CN101323942B - Production method of hot dip galvanizing steel plate - Google Patents
Production method of hot dip galvanizing steel plate Download PDFInfo
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- CN101323942B CN101323942B CN2008103032579A CN200810303257A CN101323942B CN 101323942 B CN101323942 B CN 101323942B CN 2008103032579 A CN2008103032579 A CN 2008103032579A CN 200810303257 A CN200810303257 A CN 200810303257A CN 101323942 B CN101323942 B CN 101323942B
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Abstract
The invention pertains to the field of hot-dip galvanized steel sheet manufacturing; the technical problem to be solved is to provide a production method of a hot-dip galvanized steel sheet. The production method specifically comprises the steps that: the steel plate is pickled and annealed, and hot-dip galvanizing operation is carried out; during the operation, the temperature of starting to plate is 475 to 485 DEG C; the plating temperature in the zinc pot is 450 to 460 DEG C; Fe content in plating bath is less than 0.03 percent; Al content in plating bath is 0.16 to 0.18 percent; the speed of machine unit is 100 to 110m/min; the cooling speed of the steel sheet is 0 percent; depth to span temperature is 235 to 245 DEG C. By adopting the technical conditions, the ratio Al/Zn of atomic concentration of Al and Zn in Fe-Al intermediate layer is larger than 0.9; and the circumstances that Gamma phase and Delta phase are relatively thin and Xi phase is small can not be formed in a plating layer, and the most part of the plating layer is made up of Eta phase, and the crystal grain Zn (002) with optimized orientation is formed, thus causing the performance of attachment, scratch resistance, wear resistance to be greatly improved.
Description
Technical field
The invention belongs to hot-dip galvanizing sheet steel and make the field, be specifically related to the good hot-galvanized steel plate producing process of a kind of adherence of coating.
Background technology
Hot-dip galvanizing sheet steel since its excellent corrosion resisting performance, good coating performance and clean outward appearance obtained using widely at household electrical appliance, body of a motor car with production such as plates.Requirement to hot dip galvanizing steel plate coating is the strong adhesion of coating and substrate, does not come off during the punching press distortion, in addition good welding property, corrosion resistance nature and phosphorus characteristic will be arranged, with the erosion resistance after guaranteeing paint film adhesion and painting.Yet there is the efflorescence of coating in hot-dip galvanizing sheet steel and problem such as peels off in the punch process process of practical application, and the destruction of having caused coating further has influence on the erosion resistance of coating and being coated with property.
The tack of steel plate galvanized coating also mainly is subjected to the composition of coating and the influence of weave construction except the influence of the composition that is subjected to the matrix steel plate, processing condition.Efflorescence is relevant with chemical ingredients and the phase structure peeled off with coating, and coating efflorescence amount raises with the iron level in the coating and increases.The efflorescence of coating is that the interface of Γ phase both sides forms tiny crack, runs through whole coating after the expansion and forms.When the Γ phase thickness surpasses 1.0 μ m, the efflorescence amount increases with the thickness of Γ phase, iron level in the coating is controlled at about 11%, just can hinders thick Γ and form mutually, thus resistance to chalking can major influence factors be δ phase (fine crystalline structure) and ζ (columnar structure) mutually.δ is mutually hard, and unfavorable to plasticity, ζ phase hardness is suitable with the matrix steel plate and crisp, is beneficial to the unrelieved stress that discharges in the coating when deformation, but its toughness height, easily is bonded to cause the coating surface defective on the mould or peel off.Therefore have only when the ζ in the coating has suitable proportion mutually with δ mutually, coating just has good plasticity.Coating surface ξ disappears mutually and the coating tissue of uneven fine and close δ when not occurring mutually is best coating tissue.
The base steel of hot-dip galvanizing sheet steel and the aluminium content in the Fe-Al intermediate layer between the zinc layer are major criterions weighing the coating adhesion strength in the hot-galvanized steel plate producing process of the present invention.But, contain higher aluminium amount in the Fe-Al intermediate layer, only be the prerequisite that obtains good coating adhesive power, rather than sufficient condition.Because have only when zinc in the Fe-Al intermediate layer unsaturated dissolving and when forming poor zinc sosoloid, this layer just can play adhesive attraction and stop the effect of Fe-Zn diffusion, and forms thin Fe-Zn alloy layer, at this moment, adherence of coating is better.When if the solubleness of Zn in the Fe-Al intermediate layer reaches supersaturation and has generated rich zinc sosoloid, though at this moment the Al absolute content in the middle layer does not reduce, but the percentage composition of Al but significantly descends, destroyed the uniformity of Fe-Al intermediate layer simultaneously because of the supersaturation of zinc, just make the middle layer lose adhesive attraction and prevention diffusion thus, and form thicker Fe-Zn alloy layer, the sticking power of zinc layer is degenerated simultaneously.
Make the surface form the tack of being improved coating and base steel by membrane technique by the composition of change steel plate or by the surfaceness of controlling hot-dip galvanizing sheet steel in the prior art, but do not obtain effect preferably, also do not occur at present by the composition of control coating and the method that weave construction is improved the tack of coating and base steel.
Summary of the invention
First technical problem to be solved by this invention provides a kind of production method of hot-dip galvanizing sheet steel, go into Al/Zn ratio in the zinc pot temperature control Fe-Al intermediate layer by the steel plate in the hot dip galvanizing process, reduce the formation of Fe-Zn alloy layer, adjust the optimum grain orientation of coating, improve the tack of coating.
Hot-galvanized steel plate producing process of the present invention is specially: steel plate carries out the pot galvanize operation after pickling, annealing; In the pot galvanize operating process, it is 475～485 ℃ that steel plate itself is gone into the plating bath temperature, the plating bath temperature is 450～460 ℃ in the zinc pot, Fe content＜0.03% in the plating bath, Al content 0.16～0.18% in the plating bath, unit speed 100～110m/min, the steel plate rate of cooling is 0%, height is striden temperature: 235～245 ℃, be preferably 240 ℃.
Described steel plate contains C:0.03～0.07% by weight percentage, Mn:0.01～0.03%, and Si:0.19～0.30%, P:0.006～0.019%, S:0.009～0.020%, Al:0.02～0.07%, all the other are Fe.
Described steel plate thickness is 0.8mm, and zinc-plated back zinc layer weight is 180～195g/m
2, the zinc laminar surface is through SiO
2Passivation Treatment.
The invention has the beneficial effects as follows:
(1) hot dip galvanizing process condition of the present invention makes substrate of steel plate and Fe-Al intermediate layer between the zinc coating can stop mutual diffusion mutually between Fe, the Zn, reduce the formation of Fe-Zn alloy layer, can not form the Γ phase in the coating, δ compares thin, ξ mutually seldom, the coating major part has improved the tack of hot dip galvanizing steel plate coating by the η phase composite, and the coating zinc powder such as comes off, peels off at phenomenon to be reduced;
(2) hot dip galvanizing process condition of the present invention makes the coating grain orientation optimization of hot-dip galvanizing sheet steel, and anti-zoned property, wear resistance and the adhesion property of coating obviously improve;
(3) hot dip galvanizing production process of the present invention is simple, and cost is lower.
Description of drawings
Fig. 1 is coating section electronic probe (EPMA1600 type) the wave spectrum face scanning analysis spectrogram of experimental example 1.
Fig. 2 is that optical metallographic microscope (OLYMPUS BX51 type) multiple is the metallograph of 100X, (a) is experimental example 1, (b) is comparative example 6.
Fig. 3 is experimental example 1 and comparative example 6,11 coating Fe-Al intermediate layer Al and Zn element atomic percent variation synoptic diagram.
Fig. 4 is that (shown in Figure 1) 2～4 position Al in experimental example 1～5 and comparative example 6～15 coating Fe-Al intermediate layers, Zn element average atom per-cent change synoptic diagram.
Fig. 5 is Fe, the Zn from base steel to zinc laminar surface position (shown in Figure 1) and the mass percent variation of Al element and the metallographic structure the coating in experimental example 1 and comparative example 6,11 coating, and (a) experimental example 1; (b) comparative example 6; (c) comparative example 11.
Fig. 6 is experimental example 1 and comparative example 6,11 typical X RD diffracting spectrum (a) experimental examples 1, (b) comparative example 6, (c) comparative example 11.
Fig. 7 is a U-shaped bend specimen shape synoptic diagram: 1 pliability test machine clamp, 2 bend specimens.
Fig. 8 is experimental example 1～5 sample and comparative example 6～10,11～15 sample zinc powder amount of coming off average and variances.
Fig. 9 is that experimental example 1 is located typical profile measurement figure with comparative example 6 and 11 coating cut mid-ways: 1 is that comparative example 11,2 is that experimental example 1,3 is a comparative example 6.
Embodiment
The invention will be further elaborated below in conjunction with embodiment.Embodiment only is used to illustrate the present invention, rather than limits the present invention by any way.
The preparation of embodiment 1 hot-dip galvanizing sheet steel experimental example 1～5 and comparative example 6～15
With thickness is 0.8mm, composition is C:0.03～0.07%, Mn:0.01～0.03%, Si:0.19～0.30%, P:0.006～0.019%, S:0.009～0.020%, Al:0.02～0.07%, all the other for the DX51D cold-rolled steel sheet of Fe and inevitable impurity through pickling, after the annealing, under listed each hot dip galvanizing process condition of table 1, carry out the pot galvanize operation, the plating bath initial temperature is 450 ℃ in the zinc pot, plating bath Fe content＜0.03%, Al content 0.18%, unit speed 100m/min, height is striden 240 ℃ of temperature, and rate of cooling 0% is gone into the plating bath temperature with steel plate and is adjusted into 475～485 ℃ and carries out pot galvanize operation and obtain the embodiment sample 1～No. 5; Steel plate is gone into the plating bath temperature and is adjusted into 455～465 ℃ and 440～450 ℃ respectively and carries out pot galvanize operation and obtain 6～No. 10 and 11～No. 15 comparative example samples.Zinc layer weight controls to 180～195g/m
2, the zinc laminar surface is through SiO
2Passivation Treatment.
Table 1 hot dip galvanizing process condition
The performance measurement of embodiment 2 hot-dip galvanizing sheet steel experimental examples 1～5 and comparative example 6～15
(1) coating Fe-Al intermediate layer and weave construction
Because Fe-Al middle transition layer thickness is tens between the hundreds of nanometer, conventional metallographic sample preparation means are difficult to this middle layer is shown.Metallographic sample preparation of the present invention adopts tiltedly edge sample, edge sample material is a bakelite, on hot mounting press, 3 hot-dip galvanizing sheet steel samples are sticked together with 502 seccotines, grind and polish that the back is placed side by side is at the angle of inclination with horizontal plane on 30 ° the taper liner piece, the visual range of the whole section of steel plate has approximately increased 1 times, and the Fe-Al middle layer transition layer between each coating and the base steel interface all obviously shows.
Each principal element atom and mass percent are measured by scanning of electronic probe (EPMA1600 type) wave spectrum face and some composition analysis in the coating Fe-Al intermediate layer.The used sample of EPMA all adopts the tiltedly metallographic specimen of the not etch of edge sample.From EPMA face scanning result, all experimental examples and comparative example all have dark-coloured Hei Dai Crescent e-Al intermediate layer as shown in Figure 1, and both sides are respectively base steel and zinc layer.Experimental example and each coating section of comparative example are begun to carry out the composition analysis of wave spectrum point to the zinc laminar surface by equidistant from base steel, particular location as shown in Figure 1, wherein 0 is the base steel position, 1～5 is position, Fe-Al middle layer, 6～12 is zinc layer position.
Fig. 3 is the EPMA line scanning spectrogram of the metallographic specimen of experimental example 1, experimental example 6 and comparative example 11 with EPMA measurement gained, and Al element content in the middle layer is the highest, and the Zn element begins to increase gradually to coating surface from base steel, and the Fe element reduces gradually.
Metallographic specimen is through grinding and polishing, carry out etch with 2% nitric acid alcohol etching solution after, under high-performance optics metaloscope (OLYMPUS BX51 type), carry out the metallographic photography, object lens magnification is 100 plinth X.Fig. 2 is the metallograph of experimental example and comparative example.Fig. 2 (a) can see the Fe-Al intermediate layer in the coating, thin δ phase, and the ξ phase of paucidisperse, the coating major part is by pure zinc layer η phase composite.Adhesion property through coating detects, and this experimental example (1) coating has good tack.When if the solubleness of Zn in the Fe-Al intermediate layer reaches supersaturation and has generated rich zinc sosoloid, though at this moment the Al absolute content in the middle layer does not reduce, but the percentage composition of Al but significantly descends, destroyed the uniformity of Fe-Al intermediate layer simultaneously because of the supersaturation of zinc, just make the middle layer lose adhesive attraction and prevention diffusion thus, and form thicker Fe-Zn alloy layer, δ increases mutually with ξ mutually, and the sticking power of zinc layer is degenerated simultaneously.The metallograph of the comparative example (6) that illustrates as Fig. 2 (b), though also formed the Fe-Al intermediate layer, the percentage composition of Al descends, the Fe-Zn alloy layer is increased, formed thicker δ mutually with ξ mutually, pure zinc layer η compares thin, the tack of coating obviously degenerates with respect to experimental example 1.
Fig. 4 is 2～4 position Al, a Zn element average atom per-cent in experimental example 1 and comparative example 6 and the 11 coating Fe-Al intermediate layers.Table 2 has been listed atomic percent and the Al/Zn ratio of Al and Zn in embodiment and each coating Fe-Al intermediate layer of comparative example.From above result as seen, Al element atomic percentage conc is all greater than comparative example in the experimental example Fe-Al intermediate layer, Zn element atomic percentage conc and comparative example are more or less the same, but experimental example Al/Zn ratio is all greater than 0.9, and Comparative examples A l/Zn ratio is between 0.358～0.553.
Each phase element mass percent is measured by the composition analysis of EPMA wave spectrum point in the coating tissue.According to the mass percent of each phase Fe of coating, Zn element, and the metallograph of contrast coating tissue, can judge that the δ, the ζ that exist in the coating and η are mutually.Fig. 5 show experimental example 1 (Fig. 5 a) and in comparative example 6 (Fig. 5 b) and comparative example 11 (Fig. 5 c) coating base steel begin to the mass percent of Fe, the Zn of zinc laminar surface position and Al element change and coating in metallographic structure.The phase constitution classification that table 2 is measured according to a position, zinc layer 7～12 6 has been listed the phase constitution of experimental example and each coating of comparative example.As seen, δ is all less mutually with ξ mutually in the experimental example coating, and η is mutually more for pure zinc layer; And all have in the comparative example coating thicker δ mutually with ξ mutually, pure zinc layer η compares thin.
For the good hot-dip galvanizing sheet steel of tack, to form the Fe-Al intermediate layer that contains higher Al content between base steel and the coating, and, has only zinc unsaturated dissolving and when forming poor zinc sosoloid in the Fe-Al intermediate layer, this layer just can play adhesive attraction and stop the effect of Fe-Zn diffusion, and forms thin Fe-Zn alloy layer, and δ reduces mutually with ξ mutually, at this moment, adherence of coating is better.
Table 2 hot-dip galvanizing sheet steel performance
(2) coating grain orientation
Coating surface is not done any processing, carries out coating small-angle diffraction (5 ° of grazing angles) on x x ray diffractometer x (XRD) respectively, measures the diffraction peak intensity of coating.Experimental example 1 and comparative example 6 and the 11 coating surfaces typical diffracting spectrum when 5 ° of grazing angles is seen Fig. 6.Table 2 has been listed the diffracted intensity at each sample Zn (002) peak.As seen, steel plate is gone into after the plating bath temperature brings up to 475～485 ℃, and experimental example sample 1～5 coating crystal grain presents the preferred orientation of Zn (002) direction, and the diffracted intensity at Zn (002) peak significantly strengthens, all greater than 34000cts.And steel plate goes in the comparative example 6～15 of plating bath temperature≤465 ℃, and the diffracted intensity at Zn (002) peak is between 14000～17000cts.
(3) the anti-performance that comes off of coating
Check the anti-performance that comes off of coating by " U " shape pliability test.Pliability test is carried out according to GB GB/T 232-1999 (metallic substance bend test method), and specimen preparation is with reference to GB/T 2975-1998 (steel and product made from steel mechanical property test sample position and specimen preparation).Fig. 7 shows the net shape of bend specimen.Sample is processed with wire cutting machine, use ethanol wiping specimen surface before the test, paste the scotch tape of identical size at all sample crooked position surfaces externally and internallies then, sample is processed in the enterprising line bend of flexing machine together with adhesive tape, collect the zinc powder that crooked position peels off by adhesive tape, the zinc powder amount of coming off of each coating is measured with the ICP method.Fig. 8 shows the average and the variance of experimental example and the comparative example sample zinc powder amount of coming off, and the zinc powder amount of coming off of experimental example all is significantly less than comparative example.Table 3 according to following standard to anti-performance evaluation: the ◎ that comes off of the coating of embodiment and each sample of comparative example good especially (the zinc powder amount of coming off :≤0.0100mg); Zero good (the zinc powder amount of coming off: between 0.0100～0.0300mg); △ bad a little (the zinc powder amount of coming off: between 0.0300～0.0360mg); * bad (the zinc powder amount of coming off: 〉=0.0440mg).
(4) the anti-zoned performance of coating
The anti-zoned performance test of coating is finished on U.S. CE TR UMT-2 type multifunction friction wear trier, and anti-zoned performance test is used scratch test device part, and the pressure head of scratch test is the spade diamond, and the head radius-of-curvature is 800m.Scratch test adopts the linear loading regime that increases, and selects for use loaded load to increase to 2N from 0.5N.The cut profile pattern after Ambios XP2 type contourgraph is measured each coating test is used in the test back.Fig. 9 shows in experimental example 1 and the comparative example 6 and 11 coating cut mid-way and locates typical profile measurement result.As seen, the coating scratch depth in the experimental example 1 all is significantly less than comparative example 6 and 11.Table 3 is estimated the anti-zoned performance of coating of experimental example and each sample of comparative example according to following standard: zero good (scratch depth≤7.00 μ m); △ bad a little (scratch depth is between 7.00～8.00 μ m); * bad (scratch depth 〉=8.00 μ m).
(4) cladding wearability energy
Cladding wearability can be tested on U.S. CE TR UMT-2 type multifunction friction wear trier reciprocating sliding friction test platform and finish.Last sample (to the mill sample) is the stainless steel ball of diameter 10mm, and following sample is a hot-dip galvanizing sheet steel.Reciprocating sliding friction wearing test parameter is: normal load F
n=2N, shift reciprocately amplitude D=2mm, speed of relative movement V=2mm/s, working time t=1000s, cycle index N=500.The polishing scratch profile pattern after Ambios XP2 type contourgraph is measured each coating test is used in the test back.Table 3 has been listed the average friction coefficient after embodiment and 100 the friction circulations of each sample of comparative example, and according to following standard the polishing scratch profile is estimated: zero good (the polishing scratch degree of depth≤8.00 μ m); △ bad a little (the polishing scratch degree of depth is between 8.00～10.00 μ m); * bad (the polishing scratch degree of depth 〉=10.00 μ m).
(5) adherence of coating can comprehensive evaluation
Table 3 can carry out comprehensive evaluation according to following standard to the adherence of coating of embodiment and each sample of comparative example: zero good (good zero counting is more than 2, and bad a little △ has only 1 at most); △ bad a little (good zero counting has 1, and bad a little △ counting has 2); * bad (bad * counting more than 2 or bad a little △ counting have 2, bad * counting has 1).
Table 3 hot-dip galvanizing sheet steel performance evaluation
By the evaluation result of table 3 as can be known, the present invention brings up to 475～485 ℃ with the zinc pot temperature of going into of hot dip galvanizing process process light plate, the hot-dip galvanizing sheet steel (experimental example 1～5) that obtains under the constant condition of other technologies is compared with steel plate (comparative example 6～15) in the past, Al/Zn ratio in the coating Fe-Al intermediate layer is all greater than 0.9, δ all reduces mutually with ξ mutually in the coating, and pure zinc layer η increases mutually; And experimental example (sample 1～5) coating crystal grain presents the preferred orientation of Zn (002) direction, and the diffracted intensity at Zn (002) peak significantly strengthens, all greater than 34000cts.The anti-performance that comes off of coating, anti-zoned performance and wear resisting property significantly improve, and the adhesion property of coating and base material obviously improves.
In above-mentioned experimental example and the comparative example, atomic percent ratio by Al and Zn in the measurement Fe-Al intermediate layer, and each phase constitution that exists in the coating, the preferable grain orientation of coating, and contrast the adhesion property evaluation of each coating, can judge: when Al/Zn ratio greater than 0.9, and be mainly the η phase in the coating, the diffracted intensity at the Zn of coating (002) peak is during greater than 34000cts, and the tack of coating is better.
Claims (4)
1. hot-galvanized steel plate producing process, steel plate carries out the pot galvanize operation after pickling, annealing, it is characterized in that: in the pot galvanize operating process, it is 475～485 ℃ that steel plate is gone into the plating bath temperature, and the plating bath temperature is 450～460 ℃ in the zinc pot, Fe content＜0.03% in the plating bath, Al content in the plating bath: 0.16～0.18%, unit speed: 100～110m/min, the steel plate rate of cooling is 0%, height is striden temperature: 235～245 ℃.
2. hot-galvanized steel plate producing process according to claim 1, it is characterized in that: described steel plate by weight percentage, contain C:0.03～0.07%, Mn:0.01～0.03%, Si:0.19～0.30%, P:0.006～0.019%, S:0.009～0.020%, Al:0.02～0.07%, all the other are Fe.
3. hot-galvanized steel plate producing process according to claim 1 is characterized in that: the thickness of described steel plate is 0.8mm.
4. hot-galvanized steel plate producing process according to claim 1 is characterized in that: zinc-plated back zinc layer weight is 180～195g/m
2, the zinc laminar surface is through SiO
2Passivation Treatment.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008103032579A CN101323942B (en) | 2008-07-31 | 2008-07-31 | Production method of hot dip galvanizing steel plate |
| DE112009001879.3T DE112009001879B4 (en) | 2008-07-30 | 2009-07-30 | Production process for a hot-dip galvanized steel plate |
| PCT/CN2009/073004 WO2010012235A1 (en) | 2008-07-30 | 2009-07-30 | Hot-galvanized steel sheet and production process thereof |
| JP2011520310A JP5520297B2 (en) | 2008-07-30 | 2009-07-30 | Method for producing hot-dip galvanized steel sheet |
| US13/003,619 US20110256420A1 (en) | 2008-07-30 | 2009-07-30 | Hot-dip galvanized steel plate and production method thereof |
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| US20110256420A1 (en) * | 2008-07-30 | 2011-10-20 | Pangang Group Steel Vanadium & Titanium Co., Ltd. | Hot-dip galvanized steel plate and production method thereof |
| TWI396772B (en) * | 2009-02-03 | 2013-05-21 | Nippon Steel & Sumitomo Metal Corp | Alloyed hot dip galvanized steel sheet and producing method therefor |
| US11426975B2 (en) * | 2017-07-31 | 2022-08-30 | Nippon Steel Corporation | Hot-dip galvanized steel sheet |
| CN111004971B (en) * | 2019-12-16 | 2021-05-25 | 首钢集团有限公司 | Hot-dip plated steel and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1890397A (en) * | 2003-12-19 | 2007-01-03 | 杰富意钢铁株式会社 | Method for producing alloyed zinc hot dip galvanized steel sheet |
| CN1974836A (en) * | 2006-12-18 | 2007-06-06 | 马鞍山钢铁股份有限公司 | Making process of hot galvanized fingerprint-proof plate |
| CN101161852A (en) * | 2007-11-15 | 2008-04-16 | 重庆钢铁(集团)有限责任公司 | Low alloy-consumption hot dip galvanizing technique |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1890397A (en) * | 2003-12-19 | 2007-01-03 | 杰富意钢铁株式会社 | Method for producing alloyed zinc hot dip galvanized steel sheet |
| CN1974836A (en) * | 2006-12-18 | 2007-06-06 | 马鞍山钢铁股份有限公司 | Making process of hot galvanized fingerprint-proof plate |
| CN101161852A (en) * | 2007-11-15 | 2008-04-16 | 重庆钢铁(集团)有限责任公司 | Low alloy-consumption hot dip galvanizing technique |
Non-Patent Citations (2)
| Title |
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| JP特开2002-317257A 2002.10.31 |
| JP特开2006-299309A 2006.11.02 |
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Address after: 611731 No. 1 Tianlong Road, hi tech West District, Sichuan, Chengdu Co-patentee after: Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. Patentee after: Pangang Group Institute Co., Ltd. Co-patentee after: Pangang Group Steel Vanadium & Titanium Co., Ltd. Address before: 611731 No. 1 Tianlong Road, hi tech West District, Sichuan, Chengdu Co-patentee before: Pangang Group Panzhihua Iron & Steel Research Institute Co., Ltd. Patentee before: Pangang Group Institute Co., Ltd. Co-patentee before: Panzhihua New Steel & Vanadium Co., Ltd. |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100602 Termination date: 20160731 |
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| CF01 | Termination of patent right due to non-payment of annual fee |