CN105177257A - High-nitrogen nickel-free austenitic stainless steel intergranular-corrosion-prevention processing technology - Google Patents
High-nitrogen nickel-free austenitic stainless steel intergranular-corrosion-prevention processing technology Download PDFInfo
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Abstract
The invention relates to a high-nitrogen nickel-free austenitic stainless steel intergranular-corrosion-prevention processing technology. Solution treatment is firstly carried out on materials; and then cold rolling deformation and recrystallization annealing technological treatment is carried to enable the proportion of the special grain boundary in high-nitrogen nickel-free austenitic stainless steel to be improved, and therefore the aim of improving the decay resistance of the materials is accordingly achieved. The high-nitrogen nickel-free austenitic stainless steel intergranular-corrosion-prevention performance can be obviously improved through technological treatment.
Description
Technical field
The invention belongs to stainless steel performance optimization field, be specially a kind for the treatment of process improving high nitrogen and nickel-less austenitic stainless steel anti intercrystalline corrosion ability.
Background technology
Contradiction in recent years between ever-increasing stainless steel demand and limited nickel resources is on the rise, and cause nickeliferous stainless price to rise steadily, especially the price of nickel austenite stainless steel is advanced by leaps and bounds especially; In addition, there is supersensitivity (during Ni>0.2%) to nickeliferous biological engineering material in human organ, and the human body skin allergy sickness rate caused thus improves constantly.Therefore, people have focused on sight on resource-conserving stainless steel-high nitrogen and nickel-less austenitic stainless steel.The nitrogen of q.s introduces austenitic stainless steel can make it obtain very excellent performance, can meet high-strength, high-ductility, high anti-corrosion and without the engineer applied requirement of magnetic etc., make up traditional austenitic stainless steel deficiency in these areas.Meanwhile, compared with traditional austenitic stainless steel, owing to instead of expensive nickel with nitrogen, make the material cost of this austenitic stainless steel cheaper.Therefore, high nitrogen and nickel-less austenitic stainless steel, as one of the Main way of structure iron rolled product variety adjustment, receives the great attention of various countries investigator.
But, too high nitrogen content make this new type stainless steel. corrosion resistance hot-work, welding and applied at elevated temperature time have nitride precipitation occur.There are some researches show, 23Cr-4Ni-2Mo-1N height nitrogen steel stops 2 seconds just have Cr2N phase precipitation generation at crystal boundary between 1173K and 1373K, and the precipitation of visible high-nitrogen austenitic stainless steel is difficult to avoid.High nitrogen and nickel-less austenitic stainless steel is expected to be widely used in the field such as building industry (bridge, with the antifreeze highway etc. of salt), oceanographic engineering, chemical industry due to high comprehensive performance, this just has higher requirement to the solidity to corrosion of high-nitrogen austenitic stainless steel, comprises intergranular corrosion resistance performance.But because Cr2N phase makes it have serious intergranular corrosion tendency in the precipitation of crystal boundary, directly limit development and the application of this novel advanced steel product.Add the units such as V, Ti, Nb in the oriented this kind of steel of the conventional approach addressed this problem and usually stablize N, but selectively " knife-line attack " problem when this method often can not solve molten solder, and obviously improve cost.Solid solution treatment method is also often used, and the second-phase of separating out in welding process is dissolved again.Although this method is simple, is difficult to the large structure unit processing postwelding, and still needs to prevent from heating in sensitizing temperature scope after process.As can be seen here, traditional terms of settlement is all undesirable.
In recent years, bounding engineering (GrainBoundaryEngineering, GBE), also made Grain Boundary Character distribute (GrainBoundaryCharacterDistribution, GBCD) optimization as solving the new method of crystal boundary Problem of Failure by extensive concern.Namely GBE is designed by a kind of thermomechanical treatment process and controls crystal boundary, ratio by increasing low Σ coincidence site lattice (CoincidenceSiteLattice, CSL) crystal boundary (special grain boundary) in GBCD puies forward a kind of method of heavy alloyed anti-crystal boundary failure performance.At present, Chinese scholars is improved intergranular corrosion aspect conduct extensive research at traditional austenitic stainless steel (304,316 austenitic stainless steel) GBE.The GBE technique of groping out in traditional austenitic stainless steel is small deformation amount (≤10%) low temperature (≤0.6Tm) prolonged anneal, and low Σ CSL crystal boundary ratio can reach 86%.And high nitrogen and nickel-less austenitic stainless steel has the feature of self compared with traditional austenitic stainless steel: not only have lower stacking fault energy, and have higher stability, martensitic transformation is less likely to occur in cold deformation.This just makes the microstructure evolution of high-nitrogen austenitic stainless steel in cold-rolled process, deformational behavior and microdeformation mechanism etc. all be different from traditional austenitic stainless steel, causes the travelling speed of crystal boundary in annealing process subsequently, migration pattern and crystal boundary migration motivating force etc. also can be different.As can be seen here, in traditional austenitic stainless steel, experimental GBCD Optimization Technology will no longer be applicable to this new structural material.But also there is not been reported to improve the research of high nitrogen and nickel-less austenitic stainless steel corrosion among crystalline grains aspect to GBE.Therefore, research GBE technique improves the corrosion among crystalline grains of the ferrous materials of this novel advanced person, the intergranular corrosion problem caused by the precipitation of high nitrogen and nickel-less austenitic stainless steel nitride can provide a kind of new resolving ideas and approach.
Summary of the invention
Goal of the invention: the object of the invention is to for solve high nitrogen and nickel-less austenitic stainless steel due to nitride precipitation caused by intergranular corrosion problem, provide a kind of new processing method.
Technical scheme: the present invention is achieved by the following technical solutions:
A kind of high nitrogen and nickel-less austenitic stainless steel anti intercrystalline corrosion treatment process, is characterized in that: described treatment process is following steps:
(1) high nitrogen and nickel-less austenitic stainless steel is put into heat treatment furnace and be heated to 1050 DEG C-1150 DEG C, insulation 30-60 minute, work in-process are taken out and puts into quenching-in water;
(2) taken out from water by the work in-process after quenching, carry out cold-rolling treatment after cooling, the deflection of described cold-rolling treatment is 5-10%, and in described cold-rolling treatment process, temperature is normal temperature;
(3) carry out the anneal of recrystallize, be specially and work in-process are put into heat treatment furnace be heated to 1130 DEG C ~ 1180 DEG C, and be incubated 10 minutes-72 hours; Work in-process are taken out and puts into quenching-in water.
Described high nitrogen and nickel-less austenitic stainless steel is Cr-Mn-N or Cr-Mn-Mo-N high nitrogen and nickel-less austenitic stainless steel.
Described Cr-Mn-N high nitrogen and nickel-less austenitic stainless steel comprises the composition of following mass percent:
Cr：17%-22%；
Mn：17%-20%；
N：0.4%-1.0%；
C: be less than 0.01%;
Fe: surplus,
Described Cr-Mn-Mo-N high nitrogen and nickel-less austenitic stainless steel comprises the composition of following mass percent:
Cr：17%-22%；
Mn：17%-20%；
N：0.4%-1.0%；
Mo：1.0%-2-5%；
C: be less than 0.01%;
Fe: surplus.
Advantage and effect: be can be implemented in the intergranular corrosion resistance performance not changing alloying constituent, improve material under the prerequisite that do not need to increase substantially cost by this technique.The performance relevant to crystal boundary to other, as resistance to Intergranular stress corrosion cracking performance, Corrosion Fatigue Properties etc. also can make moderate progress.
Accompanying drawing illustrates:
Fig. 1 is the ratio of special grain boundary under different distortion amount after 18Cr-18Mn-0.63N high nitrogen and nickel-less austenitic stainless steel anneals 10min at 1150 DEG C;
Fig. 2 is the relation curve of corrosion weight loss amount and etching time under 18Cr-18Mn-0.63N high nitrogen and nickel-less austenitic stainless steel different process;
Fig. 3 is the surface scan photo of sample after 12h, 24h and 48h sulfuric acid-ferric sulfate corrosion test under 18Cr-18Mn-0.63N high nitrogen and nickel-less austenitic stainless steel different process;
Fig. 4 is the cross-sectional scans photo of sample after 12h, 24h and 48h sulfuric acid-ferric sulfate corrosion test under 18Cr-18Mn-0.63N high nitrogen and nickel-less austenitic stainless steel different process;
Fig. 5 is the ratio of special grain boundary under different distortion amount after 20Cr-19Mn-2Mo-0.82N high nitrogen and nickel-less austenitic stainless steel anneals 72h at 1150 DEG C;
Fig. 6 is the relation curve of corrosion weight loss amount and etching time under 20Cr-19Mn-2Mo-0.82N high nitrogen and nickel-less austenitic stainless steel different process;
Fig. 7 is the surface scan photo of sample after 24h, 48h and 72h sulfuric acid-ferric sulfate corrosion test under 20Cr-19Mn-2Mo-0.82N high nitrogen and nickel-less austenitic stainless steel different process;
Fig. 8 is the cross-sectional scans photo of sample after 24h, 48h and 72h sulfuric acid-ferric sulfate corrosion test under 20Cr-19Mn-2Mo-0.82N high nitrogen and nickel-less austenitic stainless steel different process.
In figure: the ordinate zou of Fig. 1, Fig. 5 is special grain boundary ratio, and X-coordinate is cold-rolling thickness draught; The ordinate zou of Fig. 2, Fig. 6 is corrosion weight loss, and X-coordinate is etching time; In all the other figure, after solution treatment, sample is denoted as BM; After 7% cold deformation, 1150 DEG C of annealing 10min samples are denoted as r7%-a1150 DEG C-10min; After 10% cold deformation, 1150 DEG C of annealing 10min and 72h samples are denoted as r10%-a1150 DEG C-10min and r10%-1150 DEG C-72h respectively; After 5% cold deformation, 1150 DEG C of annealing 72h samples are denoted as r5%-1150 DEG C-72h.
embodiment:
The present invention is a kind for the treatment of process improving high nitrogen and nickel-less austenitic stainless steel anti intercrystalline corrosion ability, technological thought of the present invention is: by first carrying out solution treatment to material, then cold deformation and annealing process process is carried out, special grain boundary ratio in high nitrogen and nickel-less austenitic stainless steel is improved, thus reaches the object improving material corrosion resistance.By this art breading, the intergranular corrosion resistance performance of high nitrogen and nickel-less austenitic stainless steel can improve several times.
The concrete implementing procedure of present treatment technique is following steps:
(1) high nitrogen and nickel-less austenitic stainless steel is put into heat treatment furnace and be heated to 1050 DEG C-1150 DEG C, insulation 30-60 minute, work in-process are taken out and puts into quenching-in water;
(2) taken out from water by the work in-process after quenching, carry out cold-rolling treatment after cooling, the deflection of described cold-rolling treatment is 5-10%, and in described cold-rolling treatment process, temperature is normal temperature;
(3) carry out the anneal of recrystallize, be specially and work in-process are put into heat treatment furnace be heated to 1130 DEG C ~ 1180 DEG C, and be incubated 10 minutes-72 hours; Work in-process are taken out and puts into quenching-in water.
Now specific embodiments of the invention are presented below:
Embodiment 1
In this example, adopt Cr-Mn-N high nitrogen and nickel-less austenitic stainless steel (concrete composition is by mass percentage Cr:17.97%, Mn:18.0%, N:0.63%, C:0.056%, and all the other are Fe, is denoted as 18Cr-18Mn-0.63N high nitrogen and nickel-less austenitic stainless steel).First 18Cr-18Mn-0.63N high nitrogen and nickel-less austenitic stainless steel sheet material is carried out in chamber type electric resistance furnace 1050 DEG C insulation 1h solution treatment after shrend, then sheet material is carried out cold roller and deformed on four-high mill, reduction in thickness is 7%, then carry out in chamber type electric resistance furnace 1150 DEG C insulation 10min anneal after shrend.After this kind of processing method process, by 47.3% of the sample (hereinafter referred to as solution treatment aspect product) after only solid solution treatment process process, special grain boundary ratio is increased to that solution treatment adds the sample after thermomechanical treatment process process (hereinafter referred to as thermomechanical treatment aspect product) to 18Cr-18Mn-0.63N high nitrogen and nickel-less austenitic stainless steel 83.3%, adds 36%(Fig. 1).After 850 DEG C of insulations sensitized treatment of 2 hours, carry out sulfuric acid-ferric sulfate corrosion experiment (GB/T4334.2-2000), along with the increase of corrosion experiment time, the difference of solution treatment aspect product and thermomechanical treatment aspect product corrosion weight loss amount becomes large gradually.After corrosion 48h, the corrosion weight loss amount of thermomechanical treatment aspect product is reduced to 26%(Fig. 2 of solution treatment aspect product).Solution treatment aspect product surface layer grain comes off completely, and thermomechanical treatment aspect product top layer only has only a few crystal grain to come off (Fig. 3).Intergranular corrosion cracks depth of erosion is reduced to 177 μm of thermomechanical treatment aspect product by 379 μm of solution treatment aspect product, reduces 53.3%(Fig. 4).
Embodiment 2
In this example, adopt Cr-Mn-N high nitrogen and nickel-less austenitic stainless steel (concrete composition is by mass percentage Cr:17.97%, Mn:18.0%, N:0.63%, C:0.056%, and all the other are Fe, is denoted as 18Cr-18Mn-0.63N high nitrogen and nickel-less austenitic stainless steel).First 18Cr-18Mn-0.63N high nitrogen and nickel-less austenitic stainless steel sheet material is carried out in chamber type electric resistance furnace 1050 DEG C insulation 1h solution treatment after shrend, then sheet material is carried out cold roller and deformed on four-high mill, reduction in thickness is 10%, then carry out in chamber type electric resistance furnace 1150 DEG C insulation 10min anneal after shrend.18Cr-18Mn-0.63N high nitrogen and nickel-less austenitic stainless steel special grain boundary ratio after this kind of processing method is increased to 76.4% of thermomechanical treatment aspect product by 47.3% of solution treatment aspect product, adds 29.1%(Fig. 1).After 850 DEG C of insulations sensitized treatment of 2 hours, carry out sulfuric acid-ferric sulfate corrosion experiment (GB/T4334.2-2000), along with the increase of corrosion experiment time, the difference of solution treatment aspect product and thermomechanical treatment aspect product corrosion weight loss amount becomes large gradually.After corrosion 48h, the corrosion weight loss amount of thermomechanical treatment aspect product is reduced to 84.8%(Fig. 2 of solution treatment aspect product).Solution treatment aspect product and thermomechanical treatment aspect product surface layer grain all come off completely, but solid solution aspect product comparatively thermomechanical treatment aspect product come off more serious, and the crystal grain below top layer also occurs come off (Fig. 3).Intergranular corrosion cracks depth of erosion is reduced to 290 μm of thermomechanical treatment aspect product by 379 μm of solution treatment aspect product, reduces 23.5%(Fig. 4).
Embodiment 3
In this example, (concrete composition is by mass percentage Cr:20.17%, Mn:19.10% to adopt Cr-Mn-Mo-N high nitrogen and nickel-less austenitic stainless steel, N:0.82%, C:0.065%, Mo:2.29%, all the other are Fe, are denoted as 20Cr-19Mn-2Mo-0.82N high nitrogen and nickel-less austenitic stainless steel).First 20Cr-19Mn-2Mo-0.82N high nitrogen and nickel-less austenitic stainless steel sheet material is carried out in chamber type electric resistance furnace 1050 DEG C insulation 1h solution treatment after shrend, then sheet material is carried out cold roller and deformed on four-high mill, reduction in thickness is 5%, then carry out in chamber type electric resistance furnace 1150 DEG C insulation 72h anneal after shrend.20Cr-19Mn-2Mo-0.82N high nitrogen and nickel-less austenitic stainless steel special grain boundary ratio after this kind of processing method is increased to 79.4% of thermomechanical treatment aspect product by 47.3% of solution treatment aspect product, adds 32.1%(Fig. 5).After 850 DEG C of insulations sensitized treatment of 2 hours, carry out sulfuric acid-ferric sulfate corrosion experiment (GB/T4334.2-2000), along with the increase of corrosion experiment time, the difference of solution treatment aspect product and thermomechanical treatment aspect product corrosion weight loss amount becomes large gradually.After corrosion 72h, the corrosion weight loss amount of thermomechanical treatment aspect product is reduced to 19.8%(Fig. 6 of solution treatment aspect product).Coming off appears in solution treatment aspect product not only surface layer grain, and coming off also appears in the crystal grain below top layer, and thermomechanical treatment aspect product surface layer grain only has only a few to come off, and corrosion ditch (Fig. 7) appears in crystal boundary.Intergranular corrosion cracks depth of erosion is reduced to 130 μm of thermomechanical treatment aspect product by 430 μm of solution treatment aspect product, reduces 69.8%(Fig. 8).
Embodiment 4
In this example, adopt Cr-Mn-Mo-N high nitrogen and nickel-less austenitic stainless steel.(concrete composition is by mass percentage Cr:20.17%, Mn:19.10%, N:0.82%, C:0.065%, Mo:2.29%, and all the other are Fe, is denoted as 20Cr-19Mn-2Mo-0.82N high nitrogen and nickel-less austenitic stainless steel).First 20Cr-19Mn-2Mo-0.82N high nitrogen and nickel-less austenitic stainless steel sheet material is carried out in chamber type electric resistance furnace 1050 DEG C insulation 1h solution treatment after shrend, then sheet material is carried out cold roller and deformed on four-high mill, reduction in thickness is 10%, then carry out in chamber type electric resistance furnace 1150 DEG C insulation 72h anneal after shrend.20Cr-19Mn-2Mo-0.82N high nitrogen and nickel-less austenitic stainless steel special grain boundary ratio after this kind of processing method is increased to 54.3% of thermomechanical treatment aspect product by 47.3% of solution treatment aspect product, adds 7%(Fig. 5).Carry out 850 DEG C of insulations sensitized treatment of 2 hours, then carry out sulfuric acid-ferric sulfate corrosion experiment (GB/T4334.2-2000), along with the increase of corrosion experiment time, the difference of solution treatment aspect product and thermomechanical treatment aspect product corrosion weight loss amount becomes large gradually.After corrosion 72h, the corrosion weight loss amount of thermomechanical treatment aspect product is reduced to 45.5%(Fig. 6 of solution treatment aspect product).Coming off appears in solution treatment aspect product not only surface layer grain, and coming off also appears in the crystal grain below top layer, and thermomechanical treatment aspect product surface layer grain only has minority to come off, and the corrosion ditch of crystal boundary broadens (Fig. 7).Intergranular corrosion cracks depth of erosion is reduced to 220 μm of thermomechanical treatment aspect product by 430 μm of solution treatment aspect product, reduces 48.8%(Fig. 8).
Claims (3)
1. a high nitrogen and nickel-less austenitic stainless steel anti intercrystalline corrosion treatment process, is characterized in that: described treatment process is following steps:
(1) high nitrogen and nickel-less austenitic stainless steel is put into heat treatment furnace and be heated to 1050 DEG C-1150 DEG C, insulation 30-60 minute, work in-process are taken out and puts into quenching-in water;
(2) taken out from water by the work in-process after quenching, carry out cold-rolling treatment after cooling, the deflection of described cold-rolling treatment is 5-10%, and in described cold-rolling treatment process, temperature is normal temperature;
(3) carry out the anneal of recrystallize, be specially and work in-process are put into heat treatment furnace be heated to 1130 DEG C ~ 1180 DEG C, and be incubated 10 minutes-72 hours; Work in-process are taken out and puts into quenching-in water.
2. high nitrogen and nickel-less austenitic stainless steel anti intercrystalline corrosion treatment process according to claim 1, is characterized in that: described high nitrogen and nickel-less austenitic stainless steel is Cr-Mn-N or Cr-Mn-Mo-N high nitrogen and nickel-less austenitic stainless steel.
3. high nitrogen and nickel-less austenitic stainless steel anti intercrystalline corrosion treatment process according to claim 2, is characterized in that: described Cr-Mn-N high nitrogen and nickel-less austenitic stainless steel comprises the composition of following mass percent:
Cr：17%-22%；
Mn：17%-20%；
N：0.4%-1.0%；
C: be less than 0.01%;
Fe: surplus;
Described Cr-Mn-Mo-N high nitrogen and nickel-less austenitic stainless steel comprises the composition of following weight percent:
Cr：17%-22%；
Mn：17%-20%；
N：0.4%-1.0%；
Mo：1.0%-2-5%；
C: be less than 0.01%;
Fe: surplus.
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Cited By (13)
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| CN105586539A (en) * | 2016-02-29 | 2016-05-18 | 欧士玺 | Stainless steel valve |
| CN107245703A (en) * | 2017-05-31 | 2017-10-13 | 江苏金基特钢有限公司 | It is a kind of to reduce the method for making Nano of Intergranular Corrosion of Austenitic Stainless Steel |
| CN107937689A (en) * | 2017-11-29 | 2018-04-20 | 上海航天精密机械研究所 | Improve the method for the resistance to spot corrosion performance of stainless steel and intensity |
| CN108842044A (en) * | 2018-07-23 | 2018-11-20 | 东北大学 | A method of improving low ∑ value special grain boundary ratio in AL6XN stainless steel |
| CN109971925A (en) * | 2019-05-17 | 2019-07-05 | 淮海工学院 | Improve the thermomechanical treatment process method of austenitic stainless steel anti intercrystalline corrosion performance |
| CN111840659A (en) * | 2020-04-30 | 2020-10-30 | 中科益安医疗科技（北京）股份有限公司 | High-safety blood vessel support without nickel metal medicine elution and its making method |
| CN111850422A (en) * | 2020-04-30 | 2020-10-30 | 中科益安医疗科技（北京）股份有限公司 | High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube and preparation method thereof |
| CN113046534A (en) * | 2021-03-15 | 2021-06-29 | 长春工业大学 | Preparation method of high-nitrogen nickel-free austenitic stainless steel with high twin crystal density |
| CN113088652A (en) * | 2021-03-31 | 2021-07-09 | 长春工业大学 | Preparation method of diffusion-strengthened high-stability medical high-nitrogen nickel-free austenitic stainless steel |
| CN114934240A (en) * | 2022-04-25 | 2022-08-23 | 中国科学院金属研究所 | Preparation method of ultrahigh-strength high-corrosion-resistance high-nitrogen austenitic stainless steel |
| CN115044754A (en) * | 2022-04-26 | 2022-09-13 | 安徽工业大学 | Method for improving intergranular corrosion resistance of C-HRA-5 austenitic heat-resistant steel |
| CN115261580A (en) * | 2022-08-23 | 2022-11-01 | 华中科技大学 | Stainless steel surface grain boundary engineering treatment method based on cutting processing and product |
| CN115961216A (en) * | 2023-02-15 | 2023-04-14 | 山东烟炉节能科技有限公司 | Seabed oil and gas pipeline and preparation method thereof |
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| CN105586539A (en) * | 2016-02-29 | 2016-05-18 | 欧士玺 | Stainless steel valve |
| CN107245703A (en) * | 2017-05-31 | 2017-10-13 | 江苏金基特钢有限公司 | It is a kind of to reduce the method for making Nano of Intergranular Corrosion of Austenitic Stainless Steel |
| CN107937689A (en) * | 2017-11-29 | 2018-04-20 | 上海航天精密机械研究所 | Improve the method for the resistance to spot corrosion performance of stainless steel and intensity |
| CN108842044A (en) * | 2018-07-23 | 2018-11-20 | 东北大学 | A method of improving low ∑ value special grain boundary ratio in AL6XN stainless steel |
| CN109971925A (en) * | 2019-05-17 | 2019-07-05 | 淮海工学院 | Improve the thermomechanical treatment process method of austenitic stainless steel anti intercrystalline corrosion performance |
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| CN113088652A (en) * | 2021-03-31 | 2021-07-09 | 长春工业大学 | Preparation method of diffusion-strengthened high-stability medical high-nitrogen nickel-free austenitic stainless steel |
| CN114934240A (en) * | 2022-04-25 | 2022-08-23 | 中国科学院金属研究所 | Preparation method of ultrahigh-strength high-corrosion-resistance high-nitrogen austenitic stainless steel |
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| CN115044754A (en) * | 2022-04-26 | 2022-09-13 | 安徽工业大学 | Method for improving intergranular corrosion resistance of C-HRA-5 austenitic heat-resistant steel |
| CN115044754B (en) * | 2022-04-26 | 2023-12-15 | 安徽工业大学 | Method for improving intergranular corrosion resistance of C-HRA-5 austenitic heat-resistant steel |
| CN115261580A (en) * | 2022-08-23 | 2022-11-01 | 华中科技大学 | Stainless steel surface grain boundary engineering treatment method based on cutting processing and product |
| CN115961216A (en) * | 2023-02-15 | 2023-04-14 | 山东烟炉节能科技有限公司 | Seabed oil and gas pipeline and preparation method thereof |
| CN115961216B (en) * | 2023-02-15 | 2023-08-04 | 山东烟炉节能科技有限公司 | Submarine oil and gas transmission pipeline and preparation method thereof |
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Application publication date: 20151223 |