CA3236537A1 - Method of applying thermodiffusion zinc coating to steel pipes - Google Patents
Method of applying thermodiffusion zinc coating to steel pipes Download PDFInfo
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- CA3236537A1 CA3236537A1 CA3236537A CA3236537A CA3236537A1 CA 3236537 A1 CA3236537 A1 CA 3236537A1 CA 3236537 A CA3236537 A CA 3236537A CA 3236537 A CA3236537 A CA 3236537A CA 3236537 A1 CA3236537 A1 CA 3236537A1
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- Prior art keywords
- pipes
- container
- zinc
- coating
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 238000000576 coating method Methods 0.000 title claims abstract description 80
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 239000011701 zinc Substances 0.000 title claims abstract description 62
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910000831 Steel Inorganic materials 0.000 title claims description 25
- 239000010959 steel Substances 0.000 title claims description 25
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 238000009792 diffusion process Methods 0.000 claims abstract description 19
- 238000009738 saturating Methods 0.000 claims abstract description 18
- 230000004907 flux Effects 0.000 claims abstract description 17
- 239000000945 filler Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000003213 activating effect Effects 0.000 claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 5
- 239000010456 wollastonite Substances 0.000 claims abstract description 5
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 5
- 229910000881 Cu alloy Inorganic materials 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000011049 filling Methods 0.000 claims abstract description 4
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 15
- 238000002161 passivation Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- 229920003986 novolac Polymers 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- 150000004665 fatty acids Chemical class 0.000 claims description 5
- 229910000765 intermetallic Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012798 spherical particle Substances 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 150000003842 bromide salts Chemical class 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 150000004673 fluoride salts Chemical class 0.000 claims description 2
- 150000004694 iodide salts Chemical class 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical class [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 3
- 239000010410 layer Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 15
- 239000012190 activator Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000002775 capsule Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000005246 galvanizing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical class [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910001566 austenite Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- HSXKMKJYFOZAIV-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;copper Chemical compound [Cu].OCCN(CCO)CCO HSXKMKJYFOZAIV-UHFFFAOYSA-N 0.000 description 1
- IRMOUQGSNFXEJH-UHFFFAOYSA-N 4,6,11-trioxa-1-aza-5-aluminabicyclo[3.3.3]undecane Chemical compound [Al+3].[O-]CCN(CC[O-])CC[O-] IRMOUQGSNFXEJH-UHFFFAOYSA-N 0.000 description 1
- -1 Aluminum Triethanolamine Chemical compound 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000736772 Uria Species 0.000 description 1
- SOUKPFMUCIJVIT-UHFFFAOYSA-N [C].N(CCO)(CCO)CCO Chemical compound [C].N(CCO)(CCO)CCO SOUKPFMUCIJVIT-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QEHKBHWEUPXBCW-UHFFFAOYSA-N nitrogen trichloride Chemical compound ClN(Cl)Cl QEHKBHWEUPXBCW-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- VZGDMQKNWNREIO-OUBTZVSYSA-N tetrachloromethane Chemical group Cl[13C](Cl)(Cl)Cl VZGDMQKNWNREIO-OUBTZVSYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000003313 weakening effect Effects 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the thermochemical treatment of metal articles and to technology for applying zinc-based protective anti-corrosion thermal diffusion coatings to articles of various shapes. The present method includes loading into a container pipes and a saturating mixture containing a two-component zinc powder, an activating agent and a flux, hermetically closing the container, generating a vacuum, filling the container cavity with a non-oxidizing gas, heating, maintaining a set temperature, then cooling the container and removing the pipes. The temperature maintained is 300-425°C. As a flux, one or more tertiary amines are added to the saturating mixture. As an activating agent, a filler is used which contains one or more components selected from the group consisting of silica, wollastonite, carbon black, aluminium oxide and alloys of copper. The components are used in the following proportions: 0.1-1.0 wt% flux, 25-45 wt% filler, and the balance two-component zinc powder. The invention makes it possible to decrease the dwell time of a pipe, while producing a coating of a given thickness with improved characteristics of corrosion resistance, uniformity and density across the entire surface of the pipe.
Description
METHOD OF APPLYING THERMODIFFUSION ZINC COATING TO
STEEL PIPES
FIELD OF THE TECHNOLOGY
The invention relates to the chemical and thermal treatment of metal products, in particular it relates to the technology of applying protective anti-corrosion coatings and can be used to apply zinc-based thermodiffusion coatings to parts of different shapes, e.g. oilfield grade steel pipes, couplings, fasteners, and other articles.
BACKGROUND OF THE INVENTION
Various embodiments of the technology for application of thermodiffusion zinc-based coatings to steel products are known in the art, with the challenging problem being the ability to provide a uniform dense coating on articles of complex shape, for example, on the inner surface of the elongated pipes or tubes.
Russian Federation Patent RU2500833, MIC: C23C 10/36, published December 10, 2013, discloses a method for applying an anticorrosion coating on metal products, including pipes, by their thermodiffusion zinc-plating. The method involves loading articles/workpieces/parts into a sealed container arranged in a muffle furnace; loading a saturating mixture containing zinc powder and an inert filler; mixing the mixture and articles; filling the container with an inert gas and heating to a temperature of 350-450 C for a time sufficient to diffuse the zinc vapor onto the surface of the workpieces to form a protective s layer of a predetermined amount. In this case, the workpieces are placed in the container in a regular manner using tooling with support surfaces, and the powder saturating mixture contains zinc crystals with a purity of 0.97-0, 99%
needle-shaped with an effective surface area coefficient of 10. The saturating mixture has a particle size distribution in the range of 3-7 ,m, and its mass is 1-4% of the mass of the treated parts or 130-140% of the mass of the required coating on the surface of the treated parts.
The drawback of this method is the complexity of obtaining a uniform coating layer on the inner side of products such as long pipes.
From Russian Federation Patent No. RU2180018, IPC: C23C 10/28, C23C 30/00, published February 27, 2002, it is known A Method of Manufacturing a Powder Mixture For Applying Thermodiffusion Zinc Coating, comprising activating the powder mixture with ammonium chloride while allowing the use of micron-sized zinc powder with spherical particles, flake-like shape or elongated oblong shape.
STEEL PIPES
FIELD OF THE TECHNOLOGY
The invention relates to the chemical and thermal treatment of metal products, in particular it relates to the technology of applying protective anti-corrosion coatings and can be used to apply zinc-based thermodiffusion coatings to parts of different shapes, e.g. oilfield grade steel pipes, couplings, fasteners, and other articles.
BACKGROUND OF THE INVENTION
Various embodiments of the technology for application of thermodiffusion zinc-based coatings to steel products are known in the art, with the challenging problem being the ability to provide a uniform dense coating on articles of complex shape, for example, on the inner surface of the elongated pipes or tubes.
Russian Federation Patent RU2500833, MIC: C23C 10/36, published December 10, 2013, discloses a method for applying an anticorrosion coating on metal products, including pipes, by their thermodiffusion zinc-plating. The method involves loading articles/workpieces/parts into a sealed container arranged in a muffle furnace; loading a saturating mixture containing zinc powder and an inert filler; mixing the mixture and articles; filling the container with an inert gas and heating to a temperature of 350-450 C for a time sufficient to diffuse the zinc vapor onto the surface of the workpieces to form a protective s layer of a predetermined amount. In this case, the workpieces are placed in the container in a regular manner using tooling with support surfaces, and the powder saturating mixture contains zinc crystals with a purity of 0.97-0, 99%
needle-shaped with an effective surface area coefficient of 10. The saturating mixture has a particle size distribution in the range of 3-7 ,m, and its mass is 1-4% of the mass of the treated parts or 130-140% of the mass of the required coating on the surface of the treated parts.
The drawback of this method is the complexity of obtaining a uniform coating layer on the inner side of products such as long pipes.
From Russian Federation Patent No. RU2180018, IPC: C23C 10/28, C23C 30/00, published February 27, 2002, it is known A Method of Manufacturing a Powder Mixture For Applying Thermodiffusion Zinc Coating, comprising activating the powder mixture with ammonium chloride while allowing the use of micron-sized zinc powder with spherical particles, flake-like shape or elongated oblong shape.
2 The use of a powder mixture of this composition does not provide a dense uniform coating of sufficient thickness for the anti-corrosion protection of oilfield steel pipes.
It is also known to provide a gas reaction medium in a sealed container for diffusion galvanizing by introducing an activator, which decomposes when heated to active gases, into the powder mixture. For example, from the description of the Russian Federation Patent Application No. RU2539888, IPC:
C23C 10/36, published January 27, 2015, there is known a method for Termodiffusion Galvanizing Of Steel Products, comprising providing a powder mixture composition for thermal diffusion zinc plating comprising a zinc powder, an inert filler and an activator, and processing the steel products in said composition by heating to a temperature of 420 C. The following is added to the composition of the powder mixture for thermodiffusion zinc related processing (mass%): 25-75% zinc powder and 75-25% inert filler, and 0.5-0.8% carbon tetrachloride from the mass content of zinc powder is added as an activator. In this method an increase in the saturation capacity of the powder mixture is achieved by replacing the previously used ammonium chloride with a more effective activator - tetramine methane. When heated, the activator decomposes into carbon and chlorine. The carbon then reacts with atmospheric
It is also known to provide a gas reaction medium in a sealed container for diffusion galvanizing by introducing an activator, which decomposes when heated to active gases, into the powder mixture. For example, from the description of the Russian Federation Patent Application No. RU2539888, IPC:
C23C 10/36, published January 27, 2015, there is known a method for Termodiffusion Galvanizing Of Steel Products, comprising providing a powder mixture composition for thermal diffusion zinc plating comprising a zinc powder, an inert filler and an activator, and processing the steel products in said composition by heating to a temperature of 420 C. The following is added to the composition of the powder mixture for thermodiffusion zinc related processing (mass%): 25-75% zinc powder and 75-25% inert filler, and 0.5-0.8% carbon tetrachloride from the mass content of zinc powder is added as an activator. In this method an increase in the saturation capacity of the powder mixture is achieved by replacing the previously used ammonium chloride with a more effective activator - tetramine methane. When heated, the activator decomposes into carbon and chlorine. The carbon then reacts with atmospheric
3 oxygen and restores the oxides on the surface of the steel parts. The free chlorine atoms react with zinc, forming volatile zinc chlorides, which are then exchanged into exchange reactions, as a result of which zinc from the volatile compounds passes into the coating composition on the surface of the parts.
This s makes it possible to obtain coatings of a given thickness on hard-to-reach surfaces of parts.
The drawback of this method is the high chemical aggressiveness of free chlorine, which is released during thermal decomposition of tetrachloromethane and causes rapid wear of the equipment.
From the description of the Russian Federation useful model RU 27664, IPC Fl6L 15/08 published February 10,2003, it is known a tubing or drill string pipe, comprising a coupling and an adapter at the threaded ends, which is characterized in that on the threaded surfaces of the sleeve and the adapter a diffusion powder zinc coating with a thickness of 25+ 5-10 mu m is provided.
The disadvantage of the known technical solution is that the diffusion powder zinc coating is applied only on the sleeve, and the long tubing pipe of the protective coating does not have the coating. Given that the zinc-based coating refers to the tread type, i.e. it protects the base metal from corrosion by its own dissolution, this means that when in contact with the steel surface, zinc
This s makes it possible to obtain coatings of a given thickness on hard-to-reach surfaces of parts.
The drawback of this method is the high chemical aggressiveness of free chlorine, which is released during thermal decomposition of tetrachloromethane and causes rapid wear of the equipment.
From the description of the Russian Federation useful model RU 27664, IPC Fl6L 15/08 published February 10,2003, it is known a tubing or drill string pipe, comprising a coupling and an adapter at the threaded ends, which is characterized in that on the threaded surfaces of the sleeve and the adapter a diffusion powder zinc coating with a thickness of 25+ 5-10 mu m is provided.
The disadvantage of the known technical solution is that the diffusion powder zinc coating is applied only on the sleeve, and the long tubing pipe of the protective coating does not have the coating. Given that the zinc-based coating refers to the tread type, i.e. it protects the base metal from corrosion by its own dissolution, this means that when in contact with the steel surface, zinc
4 forms a galvanic couple, wherein the sacrificial anode is a sacrificial anode.
Therefore, the arrangement of the tubing string with alternation of pipes with a surface of different materials is undesirable. In the present case, there is an alternation of the steel and zinc-plated surface of the pipe, which inevitably s leads to the fact that accelerated dissolution of zinc will start at the interface of dissimilar metals and a corrosion process will develop.
Russian Federation Patent RU2284368, IPC: C23C 10/52, Fl 6L 58/08, discloses a method for creating a protective diffusion coating at the outer and inner surface of the pipe and its threaded sections, as well as a pump compressor pipe (tubing), produced by this method. The patent specification refers to oil assortment pipes, namely, tubing with a diameter of 60-114 mm and casing pipes with a diameter of 114-508 mm The method includes treating the threaded portions and adjacent surfaces of the tube by isothermal holding in a diffusion mixture comprising a metal powder and an inert filler powder, after which cooling is carried out in the air. This method uses a diffusion mixture containing a metal powder consisting of a mixture of zinc, copper and aluminum powders with grain size of 0, 1 ¨ 0.5 mm, with the following content of components in the diffusion mixture (mass %): Zinc 25-40, copper 0.045-0.075, aluminum 0.175-0.225, inert filler-the rest. The isothermal holding is
Therefore, the arrangement of the tubing string with alternation of pipes with a surface of different materials is undesirable. In the present case, there is an alternation of the steel and zinc-plated surface of the pipe, which inevitably s leads to the fact that accelerated dissolution of zinc will start at the interface of dissimilar metals and a corrosion process will develop.
Russian Federation Patent RU2284368, IPC: C23C 10/52, Fl 6L 58/08, discloses a method for creating a protective diffusion coating at the outer and inner surface of the pipe and its threaded sections, as well as a pump compressor pipe (tubing), produced by this method. The patent specification refers to oil assortment pipes, namely, tubing with a diameter of 60-114 mm and casing pipes with a diameter of 114-508 mm The method includes treating the threaded portions and adjacent surfaces of the tube by isothermal holding in a diffusion mixture comprising a metal powder and an inert filler powder, after which cooling is carried out in the air. This method uses a diffusion mixture containing a metal powder consisting of a mixture of zinc, copper and aluminum powders with grain size of 0, 1 ¨ 0.5 mm, with the following content of components in the diffusion mixture (mass %): Zinc 25-40, copper 0.045-0.075, aluminum 0.175-0.225, inert filler-the rest. The isothermal holding is
5 carried out for 1, 0-3.0 hours at a temperature of 440 10 c to obtain a protective coating with a thickness of 30-80 m containing the following components (mass %): iron 6-15, zinc 84.1-93.4, copper 0.4-0.6, aluminum 0, 2-0.3, wherein the coating has a microhardness defined by the reduced footprint s of the tetrahedral pyramid in the range of 4500-5250 MPa.
The disadvantage of this method is the inability to obtain a dense uniform coating on the entire surface of the pipe. This is because the method includes processing only threaded sections and adjacent surfaces of the pipe, and not all of the pipe as a whole. The use of relatively large metal powders with a grain size of 0.1-0.5 mm can result in an uneven and porous coating, which also reduces corrosion resistance. Furthermore, the coating technique of this coating comprises holding for 1-3 hours at a temperature of 430-450 C. However, this temperature for carbon steels is critical in terms of austenite transition to austenite, which occurs already when the temperature exceeds 427 C. Thus, when applying the thermodiffusion coating in this way, it is possible to change the microstructure of the steel of the pipe being treated, which can lead to a loss of its strength, which increases the risk of accident when operating the oilfield grade pipes.
The disadvantage of this method is the inability to obtain a dense uniform coating on the entire surface of the pipe. This is because the method includes processing only threaded sections and adjacent surfaces of the pipe, and not all of the pipe as a whole. The use of relatively large metal powders with a grain size of 0.1-0.5 mm can result in an uneven and porous coating, which also reduces corrosion resistance. Furthermore, the coating technique of this coating comprises holding for 1-3 hours at a temperature of 430-450 C. However, this temperature for carbon steels is critical in terms of austenite transition to austenite, which occurs already when the temperature exceeds 427 C. Thus, when applying the thermodiffusion coating in this way, it is possible to change the microstructure of the steel of the pipe being treated, which can lead to a loss of its strength, which increases the risk of accident when operating the oilfield grade pipes.
6 The prior art known to the inventors includes Russian Federation Patent No. RU2738218, IPC: C23C 26/00, published 09.12.2020, which discloses a method for applying a zinc coating to metallic articles by thermodiffusion zinc plating, includes loading the workpieces into a sealed container. The saturating zinc-containing mixture is then loaded into the container, the container cavity is filled with an inert gas and heated. As a saturating zinc-containing mixture, a two-component zinc mixture is loaded, while the first component in the form of an acicular zinc powder with a size of 3-5 microns is loaded directly into the container, and the second component in the form of a spherical zinc powder with a size of 20-25 microns is loaded into a capsule with walls that are destroyed at a temperature of 400 20 with walls, the capsule is placed in a container simultaneously with the products being processed, after which the zinc flux-zinc chloride is loaded into the container, an inert process gas and an activating agent for intensifying the adhesion process are supplied. The galvanizing process is carried out in two steps, first by heating to a temperature of 350-380 C to form a zinc inner layer on the articles by adhesion of the acicular zinc to the surface of the workpiece, and then after heating to a temperature of 400 20 C and the destruction of the capsule material, said ball-shaped zinc powder is released to form an outer coating layer.
7 The drawback of this technical solution is the need for each implementation of the method to produce a new special capsule with the walls breaking under heating to a temperature of 400 20 C. Thus, in order to reliably ensure the release of zinc powder from said capsule, it is necessary to s heat the container in the furnace with an exposure at a temperature above C, which can affect the change in the microstructure of the steel of the pipes being treated and reduce their strength.
SUMMARY OF THE INVENTION
The proposed technical solution is aimed at overcoming the drawbacks of the known prior art, as well as solving the problem of expanding an arsenal of technology, allowing the protective thermodiffusion zinc-based coatings to be applied to the long-length steel pipes usable in the oilfield industry, to completely cover their outer and inner surfaces as well as the threaded sections of the pipes.
The technical result achieved by the present invention is to reduce the duration of pipe exposure in the temperature range of thermal diffusion galvanizing when producing coatings of a given thickness with improved corrosion resistance properties, to improve uniformity and density of the
SUMMARY OF THE INVENTION
The proposed technical solution is aimed at overcoming the drawbacks of the known prior art, as well as solving the problem of expanding an arsenal of technology, allowing the protective thermodiffusion zinc-based coatings to be applied to the long-length steel pipes usable in the oilfield industry, to completely cover their outer and inner surfaces as well as the threaded sections of the pipes.
The technical result achieved by the present invention is to reduce the duration of pipe exposure in the temperature range of thermal diffusion galvanizing when producing coatings of a given thickness with improved corrosion resistance properties, to improve uniformity and density of the
8 coating on the entire surface of the pipe, as well as to reduce energy consumption and to increase productivity while ensuring the high strength of pipes processed by the method of the invention.
In order to resolve the above-noted problems, the method of the s invention proposes applying the thermodiffusion zinc-based coating on steel pipes including: loading pipes into a container; loading a saturating mixture containing a two-component zinc powder, an activating agent and flux;
hermetic closure of the container, its vacuum evacuation; filling of the container cavity with non-oxidizing gas; heating and holding at a predetermined temperature; subsequent cooling of the container and extraction of pipes. In the method, the first component of the two-component zinc powder having needle-shaped particles with a size of 3-8 microns is loaded into an internal cavity of the pipes, and the second component of the two-component zinc powder is loaded directly into the container; the exposure is carried out at a temperature of 300-425 C, wherein one or more tertiary amines are introduced as fluxes into the saturating mixture, and an activating agent is a filler comprising one or more components selected from the group consisting of silica, wollastonite, carbon black, aluminum oxide and copper alloys, with the following ratio of components (mass %):
In order to resolve the above-noted problems, the method of the s invention proposes applying the thermodiffusion zinc-based coating on steel pipes including: loading pipes into a container; loading a saturating mixture containing a two-component zinc powder, an activating agent and flux;
hermetic closure of the container, its vacuum evacuation; filling of the container cavity with non-oxidizing gas; heating and holding at a predetermined temperature; subsequent cooling of the container and extraction of pipes. In the method, the first component of the two-component zinc powder having needle-shaped particles with a size of 3-8 microns is loaded into an internal cavity of the pipes, and the second component of the two-component zinc powder is loaded directly into the container; the exposure is carried out at a temperature of 300-425 C, wherein one or more tertiary amines are introduced as fluxes into the saturating mixture, and an activating agent is a filler comprising one or more components selected from the group consisting of silica, wollastonite, carbon black, aluminum oxide and copper alloys, with the following ratio of components (mass %):
9 Flux 0.1-1.0 25-45 filler a two-component zinc powder¨the rest.
According to the present invention, the method of applying the thermodiffusion zinc-based coating is carried out primarily for coating steel pipes or tubing having the linear or drilling steel pipes up to 8 -12 m in length, wherein prior to loading into the container the outer and inner surfaces of the pipes are machined.
To obtain a uniform and quality coating layer, before loading into the container the pipes are assembled into the tooling having support surfaces to allow for regular placement of the pipes, wherein the pipes are placed into the container together with the tooling.
According to the present method, the flux composition may further comprise one or more components selected from the group comprising urea or derivatives thereof, piperazine or derivatives thereof, ammonium salts of fatty acids, chlorides, fluorides, bromides, iodides, sulfates and sulfates of fatty acids, as well as aluminum and lithium chlorides.
In the method of the invention a non-oxidizing gas is preferably a gas selected from the group consisting of argon, nitrogen or carbon dioxide, which.
This gas, after the evacuation operation fills the container at a pressure within the range of 0,1-8 atm.
s After the pipes are removed from the container, the thermodiffusion coating is passivated by applying a polymer layer. Passivation makes it possible to realize a synergistic effect of the protection in case of damage to the polymer layer. In the case of damage to the polymer layer, zinc from the iron-zinc intermetallic compound forms sparingly soluble substances preventing the development of under film corrosion at the iron-zinc intermetallide-polymer layer interface.
Further, the problem of formation of asphalt-resin-paraffin deposits (ARPD) on the inner surface is known to the oil pipes. Passivation of the inner surface of the pipes having a thermodiffusion zinc-based coating by applying a smooth polymer layer reduces the mass of the ARPD by 30-40%.
The passivation of the zinc-based diffusion coating may be performed on both the inner and outer surfaces of the zinc related processing of pipes or tubings. However, it is preferred to perform the passivation on the inner surfaces, which are exposed to the greatest impact of the corrosive environment. The passivation procedure is performed by applying a layer of the polymer composition upon the subsequent hot curing. Epoxy paints or epoxy-novolak phenolic two-component polymer compositions are used to apply the polymer layer.
As a result of implementing the present method, the pump-compressor pipes are obtained as a finished product. The outer and inner surfaces of such pipes are provided with a thermodiffusion zinc-based coating having a thickness of 20-140 microns (preferably 40-70 microns) with a microhardness in the range of 2500-3800 Mpa. The coating includes intermetallic compounds of iron and zinc of variable composition from FenZn to Fe4Zn, forming layers of gamma phase (y-phase) and delta phase (6-phase), providing corrosion resistance of the coating.
As a result of implementing of the method of the invention, a thermodiffusion zinc-based coating is produced having a predetermined thickness with improved corrosion resistance properties, uniformity and density of the coating Such coating can be obtained on the steel pump or compressor pipes and on other steel pipes for the oil industry on the entire outer and inner surfaces of the pipes. The length of such pipes is typically within the range of 8-12 m, with the inner diameter being no less than 45 mm and no more than 1000 mm. These parameters are typically determined by the capabilities of existing equipment.
To further improve corrosion resistance and durability in the severe operating conditions, the pipes are further provided with a passivating layer of s the polymer coating, which is received as a result of hot curing of epoxy or epoxy-novolak phenolic two-component polymer compositions. The passivation layer is placed on top of, or in addition to the thermodiffusion zinc-based coating, preferably on the inner surfaces of the pipes.
The pump-compressor pipes for connecting to the column can be provided with threaded portions located at the ends of the pipe, wherein the thickness of the thermodiffusion zinc-based coating on the threaded surfaces of the threaded portions of the pipe is preferably 20-25 Am. The latter is determined by the requirements for the parts threaded connections.
DETAILED DESCRIPTION OF THE INVENTION
The invention is illustrated by Examples 1-8 presented in Table 1 and Figure 1 of the drawing which illustrates the structure of the obtained coating.
Example No. 1 The method of the invention of applying a thermodiffusion zinc-based coating was carried out by providing the coating to the steel pipes having the length of 8.5 meters and the diameter of 60 mm. The batch of pipes in an amount of 50 pieces was initially subjected to mechanical (abrasive) processing s at the outer and inner surfaces thereof. Then, into the inner cavity of each pipe the first component of the saturating mixture is loaded in the form of a zinc powder with needle-shaped particles 3-8 gm, mixed with a filler in the form of carbon black (carbon black) in an amount of 25 mass %. The pipes with the applied first saturating mixture component were assembled into tooling formed with the bearing surfaces. The pipes are fixed in a predetermined position to prevent direct contact with each other, as well as to prevent the movement of the pipes relative to each other when the container is moving. In the resulting assembly, the minimum distance between the tube surfaces to be treated was 3-5 mm. The pipes were loaded into the container together with the tooling.
A second saturating mixture component containing a zinc powder having spherical particles of 8-25 gm in size mixed with a filler in the form of carbon black in an amount of 25 % wt. is then loaded directly into the container. As a flux, urotropine was introduced into the saturating mixture in an amount of no more than 1% wt. of the composition of the saturating mixture. Urotropine was a tertiary amine. After the flux was introduced, the container was closed, the lid was sealed, and the vacuum was established in the cavity of the container.
Non-oxidizing shielding gas was then injected into the cavity of the container at a pressure of 4 atm. The gas was inert relative to the components of the s saturating mixture. Nitrogen was selected as the non-oxidizing gas. The container was then placed into the oven and heated to a temperature of 380 C. The heated container was held in the oven at the temperature range of 380-400 C for 3 hours.
The container was then removed from the oven, cooled and opened. The industrial vacuum cleaner was used to remove zinc-saturating mixture residues from the container, after which step the tubes were removed. The quality of the protective coating obtained on the outer and inner surfaces of the pipes was controlled. The resulting zinc-based coating consisted of iron-zinc intermetallic compounds forming a thin layer of gamma phase (y phase) and a wider layer of dense delta phase (6 phase) with the thickness approximately 60 inn/microns and the microhardness of the coating surface of 3800 MPa, (HV400) with satisfactory continuity and density without any discontinuities or pores. The coating was formed having a uniform thickness along the entire length of the pipe at the outer and inner surfaces thereof. The resulting coating is shown in FIG. 1. The structure of the coating consists of an intermetallic compound based on the 6-phase containing 7-11.5% Fe with the remaining Zn, whereas an inner thin layer of y-phase contains 28% Fe and the rest is Zn.
To further increase the operational resistance on the inner surface of the s pipe cavity, the first two turns of the thread and the chamfer of the pipe have been coated with a polymer layer passivating the thermodiffusion zinc-based coating. The passivation layer of the polymer coating is produced by the hot curing of the epoxy-novolak phenolic two-component polymer composition.
To prepare the epoxy-novolak phenolic polymer composition, a paint material from a Majorpack series of paint in red glossy or white glossy paint was used as a base. As the second component of the two-component polymer composition was used a hardener for the paint material of the Majorpack series of paint: red glossy or white glossy is used, with a ratio of the base to the hardener in the range from 4: 1 to 10: 1.
The implementation mode of the method of the invention according to Example 1 is shown in Table 1. In addition, Table 1 also presents details of Examples 2-7 of the method, which include the same sequence of steps as in Example 1. The modes of embodiments of Examples 2-7 are characterized by different temperature and exposure duration of the container with the products being treated in the furnace.
From the data shown in Table 1, it can be seen that for a reduction in the exposure duration of the pipes in the temperature range of the thermodiffusion s zinc-based coating of 300-425 c. in the production of coatings of the predetermined thickness of 60 pm (with high quality properties), it was observed the effect of sharing a new flux¨a tertiary amine and a filler selected from the group consisting of silica, wollastonite, carbon black, aluminum oxide, and copper alloys. Under these conditions, diffusion of the zinc vapor provided a uniform, tight coating of a predetermined thickness on both the inner and outer surfaces of the steel pipes, including the threaded portions. Note that in Example 2, the coating was applied to a batch of pipes of minimum diameter (the inner diameter of the pipes was 45 mm with a pipe length of up to 12 meters). Further, in Examples 3-7, additional tertiary amine flux was added urea, piperazine and others in an amount of 0,1-0.3 % wt., which resulted in some slight increase in coating rate.
The intensification of the process of diffusion saturation of the surface of steel pipes in the present method of applying zinc-based coating by the gas thermodiffusion is achieved by replacing traditional activators with complexes of inorganic and organic substances, which at the operating temperatures decompose to activate zinc atoms and contribute to an increase in the saturation rate of the surface of the articles with a corrosion-resistant 6-phase.
Example 8 in Table 1 corresponds to the closes prior art known to the s inventors, i.e. according to RU2738218. Comparison with this reference shows that the dwell time required to obtain a coating of a given thickness of 60 iim was reduced from 3.5 hours in the reference to 3 hours in the present method.
This means that the dwell when applying the thermodiffusion zinc-based coating was reduced by 14%, which corresponds to an increase in the productivity of the present method and a reduction in energy costs. This is because the duration of operation of the electric heaters of the furnace required for heating the container and holding at a selected temperature was reduced.
Furthermore, the advantage of the coating technology of applying the thermodiffusion zinc-based coating according to the present method with respect to RU2738218 and other known analogs is the possibility of forming a thermodiffusion coating at lower temperatures (below 425 C). As shown in Table 1, a preferred temperature range is lowered to effect soaking while applying the thermodiffusion zinc-based coating to the pipes, which improves the processing quality of steel pipes. This is because the lower temperature of the application of the thermodiffusion coating does not guarantee the weakening of the high carbon steels when the tubes are directed for application of the coating after the heat treatment. As is known, the heating and holding temperature at the level above 427 C for carbon steels is critical. This is s because it corresponds to the transition of perlite to austenite, which entails a change in the microstructure of the steel and a decrease in strength. Thus, the use of the present method ensures that the strength group of the oilfield grade steel pipe is maintained after application of the thermodiffusion zinc-based coating thereto.
The corrosion resistance test of the pipes prepared according to Example 1 shows an increase in their corrosion resistance in a medium containing hydrogen sulfide and carbon dioxide at a pressure of up to 2 atmospheres and a temperature of 80 C Exposure under these conditions shows that the resistance of the coated tube was 1500 days without the corrosive damage.
Ex Temp. Gas Pres- Filler Tertiaryamine Additional Time Pipe Thread sure, Flux Flux Exposure coating coating = C atm Component /hours thickness thickness /gm /gm 1 380- nitrogen 4 soot Urotropine - 3 60 2 340- Carbon 2 Aluminum Triethanolamine _ 3 60 360 dioxide oxide 3 360- argon 1,2 Carbon Triethanolamine Uria 3 62 380 charcoal (primary amine) 4 300- nitrogen 8 Aluminum Urotropine Piperazine 3 62 320 oxide (secondary amine) 340- Carbon 2 Copper Triethanolamine Tetrabutyla 3 360 dioxide alloys mmonium stearate (ammoniu m salt of fatty acid) 6 400- Carbon 0.1 wollastonite Urotropine Lithium 2 40 425 dioxide chloride 7 320- 1,2 Soot Triethanolamine Aluminum 6 125 340 nitrogen chloride 8 400- argon 1.0 Silica Prototype: - 3,5 60 420 zinc chloride
According to the present invention, the method of applying the thermodiffusion zinc-based coating is carried out primarily for coating steel pipes or tubing having the linear or drilling steel pipes up to 8 -12 m in length, wherein prior to loading into the container the outer and inner surfaces of the pipes are machined.
To obtain a uniform and quality coating layer, before loading into the container the pipes are assembled into the tooling having support surfaces to allow for regular placement of the pipes, wherein the pipes are placed into the container together with the tooling.
According to the present method, the flux composition may further comprise one or more components selected from the group comprising urea or derivatives thereof, piperazine or derivatives thereof, ammonium salts of fatty acids, chlorides, fluorides, bromides, iodides, sulfates and sulfates of fatty acids, as well as aluminum and lithium chlorides.
In the method of the invention a non-oxidizing gas is preferably a gas selected from the group consisting of argon, nitrogen or carbon dioxide, which.
This gas, after the evacuation operation fills the container at a pressure within the range of 0,1-8 atm.
s After the pipes are removed from the container, the thermodiffusion coating is passivated by applying a polymer layer. Passivation makes it possible to realize a synergistic effect of the protection in case of damage to the polymer layer. In the case of damage to the polymer layer, zinc from the iron-zinc intermetallic compound forms sparingly soluble substances preventing the development of under film corrosion at the iron-zinc intermetallide-polymer layer interface.
Further, the problem of formation of asphalt-resin-paraffin deposits (ARPD) on the inner surface is known to the oil pipes. Passivation of the inner surface of the pipes having a thermodiffusion zinc-based coating by applying a smooth polymer layer reduces the mass of the ARPD by 30-40%.
The passivation of the zinc-based diffusion coating may be performed on both the inner and outer surfaces of the zinc related processing of pipes or tubings. However, it is preferred to perform the passivation on the inner surfaces, which are exposed to the greatest impact of the corrosive environment. The passivation procedure is performed by applying a layer of the polymer composition upon the subsequent hot curing. Epoxy paints or epoxy-novolak phenolic two-component polymer compositions are used to apply the polymer layer.
As a result of implementing the present method, the pump-compressor pipes are obtained as a finished product. The outer and inner surfaces of such pipes are provided with a thermodiffusion zinc-based coating having a thickness of 20-140 microns (preferably 40-70 microns) with a microhardness in the range of 2500-3800 Mpa. The coating includes intermetallic compounds of iron and zinc of variable composition from FenZn to Fe4Zn, forming layers of gamma phase (y-phase) and delta phase (6-phase), providing corrosion resistance of the coating.
As a result of implementing of the method of the invention, a thermodiffusion zinc-based coating is produced having a predetermined thickness with improved corrosion resistance properties, uniformity and density of the coating Such coating can be obtained on the steel pump or compressor pipes and on other steel pipes for the oil industry on the entire outer and inner surfaces of the pipes. The length of such pipes is typically within the range of 8-12 m, with the inner diameter being no less than 45 mm and no more than 1000 mm. These parameters are typically determined by the capabilities of existing equipment.
To further improve corrosion resistance and durability in the severe operating conditions, the pipes are further provided with a passivating layer of s the polymer coating, which is received as a result of hot curing of epoxy or epoxy-novolak phenolic two-component polymer compositions. The passivation layer is placed on top of, or in addition to the thermodiffusion zinc-based coating, preferably on the inner surfaces of the pipes.
The pump-compressor pipes for connecting to the column can be provided with threaded portions located at the ends of the pipe, wherein the thickness of the thermodiffusion zinc-based coating on the threaded surfaces of the threaded portions of the pipe is preferably 20-25 Am. The latter is determined by the requirements for the parts threaded connections.
DETAILED DESCRIPTION OF THE INVENTION
The invention is illustrated by Examples 1-8 presented in Table 1 and Figure 1 of the drawing which illustrates the structure of the obtained coating.
Example No. 1 The method of the invention of applying a thermodiffusion zinc-based coating was carried out by providing the coating to the steel pipes having the length of 8.5 meters and the diameter of 60 mm. The batch of pipes in an amount of 50 pieces was initially subjected to mechanical (abrasive) processing s at the outer and inner surfaces thereof. Then, into the inner cavity of each pipe the first component of the saturating mixture is loaded in the form of a zinc powder with needle-shaped particles 3-8 gm, mixed with a filler in the form of carbon black (carbon black) in an amount of 25 mass %. The pipes with the applied first saturating mixture component were assembled into tooling formed with the bearing surfaces. The pipes are fixed in a predetermined position to prevent direct contact with each other, as well as to prevent the movement of the pipes relative to each other when the container is moving. In the resulting assembly, the minimum distance between the tube surfaces to be treated was 3-5 mm. The pipes were loaded into the container together with the tooling.
A second saturating mixture component containing a zinc powder having spherical particles of 8-25 gm in size mixed with a filler in the form of carbon black in an amount of 25 % wt. is then loaded directly into the container. As a flux, urotropine was introduced into the saturating mixture in an amount of no more than 1% wt. of the composition of the saturating mixture. Urotropine was a tertiary amine. After the flux was introduced, the container was closed, the lid was sealed, and the vacuum was established in the cavity of the container.
Non-oxidizing shielding gas was then injected into the cavity of the container at a pressure of 4 atm. The gas was inert relative to the components of the s saturating mixture. Nitrogen was selected as the non-oxidizing gas. The container was then placed into the oven and heated to a temperature of 380 C. The heated container was held in the oven at the temperature range of 380-400 C for 3 hours.
The container was then removed from the oven, cooled and opened. The industrial vacuum cleaner was used to remove zinc-saturating mixture residues from the container, after which step the tubes were removed. The quality of the protective coating obtained on the outer and inner surfaces of the pipes was controlled. The resulting zinc-based coating consisted of iron-zinc intermetallic compounds forming a thin layer of gamma phase (y phase) and a wider layer of dense delta phase (6 phase) with the thickness approximately 60 inn/microns and the microhardness of the coating surface of 3800 MPa, (HV400) with satisfactory continuity and density without any discontinuities or pores. The coating was formed having a uniform thickness along the entire length of the pipe at the outer and inner surfaces thereof. The resulting coating is shown in FIG. 1. The structure of the coating consists of an intermetallic compound based on the 6-phase containing 7-11.5% Fe with the remaining Zn, whereas an inner thin layer of y-phase contains 28% Fe and the rest is Zn.
To further increase the operational resistance on the inner surface of the s pipe cavity, the first two turns of the thread and the chamfer of the pipe have been coated with a polymer layer passivating the thermodiffusion zinc-based coating. The passivation layer of the polymer coating is produced by the hot curing of the epoxy-novolak phenolic two-component polymer composition.
To prepare the epoxy-novolak phenolic polymer composition, a paint material from a Majorpack series of paint in red glossy or white glossy paint was used as a base. As the second component of the two-component polymer composition was used a hardener for the paint material of the Majorpack series of paint: red glossy or white glossy is used, with a ratio of the base to the hardener in the range from 4: 1 to 10: 1.
The implementation mode of the method of the invention according to Example 1 is shown in Table 1. In addition, Table 1 also presents details of Examples 2-7 of the method, which include the same sequence of steps as in Example 1. The modes of embodiments of Examples 2-7 are characterized by different temperature and exposure duration of the container with the products being treated in the furnace.
From the data shown in Table 1, it can be seen that for a reduction in the exposure duration of the pipes in the temperature range of the thermodiffusion s zinc-based coating of 300-425 c. in the production of coatings of the predetermined thickness of 60 pm (with high quality properties), it was observed the effect of sharing a new flux¨a tertiary amine and a filler selected from the group consisting of silica, wollastonite, carbon black, aluminum oxide, and copper alloys. Under these conditions, diffusion of the zinc vapor provided a uniform, tight coating of a predetermined thickness on both the inner and outer surfaces of the steel pipes, including the threaded portions. Note that in Example 2, the coating was applied to a batch of pipes of minimum diameter (the inner diameter of the pipes was 45 mm with a pipe length of up to 12 meters). Further, in Examples 3-7, additional tertiary amine flux was added urea, piperazine and others in an amount of 0,1-0.3 % wt., which resulted in some slight increase in coating rate.
The intensification of the process of diffusion saturation of the surface of steel pipes in the present method of applying zinc-based coating by the gas thermodiffusion is achieved by replacing traditional activators with complexes of inorganic and organic substances, which at the operating temperatures decompose to activate zinc atoms and contribute to an increase in the saturation rate of the surface of the articles with a corrosion-resistant 6-phase.
Example 8 in Table 1 corresponds to the closes prior art known to the s inventors, i.e. according to RU2738218. Comparison with this reference shows that the dwell time required to obtain a coating of a given thickness of 60 iim was reduced from 3.5 hours in the reference to 3 hours in the present method.
This means that the dwell when applying the thermodiffusion zinc-based coating was reduced by 14%, which corresponds to an increase in the productivity of the present method and a reduction in energy costs. This is because the duration of operation of the electric heaters of the furnace required for heating the container and holding at a selected temperature was reduced.
Furthermore, the advantage of the coating technology of applying the thermodiffusion zinc-based coating according to the present method with respect to RU2738218 and other known analogs is the possibility of forming a thermodiffusion coating at lower temperatures (below 425 C). As shown in Table 1, a preferred temperature range is lowered to effect soaking while applying the thermodiffusion zinc-based coating to the pipes, which improves the processing quality of steel pipes. This is because the lower temperature of the application of the thermodiffusion coating does not guarantee the weakening of the high carbon steels when the tubes are directed for application of the coating after the heat treatment. As is known, the heating and holding temperature at the level above 427 C for carbon steels is critical. This is s because it corresponds to the transition of perlite to austenite, which entails a change in the microstructure of the steel and a decrease in strength. Thus, the use of the present method ensures that the strength group of the oilfield grade steel pipe is maintained after application of the thermodiffusion zinc-based coating thereto.
The corrosion resistance test of the pipes prepared according to Example 1 shows an increase in their corrosion resistance in a medium containing hydrogen sulfide and carbon dioxide at a pressure of up to 2 atmospheres and a temperature of 80 C Exposure under these conditions shows that the resistance of the coated tube was 1500 days without the corrosive damage.
Ex Temp. Gas Pres- Filler Tertiaryamine Additional Time Pipe Thread sure, Flux Flux Exposure coating coating = C atm Component /hours thickness thickness /gm /gm 1 380- nitrogen 4 soot Urotropine - 3 60 2 340- Carbon 2 Aluminum Triethanolamine _ 3 60 360 dioxide oxide 3 360- argon 1,2 Carbon Triethanolamine Uria 3 62 380 charcoal (primary amine) 4 300- nitrogen 8 Aluminum Urotropine Piperazine 3 62 320 oxide (secondary amine) 340- Carbon 2 Copper Triethanolamine Tetrabutyla 3 360 dioxide alloys mmonium stearate (ammoniu m salt of fatty acid) 6 400- Carbon 0.1 wollastonite Urotropine Lithium 2 40 425 dioxide chloride 7 320- 1,2 Soot Triethanolamine Aluminum 6 125 340 nitrogen chloride 8 400- argon 1.0 Silica Prototype: - 3,5 60 420 zinc chloride
Claims (12)
1. A method of applying a thermodiffusion zinc-based coating to steel pipes, comprising loading pipes and a saturating mixture comprising a two-component zinc powder, an activating agent and a flux into a container, hermetically closing the container, vacuumizing, filling a container cavity with a non-oxidizing gas, heating and holding at a predetermined temperature, subsequently cooling the container and extracting the pipes, characterized in that a first component of a two-component zinc powder having needle-shaped particles with a size of 3-8 m is loaded into inner cavities of the pipes, a second component of the two-component zinc powder having spherical particles with a size of 8-25 p.m is loaded directly into the container, exposure is carried out at a temperature of 300-425 C, wherein one or more tertiary amines in an amount of 0, 1-1.0 mass % are introduced into the saturating mixture as a flux; as an activating agent a filler is used comprising one or more components selected from the group consisting of silica, wollastonite, carbon black, aluminum oxide, and copper alloys, with the following ratio of the components (by mass %):
0.1-1.0 flux 25-45 filler two-component zinc powder-the rest.
0.1-1.0 flux 25-45 filler two-component zinc powder-the rest.
2. The method according to claim 1, characterized in that prior to loading into the container, the pipes are machined from the outer and inner surfaces of the pipes.
3. The method according to claim 1, characterized in that prior to loading into the container, the pipes are assembled into the tooling, and the pipes together with the tooling are placed in the container.
4. The method according to claim 1, characterized in that the flux composition further comprises one or more components selected from the group consisting of urea or derivatives thereof, piperazine or derivatives thereof, ammonium salts of fatty acids, chlorides, fluorides, bromides, iodides, sulfates and sulfates of fatty acids, as well as aluminum chlorides and lithium chlorides.
5. The method according to claim 1, characterized in that the non-oxidizing gas is a gas selected from the group consisting of argon, nitrogen or carbon dioxide, which fill the container at a pressure of 0.1 to 8 atm.
6. The method according to claim 1, characterized in that after the pipes are removed from the container, passivation of the thermo-diffusion zinc-based coating is performed by applying a polymer layer.
7. The method according to claim 6, characterized in that passivation of the thermo-diffusion zinc-based coating on the inner surface of the pipes is performed by applying a polymer layer resulted from hot curing of epoxy or epoxy-novolak phenolic compounds, including two-component ones.
8. The method according to claim 6, characterized in that passivation of the thermo-diffusion zinc coating on the outer and inner surfaces of the pipes is performed by applying a polymer layer resulted from hot curing of epoxy or epoxy-novolak phenolic compounds, including two-component ones.
9. A steel pipe comprising a hollow body with a thermal diffusion zinc-based coating, characterized in that the coating is obtained by the method of any Claims 1-8.
10. The pipe according to claim 9, characterized in that it is made in the forrn of a pump compressor pipe, the body of which has a length of 8 ¨ 12 m, an inner diameter of at least 45 mm and comprises a thermal diffusion zinc coating on the outer and inner surfaces 20-140 j_tm, preferably 40-70 m, with a microhardness of 2500-3800 MPa, which comprises iron and zinc intermetallic compounds.
11. The pipe according to claim 10, further comprising a passivation layer of a polymer coating resulting from the hot curing of epoxy or epoxy-novolak phenolic two-component polymer compositions, located on the thermal diffusion zinc coating, preferably on the inner surface of the pipe.
12. The pipe according to any one of claims 10 or 11, characterized in that its body is provided with threaded portions located at the ends, wherein the thickness of the thermal difffision zinc coating on the threaded surfaces of the threaded portions of the pipe body is preferably 20-25 gm.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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RU2022109894A RU2785211C1 (en) | 2022-04-13 | Method for applying thermodiffusion zinc coating onto steel pipes and steel pipe with said coating | |
RU2022109894 | 2022-04-13 | ||
PCT/RU2022/050327 WO2023200359A1 (en) | 2022-04-13 | 2022-10-13 | Method of applying a zinc thermal diffusion coating to steel pipes |
Publications (1)
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CA3236537A1 true CA3236537A1 (en) | 2023-10-19 |
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CA3236537A Pending CA3236537A1 (en) | 2022-04-13 | 2022-10-13 | Method of applying thermodiffusion zinc coating to steel pipes |
Country Status (3)
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CA (1) | CA3236537A1 (en) |
MX (1) | MX2024005491A (en) |
WO (1) | WO2023200359A1 (en) |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1107899A (en) * | 1994-03-01 | 1995-09-06 | 陶锦伯 | Vacuum solid zincing method |
RU2186150C2 (en) * | 2000-09-28 | 2002-07-27 | Федеральное государственное унитарное предприятие Центральный научно-исследовательский институт черной металлургии им.И.П.Бардина | Steel product zinc plating method |
CN1330167A (en) * | 2001-07-22 | 2002-01-09 | 韩丽君 | Powder zincification process of metal and its product |
RU2424351C2 (en) * | 2009-08-17 | 2011-07-20 | Виктор Иванович Кубанцев | Procedure for application of zinc coating and installation for its implementation |
RU2595075C1 (en) * | 2015-09-29 | 2016-08-20 | Общество с ограниченной ответственностью "Полимерпром" | Thermodiffusion zinc coating method |
RU2685841C1 (en) * | 2018-10-15 | 2019-04-23 | Общество с ограниченной ответственностью "Волнар" | Composition of powder mixture for thermodiffusion treatment of steel items, method of thermodiffusion treatment of steel products |
RU2738218C1 (en) * | 2019-08-22 | 2020-12-09 | Общество с ограниченной ответственностью "ТЕХНОВАЦИНК" | Method of applying anticorrosion intermetallic coating by thermodiffusion zinc coating |
-
2022
- 2022-10-13 WO PCT/RU2022/050327 patent/WO2023200359A1/en active Application Filing
- 2022-10-13 CA CA3236537A patent/CA3236537A1/en active Pending
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MX2024005491A (en) | 2024-08-09 |
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