CA2244248C - Process for producing wear-resistant boride layers on metallic material surfaces - Google Patents
Process for producing wear-resistant boride layers on metallic material surfaces Download PDFInfo
- Publication number
- CA2244248C CA2244248C CA002244248A CA2244248A CA2244248C CA 2244248 C CA2244248 C CA 2244248C CA 002244248 A CA002244248 A CA 002244248A CA 2244248 A CA2244248 A CA 2244248A CA 2244248 C CA2244248 C CA 2244248C
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- boron
- reaction gas
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- material surfaces
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Classifications
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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
- C23C16/28—Deposition of only one other non-metal element
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Catalysts (AREA)
- Coating By Spraying Or Casting (AREA)
- Carbon And Carbon Compounds (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
A process is provided for producing wear-resistant boride layers on metal material surfaces. The process is characterized in that a boron halide selected from the group comprising boron trifluoride, boron tribromide, boron triiodide and their mixtures is mixed with hydrogen and optionally argon and/or nitrogen, in order to produce a reaction gas containing between 0.1 and 30 vol% boron halide. The resultant mixture is activated by a plasma discharge whereby boron is transferred from the plasma to the metal surface.
Description
PROCESS FOR PRODUCING WEAR-RESISTANT BORIDE LAYERS
ON METALLIC MATERIAL SURFACES
BACKGROUND OF THE INVENTION
1) Field of the Invention The invention relates to a process for producing wear-resistant boride layers on metallic material surfaces.
Wear-resistant boride layers are usually produced in practice using solid boriding agents, for example in the form of powders, pastes or granules.
A disadvantage of these processes is that they are labor-intensive in terms of packing, unpacking and cleaning the parts. Cleaning is carried out using a combination of washing and brushing or abrasive-blasting. Since the powders, pastes and granules can be used only once, problems also arise in disposing of the spent boriding agents.
In addition, the use of liquid boriding agents, for example in the form of salt melts, is also known. However, all these processes have not been able to become established owing to the problems generally associated with salt baths, viz. those relating to safety of handling, cleaning of the parts after treatment and disposal of the baths or their waste products.
In the past, there have been various attempts at boriding using gaseous boriding agents (CVD processes).
When using organic boron compounds (trimethylboron, trialkylborons), carburization occurred predominantly instead of boriding; when diborane is used, safety problems occur because of the extreme toxicity and the risk of explosion.
The use of boron trichloride as a boron donor medium has not been able to become established because of process-inherent problems in layer formation. The cause of these problems is the hydrogen chloride formation which always occurs in boriding using BC13/HZ mixtures.
In the boriding of ferrous materials using boron trichloride, the following fundamental reactions occur:
2BC13 + 3H2 + 2Fe ---> 2FeB + 6HC1 2BC13 + 3H2 + 4Fe ---> 2Fe2B + 6HC1 The hydrogen chloride gas formed in boriding using BC13 reacts with the iron of the base material to form volatile iron chlorides:
2HC1 + Fe ---> FeClz The iron chlorides have high vapor pressures at the treatment temperatures in the range 500°C-1200°C which are employed, resulting in substantial, ongoing evaporation of iron chloride. This leads to hole formation between boride layer and substrate, as is always criticized in the case of the BC13 process . Suppression of the hole formation is only possible if one succeeds in generating an impermeable boride layer within a very short time at the beginning of boriding. This is technically difficult in that to the present time it cannot be achieved reliably and reproducibly.
Apart from the purely thermal variant of CVD boriding, work on plasma-aided boriding (PACVD boriding) is also known. Hitherto, only diborane and boron trichloride have been used in this process variant, accompanied by the disadvantages which are already known from thermal CVD. An overview of the processes mentioned may be found in the review "Engineering the Surface with Boron Based Materials", Surface Engineering 1985, Vol.l, No. 3, pp.
203-217.
It is therefore an object of the invention to provide a process for producing wear-resistant boride layers on metallic materials, which process does not suffer from the abovementioned disadvantages.
ON METALLIC MATERIAL SURFACES
BACKGROUND OF THE INVENTION
1) Field of the Invention The invention relates to a process for producing wear-resistant boride layers on metallic material surfaces.
Wear-resistant boride layers are usually produced in practice using solid boriding agents, for example in the form of powders, pastes or granules.
A disadvantage of these processes is that they are labor-intensive in terms of packing, unpacking and cleaning the parts. Cleaning is carried out using a combination of washing and brushing or abrasive-blasting. Since the powders, pastes and granules can be used only once, problems also arise in disposing of the spent boriding agents.
In addition, the use of liquid boriding agents, for example in the form of salt melts, is also known. However, all these processes have not been able to become established owing to the problems generally associated with salt baths, viz. those relating to safety of handling, cleaning of the parts after treatment and disposal of the baths or their waste products.
In the past, there have been various attempts at boriding using gaseous boriding agents (CVD processes).
When using organic boron compounds (trimethylboron, trialkylborons), carburization occurred predominantly instead of boriding; when diborane is used, safety problems occur because of the extreme toxicity and the risk of explosion.
The use of boron trichloride as a boron donor medium has not been able to become established because of process-inherent problems in layer formation. The cause of these problems is the hydrogen chloride formation which always occurs in boriding using BC13/HZ mixtures.
In the boriding of ferrous materials using boron trichloride, the following fundamental reactions occur:
2BC13 + 3H2 + 2Fe ---> 2FeB + 6HC1 2BC13 + 3H2 + 4Fe ---> 2Fe2B + 6HC1 The hydrogen chloride gas formed in boriding using BC13 reacts with the iron of the base material to form volatile iron chlorides:
2HC1 + Fe ---> FeClz The iron chlorides have high vapor pressures at the treatment temperatures in the range 500°C-1200°C which are employed, resulting in substantial, ongoing evaporation of iron chloride. This leads to hole formation between boride layer and substrate, as is always criticized in the case of the BC13 process . Suppression of the hole formation is only possible if one succeeds in generating an impermeable boride layer within a very short time at the beginning of boriding. This is technically difficult in that to the present time it cannot be achieved reliably and reproducibly.
Apart from the purely thermal variant of CVD boriding, work on plasma-aided boriding (PACVD boriding) is also known. Hitherto, only diborane and boron trichloride have been used in this process variant, accompanied by the disadvantages which are already known from thermal CVD. An overview of the processes mentioned may be found in the review "Engineering the Surface with Boron Based Materials", Surface Engineering 1985, Vol.l, No. 3, pp.
203-217.
It is therefore an object of the invention to provide a process for producing wear-resistant boride layers on metallic materials, which process does not suffer from the abovementioned disadvantages.
Summary of the Invention According to the invention, this object is achieved by a process which comprises mixing at least one boron halide selected from the group consisting of boron trifluoride, boron tribromide and boron triiodide as boron source with hydrogen and possibly argon and/or nitrogen to generate a reaction gas containing from 1 to 35% by volume of boron halide and activating the resulting mixture by means of a plasma discharge so as to enable boron to be transferred from the plasma to the metal surface.
Description of the Preferred Embodiments The reaction gas can further comprise boron trichloride as boron source.
The reaction gas preferably contains from 5 to 20o by volume of boron halide, particularly preferably from 5 to 15o by volume of boron halide.
The reaction gas preferably contains from 20 to 90 o by volume of Hz, particularly preferably from 20 to 50o by volume of H2.
The reaction aas nreferahlv cnmr~ri sac hnrr-,n trifluoride.
Boron trifluoride is particularly preferably used as the boron halide.
The reaction gas is fed to the treatment space in an amount of preferably from 0.5 to 2 1 per minute, particularly preferably about 1 1/min.
Boriding is preferably carried out in the pressure range of 1-10 mbar under the action of a plasma discharge as is known, for example, from plasma coating units. The plasma discharge can be pulsed or unpulsed.
The required treatment temperatures of preferably from 400°C to 1200°C, particularly preferably from 850 to 950°C, are generated by the plasma itself or, especially in the high-temperature range above 900°C, with the aid of additional heating.
-3a-The treatment time is preferably from 30 to 240 min, particularly preferably from 30 to 120 min.
The thickness of the boride layers is usually controlled via the treatment time, with the thicknesses 07-24-1998 15:31 212 5~? 4285 CA~02244248 1998-07-27 _ P.06 4 ~ . . ._ of the layers increasing with increasing treatment t ime .
As further gases, the reaction gas can additionally compxise argon and/or nitrogen: They enable the activity of boron transfer to be controlled and sufficient heating of the specimens by the plasma to be achieved. The composition of the reaction gas can thus vary within wide limits depending on the treatment conditions and the material to be borided.
The process of the invention is particularly suitable for boriding ferrous materials.
In the process of the invention,' molecular hydrogen present in the reaction gas is converted into atomic hydrogen by means of a plasma discharge. The atomic hydrogen reduces the boron halide (BY3) and thus enables boron to be transferred to the workpiece surface, F
BY3 + 3 H --__> B + 3 FiY
H + x ME --_--y MexH
However, conversion of BY3 into BYZ by the plasma can also. occur, in which case the following reactions can then proceed:
H
3 BYa __-> B + 2 BY3 B -F- x ME ----> MexB
Subsequent to boriding, the borided material can be subjected to an aftertreatment to convert any FeB formed into Fe2B. This can be achieved, for example, by a heat-treatment process subsequent to the boriding treatment by. stopping the supply of boron halide and holding the workpiece at the treatment temperature for"'-~a further time. The duration of this diffusion treatment depends on the amount of FeB
present and is ~isual~y 20-60 min.
~5_ The process can be carried out, for example, in a unit which is suitable for plasma coating and is ~7-24-1998 15:31 212 5~? 4285 CA 02244248 1998-07-27 P.07 known per se, This consists essent~.ally of the following components:
The vacuum vessel (reactor) for accommodating the parts to be treated. The reactor should be heatable and allow operation in the temperature range from 400°C
to 1200°C.
The pumping system for evacuating the reactor and setting the working pressure.
The gas s~.zpply unit for mixing and metering in the zeaction mixture, The pulsed pl8sma power supply for generating and, maintaining the plasma discharge in the vacuum vessel, such that the power introduced can be varied within a wide range by means of the pulse frequency or pulse width.
The system for neutralizing and disposing of the gas and the system for controlling and monitoring the operating parameters,: the latter system controls and monitors the course of the process.
Example 1 After ir_troducing a 100Cr6 steel specimen into the reactor, it .s heated in the plasma of a DC glow discharge having:a constant pulse frequency (4kHz) at a pressure of 10 mbar. The specimen is additionally heated by means cf the heating of the reactor, thereby shortening the heating time. The heating and cooling of r the specimen is. carried out in a 1:1 mixture of argon and hydrogen. After the treatment temperature of 850°C
. is reached, the boron source boron trifluoride is added at such a rate that a reaction gas mixture composed of 45~ by volume of hydrogen, 40~ by volume of argon and 15~ by volume of boron trifluoride is formed. The gas mixture is fed to the vessel in an amount of 1. 1/min.
The duration of the plasma treatment is 200 min.
A metallogxaphic section shows a boride layer having a mean thickness of 42 um. Tha microhardness is 1800 HVo.os- The Payer is free of FeH.
Example 2 After introducing a 'Hastelloy B specimen into the reactor, it is heaved in the plasma of a DC glow discharge having a constant pulse frequency (4kHz). The specimen is heated tc a temperature of 850°C by means of the plasma discharge at 10 mb<:~r. The power density is controlled via the pulse width. The specimen is heated exclusively by means of the glow discharge. The heating and cooling of the specimen is carx-ied out in a 1:1 mixture of argon and hydrogen. After tlne treatment temperature is reached, the boron source boron t:rifluoride is added in such an amount that reaction mi:~ture composed of 45% by volume of hydrogen, 45o by volume of argon and loo by volume of boron trifluoride is formed. The gas mixture is fed to the vessel in an amount of 1 1/min. The treatment time is 240 mm .
A metallographic section shows a boride layer having a mean thickness of 50 ,um.
The micro hardness is 2400 Hvo 05-* Trade Mark
Description of the Preferred Embodiments The reaction gas can further comprise boron trichloride as boron source.
The reaction gas preferably contains from 5 to 20o by volume of boron halide, particularly preferably from 5 to 15o by volume of boron halide.
The reaction gas preferably contains from 20 to 90 o by volume of Hz, particularly preferably from 20 to 50o by volume of H2.
The reaction aas nreferahlv cnmr~ri sac hnrr-,n trifluoride.
Boron trifluoride is particularly preferably used as the boron halide.
The reaction gas is fed to the treatment space in an amount of preferably from 0.5 to 2 1 per minute, particularly preferably about 1 1/min.
Boriding is preferably carried out in the pressure range of 1-10 mbar under the action of a plasma discharge as is known, for example, from plasma coating units. The plasma discharge can be pulsed or unpulsed.
The required treatment temperatures of preferably from 400°C to 1200°C, particularly preferably from 850 to 950°C, are generated by the plasma itself or, especially in the high-temperature range above 900°C, with the aid of additional heating.
-3a-The treatment time is preferably from 30 to 240 min, particularly preferably from 30 to 120 min.
The thickness of the boride layers is usually controlled via the treatment time, with the thicknesses 07-24-1998 15:31 212 5~? 4285 CA~02244248 1998-07-27 _ P.06 4 ~ . . ._ of the layers increasing with increasing treatment t ime .
As further gases, the reaction gas can additionally compxise argon and/or nitrogen: They enable the activity of boron transfer to be controlled and sufficient heating of the specimens by the plasma to be achieved. The composition of the reaction gas can thus vary within wide limits depending on the treatment conditions and the material to be borided.
The process of the invention is particularly suitable for boriding ferrous materials.
In the process of the invention,' molecular hydrogen present in the reaction gas is converted into atomic hydrogen by means of a plasma discharge. The atomic hydrogen reduces the boron halide (BY3) and thus enables boron to be transferred to the workpiece surface, F
BY3 + 3 H --__> B + 3 FiY
H + x ME --_--y MexH
However, conversion of BY3 into BYZ by the plasma can also. occur, in which case the following reactions can then proceed:
H
3 BYa __-> B + 2 BY3 B -F- x ME ----> MexB
Subsequent to boriding, the borided material can be subjected to an aftertreatment to convert any FeB formed into Fe2B. This can be achieved, for example, by a heat-treatment process subsequent to the boriding treatment by. stopping the supply of boron halide and holding the workpiece at the treatment temperature for"'-~a further time. The duration of this diffusion treatment depends on the amount of FeB
present and is ~isual~y 20-60 min.
~5_ The process can be carried out, for example, in a unit which is suitable for plasma coating and is ~7-24-1998 15:31 212 5~? 4285 CA 02244248 1998-07-27 P.07 known per se, This consists essent~.ally of the following components:
The vacuum vessel (reactor) for accommodating the parts to be treated. The reactor should be heatable and allow operation in the temperature range from 400°C
to 1200°C.
The pumping system for evacuating the reactor and setting the working pressure.
The gas s~.zpply unit for mixing and metering in the zeaction mixture, The pulsed pl8sma power supply for generating and, maintaining the plasma discharge in the vacuum vessel, such that the power introduced can be varied within a wide range by means of the pulse frequency or pulse width.
The system for neutralizing and disposing of the gas and the system for controlling and monitoring the operating parameters,: the latter system controls and monitors the course of the process.
Example 1 After ir_troducing a 100Cr6 steel specimen into the reactor, it .s heated in the plasma of a DC glow discharge having:a constant pulse frequency (4kHz) at a pressure of 10 mbar. The specimen is additionally heated by means cf the heating of the reactor, thereby shortening the heating time. The heating and cooling of r the specimen is. carried out in a 1:1 mixture of argon and hydrogen. After the treatment temperature of 850°C
. is reached, the boron source boron trifluoride is added at such a rate that a reaction gas mixture composed of 45~ by volume of hydrogen, 40~ by volume of argon and 15~ by volume of boron trifluoride is formed. The gas mixture is fed to the vessel in an amount of 1. 1/min.
The duration of the plasma treatment is 200 min.
A metallogxaphic section shows a boride layer having a mean thickness of 42 um. Tha microhardness is 1800 HVo.os- The Payer is free of FeH.
Example 2 After introducing a 'Hastelloy B specimen into the reactor, it is heaved in the plasma of a DC glow discharge having a constant pulse frequency (4kHz). The specimen is heated tc a temperature of 850°C by means of the plasma discharge at 10 mb<:~r. The power density is controlled via the pulse width. The specimen is heated exclusively by means of the glow discharge. The heating and cooling of the specimen is carx-ied out in a 1:1 mixture of argon and hydrogen. After tlne treatment temperature is reached, the boron source boron t:rifluoride is added in such an amount that reaction mi:~ture composed of 45% by volume of hydrogen, 45o by volume of argon and loo by volume of boron trifluoride is formed. The gas mixture is fed to the vessel in an amount of 1 1/min. The treatment time is 240 mm .
A metallographic section shows a boride layer having a mean thickness of 50 ,um.
The micro hardness is 2400 Hvo 05-* Trade Mark
Claims (6)
1. A process for producing wear-resistant boride layers on metallic material surfaces, which comprises mixing at least one boron halide selected from the group consisting of boron trifluoride, boron tribromide and boron triiodide is boron source with hydrogen and argon and/or nitrogen to generate a reaction gas containing from 1 to 35% by volume of boron halide and activating the resulting mixture by means of a plasma discharge so as to enable boron to be transferred from the plasma to the metal surface.
2. The process as claimed in claim 1, wherein the boron source used is boron trifluoride.
3. The process as claimed in claim 1 or 2, wherein. the reaction gas contains 20-90% by volume of H2.
4. The process as claimed in one or more of claims 1 to 3, wherein the reaction gas is fed into the treatment space in an amount of from 0.5 to 2 1 per minute.
5. The process as claimed in one or more of claims 1 to 4 carried out at temperatures of from 400°C to 1200°C.
6. The process as claimed in one or more of claims 1 to 5, wherein the treatment time is from 30 to 240 minutes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19602639.3 | 1996-01-25 | ||
| DE19602639A DE19602639A1 (en) | 1996-01-25 | 1996-01-25 | Process for the production of wear-resistant boride layers on metallic material surfaces |
| PCT/EP1997/000298 WO1997027345A1 (en) | 1996-01-25 | 1997-01-23 | Process for producing wear-resistant boride layers on metal material surfaces |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2244248A1 CA2244248A1 (en) | 1997-07-31 |
| CA2244248C true CA2244248C (en) | 2001-11-20 |
Family
ID=7783662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002244248A Expired - Fee Related CA2244248C (en) | 1996-01-25 | 1997-01-23 | Process for producing wear-resistant boride layers on metallic material surfaces |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0876516B1 (en) |
| JP (1) | JP3222144B2 (en) |
| AT (1) | ATE193334T1 (en) |
| CA (1) | CA2244248C (en) |
| CZ (1) | CZ289443B6 (en) |
| DE (2) | DE19602639A1 (en) |
| HU (1) | HUP9900939A3 (en) |
| PL (1) | PL181781B1 (en) |
| SK (1) | SK282806B6 (en) |
| WO (1) | WO1997027345A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100583262B1 (en) * | 1997-12-15 | 2006-05-25 | 폭스바겐 악티엔 게젤샤프트 | Plasma boronizing |
| DE19842515C1 (en) * | 1998-09-17 | 2000-04-20 | Sabine Boehm | Surface treatment of metallic materials comprises plasma-activated thermo-chemical diffusion of a property-changing material from the plasma of a gaseous treatment atmosphere using a target positioned in an electric field |
| DE19845463A1 (en) * | 1998-10-02 | 2000-04-06 | Stiftung Inst Fuer Werkstoffte | Wear resistant boride layers are produced, e.g. on steel or titanium alloy substrates, by gas boriding using volatile boron compounds containing boron-oxygen and/or boron-nitrogen bonds |
| CZ305985B6 (en) * | 2013-02-15 | 2016-06-08 | Technická univerzita v Liberci | Guide pulleys of hardened steel for wire drawing |
| CZ305986B6 (en) * | 2013-02-15 | 2016-06-08 | Technická univerzita v Liberci | Cladded thread-cutting tools of high-speed cutting steel, especially screw-cutting taps |
| CN110512170A (en) * | 2019-10-12 | 2019-11-29 | 河海大学常州校区 | A kind of titanium alloy boronizing method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3677799A (en) * | 1970-11-10 | 1972-07-18 | Celanese Corp | Vapor phase boron deposition by pulse discharge |
| JPH07286254A (en) * | 1994-04-21 | 1995-10-31 | Sumitomo Metal Ind Ltd | Steel sheet excellent in secondary working brittleness resistance and its production |
-
1996
- 1996-01-25 DE DE19602639A patent/DE19602639A1/en not_active Withdrawn
-
1997
- 1997-01-23 CA CA002244248A patent/CA2244248C/en not_active Expired - Fee Related
- 1997-01-23 AT AT97901592T patent/ATE193334T1/en not_active IP Right Cessation
- 1997-01-23 CZ CZ19982351A patent/CZ289443B6/en not_active IP Right Cessation
- 1997-01-23 PL PL97328200A patent/PL181781B1/en not_active IP Right Cessation
- 1997-01-23 WO PCT/EP1997/000298 patent/WO1997027345A1/en active IP Right Grant
- 1997-01-23 JP JP52653797A patent/JP3222144B2/en not_active Expired - Fee Related
- 1997-01-23 SK SK1012-98A patent/SK282806B6/en not_active IP Right Cessation
- 1997-01-23 DE DE59701754T patent/DE59701754D1/en not_active Expired - Fee Related
- 1997-01-23 EP EP97901592A patent/EP0876516B1/en not_active Expired - Lifetime
- 1997-01-23 HU HU9900939A patent/HUP9900939A3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11507993A (en) | 1999-07-13 |
| CZ289443B6 (en) | 2002-01-16 |
| SK101298A3 (en) | 1998-12-02 |
| SK282806B6 (en) | 2002-12-03 |
| HUP9900939A3 (en) | 2001-01-29 |
| JP3222144B2 (en) | 2001-10-22 |
| DE59701754D1 (en) | 2000-06-29 |
| CZ235198A3 (en) | 1999-08-11 |
| EP0876516A1 (en) | 1998-11-11 |
| DE19602639A1 (en) | 1997-07-31 |
| PL328200A1 (en) | 1999-01-18 |
| CA2244248A1 (en) | 1997-07-31 |
| PL181781B1 (en) | 2001-09-28 |
| HUP9900939A2 (en) | 1999-07-28 |
| EP0876516B1 (en) | 2000-05-24 |
| WO1997027345A1 (en) | 1997-07-31 |
| ATE193334T1 (en) | 2000-06-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |