US20080081122A1 - Process for producing a rotary anode and the anode produced by such process - Google Patents
Process for producing a rotary anode and the anode produced by such process Download PDFInfo
- Publication number
- US20080081122A1 US20080081122A1 US11/542,268 US54226806A US2008081122A1 US 20080081122 A1 US20080081122 A1 US 20080081122A1 US 54226806 A US54226806 A US 54226806A US 2008081122 A1 US2008081122 A1 US 2008081122A1
- Authority
- US
- United States
- Prior art keywords
- tungsten
- hydrogen
- support member
- anode
- rotary anode
- 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.)
- Abandoned
Links
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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J35/00—X-ray tubes
- H01J35/02—Details
- H01J35/04—Electrodes ; Mutual position thereof; Constructional adaptations therefor
- H01J35/08—Anodes; Anti cathodes
- H01J35/10—Rotary anodes; Arrangements for rotating anodes; Cooling rotary anodes
- H01J35/108—Substrates for and bonding of emissive target, e.g. composite structures
Definitions
- Tungsten is used as a characteristic x-ray radiation generating material, for x-ray anode assemblies in CT scanners. Due to tungsten's high density and high atomic number, it is possible to produce gamma radiation with narrow frequency range. This explains why tungsten is the primary material of choice for x-ray generation. However, due to tungsten's density, and the stresses experienced during high rotational speed, tungsten is not the choice material of construction for the entire anode. Molybdenum (which has a high enthalpy, high melting point, lower density, and is easier to machine) is used as the base material for construction. The tungsten is then applied as a thin track along the surface of electron beam incidence to generate the x-radiation.
- Rhenium is less brittle than tungsten, and is the next element in the periodic system after tungsten, which explains its widespread use as an alloying element for tungsten.
- the first method is via powder metallurgy, where the tungsten-rhenium powder is tape cast, slip cast, roll compacted, thermally sprayed, or waterfall processed into a track which is pressed, sintered and forged along with the molybdenum substrate (see U.S. Pat. No. 6,428,904).
- the '904 patent indicates that the process described therein improves the evenness of the surface and the interface between the track and the x-ray target substrate.
- a second method describes the use of chemical vapor deposition (CVD) to apply the tungsten and molybdenum in a non-oxidizing atmosphere (see U.S. Pat. No. 4,461,020).
- CVD chemical vapor deposition
- the third and most prevalent method is plasma spray coating of the tungsten-rhenium track (see, e.g., U.S. Pat. Nos. 4,090,103, 4,390,368, 4,534,993 and 4,641,333).
- the '993 patent indicates that the plasma spray coating is carried out in a reduced pressure atmosphere of from 20 to 70 kPa.
- the '993 patent also indicates that in order to obtain optimum density, particle sizes of at most 45 ⁇ m be used.
- U.S. Pat. No. 6,132,812 describes a plasma spray technique using inductive vacuum plasma spraying.
- the '812 patent indicates that the process described therein allows for increased residence time, which improves the ability of all particle sizes to melt and be deposited on the substrate in the molten state. It is also indicated that the process results in improved fatigue crack strength, and improved density.
- the present invention is directed to an improved process for manufacturing a rotary anode for an x-ray tube, said rotary anode comprising a molybdenum support member on which a target layer consisting essentially of tungsten or a tungsten-rhenium alloy is provided by plasma spraying, the improvement comprising:
- the invention is also directed to the anode produced by the improved process.
- Hydrogen will serve to remove oxygen from the surfaces of tungsten, rhenium, and molybdenum.
- the oxygen removal will have two effects—first is to “activate” the surface of both the coating and the substrate improving adherence and secondly to remove oxygen prior to deposition resulting in an improved density and purity of the coating.
- the slightly reduced pressure will serve to remove the reactant oxygen bearing species. When referring to “slightly reduced pressure”, the closer the process is too atmospheric the more suppressed is the volatilization of tungsten oxide bearing species.
- the determination of the amount of oxygen present in the tungsten or tungsten-rhenium alloy as tungsten dioxide is readily determined.
- Techniques for measuring the oxygen content of metal powders include, for example, total x-ray fluorescence, secondary ion mass spectroscopy, x-ray photoelectron spectroscopy and Auger spectroscopy. Suitable analyzers are also available form LECO Corporation (TC400, TC500 and RO500C series). Based on the amount of oxygen measured, the actual amount of oxygen present in the form of the oxide present in the form of tungsten dioxide can then readily calculated The devices noted report the oxygen content as a % by weight per one gram sample. The moles of tungsten dioxide can then be calculated according to the following formula:
- OC is the % by weight of oxygen per 1 gram sample
- WGT is the total weight of the powder to be sprayed
- 32 is the molecular weight of oxygen
- the molybdenum support member is preheated to a temperature of from 1150° C. to 1600° C. (preferably from 1300° C. to 1500° C.) and placed in a gaseous atmosphere containing hydrogen and having a pressure of from 0.5 to 0.9 bars (preferably from 0.7 to 0.9 bars) and wherein hydrogen is present in a molar ratio of hydrogen to tungsten dioxide of from 5:1 to 50:1 (preferably in a molar ratio of from 10:1 to 30:1).
- the tungsten or tungsten-rhenium alloy is the plasma sprayed onto the support layer.
- Suitable devices for use in plasma spray coating known in the art and are commercially available. Such devices are included DC, arc and inductively coupled plasma devises. Such devices are commercially available from Progressive Technologies, Inc. (Michigan), Plasma Processes, Inc. (Alabama) and Tekna Plasma Systems Inc. (Canada).
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
-
- a) preheating the support member to a temperature of from 1150° C. to 1600° C.,
- b) placing the support member in a gaseous atmosphere containing hydrogen and having a pressure of from 0.5 to 0.9 bars and wherein hydrogen is present in a molar ratio of hydrogen to tungsten dioxide of from 5:1 to 50:1, and
- c) plasma spraying the target layer onto the support layer in said gaseous atmosphere.
The invention is also directed to the anode produced by the process.
Description
- Tungsten is used as a characteristic x-ray radiation generating material, for x-ray anode assemblies in CT scanners. Due to tungsten's high density and high atomic number, it is possible to produce gamma radiation with narrow frequency range. This explains why tungsten is the primary material of choice for x-ray generation. However, due to tungsten's density, and the stresses experienced during high rotational speed, tungsten is not the choice material of construction for the entire anode. Molybdenum (which has a high enthalpy, high melting point, lower density, and is easier to machine) is used as the base material for construction. The tungsten is then applied as a thin track along the surface of electron beam incidence to generate the x-radiation. Normally up to 10% by weight of rhenium is added to the tungsten to improve its malleability. Rhenium is less brittle than tungsten, and is the next element in the periodic system after tungsten, which explains its widespread use as an alloying element for tungsten.
- There are three conventional methods for the application of the tungsten-rhenium track. The first method is via powder metallurgy, where the tungsten-rhenium powder is tape cast, slip cast, roll compacted, thermally sprayed, or waterfall processed into a track which is pressed, sintered and forged along with the molybdenum substrate (see U.S. Pat. No. 6,428,904). The '904 patent indicates that the process described therein improves the evenness of the surface and the interface between the track and the x-ray target substrate.
- A second method describes the use of chemical vapor deposition (CVD) to apply the tungsten and molybdenum in a non-oxidizing atmosphere (see U.S. Pat. No. 4,461,020). The '020 patent indicates that this technique creates an improved bond and is an easily reproducible method.
- The third and most prevalent method is plasma spray coating of the tungsten-rhenium track (see, e.g., U.S. Pat. Nos. 4,090,103, 4,390,368, 4,534,993 and 4,641,333). The '993 patent indicates that the plasma spray coating is carried out in a reduced pressure atmosphere of from 20 to 70 kPa. The '993 patent also indicates that in order to obtain optimum density, particle sizes of at most 45 μm be used.
- U.S. Pat. No. 6,132,812 describes a plasma spray technique using inductive vacuum plasma spraying. The '812 patent indicates that the process described therein allows for increased residence time, which improves the ability of all particle sizes to melt and be deposited on the substrate in the molten state. It is also indicated that the process results in improved fatigue crack strength, and improved density.
- All of these techniques fail to address causes for porosity, as well as the impact of oxygen on the density and propensity to degas.
- The present invention is directed to an improved process for manufacturing a rotary anode for an x-ray tube, said rotary anode comprising a molybdenum support member on which a target layer consisting essentially of tungsten or a tungsten-rhenium alloy is provided by plasma spraying, the improvement comprising:
-
- a) preheating the support member to a temperature of from 1150° C. to 1600° C.,
- b) placing the support member in a gaseous atmosphere containing hydrogen and having a pressure of from 0.5 to 0.9 bars and wherein hydrogen is present in a molar ratio of hydrogen to tungsten dioxide of from 5:1 to 50:1, and
- c) plasma spraying the target layer onto the support layer in said gaseous atmosphere.
- The invention is also directed to the anode produced by the improved process.
- The general method of manufacturing rotary anodes using a plasma spray coating technique is known in the art and is described in U.S. Pat. Nos. 4,090,103, 4,390,368, 4,534,993 and 4,641,333, the disclosures of which are herein incorporated by reference.
- The use of hydrogen and a slightly reduced pressure will improve the density, adherence, and purity of the tungsten or tungsten-rhenium track. Hydrogen will serve to remove oxygen from the surfaces of tungsten, rhenium, and molybdenum. The oxygen removal will have two effects—first is to “activate” the surface of both the coating and the substrate improving adherence and secondly to remove oxygen prior to deposition resulting in an improved density and purity of the coating. The slightly reduced pressure will serve to remove the reactant oxygen bearing species. When referring to “slightly reduced pressure”, the closer the process is too atmospheric the more suppressed is the volatilization of tungsten oxide bearing species.
- The determination of the amount of oxygen present in the tungsten or tungsten-rhenium alloy as tungsten dioxide is readily determined. Techniques for measuring the oxygen content of metal powders are known and include, for example, total x-ray fluorescence, secondary ion mass spectroscopy, x-ray photoelectron spectroscopy and Auger spectroscopy. Suitable analyzers are also available form LECO Corporation (TC400, TC500 and RO500C series). Based on the amount of oxygen measured, the actual amount of oxygen present in the form of the oxide present in the form of tungsten dioxide can then readily calculated The devices noted report the oxygen content as a % by weight per one gram sample. The moles of tungsten dioxide can then be calculated according to the following formula:
-
Mole of tungsten dioxide=[OC times WGT]÷32 - where OC is the % by weight of oxygen per 1 gram sample, WGT is the total weight of the powder to be sprayed and 32 is the molecular weight of oxygen.
- The molybdenum support member is preheated to a temperature of from 1150° C. to 1600° C. (preferably from 1300° C. to 1500° C.) and placed in a gaseous atmosphere containing hydrogen and having a pressure of from 0.5 to 0.9 bars (preferably from 0.7 to 0.9 bars) and wherein hydrogen is present in a molar ratio of hydrogen to tungsten dioxide of from 5:1 to 50:1 (preferably in a molar ratio of from 10:1 to 30:1). The tungsten or tungsten-rhenium alloy is the plasma sprayed onto the support layer.
- Suitable devices for use in plasma spray coating known in the art and are commercially available. Such devices are included DC, arc and inductively coupled plasma devises. Such devices are commercially available from Progressive Technologies, Inc. (Michigan), Plasma Processes, Inc. (Alabama) and Tekna Plasma Systems Inc. (Canada).
- As noted above, a hydrogen excess is required. This improves the reduction of WO2. As the hydrogen to WO2 molar ratio increases, the temperature at which complete reduction is possible decreases, and the temperature at which the volatilization becomes detectable increases. At a hydrogen to WO2 molar ratio of 50:1, the temperature at which volatility of tungsten oxide species becomes detectable is almost 3000° C.; however, further temperature increase leads to increased volatility of elemental tungsten. At a hydrogen to WO2 ratio of 75, no further increase in temperature for onset of volatility is noted, but tungsten metal evaporation increases.
- In the presently claimed process, hydrogen is intentionally required to remove oxide species and activate the molybdenum substrate. The activation of molybdenum substrate and powder surfaces will also lead to an increase in the adherence of the tungsten or tungsten-rhenium alloy coating to the molybdenum substrate. The process effectively removes oxygen from all the metals and would increase the density of the coating. The process also will prevent any future degassing that would occur if oxide species were present in the coating.
- Although illustrated and described herein with reference to certain specific embodiments, the present invention is not intended to be limited to the details described. Various modifications may be made within the scope and range of equivalents of the claims that follow without departing from the spirit of the invention.
Claims (5)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/542,268 US20080081122A1 (en) | 2006-10-03 | 2006-10-03 | Process for producing a rotary anode and the anode produced by such process |
PCT/US2007/080286 WO2008060775A2 (en) | 2006-10-03 | 2007-10-03 | Improved process for producing a rotary anode and the anode produced by such process |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/542,268 US20080081122A1 (en) | 2006-10-03 | 2006-10-03 | Process for producing a rotary anode and the anode produced by such process |
Publications (1)
Publication Number | Publication Date |
---|---|
US20080081122A1 true US20080081122A1 (en) | 2008-04-03 |
Family
ID=39283721
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/542,268 Abandoned US20080081122A1 (en) | 2006-10-03 | 2006-10-03 | Process for producing a rotary anode and the anode produced by such process |
Country Status (2)
Country | Link |
---|---|
US (1) | US20080081122A1 (en) |
WO (1) | WO2008060775A2 (en) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4090103A (en) * | 1975-03-19 | 1978-05-16 | Schwarzkopf Development Corporation | X-ray target |
US4390368A (en) * | 1981-04-01 | 1983-06-28 | Gte Products Corporation | Flame spray powder |
US4461020A (en) * | 1981-04-07 | 1984-07-17 | U.S. Philips Corporation | Method of producing an anode and anode thus obtained |
US4534993A (en) * | 1983-01-25 | 1985-08-13 | U.S. Philips Corporation | Method of manufacturing a rotary anode for X-ray tubes and anode thus produced |
US4641333A (en) * | 1984-09-14 | 1987-02-03 | U.S. Philips Corporation | Method of manufacturing an X-ray tube rotary anode and an X-ray tube rotary anode manufactured according to this method |
US5157706A (en) * | 1990-11-30 | 1992-10-20 | Schwarzkopf Technologies Corporation | X-ray tube anode with oxide coating |
US6132812A (en) * | 1997-04-22 | 2000-10-17 | Schwarzkopf Technologies Corp. | Process for making an anode for X-ray tubes |
US6428904B2 (en) * | 1999-11-22 | 2002-08-06 | Generel Electric Company | X-ray target |
-
2006
- 2006-10-03 US US11/542,268 patent/US20080081122A1/en not_active Abandoned
-
2007
- 2007-10-03 WO PCT/US2007/080286 patent/WO2008060775A2/en active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4090103A (en) * | 1975-03-19 | 1978-05-16 | Schwarzkopf Development Corporation | X-ray target |
US4390368A (en) * | 1981-04-01 | 1983-06-28 | Gte Products Corporation | Flame spray powder |
US4461020A (en) * | 1981-04-07 | 1984-07-17 | U.S. Philips Corporation | Method of producing an anode and anode thus obtained |
US4534993A (en) * | 1983-01-25 | 1985-08-13 | U.S. Philips Corporation | Method of manufacturing a rotary anode for X-ray tubes and anode thus produced |
US4641333A (en) * | 1984-09-14 | 1987-02-03 | U.S. Philips Corporation | Method of manufacturing an X-ray tube rotary anode and an X-ray tube rotary anode manufactured according to this method |
US5157706A (en) * | 1990-11-30 | 1992-10-20 | Schwarzkopf Technologies Corporation | X-ray tube anode with oxide coating |
US6132812A (en) * | 1997-04-22 | 2000-10-17 | Schwarzkopf Technologies Corp. | Process for making an anode for X-ray tubes |
US6428904B2 (en) * | 1999-11-22 | 2002-08-06 | Generel Electric Company | X-ray target |
Also Published As
Publication number | Publication date |
---|---|
WO2008060775A2 (en) | 2008-05-22 |
WO2008060775A3 (en) | 2008-08-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU2006243448B2 (en) | Coating process for manufacture or reprocessing of sputter targets and X-ray anodes | |
RU2469126C2 (en) | Method of applying coating on substrate surface and coated product | |
RU2402625C2 (en) | Alloyed tungsten produced by chemical sedimentation from gas phase | |
US4090103A (en) | X-ray target | |
JP5065248B2 (en) | Coating method and coated product on substrate surface | |
Lungu et al. | Beryllium coatings on metals for marker tiles at JET: development of process and characterization of layers | |
JP3202081U (en) | Electrode incorporating metal-coated particles and method of surface hardening using the same | |
JP6428899B2 (en) | Method for modifying WC-based cemented carbide substrate | |
EP3150740B1 (en) | Rigid coating film, member coated with rigid coating film, production processes therefor, and target for use in producing rigid coating film | |
WO2008014801A1 (en) | A method for deposition of dispersion-strengthened coatings and composite electrode material for deposition of such coatings | |
EP2363509A1 (en) | Synthesis of metal oxides by reactive cathodic arc evaporation | |
Levashov et al. | Materials science and technological aspects of electrospark deposition of nanostructured WC‐Co coatings onto titanium substrates | |
JP2005131730A (en) | Surface-coated cermet cutting tool with hard coating layer having superior chipping resistance | |
US20080081122A1 (en) | Process for producing a rotary anode and the anode produced by such process | |
JPH0356675A (en) | Coating of ultrahard alloy base and ultrahard tool manufactured by means of said coating | |
JP4097972B2 (en) | Target for physical vapor deposition and method for producing the same | |
US20180021858A1 (en) | Surface-coated cutting tool | |
US20070207338A1 (en) | X-ray target and method for manufacturing same | |
US5199059A (en) | X-ray tube anode with oxide coating | |
GB1568463A (en) | Thin coatings of temperature resistant metals | |
JPH07102376A (en) | Coating member and its production | |
JPH10310841A (en) | Ceramic coating material, its production and high temperature member using the same material | |
Rubshtein et al. | Structure and corrosion behaviour of CrxAl (Si) yC coatings fabricated by the vacuum arc discharge technique | |
JP2019118995A (en) | Surface-coated cutting tool | |
CA1245111A (en) | Process for applying hard coatings and the like to metals and resulting product |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: H. C. STARCK INC., MASSACHUSETTS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HAYWISER, LEAH F.;SHEKHTER, LEONID N.;REEL/FRAME:018387/0178 Effective date: 20060919 |
|
AS | Assignment |
Owner name: DRESDNER BANK AG, NIEDERLASSUNG LUXEMBOURG, AS SEC Free format text: INTELLECTUAL PROPERTY RIGHTS SECURITY AGREEMENT (SENIOR);ASSIGNOR:H.C. STARCK INC.;REEL/FRAME:020036/0759 Effective date: 20071026 Owner name: DRESDNER BANK AG, NIEDERLASSUNG LUXEMBOURG, AS SEC Free format text: INTELLECTUAL PROPERTY RIGHTS SECURITY AGREEMENT (SECOND LIEN);ASSIGNOR:H.C. STARCK INC.;REEL/FRAME:020036/0851 Effective date: 20071026 Owner name: DRESDNER BANK AG, NIEDERLASSUNG LUXEMBOURG, AS SEC Free format text: INTELLECTUAL PROPERTY RIGHTS SECURITY AGREEMENT (MEZZANINE);ASSIGNOR:H.C. STARCK INC.;REEL/FRAME:020036/0864 Effective date: 20071026 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
AS | Assignment |
Owner name: GLAS TRUST CORPORATION LIMITED, AS SECURITY AGENT Free format text: SECURITY INTEREST;ASSIGNOR:H.C. STARCK INC.;REEL/FRAME:038701/0333 Effective date: 20160523 Owner name: GLAS TRUST CORPORATION LIMITED, AS SECURITY AGENT Free format text: SECURITY INTEREST;ASSIGNOR:H.C. STARCK INC.;REEL/FRAME:038701/0219 Effective date: 20160523 |
|
AS | Assignment |
Owner name: H.C. STARCK INC., GERMANY Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GLAS TRUST CORPORATION LIMITED;REEL/FRAME:057993/0198 Effective date: 20211101 Owner name: H.C. STARCK INC., GERMANY Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GLAS TRUST CORPORATION LIMITED;REEL/FRAME:057993/0188 Effective date: 20211101 Owner name: H.C. STARCK INC., GERMANY Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GLAS TRUST CORPORATION LIMITED;REEL/FRAME:057993/0178 Effective date: 20211101 Owner name: H.C. STARCK INC., GERMANY Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GLAS TRUST CORPORATION LIMITED;REEL/FRAME:057993/0103 Effective date: 20211101 Owner name: H.C. STARCK INC., GERMANY Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:GLAS TRUST CORPORATION LIMITED;REEL/FRAME:057993/0069 Effective date: 20211101 |