, and the Fe 2N phase fragility that the surface generates is bigger.
Liquid tufftriding carries out in fused sodium cyanide and potassium cyanide salt bath at first.In order to improve the activity of salt bath, dried air or oxygen is fed in the salt bath, this not only works the companion's effect of stirring, but also quicken the oxidation of cyanogen salt, make it become cyanate, cyanate and then decomposite active nitrogen, carbon atom and infiltrate the magnesium iron surface forms Fe 3N (the containing part Fe 4N) compound layer of high abrasion.Because of cyanogen salt has severe toxicity, the back replaces with nontoxic raw material (urea) prescription, and need not carry out liquid tufftriding by bubbling air in salt bath, and magnesium iron adopts 3～4 hours technological specifications of 540～560 insulation, surface hardness reaches HV550～750, nitrogenize bed thickness 0.01～0.05.Although the salt bath medium with the urea prescription is nontoxic, reaction product (fused salt) has toxicity equally, can cause environmental pollution, and is harmful.
The used medium of gas soft nitriding is nontoxic, and endogas and ammonia, urea, methane amide or trolamine and alcoholic acid mixed solution etc. are typically arranged.These media will decomposite active nitrogen, carbon atom under nitriding temperature, absorbed and the realization carbonitriding by the magnesium iron surface.The magnesium iron gas soft nitriding adopts 520～570 insulation 2～6 hours usually, handles rear surface hardness and can reach HV500～570, alloying layer thickness 0.02～0.05.Gas soft nitriding has overcome the deleterious shortcoming of liquid tufftriding reaction product, quality layer and aspect of performance near or reach the liquid tufftriding level.But for the tufftride treatment technology of magnesium iron auto parts required, surface hardness was often on the low side and do not reach requirement.
Along with the manufacturing development of modern machines,, doing stricter restriction aspect energy consumption and the environmental protection to the demands for higher performance of metallic substance.20th century the mid-1970s, a lot of old salt bath surface reinforcing methods are owing to reasons such as prussiate cause environmental pollution and are eliminated one after another.Industrial rise such as automobile not only can not lack this class technology, and an urgent demand is developed, and a kind of wear resistance is higher, corrosion stability is better and the non-harmful a kind of new type of metal salt bath surface strengthening technology of full technological process.
The salt bath formula that the QPQ nitriding treatment does not contain prussiate is taken the lead in developing by German Di Gaosha (DGUSSA) company, and increase the oxidation operation that thoroughly decomposes remaining cyanogen root together, formed the non-harmful novel metal surface strengthening technology of a kind of full technological process.U.S. Cologne company (KOLENE) has introduced this technology, and is improved, and increases again after former salt bath Combined Processing and polishes and reoxidize, and has formed the QPQ patented technology.This composite treatment technology is equivalent to carry out simultaneously thermal treatment and surperficial processing against corrosion.Can become order of magnitude ground to improve wear resistance and corrosion stability, general thermal treatment and technology against corrosion can not reach, so this technology is employed abroad, all adopt as major companies such as AM General electrical equipment, germany volkswagen, Japanese Toyota, Hondas.The relative villa weir locomotive works of China, Shandong Weifang Diesel Engine Plant, Hangzhou engine works etc. with 60～900,000 dollars from external this suite of equipment technology of having introduced, the Shanghai Volkswagen had also introduced this technology from Germany afterwards.
Usually the QPQ treatment technology comprises preheating, nitrogenize, oxidation, step such as polishes, reoxidizes.
The main effect of preheating is a moisture content of drying workpiece surface, reenters nitriding furnace after cold workpiece is heated up, in case band water conservancy project part go into to cause behind the nitriding furnace to prevent after the salt bath sputter cold workpiece go into stove after the nitriding furnace temperature descend too many.Preheating has sizable effect to the outward appearance that workpiece reduces distortion and acquisition color and luster homogeneous.
Nitrogenize is the core process of QPQ salt bath composite treatment technology.Because the decomposition of cyanate radical produces activated nitrogen atom in the nitrogenize salt bath, form wear resistance and very high compound layer and the fatigue proof diffusion layer of corrosion stability in the metallic surface.The nitrogenize operation the most important thing is the decomposition of cyanate radical in the salt bath.
The main effect of oxidation can make the cyanogen root (CN) of workpiece from the salt that nitriding furnace brings out thoroughly decompose, and eliminates public hazards; Form black oxide film at workpiece surface simultaneously, increase corrosion stability, certain benefit is also arranged improving wear resistance
In the surface treatment of magnesium iron auto parts, the technological standard that requires to reach is: surface hardness: HV
0.1〉=570, the compound layer degree of depth 〉=0.008mm, diffusion layer 〉=0.03, surface porosity≤3 grade.Nitriding process parameter in the external QPQ Combined Processing of recommending is: nitriding temperature 580, nitridation time are not more than 3 hours, CNO
-Content control: 38%.
According to external recommended parameter, the inventor adopts fixedly nitriding temperature 580, and under cyanate radical content 38% condition, nitridation time was tested four times by 1～4 hour, with metallographic method and microsclerometry depth of penetration and hardness, it concerns as Fig. 1, Fig. 2.
Test-results shows: nitridation time is to the influence (as shown in Figure 1) of depth of penetration, and nitridation time is 1 hour, and compound layer is 5 μ m; When being increased to 3 hours, along with the lengthening of time, the increase of the compound layer degree of depth is rapider, near 20 μ m.Nitridation time increases the time after extending to 3 hours again, and the compound layer increase is slower.Nitridation time extended to 4 hours by 1 hour, and along with the lengthening of nitridation time, the diffusion layer degree of depth almost linearly increases.
Nitridation time to the influence of nitrided layer hardness as shown in Figure 2, nitrogenize 1 hour, infiltration layer is the most surperficial not to have hardness decline phenomenon, but the hardness maximum is lower, HV
0.1Be about 540.Nitridation time is more than or equal to 2 hours, the most surperficial hardness decline phenomenon that all can produce of infiltration layer.Nitridation time is long more, and surface hardness descends serious more, and peak value of hardness is high more and the position is inside more moves.This is because due to layer surface compound layer tectorium increases the weight of gradually, broadens.
Fig. 3-1, Fig. 3-2, Fig. 4-1, Fig. 4-2 are nitridation time 2 hours, 3 hours infiltration layer patterns (580,38%CN
-).
The external QPQ Combined Processing nitriding process parameter of recommending can obtain gratifying effect to handling all kinds of tool steel, structure iron etc.But can not achieve one's goal for the part of handling the magnesium iron making, this may be because due to the singularity of the Chemical Composition of magnesium iron material own.Because the silicon in the magnesium iron, phosphorus content are higher, silicon is stronger than oxygen to the avidity of iron, and silicon can disturb the infiltration of nitrogen and depth of penetration is reduced during nitriding; And the phosphorus content height then has disadvantageous effect to nitrided layer hardness.So, can not need treat with a certain discrimination without exception and together the processing parameter of magnesium iron nitriding treatment.
Summary of the invention
Technical problem to be solved by this invention is to overcome the loose and hardness defective on the low side of magnesium iron layer surface that external recommendation nitriding process parameter is produced, nitriding process condition in the existing QPQ compounding method is improved, and final surface anticorrosion processing mode carried out original innovation, provide a kind of QPQ of condition optimizing to handle the method on magnesium iron auto parts surface, make cast pieces of spheroidal wear-resisting, anti-corrosion performance is more good.
Cast pieces of spheroidal disclosed by the invention surface QPQ compounding method comprises steps such as preheating, nitrogenize, oxidation, cleaning, oven dry and immersion oil, and concrete processing condition comprise:
(1) preheating: 350-380,30min;
(2) nitrogenize: temperature 580-530, CNO
-Concentration 32-34%;
(3) oxidation: 360 ℃, 10-20min;
(4) clean: clean the sticking floating thing in surface;
(5) oven dry: remove moisture content;
(6) immersion oil: containing U.S. soap of barium mahogany sulfonate, lanolin and zinc naphthenate anticorrosive additive 90 ℃ 10
#Flood 2-5min in the machinery oil.
Magnesium iron of the present invention is QT450-10, contain C:3.2～3.6%, Si:2.6～2.8%, Mn:0.6～0.7%,, P≤0.01%, S:0.016～0.03%, Mg:0.035～0.038%, Re:0.01～0.05%.
The preferred weight percentage composition of each anticorrosive additive is the U.S. soap 3-7% of barium mahogany sulfonate 3-7%, lanolin, zinc naphthenate 0.5-4% in the immersion oil step of the present invention.
The present invention is that nitriding process is improved to the characteristics of cast pieces of spheroidal surface QPQ compounding method, by a series of tests, seeks the influence to nitrogenize of temperature and cyanate radical content.
1. the influence of nitriding temperature
QT450-10 magnesium iron sample is under the condition of 38% cyanate radical, and nitridation time is because of being decided to be 3 hours, and nitriding temperature is chosen by 500-580 ℃, measures the compound layer degree of depth with metallographic method.
The relation of the compound layer degree of depth and nitriding temperature as shown in Figure 5, nitrogenize concentration is too low＜550 ℃, can not form enough compound layers;＞560 ℃, the compound layer degree of depth increases sharply.
Nitriding temperature is that only when 530 ℃ of nitrogenize, the magnesium iron specimen surface does not have hardness decline phenomenon under 3 hours the condition at nitridation time to the influence of nitrided layer hardness as shown in Figure 6; During nitriding temperature＞530 ℃, specimen surface all has hardness decline phenomenon, and nitriding temperature is high more, and hardness descends serious more.The peak value of hardness of nitrided layer hardness curve raises along with the rising of nitriding temperature, and the position of peak value is moved inward by the surface.
2.CNO
-The influence of content
Fixedly 580 ℃ of nitriding temperatures, 3 hours time, CNO
-The range of choice of content is 30～38%, and cyanate radical content to the influence of the compound layer degree of depth as shown in Figure 7.
Cyanate radical content is the important factor that influences infiltration rate and quality layer.CNO
-Be lower than at 32% o'clock, the formation speed of infiltration layer reduces, and under similarity condition, the surface compound layer that is obtained is fine and close, but the compound layer degree of depth is lower than 0.008 and do not reach technical requirements; CNO
-Content is greater than 34%, and the oxidisability of salt bath strengthens, and the formation speed of infiltration layer increases, but compound layer is with CNO
-The increase of content and loose increasing; CNO
-Content 32～34% o'clock, the infiltration layer compound layer degree of depth has corresponding raising.Compound layer surface porosity＜3 grade.
According to nitriding temperature and CNO
-The test of content is oozed number altogether to the nitrogenize of external recommendation and is carried out single factor and improve and can't obtain gratifying effect.Must be actual according to producing, seek out the processing parameter that meets the cast pieces of spheroidal processing, thereby the present invention has carried out temperature and CNO
-The improved technological test of content dual factors has finally obtained good effect.Improved technological test procedure relation as shown in Figure 8,
1., 2., 3. curve represents temperature and CNO respectively among Fig. 8
-The content dual factors are improved the mutual respective value of parameter, get nitriding temperature 580-530 ℃, CNO through repetition test
-Content 32-34%, 3 hour treatment time behind the cast pieces of spheroidal QPQ nitriding treatment, can meet technical requirements fully, and the infiltration layer pattern as shown in Figure 9.
Another outstanding feature of the present invention is to have added anticorrosive additive in the dipping machine oil in final piece surface rotproofing.
The adding of additive improves the resistance to corrosion of cast pieces of spheroidal greatly, presses GM 9540P method B standard detection through mechanical industry quality of materials inspection center, is better than the product of General Motors Overseas Corporation with the part antiseptic property of the inventive method processing.
Test name: accelerated corrosion test
Specimen method and detection foundation: GM 9540P method B (applies 1% salt fog (0.9% sodium-chlor, 0.1% calcium chloride and 0.25% sodium bicarbonate) and uses composition, be accompanied by the drying of Moderate High Temperature.Require 16 Working day of 24 hours 24 or automated cycle proofing box.)
Sample: 1. the manual axle of General Motors Overseas Corporation product is 2
2. the inventive method is handled 3 of manual axle products
The result: press GM 9540P method B, manually 16 cyclic corrosions tests of beam warp back is observed, and has one a small amount of yellow rust staining to occur at root in the Versatile manual axle product, and yellow rust spot does not appear in another root; The inventive method is handled manually, and yellow rust spot does not all appear in axle.
Handle magnesium iron auto parts parts product with the technology of the present invention and detect through Shanghai City car mass supervision institute and Shanghai Inst. of Materials, met and exceeded similar products at home and abroad at aspect of performance such as anticorrosive, wear-resisting.Present technique is pollution-free, and every environmental protection index is measured the standard that all reaches through environmental administration.
The inventive method also can be used for surface strengthening, the rotproofing of other metallic substance.
Description of drawings
Fig. 1 nitridation time and to the influence of depth of penetration
Fig. 2 nitridation time and to the influence of nitrided layer hardness
Fig. 3-1 nitridation time amplified 400 times of (400X) edge tissues infiltration layer patterns in 2 hours
Fig. 3-2 nitridation time amplified 400 times of (400X) core structure infiltration layer patterns in 2 hours
Fig. 4-1 nitridation time amplified 400 times of (400X) edge tissues infiltration layer patterns in 3 hours
Fig. 4-2 nitridation time amplified 400 times of (400X) core structure infiltration layer patterns in 3 hours
Fig. 5 nitriding temperature and to the influence of depth of penetration
Fig. 6 nitriding temperature and to the influence of nitrided layer hardness
Fig. 7 cyanate radical content is to the influence of the compound layer degree of depth
The single, double factor technological test of Fig. 8 parameter
Fig. 9-1 the inventive method is handled back cast pieces of spheroidal 400X edge tissues infiltration layer pattern
Fig. 9-2 the inventive method is handled back cast pieces of spheroidal 400X core structure infiltration layer pattern
Embodiment
The application of embodiment 1 auto parts
To handle 60,000 Buick 4T65E differential mechanism timbering materials year is example, QT450-10 spheroidal graphite cast iron, and normalizing treatment is adopted in the casting back.Hardness after the normalizing is 218-240HBS.Differential mechanism support after the normalizing remakes QPQ salt bath Combined Processing, concrete steps: work string is hung, special implement quantitatively mounts → the clean-out system oil removing, remove workpiece surface oil stain and settling → clear water rinsing → preheating, 360 ℃, 30min grasps preheating yardstick, working-surface and is bluish voilet for well, straw yellow also can, so that handle more uniformity of later workpiece outward appearance, do not produce 560 ℃ of surface imperfection → nitrogenize, 33%CNO
-, 3h, to 360 ℃ of the logical pressurized air → oxidations of bath salt, 20min, the cyanogen root of workpiece from the nitridation salt that nitriding furnace brings out thoroughly decomposed, form oxide film → cleaning → drying → 90 ℃ of immersion oil, the 3min, 10 of black at workpiece surface
#Add 4% barium mahogany sulfonate, 4% lanolin soap, 1.5% zinc naphthenate in the machinery oil.After this step QPQ handled, the differential mechanism support can reach the standard of external like product fully.
Through the technical requirements of actual measurement AM General
1. hardness: 680-780HV 〉=570HV
2. the compound layer degree of depth: 10-13 μ m 〉=8 μ m
3. the diffusion layer degree of depth: 0.05-0.07mm 〉=0.03mm
4. surface porosity: 1-2 level≤3 grade
Intensity that its heart portion maintenance of differential mechanism support is higher and good impact resistance, and surface abrasion resistance can improve tens times.Can significantly reduce and use wearing and tearing, fatigue strength improves 40-100%.The differential mechanism support reaches the AM General car gage after surface strengthening.
Embodiment 2 moulds are used
Shanghai automobile gear head factory four subsidiary factory's aluminium alloy casting dies, material is the 3Cr2W8V steel, anticipating is 1050 ℃ of quenchings, 580～600 ℃ of double temperings, hardness is at 40～45HRC.Remake QPQ salt bath Combined Processing after the thermal treatment, concrete steps: work string is hung, special implement quantitatively mounts → and the clean-out system oil removing, remove workpiece surface oil stain and settling → clear water rinsing → preheating, 360 ℃, 30min and grasp preheating yardstick, working-surface and be bluish voilet for well, straw yellow also can, so that handle more uniformity of later workpiece outward appearance, do not produce 560 ℃ of surface imperfection nitrogenize, 34%CNO
-, 3h, to 360 ℃ of the logical pressurized air → oxidations of bath salt, 20min, the cyanogen root of workpiece from the nitridation salt that nitriding furnace brings out thoroughly decomposed, form oxide film → cleaning → drying → 90 ℃ of immersion oil, the 3min, 10 of black at workpiece surface
#Add 7% barium mahogany sulfonate, 6% lanolin soap, 0.5% zinc naphthenate in the machinery oil.After this step QPQ handled, the differential mechanism support can reach the standard of external like product fully.
The working temperature of aluminium alloy compression casting model cavity reaches 600 ℃, and common failure mode is to produce thermal fatigue, wearing and tearing, burn into formation mucous membrane.
The 3Cr2W8V aluminium alloy casting die is after QPQ salt bath Combined Processing, and the surface has formed oxide film, the compound layer about 10um and the diffusion layer of the suitable degree of depth, and surface hardness is up to 900HV.Oxide film and compound layer greatly reduce the possibility of mucous membrane, have increased the probability of the fatigue crack that has produced when wear resistance and corrosion stability, diffusion layer have then reduced cold cycling effectively greatly.
Handle the work-ing life of back transfer mold and improve more than the twice, lost efficacy after remake QPQ after repairing a die and handle, still can have twice to continue to use above work-ing life.
Claims (3)
1, cast pieces of spheroidal surface QPQ compounding method comprises steps such as preheating, nitrogenize, oxidation, cleaning, oven dry and immersion oil, and wherein preheating condition is 350-380,30min; Oxidizing condition is 360 ℃, 10-20min; It is characterized in that wherein nitridation conditions is: temperature 580-530, CNO
-Concentration 32-34%; The immersion oil condition is: containing U.S. soap of barium mahogany sulfonate, lanolin and zinc naphthenate anticorrosive additive 90 ℃ 10
#Flood 2-5min in the machinery oil.
2, the surperficial QPQ compounding method of cast pieces of spheroidal according to claim 1, it is characterized in that wherein said magnesium iron is QT450-10, contain C:3.2～3.6%, Si:2.6～2.8%, Mn:0.6～0.7%,, P≤0.01%, S:0.016～0.03%, Mg:0.035～0.038%, Re:0.01～0.05%.
3, cast pieces of spheroidal according to claim 1 surface QPQ compounding method is characterized in that the weight percentage of each anticorrosive additive in the immersion oil step wherein is: barium mahogany sulfonate 3-7%, the U.S. soap 3-7% of lanolin, zinc naphthenate 0.5-4%.
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| CN101844129A (en) * | 2010-04-30 | 2010-09-29 | 怀集登云汽配股份有限公司 | Automatic rust-proof treatment device and rust-proof treatment method thereof |
| CN101851547A (en) * | 2010-06-07 | 2010-10-06 | 怀集登云汽配股份有限公司 | Rust preventive oil suitable for valve |
| CN101851547B (en) * | 2010-06-07 | 2013-01-09 | 怀集登云汽配股份有限公司 | Rust preventive oil suitable for valve |
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| CN103276345A (en) * | 2012-12-28 | 2013-09-04 | 郭伟 | QPQ salt bath composite strengthening and modifying high and new technology applied to automobile component metal surface |
| CN103276345B (en) * | 2012-12-28 | 2015-07-22 | 上海尚职纳米科技有限公司 | QPQ salt bath composite strengthening and modifying high and new technology applied to automobile component metal surface |
| CN103276344B (en) * | 2012-12-28 | 2015-09-09 | 郭伟 | Deep layer QPQ salt bath complex intensifying modification new and high technology |
| CN103205668A (en) * | 2013-04-28 | 2013-07-17 | 莱州天润机械有限公司 | Application of QPQ (Quench-Polish-Quench) salt bath composite treatment process in handle rods at two ends of die stock and cutter bar frame |
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| CN104294209A (en) * | 2014-10-28 | 2015-01-21 | 河南省广天铸件有限公司 | Salt bath nitrogen treatment technology for casting iron pan |
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