WO2009069829A1 - 連続焼鈍炉用ハースロールおよびその製造方法 - Google Patents
連続焼鈍炉用ハースロールおよびその製造方法 Download PDFInfo
- Publication number
- WO2009069829A1 WO2009069829A1 PCT/JP2008/072106 JP2008072106W WO2009069829A1 WO 2009069829 A1 WO2009069829 A1 WO 2009069829A1 JP 2008072106 W JP2008072106 W JP 2008072106W WO 2009069829 A1 WO2009069829 A1 WO 2009069829A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- continuous annealing
- hearth roll
- annealing furnace
- heat
- mass
- Prior art date
Links
- 238000000137 annealing Methods 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 13
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 53
- 239000000956 alloy Substances 0.000 claims abstract description 53
- 239000000919 ceramic Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 239000011195 cermet Substances 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 38
- 238000007751 thermal spraying Methods 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 12
- 238000005507 spraying Methods 0.000 claims description 12
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001882 dioxygen Inorganic materials 0.000 claims description 10
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000000567 combustion gas Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims 1
- 229910003470 tongbaite Inorganic materials 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 229910007948 ZrB2 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000002737 fuel gas Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 r C Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 2
- 238000007749 high velocity oxygen fuel spraying Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OFEAOSSMQHGXMM-UHFFFAOYSA-N 12007-10-2 Chemical compound [W].[W]=[B] OFEAOSSMQHGXMM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- CVMIVKAWUQZOBP-UHFFFAOYSA-L manganic acid Chemical compound O[Mn](O)(=O)=O CVMIVKAWUQZOBP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
- C21D9/562—Details
- C21D9/563—Rolls; Drums; Roll arrangements
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
- F27B9/14—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment
- F27B9/20—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path tunnel furnace
- F27B9/24—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path tunnel furnace being carried by a conveyor
- F27B9/2407—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path tunnel furnace being carried by a conveyor the conveyor being constituted by rollers (roller hearth furnace)
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
- F27B9/14—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment
- F27B9/20—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path tunnel furnace
- F27B9/24—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path tunnel furnace being carried by a conveyor
- F27B9/2469—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving in a substantially straight path tunnel furnace being carried by a conveyor the conveyor being constituted by rollable bodies
Definitions
- the present invention relates to a hearth roll for a continuous annealing furnace in which a sprayed coating is provided on the surface and build-up on the roll surface during sheet passing is suppressed, and a method for manufacturing the same.
- the build-up on the hearth roll surface is a phenomenon in which iron, manganese oxide, etc. on the steel plate surface adhere to and accumulate on the hearth roll surface. In order to prevent this, it is effective to suppress the reaction between iron, manganese oxide, etc., which are build-up sources, and the heart roll surface, or to make it easy to remove reaction products.
- a thermal sprayed alloy layer consisting only of a heat-resistant alloy is provided on the hearth roll, Carbides on the alloy layer also properly is sprayed mixture particles of oxides and carbides, on the surface the outermost layer consisting of C r 2 O 3 and A l 2 O 3 metal oxides a deposition bets in a chemical conversion film layer (See, for example, Japanese Patent Publication No. 8 — 1 9 5 3 5).
- this film has the problem that it cannot be used in an annealing furnace for a long time because WC oxidizes at high temperature and the film peels off.
- cermet film containing at least one or more of carbides such as r C, Ti C and N b C in an amount of 50 to 50% by volume, and the balance being substantially made of metal (for example, JP-A-7-1). 1 4 2 0 publication).
- the problem to be solved by the present invention is that a hearth roll for a continuous annealing furnace that can suppress build-up on the surface of the hearth roll and can be used stably for a long time in a high temperature environment in the continuous annealing furnace and its It is to provide a manufacturing method.
- Cr 3 C 2 alone cannot be densely formed. In order to form a dense film, it is necessary to make a composite with a heat-resistant alloy. However, when used for a long time in a high-temperature environment in a continuous annealing furnace, the carbon in Cr 3 C 2 diffuses into the heat-resistant alloy and the film becomes brittle and faces a new problem that the film peels off. did.
- the present inventors have suppressed the temporal change of the coating film in a high-temperature environment in a continuous annealing furnace by optimizing the composition and thermal spraying method of the heat-resistant alloy compounded with Cr 3 C 2. I found something new that I could do.
- the gist of the present invention is as follows.
- the ceramic is C Contains r 3 C 2 over 50 to 90 vol%, A 1 2 O 3 to l to 40 vol%, Y 2 0 3 to 0 to 3 vol%, and Z r B 2 to 0 to 40 vol% And the balance consists of inevitable impurities and pores, and the heat-resistant alloy contains Cr.
- a 1 to 5 to 20% by mass, and one or two of Y and S 1 are contained in an amount of 0.1 to 6% by mass, the balance being either Co or Ni 1 or 2 and unavoidable impurities, 50 to 90 V o 1% of the ceramic film is the ceramics, and the balance is the heat-resistant alloy. Hearth roll.
- the above heat-resistant alloy contains Nb in the range of 0.1 to 10% by mass and Ding 1 in the range of 0.1 to 10% by mass, either 1 type or 2 types. ) Hearth roll for continuous annealing furnace.
- the thermal spraying raw material powder is a ceramic powder and a heat-resistant alloy powder
- the ceramic powder is Cr 3 C 2 Containing more than 50 to 90 vol%, 1 to 40 vol% of A 1 2 O 3, 0 to 3 vol% of Y 2 ⁇ 3, and 0 to 4 0 ⁇ ⁇ 1% of ⁇ r ⁇ 2
- the heat-resistant alloy powder consists of 5 to 20% by mass of Cr, 5 to 20% by mass of A 1, and one or two of Y and S i.
- a continuous annealing furnace hearth characterized in that the heat-resistant alloy powder raw material powder is sprayed onto the surface of the hearth roll base material to form a cermet film on the surface of the hearth roll base material. Manufacturing method Le.
- Nb in the heat-resistant alloy powder is 0.1 to: L 0% by mass
- the particle size of Cr 3 C 2 in the ceramic powder is: The method for producing a hearth roll for a continuous annealing furnace as described in (4) or (5) above, which is 10 m.
- the thermal spraying is HVOF thermal spraying, and the supply amount of oxygen gas which is a combustion gas component of HVOF thermal spraying is set to 1 00 0 to 1 2 0 0 1 / min.
- the hearth roll for continuous annealing furnace according to the present invention can suppress build-up on the surface of the hearth roll, and can be used stably for a long time in a high temperature environment in the continuous annealing furnace.
- a hearth mouthpiece for a continuous annealing furnace having excellent buildup resistance. That is, according to the hearth roll for continuous annealing furnace and the method for manufacturing the same according to the present invention, the steel sheet flaw caused by the hearth roll for continuous annealing furnace can be prevented, and the quality of the steel sheet can be improved. Usability is enormous. Brief Description of Drawings
- FIG. 1 is a view showing a cermet sprayed coating of the present invention.
- the inventors made various types of sprayed coatings and investigated the build-up occurrence and high temperature characteristics of the sprayed coatings. As a result, we found that the following cermet films made of ceramics and heat-resistant alloys have a large effect of preventing build-up and that the films are unlikely to deteriorate even when used for a long time in a continuous annealing furnace. The present invention has been completed based on this technical knowledge.
- Z and r B 2 contain 0 ⁇ 4 0 vol%, the balance being unavoidable impurities and air holes ceramic box.
- Y 2 O 3 and Z r B 2 are optional components (optional components) added as necessary.
- One or two of Y and S i are contained in an amount of 0.1 to 6% by mass, and the balance is either one or two of Co and Ni and unavoidable impurities
- a heat-resistant alloy consisting of
- the hearth roll for a continuous annealing furnace having a cermet film on the surface
- 50 to 90% of the cermet film is ceramic, and the balance is C o N i C r A l Y, Heat-resistant alloys such as CoCrA1Y, NiCrA1Y, CoNiCrA1SiY.
- the ceramic is less than 50 V o 1%, build-up is likely to occur because the amount of heat-resistant alloy that easily reacts with iron becomes too large.
- the ceramics exceeds 90 V o 1%, the melting point of the ceramics is high and the coating becomes porous during spraying, and build-up tends to occur due to the build-up source stagnating in the pores.
- the ceramic ratio is more preferably 60 to 80 V o 1%.
- the main component of the ceramic is Cr 3 C 2 and is contained in the ceramic in an amount of more than 50 to 90 vol%.
- C r 3 C 2 is difficult to oxidize even in a high temperature environment such as in an annealing furnace, and it is difficult to react with iron and manganese oxides, so build-up can be prevented.
- C r 3 C 2 is less than 50 V o 1%, the buildup suppression effect cannot be obtained.
- C r 3 C 2 exceeds 90 vol%, the ceramic component that suppresses the diffusion of carbon in C r 3 C 2 becomes relatively small, and as a result, the film becomes brittle due to carbon diffusion.
- Cr 3 C 2 is more preferably 5 5 V o 1% or more. Furthermore, if it is more than 60 vol% A further built-up suppression effect can be obtained.
- Cr 3 C 2 is 8 5 vo 1% or less. Furthermore, if it is 80 vol% or less, the risk of embrittlement decreases.
- the particle size of Cr 3 C 2 is preferably 1 to: L 0 m. If the C r 3 C 2 particle size is less than 1 m, the surface area in contact with the heat-resistant alloy becomes large, and carbon diffusion is likely to occur.
- the Cr 3 C 2 particle size is more preferably 3 m or more, and even more preferably 5 / m or more. Further, from the viewpoint of suppressing buildup, the particle size of Cr 3 C 2 is more preferably 9 m or less, and even more preferably 8 m or less.
- a 1 2 0 3 and Y 2 0 3 both have low carbon diffusion coefficients in the material, they suppress the diffusion of C r 3 C 2 carbon into the heat-resistant alloy.
- a 1 2 O 3 is 1 to 40 vo 1% and Y 2 O 3 is 3 vo 1% or less in the film.
- a 1 2 0 3 is less than 1 V o 1%, the effect of suppressing carbon diffusion cannot be obtained.
- a l 2 0 3 exceeds 40 vol%, A 1 2 0 3 easily reacts with mangan oxide, so that the build-up resistance decreases.
- a 1 2 0 3 , 5 V It is more preferably 1% or more, and further preferably 1O vo 1% or more. Further, from the viewpoint of suppressing buildup, it is more preferably 35 V o 1% or less, and further preferably 3 O vo 1% or less.
- a 1 2 O 3 or Y 2 ⁇ 3 can also be added to the raw material powder as an oxide.
- oxidation treatment is performed on the surface of the heat-resistant alloy by oxidizing the Y or A 1 added to the heat-resistant alloy by oxidation treatment at the raw material stage, during film formation or after film formation. Is preferably formed in the form of A 1 2 O 3 or Y 2 03.
- Z r B 2 is an optional component to be added for the purpose of use at high temperatures (selection ⁇ component). Therefore, the amount of Z r B 2 may be 40 vol% or less in the film. If the amount of Z r B 2 added is less than 5 vo 1%, the effect of increasing the high temperature hardness is small, so it is more preferable to add Z r B 2 at 5 V o 1% or more. It is even better to add 15 vol% or more.
- the remainder of the ceramic described above is unavoidable impurities and pores.
- the heat-resistant alloy also contains 5 to 20% by mass of 8 1. If A 1 is less than 5% by mass, the target amount of A 1 2 0 3 cannot be obtained even after various oxidation treatments.
- Both Y and Si have the effect of stable formation of oxide film and prevention of peeling. Therefore, it is only necessary to add 0.1 to 6% by mass of any one or two of Y and Si. If Y or Si exceeds 6% by mass, the high-temperature hardness of the coating will decrease, and iron will pierce the coating and build-up will easily occur. Moreover, it is necessary to add 0.1% by mass or more of both Y and Si, and it is particularly effective to add 0.5% by mass or more.
- Nb of 0.1 to: L 0 mass% and Ti force 0.1 to 10 mass% in the heat-resistant alloy it is preferable to add one or two of Nb of 0.1 to: L 0 mass% and Ti force 0.1 to 10 mass% in the heat-resistant alloy.
- N b or T i is contained in the heat-resistant alloy, a carbide that is more stable than Cr contained in the heat-resistant alloy is formed, and the reaction between C r and carbon is suppressed. Therefore, the brittleness of the film can be suppressed for a long time. ? If ⁇ or Ding 1 is less than 0.1% by mass, the reaction suppressing effect between C r and carbon cannot be obtained. If it exceeds 10% by mass, it easily reacts with manganese oxide when oxidized, and build-up is likely to occur.
- the balance of the heat-resistant alloy described above is either one or two of Co and Ni, and Inevitable impurities.
- the ceramic powder 50 to 90 V o 1% is the ceramic powder and the balance is the heat-resistant alloy powder.
- a cermet film is formed on the surface of the hearth roll base material.
- the hearth base material stainless steel heat-resistant steel is usually used, and S C H 2 2 is particularly suitable.
- the raw material powders to be sprayed are ceramic powders such as Cr 3 C 2 and Al 2 O 3 and heat-resistant alloy powders containing Cr and A 1. These are mixed and sprayed to form a film.
- the ceramic powder and the heat-resistant alloy powder are pre-granulated and composited and sprayed to form a uniform film.
- HVO F Hi g V e l o c i t y O xy g e n -F e e l T e r ma L S p r y i n g P ro c ess
- the fuel gas is usually kerosene, C 3 H 8, and 2 H 2
- the pressure of the fuel gas is 0.11 MPa
- the flow rate of the fuel gas is 10 to 5 0 0 1 / min
- the pressure of the oxygen gas is
- the flow rate of M Pa and oxygen gas may be 1 00 to 1 2 0 0 1 / min.
- the flame of the thermal spray gun may be heated close to the hearth roll substrate, or it may be heated with a separate gas burner.
- the hearth roll base material By heating the hearth roll base material to more than 3 0 0, it can be oxidized to A l, Y in heat resistant alloys, to obtain the amount of A l 2 ⁇ 3, Y 2 o 3 for the purpose. If the heating temperature is higher than 600, the oxidation of the film Progresses too much, and the coating becomes porous and buildup is likely to occur. Further, from the viewpoint of suppressing buildup, it is more preferable to set the heating temperature range to 400 to 500.
- the flow rate of oxygen gas which is a component of HV OF combustion gas, be set to 1 00 0 to 1 2 100 I Zmin.
- the flow rate of oxygen gas By setting the flow rate of oxygen gas to 1 00 0 0 I Zmin or higher, it is possible to oxidize A 1 and Y in the heat-resistant alloy to obtain the desired amounts of A 1 2 0 3 and Y 2 0 3. it can. If the flow rate of oxygen gas is higher than 1 2 100 I Zmin, the raw material powder will oxidize excessively during thermal spraying, and the coating becomes porous and build-up is likely to occur.
- the coating it is preferable to oxidize the coating at 300 to 600 for 1 to 5 hours after thermal spraying.
- the surface of the sprayed coating may be heated with a gas burner.
- the hearth roll may be heat-treated by placing it in a furnace in an atmosphere of an inert gas such as nitrogen or argon containing a small amount of oxygen.
- a 1 and Y in the heat-resistant alloy can be oxidized to obtain target amounts of Al 2 O 3 and Y 2 O 3.
- the heating temperature is higher than 600 or longer than 5 hours, the film is excessively oxidized and the film becomes porous, and buildup is likely to occur. Further, from the viewpoint of improving the build-up resistance, it is more preferable to set the heating temperature range from 400 to 500.
- the raw material powder When the raw material powder is oxidized and then subjected to thermal spraying, it is heat treated for 1 to 5 hours in an atmosphere of 300 to 60,000 or in an inert gas (nitrogen, argon, etc.) containing a small amount of oxygen. To do. Heating less than 300 or less than 1 hour does not oxidize ⁇ or A 1. If the heating temperature is higher than 600 or longer than 5 hours, it will oxidize and become ceramics. Therefore, the melting point of the raw material powder becomes high and the film becomes porous. Further, from the viewpoint of suppressing buildup, the heat treatment temperature is more preferably in the range of 400 to 500.
- the pre-heat treatment temperature of the thermal spray raw material powder is optimally controlled, the thermal spraying conditions are optimized, and the roll heating conditions after thermal spraying are optimized.
- a 1 and Y in the heat-resistant alloy in the thermal spray coating can be oxidized to obtain the desired amounts of Al 2 O 3 and Y 2 O 3, achieving the coating configuration of the present invention. We were able to.
- the pores can be filled with chromium oxide and oxidation treatment can be performed simultaneously.
- the chrome-treated film easily reacts with manganese oxide, it is necessary to make the film less than 1 ⁇ .
- the chromate treatment is performed by immersing a part of the hearth roll in an aqueous solution containing chromic acid, or by applying and spraying an aqueous solution containing chromic acid from the surface of the hearth roll and heating at 3500 to 5500. I can make a film. By repeating this, the film thickness of the chromate treatment can be changed. However, since the thickness increases as the number of times increases, it is preferable that the treatment is terminated within about 3 times.
- the cermet sprayed coating 3 has a thickness of 50 to 300 m and a composition shown in Table 1.
- the fuel gas is kerosene
- the fuel gas pressure is 0.5 MPa
- the fuel gas flow rate is 3 0 0 1 Zmin
- the oxygen gas pressure is 0.5 MPa
- the oxygen gas flow rate was set to 7 0 0 to 1 2 0 0 1 Zm in.
- Inventive Examples No. 1 and 2 were sprayed using a raw material powder that had been previously oxidized.
- thermal spraying was performed with the oxygen gas flow rate set to 1 00 0 to 1 2 0 O l Zm i n.
- Inventive examples No. 1 3 and 1 4 were subjected to chromate treatment after thermal spraying.
- chromate treatment an aqueous solution containing chromic acid was applied to the surface of the hearth roll, and then heated at 500, and this was repeated three times.
- the hearth rolls of the inventive example and the comparative example were soaked in a continuous annealing furnace (roll: ⁇ 1 ⁇ , atmosphere: temperature 8550, nitrogen monohydrogen 3%, dew point 1 30, steel plate: tension 10 MPa, Table 1 shows the evaluation of the steel sheet used for 1 year at an average thickness of 1 mm t and a speed of 300 mpm.
- Inventive Examples 1 to 14 have no thermal spray coating peeling after 1 year of use. No buildup occurred.
- Invention Examples No. 4 to 9 containing Ti or Nb in the heat-resistant alloy and having optimized the particle size of Cr 3 C 2 do not peel off the sprayed coating even when used for 2 years, and Build up did not occur.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
- Heat Treatment Of Strip Materials And Filament Materials (AREA)
- Heat Treatments In General, Especially Conveying And Cooling (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BRPI0819856-0A BRPI0819856B1 (pt) | 2007-11-28 | 2008-11-28 | Cilindro de soleira em um forno de recozimento contínuo e seu método de produção |
JP2009543906A JP5306227B2 (ja) | 2007-11-28 | 2008-11-28 | 連続焼鈍炉用ハースロールおよびその製造方法 |
CN2008801182118A CN101878316B (zh) | 2007-11-28 | 2008-11-28 | 连续退火炉用炉底辊及其制造方法 |
US12/734,680 US8864869B2 (en) | 2007-11-28 | 2008-11-28 | Hearth roll in a continuous annealing furnace and its production method |
KR1020107007195A KR101204064B1 (ko) | 2007-11-28 | 2008-11-28 | 연속 소둔로용 하스 롤 및 그 제조 방법 |
EP08854027.3A EP2213755B1 (en) | 2007-11-28 | 2008-11-28 | Hearth roll for continuous annealing furnace and process for production of the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007307100 | 2007-11-28 | ||
JP2007-307100 | 2007-11-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009069829A1 true WO2009069829A1 (ja) | 2009-06-04 |
Family
ID=40678710
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2008/072106 WO2009069829A1 (ja) | 2007-11-28 | 2008-11-28 | 連続焼鈍炉用ハースロールおよびその製造方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US8864869B2 (ja) |
EP (1) | EP2213755B1 (ja) |
JP (1) | JP5306227B2 (ja) |
KR (1) | KR101204064B1 (ja) |
CN (1) | CN101878316B (ja) |
BR (1) | BRPI0819856B1 (ja) |
TW (1) | TWI397589B (ja) |
WO (1) | WO2009069829A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013104126A (ja) * | 2011-11-16 | 2013-05-30 | Nippon Steel & Sumitomo Metal Corp | 連続焼鈍炉用ハースロール及び連続焼鈍炉用ハースロールの製造方法 |
JPWO2016052741A1 (ja) * | 2014-10-02 | 2017-04-27 | 新日鐵住金株式会社 | ハースロール及びその製造方法 |
KR20240043773A (ko) | 2021-07-27 | 2024-04-03 | 도카로 가부시키가이샤 | 아토마이즈 분말, 용사 피막, 허스롤, 및 허스롤의 제조 방법 |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5168823B2 (ja) * | 2006-06-21 | 2013-03-27 | 新日鐵住金株式会社 | 搬送ロールおよび連続焼鈍炉用ハースロール |
CN102601340A (zh) * | 2012-04-24 | 2012-07-25 | 江苏泽金激光科技有限公司 | 铝合金压铸模具及在其内腔表面形成防护涂层的制备工艺 |
US9840553B2 (en) | 2014-06-28 | 2017-12-12 | Kodiak Sciences Inc. | Dual PDGF/VEGF antagonists |
JP6376342B2 (ja) | 2014-10-03 | 2018-08-22 | Jfeスチール株式会社 | ハースロール、連続焼鈍設備および連続焼鈍方法 |
TWI548753B (zh) | 2014-12-30 | 2016-09-11 | 財團法人工業技術研究院 | 組成物及應用其製成之塗層結構 |
AU2016381964B2 (en) | 2015-12-30 | 2024-02-15 | Kodiak Sciences Inc. | Antibodies and conjugates thereof |
CN106363774A (zh) * | 2016-08-30 | 2017-02-01 | 江苏南山冶金机械制造有限公司 | 一种炉辊的耐火处理方法 |
CN112203679A (zh) | 2018-03-02 | 2021-01-08 | 科达制药股份有限公司 | Il-6抗体及其融合构建体和缀合物 |
CN109911546A (zh) * | 2019-03-12 | 2019-06-21 | 富华中元江苏重机科技有限公司 | 一种耐磨回火托辊 |
CN114786731A (zh) | 2019-10-10 | 2022-07-22 | 科达制药股份有限公司 | 治疗眼部病症的方法 |
JP7316923B2 (ja) * | 2019-12-23 | 2023-07-28 | 日本製鉄株式会社 | 連続焼鈍炉用ハースロール |
CN114318203B (zh) * | 2020-09-29 | 2023-11-17 | 宝武装备智能科技有限公司 | 耐高温抗积瘤复合梯度涂层及其制备方法 |
CN115044762A (zh) * | 2022-08-17 | 2022-09-13 | 靖江市润新表面工程技术有限公司 | 硅钢炉辊及其加工方法 |
CN115584461A (zh) * | 2022-08-26 | 2023-01-10 | 武汉钢铁有限公司 | 一种防止炭套辊芯渗碳的方法、隔离涂层及炉底辊 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01176064A (ja) * | 1987-12-28 | 1989-07-12 | Kubota Ltd | 耐ビルドアップ性にすぐれた溶射皮膜の形成方法 |
JPH0386306A (ja) | 1989-08-30 | 1991-04-11 | Nittetsu Hard Kk | 耐摩耗性に優れた製鉄機械プロセスロール |
JPH03272959A (ja) * | 1990-03-20 | 1991-12-04 | Tocalo Co Ltd | 耐ビルドアップ性ならびに高温耐摩耗性に優れる搬送用ロール |
JPH06116703A (ja) | 1992-10-01 | 1994-04-26 | Nittetsu Hard Kk | 耐熱耐摩耗性ハースロール |
JPH0711420A (ja) | 1993-06-25 | 1995-01-13 | Nippon Steel Corp | 熱処理炉用ロール |
JPH0978219A (ja) * | 1995-09-11 | 1997-03-25 | Nittetsu Hard Kk | 溶射薄肉皮膜を有するプロセスロール |
WO2001034866A1 (fr) * | 1999-11-09 | 2001-05-17 | Kawasaki Steel Corporation | Poudre de cermet pour revetement pulverise presentant une excellente resistance de montage et rouleau dote de ce revetement pulverise |
JP2005105338A (ja) * | 2003-09-30 | 2005-04-21 | Nippon Steel Corp | 搬送ロール及び連続焼鈍炉用ハースロール |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0819535B2 (ja) | 1989-08-17 | 1996-02-28 | トーカロ株式会社 | 高温熱処理炉用ロールおよびその製造方法 |
JP3356889B2 (ja) * | 1994-08-26 | 2002-12-16 | プラクスエア エス ティ テクノロジー インコーポレイテッド | 耐久性に優れたハースロール |
CN100507067C (zh) * | 2005-04-30 | 2009-07-01 | 宝山钢铁股份有限公司 | 高温耐磨、抗结瘤炉内辊喷涂材料 |
-
2008
- 2008-11-28 WO PCT/JP2008/072106 patent/WO2009069829A1/ja active Application Filing
- 2008-11-28 BR BRPI0819856-0A patent/BRPI0819856B1/pt active IP Right Grant
- 2008-11-28 EP EP08854027.3A patent/EP2213755B1/en active Active
- 2008-11-28 US US12/734,680 patent/US8864869B2/en active Active
- 2008-11-28 TW TW097146274A patent/TWI397589B/zh active
- 2008-11-28 CN CN2008801182118A patent/CN101878316B/zh active Active
- 2008-11-28 KR KR1020107007195A patent/KR101204064B1/ko active IP Right Grant
- 2008-11-28 JP JP2009543906A patent/JP5306227B2/ja active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01176064A (ja) * | 1987-12-28 | 1989-07-12 | Kubota Ltd | 耐ビルドアップ性にすぐれた溶射皮膜の形成方法 |
JPH0386306A (ja) | 1989-08-30 | 1991-04-11 | Nittetsu Hard Kk | 耐摩耗性に優れた製鉄機械プロセスロール |
JPH03272959A (ja) * | 1990-03-20 | 1991-12-04 | Tocalo Co Ltd | 耐ビルドアップ性ならびに高温耐摩耗性に優れる搬送用ロール |
JPH06116703A (ja) | 1992-10-01 | 1994-04-26 | Nittetsu Hard Kk | 耐熱耐摩耗性ハースロール |
JPH0711420A (ja) | 1993-06-25 | 1995-01-13 | Nippon Steel Corp | 熱処理炉用ロール |
JPH0978219A (ja) * | 1995-09-11 | 1997-03-25 | Nittetsu Hard Kk | 溶射薄肉皮膜を有するプロセスロール |
WO2001034866A1 (fr) * | 1999-11-09 | 2001-05-17 | Kawasaki Steel Corporation | Poudre de cermet pour revetement pulverise presentant une excellente resistance de montage et rouleau dote de ce revetement pulverise |
JP2005105338A (ja) * | 2003-09-30 | 2005-04-21 | Nippon Steel Corp | 搬送ロール及び連続焼鈍炉用ハースロール |
Non-Patent Citations (1)
Title |
---|
See also references of EP2213755A4 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013104126A (ja) * | 2011-11-16 | 2013-05-30 | Nippon Steel & Sumitomo Metal Corp | 連続焼鈍炉用ハースロール及び連続焼鈍炉用ハースロールの製造方法 |
JPWO2016052741A1 (ja) * | 2014-10-02 | 2017-04-27 | 新日鐵住金株式会社 | ハースロール及びその製造方法 |
US10088236B2 (en) | 2014-10-02 | 2018-10-02 | Nippon Steel & Sumitomo Metal Corporation | Hearth roll and manufacturing method therefor |
KR20240043773A (ko) | 2021-07-27 | 2024-04-03 | 도카로 가부시키가이샤 | 아토마이즈 분말, 용사 피막, 허스롤, 및 허스롤의 제조 방법 |
DE112022003712T5 (de) | 2021-07-27 | 2024-05-23 | Sanyo Special Steel Co., Ltd. | Verdüstes pulver, thermische spritzbeschichtung, herdrolle und verfahren zur herstellung einer herdrolle |
Also Published As
Publication number | Publication date |
---|---|
US20100230874A1 (en) | 2010-09-16 |
EP2213755A1 (en) | 2010-08-04 |
BRPI0819856B1 (pt) | 2019-09-17 |
CN101878316B (zh) | 2012-09-19 |
CN101878316A (zh) | 2010-11-03 |
JPWO2009069829A1 (ja) | 2011-04-21 |
JP5306227B2 (ja) | 2013-10-02 |
TW200936772A (en) | 2009-09-01 |
KR101204064B1 (ko) | 2012-11-22 |
TWI397589B (zh) | 2013-06-01 |
EP2213755A4 (en) | 2012-09-19 |
BRPI0819856A2 (pt) | 2016-06-28 |
EP2213755B1 (en) | 2013-07-24 |
KR20100066536A (ko) | 2010-06-17 |
US8864869B2 (en) | 2014-10-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2009069829A1 (ja) | 連続焼鈍炉用ハースロールおよびその製造方法 | |
JP4332449B2 (ja) | 鋼板の連続焼鈍炉用ハースロールに被覆した溶射被膜 | |
JP4229508B2 (ja) | 高温ハースローラー | |
JP3522590B2 (ja) | 高硬度炭化物サーメット溶射皮膜被覆部材およびその製造方法 | |
JPH02236266A (ja) | 溶融金属用部材およびその製造方法 | |
JPH08143384A (ja) | 炭素部材およびその製造方法 | |
JP2986590B2 (ja) | 耐溶融金属性に優れる溶射用粉末材料および溶射皮膜 | |
JP3338734B2 (ja) | 耐溶融金属用部材およびその製造方法 | |
JP4774786B2 (ja) | 炉内構造物被覆用溶射被膜およびその形成方法 | |
JPH08143385A (ja) | 複合皮膜を有する炭素部材とその製造方法 | |
WO2009150867A1 (ja) | 溶射材料及びハースロール | |
JP4009255B2 (ja) | サーメット粉末ならびに耐ビルドアップ性および耐酸化性に優れた炉内ロール | |
WO2016068189A1 (ja) | 溶射用粉末、溶射皮膜、皮膜、及び溶融金属浴中ロール | |
JP2592628B2 (ja) | 耐ビルドアップ性にすぐれた溶射皮膜の形成方法 | |
JPH01122611A (ja) | 高温鋼材用搬送ロール | |
JP2005281032A (ja) | 焼結用グラファイトトレー | |
KR20110076566A (ko) | 고망간 냉연강판의 소둔시 사용되는 소둔 롤의 용사 코팅재 및 용사 코팅방법 | |
JP5627089B2 (ja) | 炭素材料及びその製造方法 | |
JPH04315A (ja) | 耐ビルドアップ性,耐剥離性および耐摩耗性に優れる高温用搬送ロール | |
TW202144180A (zh) | 耐磨板及其製造方法 | |
JP2009102683A (ja) | 溶射用粉末 | |
JP2006118026A (ja) | 表面被覆用材料および熱処理炉用ロール | |
JPH0742564B2 (ja) | 硬質溶射皮膜の製造方法 | |
JP2008223114A (ja) | サーメット粉末、表層にサーメットを有するロール、および、表層にサーメットを有するロールの製造方法 | |
TW201011108A (en) | High temperature hearth roll melting spray coating |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200880118211.8 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 08854027 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009543906 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2008854027 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 20107007195 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2493/DELNP/2010 Country of ref document: IN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12734680 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: PI0819856 Country of ref document: BR Kind code of ref document: A2 Effective date: 20100526 |