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EP0218916A1 - Verfahren zum Aufbringen einer Sulfidschicht auf einen metallischen Körper - Google Patents

Verfahren zum Aufbringen einer Sulfidschicht auf einen metallischen Körper Download PDF

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Publication number
EP0218916A1
EP0218916A1 EP86112510A EP86112510A EP0218916A1 EP 0218916 A1 EP0218916 A1 EP 0218916A1 EP 86112510 A EP86112510 A EP 86112510A EP 86112510 A EP86112510 A EP 86112510A EP 0218916 A1 EP0218916 A1 EP 0218916A1
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EP
European Patent Office
Prior art keywords
sulphur
gasified
sulphide
case
cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP86112510A
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English (en)
French (fr)
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EP0218916B1 (de
Inventor
Yifei Zhang
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Individual
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Individual
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Publication of EP0218916A1 publication Critical patent/EP0218916A1/de
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Expired - Lifetime legal-status Critical Current

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    • 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
    • C23C8/36—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 using ionised gases, e.g. ionitriding
    • C23C8/38—Treatment of ferrous surfaces

Definitions

  • the present invention relates to a process and an equipment to form a sulphide case at the surfaces of metal parts, more particularly, relates to such a process and an equipment that are used to form a sulphide case at the surfaces of the metal parts by means of gas sulphuriz­ing.
  • Sulphurizing is one of the surface-treating procedures for metal parts. Since a ferrous sulphide case can be formed by sulphurizing, and ferrous sulphide is a kind of solid lubricant, therefore if there is a sulphide case between two contacting surfaces of friction parts, the friction coefficient may be decreased. Furthermore, a sulphide case may separate the basic metal of two friction parts from direct contact with each other, and thereby the surface of part provides fine resistance to wear and to seizure. Therefore recent years the study on sulphurizing has been further developed and paid a great attention to.
  • the Huanan Polytechnical College has developed a sulphurizing process with a single gas instead of the said nitrosulphurizing in which a sulphide is used as medium and special-purpose sulphurizing furnace is used to hold temperature at 160°C and more, and thereby a case containing ferrous sulphide (FeS) and iron disulphide (FeS2) form at the surface of part (see “Heat Treatment of Metals" Vol.5, 1983).
  • FeS ferrous sulphide
  • FeS2 iron disulphide
  • the sulphurizing atmosphere contains some other components, which has a detrimental influence on the quality of the case, much more some sulphides are poisonous, such as H2S.
  • ferrous sulphide but also iron disulphide formed with the said process in which the former is favourable and the latter is harmful to the resistance to wear. Besides these, the treating temperature used in the said process is rather high.
  • the process is a lightless discharge, namely, the sulphur-contain­ing gas is ionized under a low-voltage field condition (300-500 V).
  • the solid sulphur which is loaded in a steel box is also located on the cathode table along with the parts being treated and thereby it is difficult to control the sulphur-gasifying temperature and the gasifying quantity.
  • the part and the solid sulphur are heated by an inert gas discharge, therefore, the inert gas would be pumped out from the vacuum furnace after the temperature is raised to the desirable level in order to leave the sulphur-containing gas in the furnace and thus the operation is complicated and expensive.
  • the process of the present invention is an improved and developed version of the solid suphur-gasifying and sulphurizing process mentioned above.
  • One of the objects of the present invention is to provide a sulphurizing process by means of direct heating the solid sulphur and gasifying it, which process overcomes the shortcomings mentioned above resulted from the said processes, and to attain a better sulphurizing quality than that resulted from other processes, an even and single constituent existed in the sulphurized case and thick case.
  • the other object of the present invention is to provide an equipment to carry out the process of the present invention.
  • the keypoint of the gas sulphurizing is to produce a sulphur-containing gas.
  • the advantages resulted from the present process in which the sulphur-containing gas is made from the pure solid sulphur, not from sulphide, by direct heating are: the component of the gas is single, not like sulphide containing other components and thus it makes the controlling and the regulating simple; the component (ferrous sulphide) of the sulphurized case at the surface is also single and there is no influence and disturbance resulted from other elements.
  • Sulphur is presented as a solid state under normal atmosphere and the boiling point of which is 441°C.
  • the boiling point would be lowered rapidly at low pressure, for example, the boiling point is 188.8°C at 1 Torr, and the boiling point would be less when the pressure decreases further.
  • the parts located on the cathode table of vacuum furnace will be sulphurized by means of heating and gasifying sulphur at low pressure (I-10 ⁇ 2 Torr), applying a direct voltage field to ionize the gasified sulphure and bombarding the cathode with the high-speed positive sulphur ions, thus the parts located on cathode table is sulphurized.
  • the process of present invention is chacterized by that the sulphur-containing gas is glow discharged under the action of high voltage (450-1500 V) field and the duration of glow discharge ganerally is 1-4 hours. Because of the glow discharging, the sulphuriz­ing is speeded up and the sulphurized case depth is increased. Furthermore, because of the glow discharging, the parts may be heated only by means of electron bombarding. Generally, the temperature of parts is controlled between 140-300°C. Therefore, the temperature of the heated parts may be regulated through regulating the field voltage, but in the case of lightless discharging, the parts are heated only through inert gas.
  • the heating and gasifying of sulphure are flexible, for example, they may be carried out by means of a low voltage supply when sulphur is located on the cathode table just as the case of lightless discharging, or sulphur is located in the furnace other than the cathode table, or even outside the furnace.
  • the gas-sulphurizing operation may be carried out following the carburizing, nitriding or carbonitriding when the furnace temperature is lowered to the sulphurizing levle.
  • the working hours and energy resource consumption may be extremely reduced.
  • Fig. 1 is a schematic diagram of the equipment according to present invention.
  • the part to be treated 5 is loaded on the cathode table 4 in the reacting chamber I of vacuum furnace.
  • the part is a ball bearing made of Gr15.
  • the temperature of part 5 is measured and controlled with a thermocouple 7 and a temperature meter 12.
  • Solid sulphur is loaded in the vapourizer 6 and the temperature of vaporizer is measured and controlled with a thermocouple 8 and a temperature meter 10.
  • the vaporizer 6 is heated with electric energy supplied from the low-voltage supply 11.
  • the vaporizer shown in the figure is located in the reacting chamber 1, outside the cathode table 4, but it may be located on the cathode 4 or outside the reacting chamber 1 (furnace).
  • the steps to sulphurize are as follows: firstly, the vacuum pump 16 is started, in the meantime, the reacting chamber 1 is pumped out; then the low voltage supply 11 is turned on when the pressure reaches about 10 ⁇ 2 Torr, and thus the temperature of vaporizer 6 starts to raise, because the pressure is lowered to 10 ⁇ 2 Torr, solid sulphur will be gasified when the vaporizer 6 is heated to more than 140°C (the gasifying temperature of solid sulphur ranges from 140°C to 200°C in this embodiment); when the gasified sulphur enters the reacting chamber 1, the pressure in the reacting chamber 1 is gradually raising, the temperature of vaporizer 6 is controlled by regulating the current supplied from the low-votage supply 11 and thereby the quantity of gas resulted from sulphur gasifying may be regulated and controlled; further, the pressure in the reacting chamber 1 may also be controlled; of course, the pressure in the reacting chamber 1 may also be controlled through regulating the relation between the vapourizing speed and the pumping speed (i.
  • the vacuum pump still keeps running; when the pressure in the reacting chamber 1 is steadily in the desirable range (about 1 Torr for the present embodiment) through known precedures, the high voltage direct supply 3 (voltage ranges from 0 V to 1500 V) is turned on and the voltage of which is controlled between 450 V and 1500 V, then a high voltage field is formed among the cathode 4, part 5 and anode 2, then, by the action of the field, gaseous sulphur is ionized and the positive sulphur ions will bombard the cathode 4 and part 5 to form glow discharge and thereby to raise the temperature of the part; finally, because of the physical and chemical reactions existing between gaseous sulphur and the part, a case of sulphide is formed at the surface of the part, generally, the duration of glow discharge is controlled between 1 h and 4 hs, the part temperature is controlled between 140°C and 300°C.
  • the temperature-controlling means is conventional.
  • the sulphurized rolling bearing is a 204 single-row radial ball bearing.
  • the bearing is subjected to a life test with a model 7501-type lever tester.
  • the testing conditions are: 2400 r/min, radial load 190 kg, no lubricant agent.
  • the bearing tested ran continually for 200 hrs without fatigue damage.
  • the bearings ball, outer races inner races and cages
  • the case depth of sulphurizing is 120 ⁇ m which is extremely greater than the case depth formed with other processes.
  • Ferrous sulphide would be formed at the surface by means of the process and equipment and the case depth generally is 100-120 ⁇ m, at least 20 ⁇ m.
  • the equipment introduced in the embodiments mentioned above is the main body of the equipment.
  • the equipment In order to make the equipment run normal, the equipment should be equipped with some devices such as vacuum gauge 9 for controlling pressure, flow meter I9 for controlling flow, some valves I3,I4,I8, waste gas filter I7, cold trap I5 for condensating reactant, gas bomb 20 and observing window 2I, which all are known for the skills in the art.
  • the present invention may be applied not only to the parts made of steel or iron for forming ferrous sulphide at the surface but also to the parts made of other metals for forming a sulphide case at the surface, for example, for forming NiS, Nis2, at the surface of parts made of Ni or Ni alloy, for forming MoS2 at the surface of parts made of Mo and Mo alloy, for forming CuS, CuS2 at the surface of parts made of Cu and Cu alloy and for forming CoS at the surface of parts made of Co and Co alloy.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Chemical Vapour Deposition (AREA)
EP86112510A 1985-09-10 1986-09-10 Verfahren zum Aufbringen einer Sulfidschicht auf einen metallischen Körper Expired - Lifetime EP0218916B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN85106828A CN85106828B (zh) 1985-09-10 1985-09-10 金属零件表面形成硫化物层的方法及设备
CN85106828 1985-09-10

Publications (2)

Publication Number Publication Date
EP0218916A1 true EP0218916A1 (de) 1987-04-22
EP0218916B1 EP0218916B1 (de) 1991-12-27

Family

ID=4795305

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86112510A Expired - Lifetime EP0218916B1 (de) 1985-09-10 1986-09-10 Verfahren zum Aufbringen einer Sulfidschicht auf einen metallischen Körper

Country Status (4)

Country Link
EP (1) EP0218916B1 (de)
JP (1) JPS6289858A (de)
CN (1) CN85106828B (de)
DE (1) DE3683119D1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2688010A1 (fr) * 1992-03-02 1993-09-03 Innovatique Sa Procede pour la formation, sur une piece d'acier ou d'alliage d'acier d'une couche superficielle en un compose sulfure presentant des proprietes antifriction.
US6468679B1 (en) 1997-11-07 2002-10-22 Xinhui Zhang Metal-based gradient composite material having good lubrication and wear resistance property, the production and the use of the same

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH671407A5 (de) * 1986-06-13 1989-08-31 Balzers Hochvakuum
CN1296515C (zh) * 2004-05-13 2007-01-24 上海交通大学 自辉光等离子体基离子注入或者注入且沉积装置
WO2009067858A1 (en) 2007-10-31 2009-06-04 China Petroleum & Chemical Corporation A predeactivation method and a deactivation method during initial reaction for a continuous reforming apparatus
CN102505106A (zh) * 2011-12-30 2012-06-20 瓦房店轴承集团有限责任公司 风力发电主轴轴承的表面处理工艺
CN102776472A (zh) * 2012-07-23 2012-11-14 宁波市鸿博机械制造有限公司 提高汽车转向泵定子的耐磨性能的方法
CN103397305B (zh) * 2013-08-06 2015-08-26 深圳先进技术研究院 硒化/硫化处理装置
CN110408885B (zh) * 2019-08-27 2021-06-11 南京工程学院 一种车用轻型齿轮及其制造工艺

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1273518A (fr) * 1960-10-28 1961-10-13 Ass Elect Ind Perfectionnements aux appareils de vaporisation sous vide
GB1133397A (en) * 1966-09-08 1968-11-13 Hughes Aircraft Co Method for the rapid deposition of metallic films using a plasma of the material to be deposited
US3472679A (en) * 1965-08-25 1969-10-14 Xerox Corp Coating surfaces
GB1474358A (en) * 1974-12-03 1977-05-25 Seiko Instr & Electronics Method of plating a substrate with a precious metal
US4039416A (en) * 1975-04-21 1977-08-02 White Gerald W Gasless ion plating
EP0047456A1 (de) * 1980-09-08 1982-03-17 Ayao Wada Ionenplattieren ohne Zuführung eines Gases

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1273518A (fr) * 1960-10-28 1961-10-13 Ass Elect Ind Perfectionnements aux appareils de vaporisation sous vide
US3472679A (en) * 1965-08-25 1969-10-14 Xerox Corp Coating surfaces
GB1133397A (en) * 1966-09-08 1968-11-13 Hughes Aircraft Co Method for the rapid deposition of metallic films using a plasma of the material to be deposited
GB1474358A (en) * 1974-12-03 1977-05-25 Seiko Instr & Electronics Method of plating a substrate with a precious metal
US4039416A (en) * 1975-04-21 1977-08-02 White Gerald W Gasless ion plating
EP0047456A1 (de) * 1980-09-08 1982-03-17 Ayao Wada Ionenplattieren ohne Zuführung eines Gases

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENTS ABSTRACTS OF JAPAN, vol. 1, no. 120, 12th Oktober 1977, page 2834 C 77; & JP-A-52 82 683 (SUWA SEIKOSHA K.K.) 11-07-1977 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2688010A1 (fr) * 1992-03-02 1993-09-03 Innovatique Sa Procede pour la formation, sur une piece d'acier ou d'alliage d'acier d'une couche superficielle en un compose sulfure presentant des proprietes antifriction.
US6468679B1 (en) 1997-11-07 2002-10-22 Xinhui Zhang Metal-based gradient composite material having good lubrication and wear resistance property, the production and the use of the same

Also Published As

Publication number Publication date
CN85106828A (zh) 1987-03-11
CN85106828B (zh) 1987-09-09
EP0218916B1 (de) 1991-12-27
JPS6289858A (ja) 1987-04-24
JPS6357501B2 (de) 1988-11-11
DE3683119D1 (de) 1992-02-06

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