CN103590034B - The alloy powder of middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloying and Alloying Treatment technique - Google Patents
The alloy powder of middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloying and Alloying Treatment technique Download PDFInfo
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Abstract
The present invention aims to provide a kind of alloy powder and Alloying Treatment technique of middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloying, and wherein alloy powder comprises WC, TiC, B, Ni, Cr, Co, Si, Mo, Y2O3Powder constituent. The present invention also provides a kind of alloy powder treatment process, this technique comprises by pending roller surface polishing rust cleaning, with organic solvent removes surface and oil contaminant, aforementioned alloy powder is mixed with varnish ethanolic solution, the mixed liquor of gained is evenly sprayed on to the pending working face of roll, air-dry rear employing laser breaker roll surface is scanned, make alloy powder and roll top layer melt-blended, form the steps such as laser alloying coating. Adopt the roll that alloy powder of the present invention and Alloying Treatment technique are middle nickel chromium triangle infinitely chilled ductile cast iron to material to carry out Laser Alloying Treatment, the alloy of roll working surface formative tissue fine layer by layer, has strengthened microhardness and has promoted roll steel transportation amount.
Description
Technical field
The invention belongs to metallurgical technology field, be specially and relate to a kind of metal laser alloy powder for alloying and alloyingTreatment process, is particularly applied to alloy powder and the alloying place of middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloyingScience and engineering skill.
Background technology
Are directly connected to production efficiency, product quality and the economic benefit of enterprise in roll quality and service life, state of ChinaProduce roll, especially nickel chromium triangle infinitely chilled cast iron roll performance generally lower than same kind of products at abroad, high performance roll still relies onImport. Therefore how to improve Domestic Rolls quality and precision, improve its service life, reduce production costs and become current urgent need solutionProblem certainly.
The key factor that affects roller performance, product quality and service life thereof is 500 DEG C of high temperature (>) wearability. TraditionIn technique, need to add the precious metal elements such as a high proportion of nickel, chromium in steel and breaker roll carries out surface peening more, but conventionalSurface strengthening technology all can not effectively improve and roll as flame hardening, high mid frequency induction hardening, plasma spraying, surfacing and arc surfacing etc.The high temperature resistance wearing and tearing of roller surface and cold-and-heat resistent fatigue behaviour.
And in prior art, also having application laser ceramic alloy technology breaker roll to process, object is to improve roll workMake hardness and the high temperature abrasion resistance of layer. The treatment effect of laser alloying technology and the formulation selection of alloy powder have close passSystem. In currently available technology, be mostly to add cemented carbide powder, as SiC, WC, TiC etc., or laser surface alloying mistakeJourneySitu generates and strengthens the wearability of alloying coating as intermetallic compounds such as carbide, nitride, borides, although canTo form the alloy-layer of high rigidity, high abrasion at steel surface, the service life of improving to a certain extent roll, but becauseIts formulation selection is reasonable not, has penetrating crack and pore while being applied in cast iron materials, has a strong impact on the surface of alloy-layerQuality, its service life and technique effect are all undesirable, particularly on large area roll, apply also in the experimental exploring stage,The greatest problem existing is at present that alloy-layer easily comes off in the operation of rolling, has had a strong impact on the application effect of Laser Alloying TreatmentReally, limited applying of this technology.
Summary of the invention
The present invention aim to provide a kind of middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloying alloy powder andAlloying Treatment technique, adopts above-mentioned alloying powder and laser ceramic alloy treatment process to prepare and rolling at roller surfaceThe alloy-layer of difficult drop-off in process processed, this alloy-layer has fine microstructures, is smelting without hole and crackle, alloying layer and base materialGold combination, the feature that bond strength is high, and the alloying layer forming has higher microhardness, high temperature abrasion resistance, resistance to punchingHitting property, hot-cracking resistance, thereby the service life of improving such hot roll.
The alloy powder of middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloying of the present invention, it is by following heavyThe powder stock of amount part is prepared from: WC26～29 part, TiC21～25 part, B4～7 part, Ni13～16 part,Cr6～9 part, Si0.3～2 part, Co12～15 part, Y2O30.3～2 part, Mo3～6 part.
Described WC is tungsten carbide, and TiC is titanium carbide, and B is boron, and Ni is nickel, and Cr is chromium, and Co is cobalt, and Si isSilicon, Mo is molybdenum, Y2O3For yittrium oxide.
The preparation method of the alloy powder of described middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloying is: getGranularity is the alloy powder of 80～150nm, weighs each powder weight by powder mixture ratio with high-precision electronic scale, pours mixed powder intoIn vessel, fully mix, obtain alloy powder product.
The present invention also provides a kind of alloy powder centering nickel chromium triangle of grain roll laser surface alloying that uses infinitely coldHard cast iron roller surface carries out the method for Laser Alloying Treatment, comprises the following steps:
A, by pending roller surface polishing rust cleaning, remove surface and oil contaminant;
B, varnish and absolute ethyl alcohol are configured to varnish ethanolic solution according to the volume ratio of 1-3:40-60;
C, described alloy powder is mixed according to the weight ratio of 1-3:10-20 with varnish ethanolic solution, stir, closedGold powdery paints;
D, alloy powder coating is sprayed on the pending surface of roll, natural air drying forms alloy powder coating;
E, the roll that sprays alloy powder coating is lifted in laser-processing system, adopts laser breaker roll surface to scan, make to closeBronze end and roll top layer are melt-blended, after solidifying, form laser alloying coating at roller surface.
Described steps A remove organic solvent that surface and oil contaminant adopts be kerosene, gasoline, acetone, toluene, trichloro-ethylene,The mixing of one or more in tetrachloro-ethylene, depending on different greasy dirt compositions.
Alloy powder coating thickness in described step D is 0.05～0.15mm.
Described laser-processing system scans by following technological parameter breaker roll surface: power output is 4000～4500W,Sweep speed is 3.0～4.0m/min, and spot size is 2.0～3.0mm, and hot spot overlapping rate is 30%.
The alloy powder of described middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloying and Alloying Treatment technique, forThe laser surface alloying of grain roll, preferably centering nickel chromium triangle infinitely chilled cast iron roll laser surface alloying, described middle castingIn iron roll, the percentage by weight of each composition is: C2.9～3.7, Si0.6～1.2, Mn0.3～1.1, P≤0.25, S≤0.12, Cr0.7～1.2, Ni1.1～2.0, Mo0.2～0.6, Fe surplus.
The alloy powder that the present invention selects is the nano ceramic powder that tungsten carbide and titanium carbide are main hard phase, in order to enterStep refining tissue and enhancing toughness, inventor has gone out unique alloy powder formula by lot of experiments. Of the present inventionThe core technology point of alloy powder comprises two parts, changes the mass ratio of tungsten carbide and titanium carbide and adds new unique proportioningAlloying element. Alloy powder of the present invention comprises B, Ni, Cr, Co, Si, Y2O3, Mo, by developing these compositionsUnique proportioning in conjunction with the ratio combination of tungsten carbide and titanium carbide, forms and the closely cooperating of irony roll laser treatment after,Form alloying layer have fine microstructures, without hole and crackle, alloying layer and base material be metallurgical binding, bond strength is highFeature, this is that prior art is beyond one's reach, and the alloying layer forming have higher microhardness, high temperature abrasion resistance,Resistance to impact, hot-cracking resistance, thereby the service life of improving such hot roll, make the irony roll alloying can be really significantlyDegree promotes operating efficiency and the service life of roll.
In the situation that alloy powder is selected, what laser alloying surface quality was also had to considerable influence is laser processing technologyParameter, should be laser power, sweep speed and spot diameter from its main technological parameter of angle of working control. InventionThe power bracket that people obtains processing low-alloy cast iron roll after deliberation is afterwards: 4000～5000W; Sweep speed is: 3～4m/min;Spot diameter is: 2.0～3.0mm; By repeatedly laser alloying experiment discovery, when laser power increases, sweep speed reducesTime, the roughness on surface increases. When laser power is within the scope of 4000-4500W, sweep speed below 4.0m/min,Spot diameter is thinner, and surface is more smooth smooth. In the time that laser increases laser power, must increase sweep speed simultaneously and dwindle lightThe slightly degree of making on spot diameter alloy-layer surface just can reduce, and surperficial macro morphology takes a turn for the better. By laser alloying test repeatedly, reallyThe technological parameter of having determined to optimize is P=4000～4500W, v=3.0～4.0m/min, D=2.0～3.0mm.
Adopting alloy powder of the present invention and Alloying Treatment technique to irony roll, is mainly screw-thread steel and shaped steelIn roll, planishing roll carries out Laser Alloying Treatment, at the alloy of roll working surface formative tissue fine layer by layer, its thickness reachesIn the time of 0.4mm, just can obtain good effect, its microhardness is up to Hv0.11150, and roll steel transportation amount improves than former rollMore than 180%, more durable more than 50% than common alloy-layer, and laser alloying roll can effectively suppress in the course of the workThe expansion of cold and hot fatigue crack, reduces roll breakage phenomenon, and steel rolling production operational availability is improved more than 9%. Alloy powder of the present inventionFormula is applicable to being applied on middle nickel chromium triangle infinitely chilled cast iron roll, the formula of this alloy powder and middle nickel chromium triangle infinitely chilled cast iron rollCooperation can be more tight, after laser treatment, can realize the best effect, its alloy-layer fine microstructures, nothingThe metallurgical binding of hole and crackle, alloying layer and base material is the tightst, and its intensity reaches the feature of best effects, has outstandingSubstantive distinguishing features and significant progressive.
Alloy powder of the present invention and Alloying Treatment technique are done installation experiment in medium-sized steel rolling mill, and roll operates steadily,Roll steel transportation amount increases substantially has realized considerable economic benefit.
Detailed description of the invention:
Embodiment 1
Alloy powder is to be that 80～90nm material powder mixes by following granularity: WC26g, TiC25g, B7g, Ni16g,Cr9g、Co12g、Si2g、Mo3g、Y2O32g。
Weigh each powder weight by powder mixture ratio with high-precision electronic scale, pour in meal mixer ware and fully mix,Obtain alloy powder.
Use this alloy powder grain roll laser surface alloying treatment process, comprise the following steps:
Step 1, remove surface by pending middle nickel chromium triangle infinitely chilled cast iron roll surface finish rust cleaning, with the mixed liquor of acetone, tolueneGreasy dirt;
Step 2, the alloy powder of aforementioned grain roll laser surface alloying is mixed with varnish ethanolic solution, stir.
Wherein varnish and absolute ethyl alcohol are configured to varnish ethanolic solution according to the volume ratio of 1:40, described alloy powder and varnish ethanolSolution mixes according to the weight ratio of 1:10.
Step 3, paint spray gun the mixed liquor of step 2 gained is evenly sprayed on the pending working face of roll, natureAfter air-dry, guarantee that powder coating thickness reaches 0.10mm.
Step 4, the roll that dusts is lifted into high-power CO2In laser-processing system, employing laser power 4.4KW,The laser technical parameters breaker roll table of laser spot diameter 2.0mm, laser scanning speed 3.5m/min, hot spot overlapping rate 30%Face scans, and makes preset alloy powder and roll top layer melt-blended rapidly, after rapid solidification, forms the degree of depth at roller surfaceThe laser alloying coating of 0.5mm.
After laser alloying, the pattern of alloy-layer is dendrite or born of the same parents-dendrite, being organized as by showing of whole alloy-layerAnd in be hypereutectic, eutectic structure. The average hardness of alloy-layer is 1000HV.
Embodiment 2
Alloy powder is to be that 85～100nm material powder mixes: WC29g, TiC21g, B4g, Ni by following granularity13g、Cr6g、Co12g、Si1g、Mo6g、Y2O31g. Weigh each powder by powder mixture ratio with high-precision electronic scaleEnd weight, pours in meal mixer ware and fully mixes, and obtains alloy powder product.
Grain roll laser surface alloying treatment process, comprises the following steps:
Step 1, remove by pending middle nickel chromium triangle infinitely chilled cast iron roll surface finish rust cleaning, with the mixed liquor of kerosene, gasolineSurface and oil contaminant;
Step 2, the alloy powder of aforementioned grain roll laser surface alloying is mixed with varnish ethanolic solution, stir.
Wherein varnish and absolute ethyl alcohol are configured to varnish ethanolic solution according to the volume ratio of 1:60, described alloy powder and varnish secondAlcoholic solution mixes according to the weight ratio of 1:20.
Step 3, paint spray gun the mixed liquor of step 2 gained is evenly sprayed on the pending working face of roll, natureAfter air-dry, guarantee that powder coating thickness reaches 0.10mm.
Step 4, the roll that dusts is lifted into high-power CO2In laser-processing system, employing laser power 4.0KW,The laser technical parameters breaker roll surface of laser spot diameter 2.5mm, laser scanning speed 3m/min, hot spot overlapping rate 30% is enteredLine scanning, makes preset alloy powder and roll top layer melt-blended rapidly, after rapid solidification, forms degree of depth 0.4mm at roller surfaceLaser alloying coating.
After laser alloying, the pattern of alloy-layer is dendrite or born of the same parents-dendrite, being organized as by showing of whole alloy-layerAnd in be hypereutectic, eutectic structure. The average hardness of alloy-layer is 994HV.
Embodiment 3
Alloy powder is to be that 95～110nm material powder mixes: WC27g, TiC22g, B6g, Ni by following granularity14g、Cr7g、Co14g、Si0.6g、Mo5g、Y2O30.3g. Weigh each powder by powder mixture ratio with high-precision electronic scaleEnd weight, pours in meal mixer ware and fully mixes, and obtains alloy powder product.
Grain roll laser surface alloying treatment process, comprises the following steps:
Step 1, by pending middle nickel chromium triangle infinitely chilled cast iron roll surface finish rust cleaning, mixed with trichloro-ethylene, tetrachloro-ethyleneClose liquid and remove surface and oil contaminant;
Step 2, the alloy powder of aforementioned grain roll laser surface alloying is mixed with varnish ethanolic solution, stir.
Wherein varnish and absolute ethyl alcohol are configured to varnish ethanolic solution according to the volume ratio of 1:50, described alloy powder and varnish secondAlcoholic solution mixes according to the weight ratio of 1:15.
Step 3, paint spray gun the mixed liquor of step 2 gained is evenly sprayed on the pending working face of roll, natureAfter air-dry, guarantee that powder coating thickness reaches 0.10mm.
Step 4, the roll that dusts is lifted into high-power CO2In laser-processing system, employing laser power 4.5KW,The laser technical parameters breaker roll table of laser spot diameter 3.0mm, laser scanning speed 4.0m/min, hot spot overlapping rate 30%Face scans, and makes preset alloy powder and roll top layer melt-blended rapidly, after rapid solidification, forms the degree of depth at roller surfaceThe laser alloying coating of 0.4mm.
After laser alloying, the pattern of alloy-layer is dendrite or born of the same parents-dendrite, being organized as by showing of whole alloy-layerAnd in be hypereutectic, eutectic structure. The average hardness of alloy-layer is 1115HV.
Embodiment 4
Alloy powder is to be that 120～130nm material powder mixes: WC28g, TiC23g, B4g, Ni by following granularity13g、Cr8g、Co12g、Si0.3g、Mo5g、Y2O30.5g. Weigh each powder by powder mixture ratio with high-precision electronic scaleEnd weight, pours in meal mixer ware and fully mixes, and obtains alloy powder product.
Grain roll laser surface alloying treatment process, comprises the following steps:
Step 1, remove surface and oil contaminant by pending middle nickel chromium triangle infinitely chilled cast iron roll surface finish rust cleaning, with acetone;
Step 2, the alloy powder of aforementioned grain roll laser surface alloying is mixed with varnish ethanolic solution, stir.
Wherein varnish and absolute ethyl alcohol are configured to varnish ethanolic solution according to the volume ratio of 3:40, described alloy powder and varnish secondAlcoholic solution mixes according to the weight ratio of 3:20.
Step 3, paint spray gun the mixed liquor of step 2 gained is evenly sprayed on the pending working face of roll, natureAfter air-dry, guarantee that powder coating thickness reaches 0.10mm.
Step 4, the roll that dusts is lifted into high-power CO2In laser-processing system, employing laser power 4.4KW,The laser technical parameters breaker roll table of laser spot diameter 2.5mm, laser scanning speed 3.5m/min, hot spot overlapping rate 30%Face scans, and makes preset alloy powder and roll top layer melt-blended rapidly, after rapid solidification, forms the degree of depth at roller surfaceThe laser alloying coating of 0.4mm.
After laser alloying, the pattern of alloy-layer is dendrite or born of the same parents-dendrite, being organized as by showing of whole alloy-layerAnd in be hypereutectic, eutectic structure. The average hardness of alloy-layer is 1050HV.
Embodiment 5
Alloy powder is to be that 140～150nm material powder mixes: WC29g, TiC23g, B7g, Ni by following granularity15g、Cr8g、Co13g、Si0.8g、Mo6g、Y2O31.2g. Weigh each powder by powder mixture ratio with high-precision electronic scaleEnd weight, pours in meal mixer ware and fully mixes, and obtains alloy powder product.
Grain roll laser surface alloying treatment process, comprises the following steps:
Step 1, remove surface and oil contaminant by pending middle nickel chromium triangle infinitely chilled cast iron roll surface finish rust cleaning, with kerosene;
Step 2, the alloy powder of aforementioned grain roll laser surface alloying is mixed with varnish ethanolic solution, stir.
Wherein varnish and absolute ethyl alcohol are configured to varnish ethanolic solution according to the volume ratio of 3:60, described alloy powder and varnish secondAlcoholic solution mixes according to the weight ratio of 3:20.
Step 3, paint spray gun the mixed liquor of step 2 gained is evenly sprayed on the pending working face of roll, natureAfter air-dry, guarantee that powder coating thickness reaches 0.10mm.
Step 4, the roll that dusts is lifted into high-power CO2In laser-processing system, employing laser power 4.0KW,The laser technical parameters breaker roll table of laser spot diameter 2.5mm, laser scanning speed 3.5m/min, hot spot overlapping rate 30%Face scans, and makes preset alloy powder and roll top layer melt-blended rapidly, after rapid solidification, forms the degree of depth at roller surfaceThe laser alloying coating of 0.4mm.
After laser alloying, the pattern of alloy-layer is dendrite or born of the same parents-dendrite, being organized as by showing of whole alloy-layerAnd in be hypereutectic, eutectic structure. The average hardness of alloy-layer is 1100HV.
Embodiment 6
Adopt alloy powder proportioning of the present invention to be: WC27g, TiC22g, B6g, Ni14g, Cr7g, Co14g、Si0.6g、Mo5g、Y2O30.3g。
Adopt grain roll laser surface alloying treatment process of the present invention, step is as follows:
Step 1, by pending middle nickel chromium triangle infinitely chilled cast iron roll surface finish rust cleaning, mixed with trichloro-ethylene, tetrachloro-ethyleneClose liquid and remove surface and oil contaminant;
Step 2, the alloy powder of aforementioned grain roll laser surface alloying is mixed with varnish ethanolic solution, stir.
Wherein varnish and absolute ethyl alcohol are configured to varnish ethanolic solution according to the volume ratio of 1: 50, described alloy powder and varnish secondAlcoholic solution mixes according to the weight ratio of 1: 15.
Step 3, paint spray gun the mixed liquor of step 2 gained is evenly sprayed on the pending working face of roll, natureAfter air-dry, guarantee that powder coating thickness reaches 0.10mm.
Step 4, the roll that dusts is lifted into high-power CO2In laser-processing system, employing laser power 4.5KW,The laser technical parameters breaker roll table of laser spot diameter 3.0mm, laser scanning speed 4.0m/min, hot spot overlapping rate 30%Face scans, and makes preset alloy powder and roll top layer melt-blended rapidly, after rapid solidification, forms the degree of depth at roller surfaceThe laser alloying coating of 0.4mm.
Embodiment 7
Adopt alloy powder of the present invention and Alloying Treatment technique to carry out the middle nickel chromium triangle of Laser Alloying Treatment infinitely coldHard cast iron roll does installation experiment in medium-sized steel rolling mill, wherein respectively to adopt alloy powder Laser Alloying Treatment of the present invention,The two class rolls that do not carry out Laser Alloying Treatment carry out contrast experiment, draw respectively their runnability.
Table 1 is the two class rolls that adopt alloy powder Laser Alloying Treatment of the present invention, do not carry out Laser Alloying TreatmentRunnability contrast:
Table 1
| Treatment process | Powder laser alloying of the present invention | Without surface alloying processing |
| Case hardness (HV) | 950-1115 | 706 |
| Average single groove rolling is (ten thousand tons) | 0.56 | 0.2 |
| Each turning amount (mm) | 5 | 7 |
| Roll turning number of times (inferior) | 9 | 7 |
| The total amount of rolling of one secondary roll (ten thousand tons) | 35.28 | 9.8 |
| Ton steel roll expense (unit) | 0.1978 | 0.2346 |
| Ten thousand tons of steel change and roll roll change number of times (inferior) | 1.8 | 5 |
| Ten thousand tons of steel change and roll roll change total time (minute) | 9 | 25 |
Claims (8)
1. in, an alloy powder for nickel chromium triangle infinitely chilled cast iron roll laser surface alloying, is characterized in that, it be byThe powder stock of following weight parts is prepared from: WC26～29 part, TiC21～25 part, B4～7 part, Ni13～16 parts, Cr6～9 part, Si0.3～2 part, Co12～15 part, Y2O30.3～2 part, Mo3～6 part.
2. the alloy powder of middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloying according to claim 1, itsBe characterised in that, its using method comprises the following steps:
A, by the rust cleaning of pending grain roll surface finish, remove surface and oil contaminant;
B, varnish and absolute ethyl alcohol are configured to varnish ethanolic solution according to the volume ratio of 1-3:40-60;
C, described alloy powder is mixed according to the weight ratio of 1-3:10-20 with varnish ethanolic solution, stirs,Obtain alloy powder coating;
D, alloy powder coating is sprayed on the pending surface of roll, natural air drying forms alloy powder coating;
E, the roll that sprays alloy powder coating is lifted in laser-processing system, adopts laser breaker roll surface to sweepRetouch, make alloy powder and roll top layer melt-blended, after solidifying, form laser alloying coating at roller surface.
3. the alloy powder of middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloying according to claim 1, itsBe characterised in that, in grain roll, the percentage by weight of each composition is: C2.9～3.7, Si0.6～1.2, Mn0.3～1.1, P≤0.25, S≤0.12, Cr0.7～1.2, Ni1.1～2.0, Mo0.2～0.6, Fe surplus.
4. one kind is used the alloy of middle nickel chromium triangle infinitely chilled cast iron roll laser surface alloying as claimed in claim 1Powder carries out the method for Laser Alloying Treatment to grain roll surface, it is characterized in that, comprises the following steps:
A, by pending roller surface polishing rust cleaning, remove surface and oil contaminant;
B, varnish and absolute ethyl alcohol are configured to varnish ethanolic solution according to the volume ratio of 1-3:40-60;
C, described alloy powder is mixed according to the weight ratio of 1-3:10-20 with varnish ethanolic solution, stirs,Obtain alloy powder coating;
D, alloy powder coating is sprayed on the pending surface of roll, natural air drying forms alloy powder coating;
E, the roll that sprays alloy powder coating is lifted in laser-processing system, adopts laser breaker roll surface to sweepRetouch, make alloy powder and roll top layer melt-blended, after solidifying, form laser alloying coating at roller surface.
5. method according to claim 4, is characterized in that: described steps A is removed having of surface and oil contaminant employingMachine solvent is one or more mixing in kerosene, gasoline, acetone, toluene, trichloro-ethylene, tetrachloro-ethylene.
6. method according to claim 4, is characterized in that: the alloy powder coating thickness in described step DBe 0.05～0.15mm.
7. method according to claim 4, is characterized in that, laser-processing system is by following technological parameter breaker rollSurface is scanned: power output is 4000～4500W, and sweep speed is 3.0～4.0m/min, and spot size is2.0～3.0mm, hot spot overlapping rate is 30%.
8. method as claimed in claim 4, is characterized in that, the percentage by weight of each composition in described grain rollFor: C2.9～3.7, Si0.6～1.2, Mn0.3～1.1, P≤0.25, S≤0.12, Cr0.7～1.2,Ni1.1～2.0, Mo0.2～0.6, Fe surplus.
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