RU2052535C1 - Method for thermochemical treatment of hollow steel products - Google Patents
Method for thermochemical treatment of hollow steel products Download PDFInfo
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- RU2052535C1 RU2052535C1 SU925011449A SU5011449A RU2052535C1 RU 2052535 C1 RU2052535 C1 RU 2052535C1 SU 925011449 A SU925011449 A SU 925011449A SU 5011449 A SU5011449 A SU 5011449A RU 2052535 C1 RU2052535 C1 RU 2052535C1
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- mpa
- treatment
- gas
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- hollow steel
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- 238000011282 treatment Methods 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 13
- 229910000831 Steel Inorganic materials 0.000 title abstract description 7
- 239000010959 steel Substances 0.000 title abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 230000000930 thermomechanical effect Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000002344 surface layer Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005121 nitriding Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/20—Carburising
- C23C8/22—Carburising of ferrous surfaces
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/24—Nitriding
- C23C8/26—Nitriding of ferrous surfaces
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M61/00—Fuel-injectors not provided for in groups F02M39/00 - F02M57/00 or F02M67/00
- F02M61/16—Details not provided for in, or of interest apart from, the apparatus of groups F02M61/02 - F02M61/14
- F02M61/166—Selection of particular materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Heat Treatment Of Articles (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Fire-Extinguishing Compositions (AREA)
- Housings And Mounting Of Transformers (AREA)
- Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
- Heat Treatments In General, Especially Conveying And Cooling (AREA)
- Treatment Of Sludge (AREA)
Abstract
Description
Изобретение относится к способу термохимической обработки полых тел и отверстий или стальных деталей с труднодоступными снаружи поверхностями с помощью реакционно-способных газов при температурах выше 450оС.The invention relates to a process for the thermochemical treatment and hollow bodies holes or steel parts with difficult to access from outside surfaces using reactive gases at temperatures above 450 ° C.
Известны способы, согласно которым стальные изделия подергают азотированию под давлением в автоклаве в атмосфере газообразного аммиака. Known methods according to which steel products are nitrated under pressure in an autoclave in an atmosphere of gaseous ammonia.
Однако эти способы не применяются для обработки стальных деталей с труднодоступными снаружи поверхностями или полостями. However, these methods are not applied to the processing of steel parts with surfaces or cavities that are difficult to access from the outside.
Задача изобретения создание способа равномерной термохимической обработки полых тел и отверстий или стальных деталей с труднодоступными снаружи поверхностями реакционно-способными газами при температурах выше 450оС, который был бы легкоосуществимым и обеспечивал равномерную обработку поверхностных слоев и труднодоступных снаружи поверхностей.Object of the invention provide a method for the uniform thermochemical treatment of hollow bodies and openings or steel parts with difficult to access from the outside surfaces of reactive gases at temperatures above 450 C, which would be provided legkoosuschestvimym and uniform treatment of the surface layers on the outside and hard surfaces.
Это достигается тем, что обработку проводят при давлении выше 0,2 мПа. This is achieved by the fact that the treatment is carried out at a pressure above 0.2 MPa.
Предпочтительно для азотирования в качестве реакционно-способного газа использовать аммиак. При этом было установлено, что к аммиаку целесообразно добавлять 5-95 об. молекулярного азота. It is preferable to use ammonia as a reactive gas for nitriding. It was found that it is advisable to add 5-95 vol.% To ammonia. molecular nitrogen.
Для науглероживания в качестве реакционно-способного газа используют газ, способный выделять углерод, предпочтительно метан или его смеси при 870-1000оС. Кроме того, обработку реакционно-способным газом предпочтительно проводить при постоянном давлении.For carburization as the reactive gas is a gas capable of releasing carbon, preferably methane or mixtures thereof at about 870-1000 C. In addition, the processing of a reactive gas is preferably carried out at a constant pressure.
При сжатии реакционно-способного газа на стадии обработки до давления выше 0,2 мПа указанные трудности не возникают. Повышенное давление реакционно-способного газа внутри полого тела обеспечивает быстрое и качественное образование модифицированных поверхностных слоев. Содержащегося в реакционно-способном газе количества реакционно-способного компонента достаточно для образования поверхностных слоев из соединений требуемой толщины, соответственно, повышения твердости поверхностных слоев детали на нужную глубину. Хотя внутри полостей и происходит обеднение газа по реакционно-способным компонентам, однако, не до такой степени, когда, например, нарушаются условия для роста слоев соединений. When compressing the reactive gas at the processing stage to a pressure above 0.2 MPa, these difficulties do not arise. The increased pressure of the reactive gas inside the hollow body provides rapid and high-quality formation of modified surface layers. The amount of reactive component contained in the reactive gas is sufficient to form surface layers from compounds of the required thickness, respectively, to increase the hardness of the surface layers of the part to the desired depth. Although depletion of gas by reactive components occurs inside the cavities, however, it is not to the extent that, for example, the conditions for the growth of layers of compounds are violated.
Концентрация реакционно-способного газа и внутри, и снаружи настолько высока, что при связывании, например, N, С или В, с обрабатываемым материалом, концентрация этих компонентов снижается меньше, чем в тех случаях, когда обработку проводят при нормальном или пониженном давлениях. Чем больше рабочее давление, при котором проводят обработку, превышает 0,2 мПа, тем меньше процентное изменение состава реакционно-способного газа за счет его диффузии в обрабатываемые детали или взаимодействия с их материалом. The concentration of the reactive gas both inside and outside is so high that when binding, for example, N, C or B, with the processed material, the concentration of these components decreases less than when the treatment is carried out at normal or reduced pressure. The greater the working pressure at which the treatment is carried out, exceeds 0.2 MPa, the smaller the percentage change in the composition of the reactive gas due to its diffusion into the workpiece or interaction with their material.
Различие между качеством обработки внутренних и наружных поверхностей становится очень незначительным. В результате становятся излишними дополнительное введение или циркуляция газа во внутреннем пространстве обрабатываемых деталей. The difference between the quality of processing of internal and external surfaces becomes very small. As a result, additional introduction or circulation of gas in the interior of the workpieces becomes unnecessary.
В качестве реакционно-способных газов можно использовать, например, аммиак, углеводород, например, метан, или выделяющие бор газы, например трифторид бора. Рабочее давление находится в пределах 0,2-10 мПа, причем верхний предел зависит от конструкции, используемой для обработки печи. As reactive gases, for example, ammonia, a hydrocarbon, for example methane, or boron-releasing gases, for example boron trifluoride, can be used. The operating pressure is in the range of 0.2-10 MPa, with the upper limit depending on the design used to process the furnace.
Способ иллюстрируется чертежом. The method is illustrated in the drawing.
П р и м е р. Форсунки конструкции, изображенной на чертеже, выполненные из стали 16М с 5, подвергают азотированию в газовой смеси, состоящей из 50 об. аммиака и 50 об. азота, при давлении 0,5 МПа течение 2 ч при 500оС. Обработку проводят в печи, которая может работать под давлением. Форсунки при этом загружают в рабочее пространство печи беспорядочно, внасыпную. После окончания обработки определяют толщину азотированного слоя на наружной поверхности форсунки и на внутренней поверхности отверстия/точки, в которых проводятся измерения, указаны на чертеже.PRI me R. The nozzles of the design shown in the drawing, made of steel 16M with 5, are nitrided in a gas mixture consisting of 50 vol. ammonia and 50 vol. nitrogen, at a pressure of 0.5 MPa for 2 hours at 500 C. The treatment is carried out in a furnace which can operate under pressure. At the same time, nozzles are loaded into the working space of the furnace randomly, in bulk. After processing, determine the thickness of the nitrided layer on the outer surface of the nozzle and on the inner surface of the holes / points at which measurements are taken are indicated on the drawing.
При этом были получены следующие результаты:
наружная поверхность: поз.а, толщина слоя 40 мкм
внутренняя поверхность: поз.b, толщина слоя 35 мкм
внутренняя поверхность: поз.с, толщина слоя 31 мкм
отверстие форсунки: поз. d, толщина слоя 30 мкм.The following results were obtained:
outer surface: pos.a, layer thickness 40 microns
inner surface: pos.b, layer thickness 35 μm
inner surface: pos., layer thickness 31 μm
nozzle hole: pos. d, a layer thickness of 30 μm.
Диаметр отверстия 0,2 мм. The diameter of the hole is 0.2 mm.
Процесс азотирования прошел и на внутренних поверхностях выходных отверстий форсунок на ее острие диаметром 0,2 и длиной 1,5 мм. Толщина азотированного слоя при этом была такая же, как и во всех точках внутренней поверхности отверстий. The nitriding process also took place on the inner surfaces of the nozzle outlet openings at its tip with a diameter of 0.2 and a length of 1.5 mm. The thickness of the nitrided layer was the same as at all points of the inner surface of the holes.
Таким же образом можно осуществлять и науглероживание, используя в качестве реакционно-способного газа метан. Процесс при этом проводят при давлении 0,8 мПа и температуре 940оС. В этом случае, как и при азотировании, науглероживание внутренних и наружных поверхностей протекает на одинаковую глубину.In the same way, carburization can be carried out using methane as a reactive gas. The process thus carried out at a pressure of 0.8 MPa and a temperature of about 940 C. In this case, as in the nitriding, carburizing the inner and outer surfaces proceeds at the same depth.
Высокая концентрация реакционно-способных компонентов в рабочем газе позволяет плотно размещать обрабатываемые детали в рабочем пространстве печи. В случае известных способов для равномерной обработки отдельные детали приходилось размещать на определенном расстоянии друг от друга, которое определялось эмпирически. При рабочем давлении выше 0,2 мПа это расстояние уменьшается, не сказываясь отрицательно на равномерности обработки. The high concentration of reactive components in the working gas allows you to tightly place the workpiece in the working space of the furnace. In the case of known methods for uniform processing of individual parts had to be placed at a certain distance from each other, which was determined empirically. At a working pressure above 0.2 MPa, this distance decreases, without affecting the uniformity of processing.
При нитронауглероживании в качестве реакционно-способного газа используют смесь аммиака и азота с добавками диоксида или моноксида углерода и при желании воздуха, причем содержание этих добавок может варьироваться в пределах от нескольких до 50 об. When nitrocarburizing, a mixture of ammonia and nitrogen with addition of carbon dioxide or carbon monoxide and, if desired, air is used as a reactive gas, the content of these additives can vary from a few to 50 vol.
Для науглероживания можно использовать любые известные применяющиеся для этой цели газы, такие, как метан, эндогазы, смеси азота и метанола или природного газа и воздуха. For carburization, any known gases used for this purpose can be used, such as methane, endogases, mixtures of nitrogen and methanol or natural gas and air.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4115135.6 | 1991-05-08 | ||
| DE4115135A DE4115135C1 (en) | 1991-05-08 | 1991-05-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| RU2052535C1 true RU2052535C1 (en) | 1996-01-20 |
Family
ID=6431301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SU925011449A RU2052535C1 (en) | 1991-05-08 | 1992-05-07 | Method for thermochemical treatment of hollow steel products |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0512254B2 (en) |
| JP (1) | JP3258071B2 (en) |
| AT (1) | ATE139579T1 (en) |
| CZ (1) | CZ288263B6 (en) |
| DE (2) | DE4115135C1 (en) |
| ES (1) | ES2088515T5 (en) |
| HU (1) | HU209457B (en) |
| PL (1) | PL291528A1 (en) |
| RU (1) | RU2052535C1 (en) |
| TW (1) | TW223128B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2651841C2 (en) * | 2015-12-23 | 2018-04-24 | Олег Владимирович Ольшанский | Method for processing metal parts under conditions of acoustic resonant action of flow of compressible air and gaseous chemical reagents and device for implementation thereof |
| RU2687385C2 (en) * | 2013-04-17 | 2019-05-13 | Альд Вакуум Текнолоджиз Гмбх | Method and device for thermo-chemical hardening of parts |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4445154A1 (en) * | 1994-12-17 | 1996-06-20 | Fischer Artur Werke Gmbh | Process for producing an expansion anchor made of corrosion-resistant steel |
| DE10062862C2 (en) * | 2000-12-16 | 2003-03-27 | Ald Vacuum Techn Ag | Device for the uniform thermochemical treatment of metallic workpieces with a reactive gas |
| DE10109565B4 (en) | 2001-02-28 | 2005-10-20 | Vacuheat Gmbh | Method and device for partial thermochemical vacuum treatment of metallic workpieces |
| DE10139620A1 (en) * | 2001-08-11 | 2003-02-27 | Bosch Gmbh Robert | Fuel injection valve for internal combustion engines and a method for hardening the same |
| DE102004058838B4 (en) * | 2004-12-06 | 2007-11-29 | Schramm, Armin | Nozzle insert made of steel |
| DE102005061781A1 (en) * | 2005-12-23 | 2007-06-28 | Schaeffler Kg | Injector for automotive fuel injection system has laser-cut micro detents in contact zone sidewall around piston |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB114446A (en) * | 1917-01-27 | 1918-03-27 | British Carbonizing Company Lt | Improvements in or relating to the Carburization and Case-hardening of Iron and Steel Articles. |
| GB749992A (en) * | 1951-09-21 | 1956-06-06 | United States Steel Corp | Methods for nitriding metallic surfaces |
| US2779697A (en) * | 1955-09-26 | 1957-01-29 | United States Steel Corp | Method of nitriding metallic surfaces |
| GB1309257A (en) * | 1970-02-18 | 1973-03-07 | Millingford Eng Co Ltd | Method of nitriding hollow bodies |
| JPS52145343A (en) * | 1976-05-29 | 1977-12-03 | Kiyoichi Ogawa | Pressurized nitriding |
| US4160680A (en) * | 1976-11-05 | 1979-07-10 | Sola Basic Industries, Inc. | Vacuum carburizing |
| DE2851983B2 (en) * | 1978-12-01 | 1980-11-06 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for carburizing hollow bodies, in particular nozzles |
| DE4036381C1 (en) * | 1990-11-15 | 1991-08-14 | Degussa Ag, 6000 Frankfurt, De |
-
1991
- 1991-05-08 DE DE4115135A patent/DE4115135C1/de not_active Expired - Lifetime
- 1991-08-26 PL PL29152891A patent/PL291528A1/en unknown
- 1991-08-28 TW TW080106842A patent/TW223128B/zh active
- 1991-12-09 HU HU913870A patent/HU209457B/en not_active IP Right Cessation
-
1992
- 1992-04-03 ES ES92105758T patent/ES2088515T5/en not_active Expired - Lifetime
- 1992-04-03 EP EP92105758A patent/EP0512254B2/en not_active Expired - Lifetime
- 1992-04-03 DE DE59206595T patent/DE59206595D1/en not_active Expired - Lifetime
- 1992-04-03 AT AT92105758T patent/ATE139579T1/en active
- 1992-05-06 JP JP11353092A patent/JP3258071B2/en not_active Expired - Fee Related
- 1992-05-06 CZ CS19921375A patent/CZ288263B6/en not_active IP Right Cessation
- 1992-05-07 RU SU925011449A patent/RU2052535C1/en active
Non-Patent Citations (1)
| Title |
|---|
| Патент США N 2779697, кл. C 23C 11/16, 1957. * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2687385C2 (en) * | 2013-04-17 | 2019-05-13 | Альд Вакуум Текнолоджиз Гмбх | Method and device for thermo-chemical hardening of parts |
| RU2651841C2 (en) * | 2015-12-23 | 2018-04-24 | Олег Владимирович Ольшанский | Method for processing metal parts under conditions of acoustic resonant action of flow of compressible air and gaseous chemical reagents and device for implementation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| PL291528A1 (en) | 1992-11-16 |
| CZ288263B6 (en) | 2001-05-16 |
| DE4115135C1 (en) | 1992-02-27 |
| HUT61056A (en) | 1992-11-30 |
| EP0512254A3 (en) | 1993-03-24 |
| JP3258071B2 (en) | 2002-02-18 |
| HU209457B (en) | 1994-06-28 |
| EP0512254B1 (en) | 1996-06-19 |
| EP0512254B2 (en) | 2000-01-19 |
| CS137592A3 (en) | 1992-12-16 |
| ATE139579T1 (en) | 1996-07-15 |
| ES2088515T5 (en) | 2000-05-01 |
| DE59206595D1 (en) | 1996-07-25 |
| JPH05132753A (en) | 1993-05-28 |
| ES2088515T3 (en) | 1996-08-16 |
| EP0512254A2 (en) | 1992-11-11 |
| HU913870D0 (en) | 1992-02-28 |
| TW223128B (en) | 1994-05-01 |
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