CN102796959A - Corrosion-resistant plastic mold steel and preparation method thereof - Google Patents
Corrosion-resistant plastic mold steel and preparation method thereof Download PDFInfo
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Abstract
The invention relates to novel corrosion-resistant mold steel which comprises the following chemical components in percentage by weight: 0.16-0.24% of C, less than or equal to 0.15% of Si, less than or equal to 0.15% of Mn, less than 0.015% of P, less than 0.005% of S, 12.00-12.60% of Cr, 0.13-0.20% of N, 0.03-0.08% of Ta, 0.30-0.37% of C and N, and the balance being Fe and unavoidable impurities. The invention also relates to a preparation method of the novel corrosion-resistant mold steel. The preparation method comprises the following steps of: smelting and pouring to form an electrode bar in a vacuum induction furnace; carrying out electroslag remelting so as to form electroslag ingots; heating and forging steel ingots into forging stocks; and carrying out annealing treatment on the forging stocks, wherein the ingots are heated to the temperature of 1100-1200 DEG C and kept for 1-2 hours before forging, and in the annealing treatment of the forging stocks, the annealing temperature is 830-860 DEG C, and the temperature is kept for 3-4 hours. The mold steel provided by the invention has high-corrosion-resistant performance, high polishing performance, and low linear expansion coefficient, and is suitable for the preparation of a corrosion-resistant fine plastic mold.
Description
Technical field
The present invention relates to a kind of plastic die steel, relate in particular to a kind of good corrosion resistance that has, polishing performance is good, and the plastic die steel that cost of alloy is low is used for the manufacturing of corrosion resistant precise plastic mould.
Background technology
Plastics are of a great variety, comprise that automobile component are like lampshade, panel board, opticinstrument component such as camera lens, household appliances shell, PVC daily plastic goods etc.Wherein the plastics of appliance shell use are the ABS+ fire retardants.Some plastics such as SE, Fluroplast-4, flame retardant resistance ABS etc. can decomposite corrosive gasess such as hydrogenchloride, hydrogen fluoride, sulfurous gas, and mould is had certain corrosive nature, therefore require the mould of these type of plastics should have corrosion resistance nature.The steel grade that can satisfy corrosion-resistant corrosive nature requirement is a stainless steel.Stainless widespread use has formed series stainless steels such as Martensite Stainless Steel, ferritic stainless steel, austenitic stainless steel.Austenite and ferritic stainless steel can not satisfy the requirement (HRC >=46) of die steel to hardness because of intensity is low, and Martensite Stainless Steel is the one type of stainless steel that can adjust its performance through thermal treatment, is one type of hardenable stainless steel.The stainless characteristic of this type has determined it in equilibrium phase diagram, must have the existence of austenite phase region and can make alloy form corrosion resistant passive film.Therefore Martensite Stainless Steel becomes the first-selected steel grade of corrosion-resistant plastic die steel, and typical grade of steel is 4Cr13 and 4Cr16Mo.
The chemical ingredients of 4Cr13 consists of C:0.36-0.45%, Si≤0.60%, Mn≤0.80%, P≤0.04%, S≤0.03%, Cr:12.00-14.00%, Ni≤0.60%.Higher because of C and Cr content, Cr is the strong carbide forming element, so very easily form a large amount of carbide in the 4Cr13 steel, referring to accompanying drawing 1 (a), the existence of carbide causes corrosion resistance nature and polishing performance to descend.The chemical ingredients of 4Cr16Mo is C:0.33-0.43%, Mn:0.30-1.00%, Si:0.30-1.00%, S≤0.030%; P≤0.030%, Cr:15.00-17.00%, Ni:0.10-1.0%; Mo:1.0-1.30%, the Cr content among the 4Cr16Mo further improves, and has dwindled the γ phase region; Be easy to form the high temperature ferritic phase, when the Ni content in the steel is lower than 0.32%, produce the high temperature ferritic phase, referring to accompanying drawing 1 (b); 4Cr16Mo reaches about 0.4% because of carbon content, has a large amount of carbide in the steel equally, influences corrosion resistance nature and polishing performance.And the Ni that contains expensive, alloying elements such as Mo, material cost is high.
CN1676653A discloses a kind of 4Cr16Mo steel, and its chemical ingredients is C:0.33-0.43%, Mn:0.30-1.00%, Si:0.30-1.00%, S≤0.045%, P≤0.045%, Cr:14-18%, Ni:0.10-1.00%, Mo:0.80-1.50%; All the other are Fe.
CN1948541A discloses a kind of corrosion resistant mould steel, and its chemical ingredients is C:0.30-0.45%, Mn:0.5-1.00%; Si:0.2-0.80%, S≤0.03%, P≤0.03%; Cr:16.00-18.00%, Mo:1.00-1.50%, V:0.10-0.40%; Ni:0.30-1.00%, N:0.02-0.12%, all the other are Fe.
CN1676653A and CN1948541A are 16%Cr series corrosion resistant mould steel; And added alloying elements such as Ni, Mo, V, improve corrosion resistance nature through adding the Mo element, but do not reduce carbon content; Exist a large amount of carbide to influence corrosion resistance nature in the steel; Therefore, corrosion resistance nature is not obviously improved, and the alloying cost of composition is higher.
Summary of the invention
The present invention provides a kind of novel corrosion resistant plastic die steel.
For overcoming existing corrosion resistant mould steel carbide segregation, organizing shortcoming restive and that cost of alloy is high; The present invention adopts the microalloying thinking to design the lower corrosion-resistant plastic die steel of a kind of alloying element content; Through adding the composition mentality of designing that C falls in N, and the total amount of control C+N one reasonably interval, thereby reduce the carbide in the steel; Improve the corrosion resistance nature of material, and guarantee the use hardness requirement of mould; Add a small amount of alloying element Ta crystal grain thinning in addition, improve toughness, make steel grade have the highly corrosion resistant performance, high polishing performance, low distortion and characteristics cheaply.
For realizing above-mentioned purpose, the weight percent chemical ingredients of corrosion-resistant plastic die steel of the present invention is: C:0.16-0.24%, Si≤0.15%; Mn≤0.15%, P＜0.015%, S＜0.005%; Cr:12.00-12.60%, N:0.13-0.20%, Ta:0.03-0.08%; C+N=0.30-0.37%, surplus is Fe.
Composition of the present invention designs based on following principle:
C：0.16-0.24％
C is the hardness that improves steel and intensity effective elements the most, and the solution strengthening effect is remarkable, is the requisite element of assurance die steel hardness.C is the indispensable fundamental element that forms various carbide such as chromium carbide, and the C too high levels can cause increasing of carbide quantity in the steel and gather partially, reduces toughness and corrosion resistance nature.C content is crossed the low high firmness requirement that can not satisfy die steel.Control C:0.16-0.24% among the present invention.Be preferably 0.17-0.24%, or 0.16-0.23%.
N：0.13-0.20％
N is an element with remarkable solution strengthening effect, and the same solid solution with C of N forms interval type sosoloid in iron; Through adding the solution strengthening effect that minor N play, created condition for reducing carbon content, the main thought of steel grades design of the present invention is exactly for C with N; Reach and reduce C content, reduce carbide, improve corrosion resistance nature and polishing performance; Control N content is 0.13-0.20% among the present invention, considers the high firmness requirement of die steel, needs to guarantee C+N=0.30～0.37%.
Si≤0.15％
Containing a spot of Si in the steel has desoxydatoin preferably, but the Si too high levels then reduces the welding and the machinability of steel.Control Si content is≤0.15% among the present invention, preferably, and Si:0.10-0.15%.
Mn≤0.15％
Mn too high levels in the steel has the phenomenon that causes grain coarsening, increases the temper brittleness of steel simultaneously, so the present invention is controlled at lower content range with Mn content, preferred Mn≤0.15%, more preferably Mn:0.10-0.15%.
P＜0.015％
The P element is prone to gather partially at the crystal boundary place in steel, causes the fragility of steel to increase, so the P content in the steel should be low as far as possible.Control P＜0.015% among the present invention
S＜0.005％
S element form with sulfide in steel exists, and reduces the lateral extension and the toughness properties of steel, so the P content in the steel should be low as far as possible.Control S＜0.005% among the present invention.
Cr：12.00-12.60％
Cr is the element with passivation tendency, and the vital role of Cr is the corrosion resistance nature that significantly improves steel, and Cr content reaches at 12% o'clock and just has significant corrosion resistance nature in the steel.Cr also is the alloying element of postponing perlitic transformation strongly, helps the raising of hardening capacity; Cr is the element that dwindles the γ phase region, and the Cr too high levels will obtain ferritic structure, causes intensity to reduce, the corrosion resistance nature variation, so Cr content is unsuitable too high.Control Cr content is 12.0-12.60% among the present invention, is preferably 12.0-12.50%.
Also add micro-Ta:0.03-0.08% among the present invention, in steel, add micro-Ta element and can play the effect that crystal grain thinning improves the impelling strength of steel, improve welding property.The Ta too high levels then reduces the hardening capacity of steel, and therefore, control Ta content is 0.03-0.08% among the present invention, is preferably 0.035-0.075%.
The present invention also provides the method for manufacture of above-mentioned die steel.This method comprises:
Vacuum induction melting pours into electrode bar → esr and becomes ESR ingot → steel ingot heats forged to become forging stock → forging stock anneal.
Preferably, vacuum induction melting pours into Φ 200mm electrode bar.
Preferably, esr becomes the ESR ingot of Φ 300mm.
Preferably, the steel ingot heats forged becomes the forging stock of 100*100mm.
Wherein, ESR ingot is heated to 1100-1200 ℃ earlier before forging, and is incubated 1-2 hour and forges afterwards, and the too high forging process of Heating temperature is prone to produce the burning defective, and Heating temperature is crossed low forging process and is prone to the generation surface crack.Forging stock need carry out anneal, and annealing temperature is 830-860 ℃, is incubated 3-4 hour, and stove is chilled to room temperature afterwards.Annealing temperature is too high to be prone to cause crystal grain thick, and annealing temperature is crossed to hang down and is prone to cause annealed structure inhomogeneous.For example, forging stock quenches+temper after being processed into mould, 1020 ℃ of quenching temperatures, and soaking time: thickness 100mm is incubated 2 hours; 250 ℃ of tempering temperatures, soaking time: thickness 100mm is incubated 4 hours.
The composition of die steel of the present invention and technology have following advantage:
The proportioning of chemical ingredients is more reasonable, passes through to add a certain amount of N element for the mentality of designing of C with N, effectively reduces the content of C element, makes the carbide segregation situation of steel obtain very big improvement.Cr content is not very high simultaneously, has both guaranteed the requirement of corrosion resistance nature, has played the effect that prevents that the high temperature ferritic phase from separating out again, makes steel grade of the present invention have the characteristics of highly corrosion resistant performance and high polishing performance.
Description of drawings
Fig. 1 be contrast grade of steel 4Cr13 quenching (1020 ℃ * 2h)+(250 ℃ * 4h) metallographic structure of attitude, the white granular pattern is organized as carbide in the picture, and forms network-like distribution in tempering.
Fig. 2 be contrast grade of steel 4Cr16Mo (containing 0.32%Ni) quenching (1020 ℃ * 2h)+tempering (250 ℃ * 4h) metallographic structure of attitude, white bulk is organized as the high temperature ferritic phase in the picture, white light tone globular structure is a carbide.
Fig. 3 be steel grade of the present invention quenching (1020 ℃ * 2h)+tempering (250 ℃ * 4h) metallographic structure of attitude, homogeneity of structure is better, no block high temperature ferritic phase exists with tangible granular carbide in the tissue.
Embodiment
Below through embodiment characteristics of the present invention and effect are described.
The chemical ingredients of embodiment 1-5 is seen table 1.
Table 1 embodiment and contrast grade of steel chemical ingredients
Composition according to the foregoing description; Adopt vacuum induction furnace smelting to become the electrode bar of Φ 200mm; Carry out esr then; The ESR ingot specification is Φ 300mm, and to become cross-sectional area be the forging stock of 100mm * 100mm to heats forged afterwards, inspection by sampling corrosion resistance nature, polishing performance and linear expansivity and metallographic structure.The concrete processing parameter of embodiment is seen table 2.
Table 2 embodiment processing parameter
Test Example 1: erosion rate (GB/T 10125-1997, artificial atmosphere corrosion test salt-fog test)
Measured erosion rate in 72 hours with the spraying of the 5%NaCl aqueous solution, the result sees table 3.
Test Example 2: polishing performance
On automatic polishing machine, polish, burnishing parameters is: the time is 2 minutes, and pressure is 180N, and rotating speed is 300N/min.Sample hardness is HRC46-48, and size of sample Φ 30mm tests the polished surface roughness to the sample after the polishing in the enterprising line scanning of AFM.The result sees table 3.
Test Example 3: linear expansivity
The cylinder sample of Φ 5 * 25mm is produced in line cutting, in the rearmounted lambda line dilatometer of surface grinding (model is DIL402C), vacuumizes the logical argon shield in back and makes an experiment, and is heated to 100 ℃, the test coefficient of expansion with the rate of heating of 5 ℃/min.The result sees table 3.
Table 3 embodiment and contrast grade of steel performance test results
Compare with existing 4Cr13 corrosion resistant mould steel, steel grade corrosion resistance nature of the present invention significantly improves.Under the situation of Rockwell hardness HRC46-48, adopt concentration to carry out 72 hours salt-fog test for the 5%NaCl aqueous solution, erosion rate is 0.45-0.57 (g/m
2And the erosion rate of 4Cr13 is 0.88% (g/m .h),
2.h).
Compare with existing 4Cr13 corrosion resistant mould steel, steel grade polishing performance of the present invention significantly improves.Under the situation of Rockwell hardness HRC46-48, the roughness Ra after the steel grade polishing of the present invention is 3.2-3.8nm; And the roughness Ra after the 4Cr13 polishing is 6.3nm
Compare with existing 4Cr16Mo corrosion resistant mould steel; Steel grade of the present invention does not contain alloying elements such as Ni, Mo, V; Alloying element content has reduced by 3.6%, thereby has reduced manufacturing cost, has improved the competitiveness of product in market; And obtained lower linear expansivity, 100 ℃ of linear expansivitys of steel grade of the present invention are: 9.6-9.9 (10
-6//K), contrast grade of steel 4Cr13 is 10.6 (10
-6//K), contrast grade of steel 4Cr16Mo is 11.8 (10
-6//K).
It is thus clear that; Embodiments of the invention are compared with the contrast grade of steel; Corrosion resistance nature and polishing performance are significantly increased, and have lower linear expansivity, so steel grade of the present invention has the highly corrosion resistant performance; The characteristics of high polishing performance and low distortion are applicable to the accurate corrosion-resistant plastic die steel that minute surface is had relatively high expectations.
Fig. 1 be contrast grade of steel 4Cr13 quenching (1020 ℃ * 2h)+(250 ℃ * 4h) metallographic structure of attitude, the white granular pattern is organized as carbide in the picture, and forms network-like distribution in tempering.
Fig. 2 be contrast grade of steel 4Cr16Mo (containing 0.32%Ni) quenching (1020 ℃ * 2h)+tempering (250 ℃ * 4h) metallographic structure of attitude, white bulk is organized as the high temperature ferritic phase in the picture, white light tone globular structure is a carbide.
Fig. 3 be steel grade of the present invention quenching (1020 ℃ * 2h)+tempering (250 ℃ * 4h) metallographic structure of attitude, homogeneity of structure is better, no block high temperature ferritic phase exists with tangible granular carbide in the tissue.
It is thus clear that chemical ingredients proportioning of the present invention is more reasonable, pass through to add a certain amount of N element for the mentality of designing of C with N, effectively reduce the content of C element, make the carbide segregation situation of steel obtain very big improvement.Cr content is not very high simultaneously, has both guaranteed the requirement of corrosion resistance nature, has played the effect that prevents that the high temperature ferritic phase from separating out again, makes steel grade of the present invention have the characteristics of highly corrosion resistant performance and high polishing performance.
Because the present invention has overcome existing corrosion resistant mould steel carbide segregation, has organized shortcoming restive and that cost of alloy is high; Adopt the microalloying thinking to design the lower corrosion-resistant plastic die steel of a kind of alloying element content; Reduce manufacturing cost, improved product competitiveness.
Claims (10)
1. die steel, its weight percent chemical ingredients is: C:0.16-0.24%, Si≤0.15%; Mn≤0.15%, P＜0.015%, S＜0.005%; Cr:12.00-12.60%, N:0.13-0.20%, Ta:0.03-0.08%; C+N=0.30-0.37%, surplus is Fe and unavoidable impurities.
2. die steel as claimed in claim 1 is characterized in that, C:0.17-0.24%, or C:0.16-0.23%.
3. according to claim 1 or claim 2 die steel is characterized in that Si:0.10-0.15%.
4. like the arbitrary described die steel of claim 1-3, it is characterized in that Mn:0.10-0.15%.
5. like the arbitrary described die steel of claim 1-4, it is characterized in that Cr:12.0-12.50%.
6. like the arbitrary described die steel of claim 1-5, it is characterized in that Ta:0.035-0.075%.
7. like the arbitrary described die steel of claim 1-6, it adopts concentration to carry out 72 hours salt-fog test for the 5%NaCl aqueous solution under the situation of Rockwell hardness HRC46-48, and erosion rate is 0.45-0.57 (g/m
2.h), the roughness Ra after the polishing is 3.2-3.8nm; 100 ℃ of linear expansivitys are: 9.6-9.9 (10
-6//K).
8. like the method for manufacture of the arbitrary described die steel of claim 1-7, comprising:
Pour into electrode bar at vacuum induction melting;
Esr becomes ESR ingot again;
The steel ingot heats forged becomes forging stock;
The forging stock anneal;
Wherein, steel ingot is heated to 1100-1200 ℃ of temperature before forging;
In the forging stock anneal, annealing temperature is 830-860 ℃, is incubated 3-4 hour.
9. method as claimed in claim 8 is characterized in that, steel ingot is heated to 1100-1200 ℃ of temperature before forging, and is incubated 1-2 hour.
10. like claim 8 or 9 described methods, it is characterized in that stove is chilled to room temperature after the forging stock annealing.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103334062A (en) * | 2013-07-15 | 2013-10-02 | 湖北上大模具材料科技有限公司 | Novel precipitation hardening plastic die steel and processing technology thereof |
| CN103866197A (en) * | 2014-03-31 | 2014-06-18 | 江苏联峰能源装备有限公司 | Corrosion-resistant plastic die steel and production method thereof |
| CN107557670A (en) * | 2017-10-24 | 2018-01-09 | 山西太钢不锈钢股份有限公司 | Austenitic stainless steel and preparation method and application |
| CN107858593A (en) * | 2017-11-18 | 2018-03-30 | 蚌埠市华鼎机械科技有限公司 | A kind of preparation method of Heat-resistant stable, impact-resistant alloy mold |
| CN110230002A (en) * | 2019-07-30 | 2019-09-13 | 攀钢集团江油长城特殊钢有限公司 | A kind of martensite steel and preparation method thereof |
| CN112375987A (en) * | 2020-11-20 | 2021-02-19 | 河南中原特钢装备制造有限公司 | Nitrogen-added corrosion-resistant plastic die steel and manufacturing method thereof |
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| CN101798861A (en) * | 2010-03-08 | 2010-08-11 | 韩旭 | Heat-preserving and insulating and muffling system structure of steel mesh fiber spraying hanging panel |
| CN101967608A (en) * | 2010-11-12 | 2011-02-09 | 上海大学 | Nitrogen-containing corrosion-resistance plastic die steel and preparation process thereof |
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| CN101294259A (en) * | 2007-04-23 | 2008-10-29 | 大同特殊钢株式会社 | Hot die steel for die-casting |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103334062A (en) * | 2013-07-15 | 2013-10-02 | 湖北上大模具材料科技有限公司 | Novel precipitation hardening plastic die steel and processing technology thereof |
| CN103334062B (en) * | 2013-07-15 | 2015-09-30 | 湖北上大模具材料科技有限公司 | A kind of precipitation-hardening plastic die steel and complete processing thereof |
| CN103866197A (en) * | 2014-03-31 | 2014-06-18 | 江苏联峰能源装备有限公司 | Corrosion-resistant plastic die steel and production method thereof |
| CN103866197B (en) * | 2014-03-31 | 2016-04-20 | 江苏联峰能源装备有限公司 | A kind of plastic die steel and manufacture method thereof with erosion resistance |
| CN107557670A (en) * | 2017-10-24 | 2018-01-09 | 山西太钢不锈钢股份有限公司 | Austenitic stainless steel and preparation method and application |
| CN107858593A (en) * | 2017-11-18 | 2018-03-30 | 蚌埠市华鼎机械科技有限公司 | A kind of preparation method of Heat-resistant stable, impact-resistant alloy mold |
| CN110230002A (en) * | 2019-07-30 | 2019-09-13 | 攀钢集团江油长城特殊钢有限公司 | A kind of martensite steel and preparation method thereof |
| CN112375987A (en) * | 2020-11-20 | 2021-02-19 | 河南中原特钢装备制造有限公司 | Nitrogen-added corrosion-resistant plastic die steel and manufacturing method thereof |
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