US3851471A - Hot-gas engine and method of manufacturing same - Google Patents

Hot-gas engine and method of manufacturing same Download PDF

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Publication number
US3851471A
US3851471A US00372282A US37228273A US3851471A US 3851471 A US3851471 A US 3851471A US 00372282 A US00372282 A US 00372282A US 37228273 A US37228273 A US 37228273A US 3851471 A US3851471 A US 3851471A
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United States
Prior art keywords
silicon nitride
layer
heater
walls
engine
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Expired - Lifetime
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US00372282A
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English (en)
Inventor
G Asselman
A Castelijns
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US Philips Corp
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US Philips Corp
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Publication date
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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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/345—Silicon nitride
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02G—HOT GAS OR COMBUSTION-PRODUCT POSITIVE-DISPLACEMENT ENGINE PLANTS; USE OF WASTE HEAT OF COMBUSTION ENGINES; NOT OTHERWISE PROVIDED FOR
    • F02G1/00—Hot gas positive-displacement engine plants
    • F02G1/04—Hot gas positive-displacement engine plants of closed-cycle type
    • F02G1/043—Hot gas positive-displacement engine plants of closed-cycle type the engine being operated by expansion and contraction of a mass of working gas which is heated and cooled in one of a plurality of constantly communicating expansible chambers, e.g. Stirling cycle type engines
    • F02G1/053—Component parts or details
    • F02G1/055—Heaters or coolers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2225/00—Synthetic polymers, e.g. plastics; Rubber
    • F05C2225/08—Thermoplastics

Definitions

  • a hot-gas engine containing a working medium which consists mainly hydrogen.
  • the walls of the working spaces of the engine which are at a higher temperature during operation are covered with a silicon nitride layer.
  • the shape of the relevant wall portions is concave, and they are made of a material having a thermal expansion coefficient of the same order or larger than that of the deposited silicon nitride.
  • the silicon nitride layer is deposited by bringing the relevant wall portions in contact at higher temperature with a flowing gas mixture containing silicon in a volatile compound and furthermore containing hydrogen.
  • the invention relates to a hot-gas engine comprising at least one variably volume space of higher mean temperature which communicates with at least one variable volume space of lower mean temperature, each of the connections between said spaces incorporating a heater, a regenerator and a cooler; said spaces and the connections therebetween are filled with a working medium which consists mainly of hydrogen and which can flowto and fro through the regenerator.
  • Hot-gas engines of the kind set forth are known.
  • the working medium completes a cycle such that this medium is compressed under the influence of a piston when it is situated mainly in a space of lower mean temperature.
  • the medium flows, via cooler, regenerator and heater, while taking up heat in the latter two, to a space of higher mean temperature where the working medium expands.
  • Air or helium can be used as the working medium, but particularly the use of hydrogen is very advanta- 'geous because of its low flow losses. Even though this was known, hydrogen was not used thus far because hydrogen very quickly diffuses through the construction materials available for the walls of the engine at higher temperatures. As a result, the engine power is reduced and the escaped hydrogen must be replenished. This implies very frequent engine maintenance, which is not acceptable in practice.
  • SUMMARY OFTHE NEW INVENTION reach a high temperature during operation, are provided on their inner side with a layer of silicon nitride; the relevant wall portions have a concave shape on their inner side and are made of a material having a ment being necessary.
  • the silicon nitride layer is deposited by bringing the relevant wall portions in contact at higher temperature with a flowing gas mixture which contains silicon in a volatile compound and which further contains for example hydrogen.
  • a-further embodiment of the hot-gas engine according to the invention is characterized in that the silicon nitride layer is deposited at a temperature which is higher than 750 C and which does not differ by more than C from the maximum temperature occuring during operation.
  • the deposition of a layer should generally be effected at temperatures of between 750 C and 900 C, an amorphous and properly gastight layer then being obtained. At lower temperatures, the growth rate of the layer is too small, while beyond 900 C the layer becomes increasingly crystalline, which does not benefit the gastightness.
  • the layer thickness usually lies between 0.1 pm and l urn.
  • the invention furthermore relates to a method of manufacturing a hot-gas engine which is provided with a heater which is composed of a number of pipes which are connected by soldering to the generator on the one side and on the otherside to the space of higher mean temperature.
  • the method is characterized in that the pipes are soldered to the regenerator and the space of higher temperature in a soldering oven, after which the assembly is cooled, the pipes being rinsed through with a gas mixture containing silicon in a volatile compound and furthermore containing forexample hydrogenia when a temperature of 900 C is reached, a layer of silicon nitride then being formed on the inner wall of the pipes.
  • Another method of manufacturing a hot-gas engine according to the invention is characterized in that the hot-gas engine is filled, after assembly, with agas mixture which contains silicon in a volatile compound and which furthermore contains for example hydrogen, after which the temperature of the engine is raised to the value required for the deposition of the layer by means of its own heating system, the engine being subsequently started and the gas mixture being guided along the hot portions, a layer of silicon nitride then being deposited on said portions.
  • the reference 1 denotes a cylinder in which a piston -2 and a displacer 3 are arranged to be movable.
  • the heater 9 consists of a ring of pipes, one end of the pipes 1 l of which communicating with the regenerator 8 and their other end communicating with a ring duct 12, the pipes 13 connecting the ring duct 12 to the expansion space 10.
  • a pre-heater 14 Arranged about the heater 9 is a pre-heater 14 in which air and compound gases are heat exchange. This pre-heated air is applied to a burner 15 which receives fuel via a duct 1 it is assumed that the operation of an engine of this kind is known. Hydrogen is present as the working medium in the space inside the engine.
  • the pipes constituting the heater 9 are provided on their inner side with a layer of silicon nitride.
  • This silicon nitride can be deposited on the pipes, for example, by heating the pipes prior to mounting in an isothermal oven to a tempera ture of between 750 C and 900C, and by subsequently feeding a gas mixture, containing silicon in a volatile compound and furthermore containing for example ammonia, through these pipes.
  • Heater pipes which are made of Multimet expansion coefficient 18.1-/C on the average from 20-1000C) and having a inner diameter of 3mm and a length of 700 mm can thus be heated to 840 C in an isothermal oven.
  • a mixture of 5% silane (SiH.,) in argon ammonia (NH and hydrogen ratio in volume parts of equal pressure and temperature 0.05 1) 1 :50 is fed at a rate of 2.6 litres per minute. in minutes a homogeneous layer having a thickness of 0.12 pm was thus obtained.
  • the hydrogen diffusion coefficient of this pipe amounted to 0.15 cm mmldm hour, atm., at 750 C and 30 atm.
  • Another possibility of depositing the silicon nitride layer is to introduce a gas mixture of the described kind as the working medium, after which the temperature of the heater is raised to the value desired for deposition of the layer, by means of the burner, and the engine is started.
  • the gas mixture will then flow to and fro, during which a layer of silicon nitride will be deposited on the hot portions.
  • the thickness of the deposited layer lies in the order of some tenths of micrometres. Deposition takes place at temperatures of between 750C and 900C because beyond this value the layer becomes increasingly crystalline with the result that the hydrogen diffusion starts to increase again.
  • the layer formed is amorphous and has a thermal expansion coefficient in the order of 4 X 10/C between 0 C and 1,000 C; in combination with the concave shape of the inner surface of the pipes and the expansion coefficient of the material of the pipe which is larger than that of the deposited silicon nitride, a layer is then formed which very effectively prevents hydrogen diffusion also after prolonged operation.
  • Some of the materials which are suitable for the pipes are already said Multimet and lnconel, Hayenes 25 and Hastelloy.
  • the composition and expansion coefficient thereof are:
  • Multimet Co 18.5; Ni 19; Cr 20; Mn 1; Ta 0.75; W
  • Haynes 25 Co 52; Ni 10; Cr 20; Fe 3; W 15; expansion coefficient 16.5 X 10""'( 20900 0 Hastelloy: Co 1.5; Ni remainder; Cr 22; Fe 18.5; Mo
  • the deposited silicon nitride layer enables the use of hydrogen as the working medium in a hot-gas engine, thus offering all relevant advantages without frequent maintenance being necessary.
  • a hot gas engine operable with a working medium and including variable volume compression and expansion chambers operable at respectively higher and lower mean temperatures, said chambers having walls with inner surfaces that define the compression and expansion spaces therein, connection means including a regenerator through which said chambers communicate, and a heater formed of pipes the walls of which have inner surfaces which define heater space which communicates with said expansion space, wherein said expansion chamber walls and heater pipe walls are heated to high temperatures during operation of the engine, the improvement in combination there with comprising a layer of silicon nitride on the inner surfaces of walls of at least one of said heater pipe and expansion chamber elements.
  • said heater pipe material comprises one of the materials selected from the group consisting of Multimet, Inconel, Haynes 25, and Hastelloy.
  • a method according to claim 12 comprising the further steps of forming a layer of said silicon nitride on the inner surfaces of said expansion chamber as such layer is formed on said heater pipe surfaces.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Ceramic Products (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
US00372282A 1972-07-01 1973-06-21 Hot-gas engine and method of manufacturing same Expired - Lifetime US3851471A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL7209298A NL7209298A (enrdf_load_stackoverflow) 1972-07-01 1972-07-01

Publications (1)

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US3851471A true US3851471A (en) 1974-12-03

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US00372282A Expired - Lifetime US3851471A (en) 1972-07-01 1973-06-21 Hot-gas engine and method of manufacturing same

Country Status (11)

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US (1) US3851471A (enrdf_load_stackoverflow)
JP (1) JPS523051B2 (enrdf_load_stackoverflow)
AT (1) AT324777B (enrdf_load_stackoverflow)
AU (1) AU466793B2 (enrdf_load_stackoverflow)
BE (1) BE801750A (enrdf_load_stackoverflow)
BR (1) BR7304792D0 (enrdf_load_stackoverflow)
CA (1) CA1003650A (enrdf_load_stackoverflow)
FR (1) FR2191616A5 (enrdf_load_stackoverflow)
GB (1) GB1426189A (enrdf_load_stackoverflow)
IT (1) IT990833B (enrdf_load_stackoverflow)
NL (1) NL7209298A (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100434685C (zh) * 2003-10-30 2008-11-19 独立行政法人宇宙航空研究开发机构 斯特林发动机

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5743953A (en) * 1980-08-29 1982-03-12 Fujitsu Ltd Ferrosilicon sintered thin plate
JPS5743954A (en) * 1980-08-29 1982-03-12 Fujitsu Ltd Ferrosilicon sintered thin plate
GB8409047D0 (en) * 1984-04-07 1984-05-16 Mixalloy Ltd Production of metal strip

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100434685C (zh) * 2003-10-30 2008-11-19 独立行政法人宇宙航空研究开发机构 斯特林发动机

Also Published As

Publication number Publication date
BE801750A (fr) 1974-01-02
AT324777B (de) 1975-09-25
CA1003650A (en) 1977-01-18
BR7304792D0 (pt) 1974-08-15
DE2328792B2 (de) 1976-06-10
JPS523051B2 (enrdf_load_stackoverflow) 1977-01-26
JPS4943041A (enrdf_load_stackoverflow) 1974-04-23
AU466793B2 (en) 1975-11-06
FR2191616A5 (enrdf_load_stackoverflow) 1974-02-01
DE2328792A1 (de) 1974-01-17
AU5741073A (en) 1975-01-09
NL7209298A (enrdf_load_stackoverflow) 1974-01-03
IT990833B (it) 1975-07-10
GB1426189A (en) 1976-02-25

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