CN101208160A - Process for producing seamless tube - Google Patents
Process for producing seamless tube Download PDFInfo
- Publication number
- CN101208160A CN101208160A CNA2006800105011A CN200680010501A CN101208160A CN 101208160 A CN101208160 A CN 101208160A CN A2006800105011 A CNA2006800105011 A CN A2006800105011A CN 200680010501 A CN200680010501 A CN 200680010501A CN 101208160 A CN101208160 A CN 101208160A
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 72
- 238000005096 rolling process Methods 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000314 lubricant Substances 0.000 claims description 62
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 229910002804 graphite Inorganic materials 0.000 claims description 21
- 239000010439 graphite Substances 0.000 claims description 21
- 210000000981 epithelium Anatomy 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
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- 239000000463 material Substances 0.000 claims description 13
- 238000007591 painting process Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 230000006978 adaptation Effects 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
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- 239000007864 aqueous solution Substances 0.000 claims description 5
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- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 5
- 229940072033 potash Drugs 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000011684 sodium molybdate Substances 0.000 claims description 5
- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 abstract description 21
- 238000001816 cooling Methods 0.000 abstract description 7
- 230000001050 lubricating effect Effects 0.000 description 23
- 238000001035 drying Methods 0.000 description 19
- 239000007921 spray Substances 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
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- 239000010959 steel Substances 0.000 description 6
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 229940117958 vinyl acetate Drugs 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- -1 can list sericite Inorganic materials 0.000 description 3
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- 238000005553 drilling Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 229910052615 phyllosilicate Inorganic materials 0.000 description 2
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- ZPECLGVYJKUVTC-UHFFFAOYSA-N 4-ethoxytriazine Chemical class CCOC1=CC=NN=N1 ZPECLGVYJKUVTC-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- XDILZEPJCPEDLT-UHFFFAOYSA-N [Na].[O-][N+]1=CC=CC=C1S Chemical compound [Na].[O-][N+]1=CC=CC=C1S XDILZEPJCPEDLT-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000000637 arginyl group Chemical class N[C@@H](CCCNC(N)=N)C(=O)* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
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- 230000009193 crawling Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B25/00—Mandrels for metal tube rolling mills, e.g. mandrels of the types used in the methods covered by group B21B17/00; Accessories or auxiliary means therefor ; Construction of, or alloys for, mandrels or plugs
- B21B25/04—Cooling or lubricating mandrels during operation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B17/00—Tube-rolling by rollers of which the axes are arranged essentially perpendicular to the axis of the work, e.g. "axial" tube-rolling
- B21B17/02—Tube-rolling by rollers of which the axes are arranged essentially perpendicular to the axis of the work, e.g. "axial" tube-rolling with mandrel, i.e. the mandrel rod contacts the rolled tube over the rod length
- B21B17/04—Tube-rolling by rollers of which the axes are arranged essentially perpendicular to the axis of the work, e.g. "axial" tube-rolling with mandrel, i.e. the mandrel rod contacts the rolled tube over the rod length in a continuous process
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Lubricants (AREA)
Abstract
A process which comprises: a first coating step in which a first liquid is applied to the surface of a high-temperature mandrel bar immediately after preceding stretching/rolling to thereby form a water-resistant coating film; a water-cooling step in which the mandrel bar which has undergone the first coating step is cooled with water; a second coating step in which a second liquid is applied to the mandrel bar surface which has undergone the water-cooling step to thereby infiltrate the second liquid into the water-resistant coating film and impart high-temperature adhesion; and a stretching/rolling step, wherein in this stretching/rolling step, the stretching/rolling of a hollow shell with this mandrel bar is initiated within 10 seconds after the second coating step.
Description
Technical field
The present invention relates to utilize the manufacture method of the seamless pipe of Mannesmann-mandrel mill mode, the manufacture method of particularly following seamless pipe: to material is that the hollow bloom of high-alloy steel such as stainless steel or 13Cr steel is when carrying out drawing/rolling, prevent burn-back, effectively the generation of killer tube defect in inner surface as the plug and the hollow bloom of inner surface control tool.
Background technology
Seamless pipe uses at a lot of industrial fields such as the energy, automobile, chemistry, industrial machine, building.Particularly seamless pipe is used for the conveying of oil well pipe, unstrpped gas mostly, is bringing into play important effect in world's energy resources exploitation association area.
The manufacturing that utilizes the seamless pipe of Mannesmann-mandrel mill mode is to carry out through operation for example shown in Figure 3.At first, putting into rotation siege formula heating furnace 2 as the steel billet 1 of the raw material of seamless pipe heats.The steel billet 1 that is rotated siege formula heating furnace 2 heating is become hollow bloom 4 by roll piercing mill (drilling/rolling machine) 3 drilling/rollings after extracting out in the stove.Then,, to its inner plug 5a that inserts, carry out drawing/rolling, become pipe 4a by mandrel mill 5 from rear end side for hollow bloom 4.And then from pipe 4a, extract plug 5a thereafter out.
In the manufacturing of the above-mentioned seamless pipe that utilizes Mannesmann-mandrel mill mode, when hollow bloom 4 being carried out drawing/rolling with mandrel mill, plug 5a is inserted in 1100～1200 ℃ the hollow bloom 4 usually, be exposed under the state of easy burn-back, thereby its outer surface application of lubricating.The lubricant of this coating plays the effect of protection tunicle,, prevents the welding that is caused by the burn-back between plug 5a and the hollow bloom 4 that is.As the lubricant on the surface that is applied to plug 5a, use the lubricant for hot rolling of greasy property excellence under the heat condition.Since cheap and have excellent lubricating property, use for example with the water miscible graphite base lubricant of graphite mostly as principal component.This lubricant supplies to production line from storage tank usually, from being configured in the annular nozzle that is about to plug 5a is inserted into the position before the hollow bloom 4, towards the surface by its inner plug 5a to spray shape jet lubrication agent.Like this, be coated with the lubricant of the regulation total amount of rule of thumb determining on the surface of plug 5a.
The external diameter shape of the pipe that obtains by the mandrel mill drawing/rolling and the rotating speed that wall thickness is subjected to each bench roller and the influence of roller pass shape, and be affected according to the variation of the coefficient of friction between plug 5a and the hollow bloom 4.Promptly, as the lubricant that is applied to plug 5a, use to reduce and hollow bloom 4 between the lubricant of coefficient of friction, thus, make in the hollow bloom 4 drawing/rolling processes at circumferencial direction and length direction and be out of shape equably and obtain having the stable external diameter shape and the pipe of Thickness Distribution.
Behind drawing/rolling, use the excellent demoulding (bar stripper) from pipe 4a, to extract plug 5a out.But, at this moment, be applied under the situation of poor lubricity of lubricant of plug 5a outer surface, pipe 4a and plug 5a burn-back, inner surface produces defective.Perhaps, plug 5a is not drawn out of.
Usually, in hot-working, tool surfaces and machined material surface produces oxide skin, the iron oxide epithelium that is formed by this oxide skin, particularly by densification and lower FeO, the Fe of hardness ratio
3O
4The epithelium that forms can bring desirable influence to adding the lubricity in man-hour.But ordinary steels such as stainless steel such as the SUS304 of JIS specification defined system, SUS316 system, SUS347 system, SUS410 system and SUS430 system or steel alloys such as STBA25, STBA26 and carbon steel are different, are difficult to generate oxide skin.In addition, these steel have engineering properties such as high strength, high tenacity, thereby employed instrument also needs to use the stable on heating low-alloy instrument that is with its Co-Mo such as JIS-SKD61 that are suitable for mutually system, Cr-Mo-V.Itself also is difficult to generate oxide skin the instrument of such material.Therefore, rolling load and coefficient of friction in the processing uprise, plug 5a and hollow bloom 4 easy burn-backs.Blemish often takes place thus.The pipe product of stainless steel or steel alloy is owing to require the surface texture of height, thereby when producing such blemish, even it is slight, also can not be directly as product turnout, and need carry out subsequent fine processing such as surface grinding and handle.In addition, when tube-surface produced dark defective, this pipe became substandard products.Therefore, in the manufacturing of the seamless pipe that utilizes Mannesmann-mandrel mill mode, the performance of lubricant that is applied to the surface of plug 5a not only influences product quality but also can bring significant impact to productivity ratio.
Usually, after plug is inserted in 1100～1200 ℃ the hollow bloom, be supplied in drawing/rolling processing, thereby drawing/rolling becomes 100～400 ℃ high temperature after just having finished.Therefore, plug before in being fed into the drawing/rolling of next hollow bloom during, be cooled, and application of lubricating once more.
For the lubricant that is applied to this plug, following technology is disclosed in patent documentation 1: make by comprising powdered graphite and having that first liquid of the water-soluble resin of property is solidified in reaction, two liquid formed with second liquid that comprises boric acid etc. carry out chemical reaction, make lubricating film after the curing between hollow bloom and plug, prevent burn-back.
In addition, disclose a kind of one-pack-type lubricant in patent documentation 2, its water-soluble resin with first liquid of above-mentioned patent documentation 1 replaces to polymer, and also comprises mica.
In addition, in patent documentation 3, disclose following technology, repeatedly be coated with same lubricant, guaranteed the lubricant epithelium of specific thickness, prevented burn-back.
Patent documentation 1: Japanese kokai publication sho 63-230797 communique
Patent documentation 2: Japanese kokai publication hei 8-165489 communique
Patent documentation 3: TOHKEMY 2004-34072 communique
Summary of the invention
The problem to be solved in the present invention
The plug of extracting out from pipe is sent back to excellent cooled region, be cooled to proper temperature after, supply in the drawing/rolling of next pipe, carry out so-called recycling.At cooled region, cooling means that can field by using is free cold-peace water-cooled, under the situation in the space that makes a plurality of plug standbies that is difficult to guarantee that fully air cooling is required, adopts short water-cooled cool time.In this case, plug is fed in the short time in the drawing/rolling of next hollow bloom after water-cooled.
Plug is by under the situation of water-cooled, as the opportunity on the surface that lubricant is coated onto rod, usually consider following both, promptly the drawing/rolling of the last hollow bloom water that just finished back (before the water-cooled) and water-cooled rear surface evaporates fully and is about to next hollow bloom is carried out before the drawing/rolling.Under the situation about being coated with after drawing/rolling just finishes, the plug of answering application of lubricating is 100～400 ℃ a high temperature, and next operation is carried out water-cooled, thereby except requiring anti-burn-back, also requires hear resistance, resistance to water.In addition, before soon next hollow bloom being carried out drawing/rolling, under the situation of application of lubricating,, need behind application of lubricating, form lubricating film in the short time after the water-cooled with sufficient anti-burn-back for enhancing productivity.That is, lubricant requires rapid-drying properties.
In addition, be to suppose to use substantially at normal temperatures at patent documentation 2 disclosed lubricants, and do not consider resistance to water, thereby, use after water-cooled though have to, owing to do not consider rapid-drying properties, thereby existence and the identical problem of patent documentation 1 disclosed lubricant.
In addition, patent documentation 3 disclosed technology are because the rapid-drying properties after the desired hear resistance of the not mentioned lubricant that is coated with before water-cooled, resistance to water and the water-cooled, thereby are not given in plug by the enlightenment that specifically should how to use under the situation of water-cooled.
Therefore, problem of the present invention is to provide the manufacture method of seamless pipe, it guarantees sufficient productivity ratio under by the situation of the operation of water-cooled comprising plug, and form lubricating film at mandrel surface with excellent anti-burn-back performance, even if processed material is stainless steel, high-alloy steel, also be difficult for making tube-surface to produce defective.
The method that is used to deal with problems
When addressing the above problem, the inventor furthers investigate, and obtains following opinion.
(1) by behind drawing/rolling just to the high temperature plug application of lubricating before the water-cooled, can obtain fully thick epithelium, and can make it fully dry at short notice.
(2) lubricant of coating before the water-cooled (below be called " first liquid ".) need be to the hear resistance of the highest 400 ℃ of left and right sides high temperature and the resistance to water of in ensuing water-cooled operation, not washed off.
(3) wherein, even have above-mentioned stable on heating first liquid, formed epithelium Yin Gaowen and become the epithelium of porous (porous) easily is poor to the adaptation of mandrel surface.Therefore, constant with present state, then anti-burn-back deficiency.Particularly remarkable under the situation of stainless steel, high-alloy steel.In addition, also have following situation: during the drawing/rolling first being processed, epithelium contacts with on every side parts, is partly peeled off.
(4) in order to remedy this problem, if after the water-cooled, will more low viscous lubricant (below be called " second liquid ".) above first liquid, be coated with, can infiltrate in the above-mentioned porous epithelium, lubricating film is made fine and close tunicle.In addition, give the composition of anti-burn-back, can strengthen anti-burn-back by the interpolation of second liquid.By more than, can improve the adaptation of lubricating film and plug, improve anti-burn-back.In addition, also can repair lubricating film in the position that part is peeled off.
(5) do not have the water-cooled operation behind coating second liquid, thereby second liquid does not require resistance to water.
(6) wherein, owing to be accompanied by drawing/rolling after just being coated with, thereby second liquid requires rapid-drying properties.When use does not have second liquid of rapid-drying properties, when drawing/rolling, form not desciccator diaphragm, the adaptation variation.If this is owing to fully dry by the time, then can bring bad influence to productivity ratio.
The present invention is based on that above-mentioned opinion finishes, and its purport is as described below.
The described invention of claim 1 is a kind of manufacture method of seamless pipe, it is characterized in that, comprises following operation:
First painting process, the mandrel surface after just finishing previous drawing/rolling is coated with first liquid and forms the resistance to water epithelium;
The water-cooled operation is to carrying out water-cooled through the plug behind first painting process;
Second painting process, second liquid that will contain the inorganic lubricant of temperature flowing excellence is applied to through the mandrel surface after the water-cooled operation, makes this second liquid infiltrate the resistance to water epithelium, gives its high temperature adaptation;
The drawing/rolling operation,
Wherein, this drawing/rolling operation is the drawing/rolling that began to carry out hollow bloom in 10 seconds with interior use plug behind second painting process.
At this, the high temperature plug that " just having finished the plug of the high temperature behind the drawing/rolling " is meant in the hollow bloom that inserts 1100～1200 ℃ and extracts out from the pipe that just finishes behind the drawing/rolling, usually, its temperature is 100～400 ℃.In addition, " resistance to water " even be meant the injection of usually accepting water, and its more than half (50 quality %) also do not lose and remain in mandrel surface.For the content of concrete evaluation method, as described later.In addition, " high temperature adaptation " is meant: be inserted in 1100～1200 ℃ the hollow bloom even if be endowed the plug of lubricant epithelium, this lubricant epithelium also is difficult for because of coming off with contacting from mandrel surface of hollow bloom.This evaluation is specifically judged by the burn-back that whether produces between plug and hollow bloom inner peripheral surface.
The described invention of claim 2 is the manufacture method of seamless pipe according to claim 1, it is characterized in that,
First liquid comprises the solid lubricant of 20～40 quality %, the water-dispersed resin of 10～30 quality %, uses the aqueous solution or aqueous dispersions;
Second liquid is the aqueous solution or the dispersion liquid of the solid lubricant of more than one and 0～30 quality % in amine borate, potassium borate, potassium molybdate or sodium molybdate, potash or the sodium carbonate that comprises 5～30 quality %.
The described invention of claim 3 is the manufacture method of seamless pipe according to claim 2, it is characterized in that, solid lubricant is graphite, mica or their mixture.
The described invention of claim 4 is according to the manufacture method of each described seamless pipe in the claim 1～3, it is characterized in that, first painting process carries out under 100～400 ℃ of plug temperature, and second painting process carries out under 60～150 ℃ of plug temperature.
The described invention of claim 5 is according to the manufacture method of each described seamless pipe in the claim 1～4, it is characterized in that, the material of hollow bloom is steel alloy or the stainless steel that contains the above Cr of 5 quality %.
The invention effect
According to the present invention, a kind of manufacture method of seamless pipe can be provided, it is under comprising that plug is by the situation of the operation of water-cooled, keep sufficient productivity ratio, and form lubricating film at mandrel surface with excellent anti-burn-back performance, even if processed material is stainless steel or high-alloy steel, also be difficult for making tube-surface to produce defective.
Such effect of the present invention and interests can be understood from the best mode that is used to carry out an invention that the following describes.
Description of drawings
Fig. 1 is the figure of the circulation of expression plug.
Fig. 2 is the figure of the anti-burn-back evaluation test machine of expression.
Fig. 3 is the figure of the manufacturing process of schematic representation seamless pipe.
Symbol description
1: the round steel sheet; 2: rotation siege formula heating furnace; 3: the drilling/rolling machine; 4: hollow bloom; 4a: pipe; 5: mandrel mill; 5a: plug; 6: the fixed diameter rolling machine; 7: cooling bed; 40: rolling testing machine; 41: the tabular instrument; 42: roller; 43: testpieces
The specific embodiment
Fig. 1 (A) is the figure of the utilization circulation of the plug in the manufacture method of seamless pipe of expression an embodiment of the invention.In addition, as a reference, the figure of the utilization circulation of existing plug is shown in order to compare among Fig. 1 (B).
In Fig. 1 (A), the plug that supplies to the drawing/rolling that mandrel mill carries out is extracted out from pipe, under the state of 100～400 ℃ high temperature, is coated with first liquid (recovering lubricated).Then, implement the water cooling spray, the mandrel surface that is reduced to 60～150 ℃ in temperature is coated with second liquid (inserting lubricated).After this plug that is coated with second liquid is being fed in the drawing/rolling of mandrel mill once more.After being coated with second liquid, the drawing/rolling time before is in 10 seconds up to beginning next time.
On the other hand, in the existing utilization circulation shown in Fig. 1 (B), the liquor that is coated with in the operation shown in the coating of first liquid mainly uses for the purpose of cooling off plug in ensuing chilling spray equably, and it is more than half owing to chilling spray runs off.Then, in the coating of second liquid, be coated with the lubricant of bearing lubricating function.Yet, be applied to cooled plug after, drying needs the time, thereby, need be used to make plug to be detained the zone of stipulated time, i.e. " lubricating chamber ".
In the utilization of the plug in the manufacture method of the seamless pipe of the one embodiment of the present invention circulation, do not need the lubricating chamber shown in Fig. 1 (B), and, can just insert lubricated after, begin drawing/rolling next time immediately, thereby can enhance productivity.
Then, employed first liquid of manufacture method, second liquid to the seamless pipe of present embodiment describes.
(first liquid)
In first liquid, the material that uses as its base is the solid lubricant that is made of graphite, mica or these mixture etc.Be limited to 40 quality % on the content of the solid lubricant overall, be preferably 35 quality % with respect to lubricant.When the content of solid lubricant is too much, sprays coating and become difficult.In addition,, can not spray with the spray shape to the surface of plug to the supply of the production line difficulty that also becomes from the storage tank of lubricant from nozzle.The content of the solid lubricant overall with respect to lubricant following is limited to 20 quality %, is preferably 25 quality %.When the content of solid lubricant was very few, anti-burn-back performance step-down particularly carried out might producing than poly-injury under the situation of drawing/rolling at the hollow bloom to stainless steel, high-alloy steel material.
Graphite can be any in natural product or the composite.In addition, preferably to use purity be more than 81% to graphite and average grain diameter is the following materials of 40 μ m.This is because if purity less than 81%, the then alumina (Al to exist as field trash
2O
3), silica (SiO
2) to wait inorganic matter be that the impurity of main body can hinder its lubricity.In addition, this is because average grain diameter is 40 μ m when above, can not suitably disperse in first liquid, can not successfully supply to the plug when using and the surface of hollow bloom, and can not preserve under the state of dispersion stably.
Mica can use any in natural mica, the synthetic mica.As natural mica, can list sericite, muscovite, phlogopite etc.In addition, as synthetic mica, can list four silication muscovites, four silication paragonites or fluorophologopite etc.For the lubricity that improves under the condition of high temperature about 1000 ℃ contains mica.Mica is identical with above-mentioned graphite, improves the lubricant effect between plug and the hollow bloom, and in addition, graphite reduces coefficient of friction, and mica has the effect that plug is separated with hollow bloom and prevent their weldings, prevent to produce defect in inner surface.In addition, preferably to use average grain diameter be that 40 μ m are following, purity is the material more than 81% to mica.This is can not suitably disperse when surpassing 40 μ m owing to average grain diameter, is difficult to successfully supply to lubricated face.In addition, if purity less than 81%, then alumina (Al to exist as field trash
2O
3), silica (SiO
2) to wait inorganic matter be that the impurity of main body can hinder its lubricity.
The water-dispersed resin that is cooperated in this first liquid is in order stably to disperse the solid lubricant as base in water, can easily to supply with during use, make it be deployed into plug and hollow bloom surface equably, and gives auxiliary lubricity and contain.
As the water-dispersed resin that is cooperated in first liquid, can list vinyl acetate polymer, acrylate polymer, methacrylate polymers or their two or more copolymer, ethylene vinyl acetate copolymer etc.It is the following materials of 40 μ m that water-dispersed resin preferably uses average grain diameter.This is owing to if average grain diameter surpasses 40 μ m when becoming big, can not suitably disperse, and can not successfully supply to lubricated face in use.Be limited to 30 quality % on the content that water-dispersed resin is overall with respect to lubricant, be preferably 25 quality %.When the content of water-dispersed resin was too much, the viscosity of lubricant was too high, sprayed coating and became difficult.On the other hand, water-dispersed resin following is limited to 10 quality %, is preferably 15 quality %.This is because content when very few, and adaptation, resistance to water variation are also peeled off.
In addition, in order to improve high temperature tack, and solid lubricants such as graphite, mica are suitably disperseed and sedimentation, can not lose for example range fit water soluble polymer below the 3 quality % of resistance to water plug.As water soluble polymer, can list polysaccharides such as methylcellulose, carboxymethyl cellulose or poly candy, arginine salt.
In order to contain water at the even application of lubricating of mandrel surface.It contains quantity not sufficient 30 quality %, and then the viscosity of lubricant is too high, handles the difficulty that becomes.On the other hand, if content surpasses 70 quality %, the fierce boiling explosion phenomenon that produces not only can not obtain uniform epithelium, and tack worsens the adhesion amount that can not obtain stipulating.Therefore, the content of water is 30～70 quality %, preferred 40～60 quality %.
Can in above-mentioned lubricant, add commercially available silicone-based defoamers, 1 such as dimethyl siloxane usually with the scope of 0.01～2.0 quality % respectively as required, thiazolines such as 2-benzisothiazole-3-ketone system, hexahydroxy-1,3, anticorrisive agents such as pyridine system such as 5-three (2-ethoxy)-triazines such as s-triazine system, 2-pyridinethiol-1-oxide sodium salt.Under the situation of adding defoamer, can prevent the foaming of liquid, under the situation of adding anticorrisive agent, can prevent the corruption of liquid.
The adhesion amount expectation of first liquid that mandrel surface was coated with is counted 50～150g/m with solid lubricant
2, be preferably 80～120g/m
2When the adhesion amount of first liquid is too much, form the epithelium that prevents the required above thickness of burn-back, economic aspect is unfavorable.When the adhesion amount of first liquid is very few, can not obtain necessary anti-burn-back performance.
(second liquid)
Second liquid that is applied to the mandrel surface after the water-cooled is the aqueous solution or the aqueous dispersions of the solid lubricant of more than one and 0～30 quality % in amine borate, potassium borate, potassium molybdate or sodium molybdate, potash or the sodium carbonate that comprises 5～30 quality %.
As spendable amine borate, can use MEA, monoisopropanolamine, diethanol amine, triethanolamine etc., soluble salt gets final product in the water so long as be formed on.
Can cooperate solid lubricant as required in second liquid.As spendable solid lubricant, identical with the situation of first liquid, can use the material of forming by graphite, mica or their mixture etc.In addition, also use phyllosilicate in addition, perhaps, also can use phyllosilicate separately.
The combined amount upper limit that is coupled to the solid lubricant of second liquid is 40 quality %, is preferably 30 quality % with respect to the second liquid total amount.Be coupled to solid lubricant in second liquid when too much, be difficult to penetrate in the porous epithelium of first liquid, can not fully improve the adaptation of lubricating film.On the other hand, in second liquid, do not cooperate under the situation of solid lubricant, sometimes the anti-burn-back deficiency of formed lubricating film.
Embodiment
These first liquid and second liquid are applied to specimen surface, carry out following evaluation.
(1) resistance to water
8 kind of first liquid (graphite 30 quality %, water-dispersed resin 5～40 quality %) of its composition shown in the table 1 sprayed be applied to the metal system sample that is heated to 300 ℃, and to make adhesion amount be about 100g/m
2, after 5 seconds, apply chilling spray continuously, be performed until water and do not seethe with excitement till (about 100 ℃).The condition of chilling spray is as described below.
Nozzle: spray spout
Hydraulic pressure: about 0.2MPa
Flow: 10L/ minute
Water temperature: 20～25
In addition, graphite uses flaky graphite (purity is more than 81%), and water-dispersed resin is that vinyl acetate is that resin and vinyl acetate acrylic resin are 1: 1.
The situation of peeling off with following benchmark evaluation epithelium at this moment.
(resistance to water metewand)
Zero: almost unstripped (released part is not enough overall 15%.)。
△: the ratio with 15% above less than 80% is peeled off.
*: major part is peeled off (released part be overall more than 80%).
Table 1 illustrates the result.In addition, also put down in writing the result of observed injection coating in above-mentioned test in the table 1.Spraying the evaluation of coating carries out based on following benchmark.
(spraying the coating metewand)
Zero: can spray uniformly at the whole face of coated face.
△: whole coating has inequality slightly for coated face.
*: for whole crawling of coated face.
Table 1
(quality %)
| Graphite | Water-dispersed resin | Spray coating | Resistance to water |
| 30.0 | 40.0 | × | - |
| 35.0 | × | - | |
| 30.0 | △ | ○ | |
| 25.0 | ○ | ○ | |
| 20.0 | ○ | ○ | |
| 15.0 | ○ | ○ | |
| 10.0 | ○ | △ | |
| 5.0 | ○ | × |
(2) drying property and anti-burn-back evaluation test
By Fig. 2 the rolling testing machine 40 of summary is shown, estimates drying property and anti-burn-back.This rolling testing machine 40 has been simulated the drawing/rolling situation of the separate unit of mandrel mill.The testpieces 43 that has heated is rolled being configured to move freely and be coated with between the tabular instrument 41 of lubricant and the roller 42, investigates the damage status of the tabular instrument 41 after rolling on the surface to rolling direction (left and right directions among Fig. 2).
Rolling condition:
Heating-up temperature: 1000 ℃
Roller peripheral speed: 392.5mm/ second
Instrument translational speed: 15mm/ second
Reduction ratio: 30%
Table 2
First liquid (quality %)
| Embodiment | Comparative example | ||||
| 1 | 2 | 3 | 4 | 5 | |
| Graphite | 30.0 | - | 15.0 | 45.0 | 15.0 |
| Mica | - | 30.0 | 15.0 | - | - |
| Water-dispersed resin | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 |
| Dispersant | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Water | 43.0 | 43.0 | 43.0 | 28.0 | 58.0 |
Table 3
Second liquid (embodiment) (quality %)
| Embodiment | ||||||||
| A | B | C | D | E | F | G | H | |
| Graphite | 20.0 | - | 15.0 | 20.0 | - | 20.0 | 20.0 | 20.0 |
| Mica | - | 20.0 | 15.0 | - | - | - | - | - |
| Amine borate | - | - | - | - | 30.0 | - | - | - |
| Potassium borate | - | - | - | 5.0 | - | - | - | - |
| Sodium molybdate | 15.0 | 15.0 | 15.0 | - | - | - | - | - |
| Potassium molybdate | - | - | - | - | - | 15.0 | - | - |
| Sodium carbonate | - | - | - | - | - | - | 15.0 | - |
| Potash | - | - | - | - | - | - | - | 15.0 |
| Dispersant | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 | 2.0 |
| Water | 63.0 | 63.0 | 53.0 | 73.0 | 68.0 | 63.0 | 63.0 | 63.0 |
Table 4
Second liquid (comparative example) (quality %)
| Comparative example | |||
| I | J | K | |
| Graphite | 35.0 | 20.0 | 20.0 |
| Mica | - | - | - |
| Amine borate | - | 3.0 | 35.0 |
| Potassium borate | - | - | - |
| Sodium molybdate | 15.0 | - | - |
| Potassium molybdate | - | - | - |
| Sodium carbonate | - | - | - |
| Potash | - | - | - |
| Dispersant | 2.0 | 2.0 | 2.0 |
| Water | 48.0 | 75.0 | 43.0 |
In addition, graphite uses flaky graphite (purity is more than 81%), and water-dispersed resin is that vinylacetate is that resin and vinyl acetate acrylic resin are 1: 1.
Drying property by following reference recording lubricant and rolling after the burn-back situation of tabular instrument 41.
(metewand of drying property)
Dry: zero
There is not drying: △ a little
Not dry: *
(metewand of burn-back)
There is not burn-back: zero
Burn-back is little: △
Burn-back is big: *
The result of drying property shown in table 5, the table 6 and anti-burn-back evaluation test.
Table 5
Drying property
Table 6
Anti-burn-back
First liquid 4 be owing to can not spray coating, thereby can't test.First liquid 5 is because the amount of solid lubricant is few, thereby anti-burn-back is poor.The second liquid D, E are owing to drying property reduces, thereby anti-burn-back is poor.The second liquid I is because solid lubricant is many, thereby poor permeability, and anti-burn-back is poor.The second liquid K is because inorganic lubricant is many, thereby poor permeability, and anti-burn-back is poor.The second liquid J is because inorganic lubricant is few, thereby anti-burn-back is poor.
More than; be combined in think tool practicality at present and the present invention preferred embodiment has been described; but the present invention is not limited to embodiment disclosed in this specification; as long as can suitably change in the scope of the purport of invention of acquisition or thought in overall not breaking away from accessory rights claim and specification, follow the manufacture method of the seamless pipe of such change also to should be understood to be included in protection scope of the present invention.
Claims (5)
1. the manufacture method of a seamless pipe is characterized in that, it comprises:
First painting process, the mandrel surface after just finishing previous drawing/rolling is coated with first liquid and forms the resistance to water epithelium;
The water-cooled operation is to carrying out water-cooled through the plug behind above-mentioned first painting process;
Second painting process, second liquid that will contain the inorganic lubricant of temperature flowing excellence is applied to through the mandrel surface after the above-mentioned water-cooled operation, makes this second liquid infiltrate above-mentioned resistance to water epithelium, gives its high temperature adaptation;
The drawing/rolling operation,
Wherein, above-mentioned drawing/rolling operation is the drawing/rolling that began to carry out hollow bloom in 10 seconds with the above-mentioned plug of interior use behind above-mentioned second painting process.
2. the manufacture method of seamless pipe according to claim 1 is characterized in that,
Described first liquid comprises the solid lubricant of 20～40 quality %, the water-dispersed resin of 10～30 quality %, and uses the aqueous solution or aqueous dispersions;
Described second liquid is the aqueous solution or the aqueous dispersions of the solid lubricant of more than one and 0～30 quality % in amine borate, potassium borate, potassium molybdate or sodium molybdate, potash or the sodium carbonate that comprises 5～30 quality %.
3. the manufacture method of seamless pipe according to claim 2 is characterized in that, described solid lubricant is graphite, mica or these mixture.
4. according to the manufacture method of each described seamless pipe of claim 1～3, it is characterized in that described first painting process carries out under 100～400 ℃ of plug temperature, described second painting process carries out under 60～150 ℃ of plug temperature.
5. according to the manufacture method of each described seamless pipe of claim 1～4, it is characterized in that the material of described hollow bloom is steel alloy or the stainless steel that contains the above Cr of 5 quality %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP100978/2005 | 2005-03-31 | ||
| JP2005100978 | 2005-03-31 | ||
| PCT/JP2006/306928 WO2006106961A1 (en) | 2005-03-31 | 2006-03-31 | Process for producing seamless tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101208160A true CN101208160A (en) | 2008-06-25 |
| CN101208160B CN101208160B (en) | 2010-05-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800105011A Expired - Fee Related CN101208160B (en) | 2005-03-31 | 2006-03-31 | Process for producing seamless tube |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1872878B1 (en) |
| JP (1) | JP4705096B2 (en) |
| CN (1) | CN101208160B (en) |
| BR (1) | BRPI0609605B1 (en) |
| WO (1) | WO2006106961A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102753666A (en) * | 2010-02-15 | 2012-10-24 | 住友金属工业株式会社 | Lubricant for hot-rolling tools, and method for surface treatment of mandrel bar for use in producing seamless pipe by hot rolling |
| CN102971094A (en) * | 2010-06-28 | 2013-03-13 | Sms米尔股份有限公司 | Process for hot-rolling metallic hollow bodies and corresponding hot-rolling mill |
| CN103433283A (en) * | 2013-08-28 | 2013-12-11 | 无锡欧龙特种钢管有限公司 | Pipe mill graphite core rod water blowing device |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL2580003T3 (en) | 2010-06-08 | 2017-07-31 | Coating Management Switzerland Gmbh | Method for producing seamless pipes |
| DE102010052084B3 (en) * | 2010-11-16 | 2012-02-16 | V&M Deutschland Gmbh | Process for the economic production of seamless hot-rolled tubes in continuous tube rolling mills |
| JP6287713B2 (en) * | 2014-09-09 | 2018-03-07 | 新日鐵住金株式会社 | Lubricating composition for hot pipe making |
| JP6156314B2 (en) * | 2014-10-07 | 2017-07-05 | Ｊｆｅスチール株式会社 | Mandrel bar cooling method and cooling equipment |
| JP6881165B2 (en) * | 2017-09-04 | 2021-06-02 | 日本製鉄株式会社 | Manufacturing method of seamless steel pipe |
| DE102019104540B4 (en) * | 2019-02-22 | 2021-08-19 | Chemische Fabrik Budenheim Kg | Lubricant and its use for the hot forming of metals |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1438215A (en) * | 1974-05-08 | 1976-06-03 | Lonz Ltd | High temperature lubricant |
| JPS61252293A (en) * | 1985-04-30 | 1986-11-10 | Hoechst Gosei Kk | Lubricant for metal working and method of using same |
| JPS63230797A (en) * | 1987-03-19 | 1988-09-27 | Sumitomo Metal Ind Ltd | Rapid-curable heat-resistant lubricant |
| CH674477A5 (en) * | 1988-03-30 | 1990-06-15 | Lonza Ag | |
| CN1042951C (en) * | 1990-11-09 | 1999-04-14 | 上海宝山钢铁总厂 | Water-resistant lubricant for steel thermoplasticity processing |
| ES2143480T3 (en) * | 1992-02-06 | 2000-05-16 | Timcal Ag | LUBRICATING AGENT FOR CHUCKS FOR THE MANUFACTURE OF SEAMLESS PIPES. |
| JP2910592B2 (en) * | 1994-12-13 | 1999-06-23 | 住友金属工業株式会社 | Lubricant composition for hot working |
| TW571000B (en) * | 2001-10-19 | 2004-01-11 | Nihon Parkerizing | Methods of preparing metal wires for plastic processing |
| JP4193427B2 (en) * | 2002-07-02 | 2008-12-10 | 住友金属工業株式会社 | Manufacturing method and manufacturing apparatus for seamless steel pipe |
-
2006
- 2006-03-31 CN CN2006800105011A patent/CN101208160B/en not_active Expired - Fee Related
- 2006-03-31 WO PCT/JP2006/306928 patent/WO2006106961A1/en active Application Filing
- 2006-03-31 EP EP06730876A patent/EP1872878B1/en not_active Ceased
- 2006-03-31 JP JP2007511196A patent/JP4705096B2/en not_active Expired - Fee Related
- 2006-03-31 BR BRPI0609605-0A patent/BRPI0609605B1/en not_active IP Right Cessation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102753666A (en) * | 2010-02-15 | 2012-10-24 | 住友金属工业株式会社 | Lubricant for hot-rolling tools, and method for surface treatment of mandrel bar for use in producing seamless pipe by hot rolling |
| US8656748B2 (en) | 2010-02-15 | 2014-02-25 | Nippon Steel & Sumitomo Metal Corporation | Lubricant for hot-rolling tools, and surface treatment method for mandrel bar for use in producing hot rolling seamless tubes |
| CN102971094A (en) * | 2010-06-28 | 2013-03-13 | Sms米尔股份有限公司 | Process for hot-rolling metallic hollow bodies and corresponding hot-rolling mill |
| CN102971094B (en) * | 2010-06-28 | 2015-11-25 | Sms米尔股份有限公司 | For being carried out the method for the slender hollow body of hot-rolling metal by roll plug |
| CN103433283A (en) * | 2013-08-28 | 2013-12-11 | 无锡欧龙特种钢管有限公司 | Pipe mill graphite core rod water blowing device |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006106961A1 (en) | 2006-10-12 |
| CN101208160B (en) | 2010-05-19 |
| JPWO2006106961A1 (en) | 2008-09-18 |
| EP1872878B1 (en) | 2011-12-28 |
| JP4705096B2 (en) | 2011-06-22 |
| BRPI0609605B1 (en) | 2019-07-02 |
| BRPI0609605A2 (en) | 2010-04-20 |
| EP1872878A1 (en) | 2008-01-02 |
| EP1872878A4 (en) | 2009-01-21 |
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