US3723289A - Method and apparatus for plasma treatment of substrates - Google Patents
Method and apparatus for plasma treatment of substrates Download PDFInfo
- Publication number
- US3723289A US3723289A US00171282A US3723289DA US3723289A US 3723289 A US3723289 A US 3723289A US 00171282 A US00171282 A US 00171282A US 3723289D A US3723289D A US 3723289DA US 3723289 A US3723289 A US 3723289A
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- US
- United States
- Prior art keywords
- envelope
- substrate
- electrodes
- plasma
- chamber
- 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.)
- Expired - Lifetime
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32082—Radio frequency generated discharge
- H01J37/32091—Radio frequency generated discharge the radio frequency energy being capacitively coupled to the plasma
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/30—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M14/34—Polyamides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/02—Details
- H01J37/18—Vacuum locks ; Means for obtaining or maintaining the desired pressure within the vessel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32733—Means for moving the material to be treated
- H01J37/32743—Means for moving the material to be treated for introducing the material into processing chamber
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32733—Means for moving the material to be treated
- H01J37/32752—Means for moving the material to be treated for moving the material across the discharge
- H01J37/32761—Continuous moving
- H01J37/3277—Continuous moving of continuous material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/32—Processing objects by plasma generation
- H01J2237/33—Processing objects by plasma generation characterised by the type of processing
- H01J2237/336—Changing physical properties of treated surfaces
Definitions
- ABSTRACT A method and apparatus for efficiently generating a gaseous plasma particularly for the treatment of substrates.
- a radio frequency electrical signal is applied to two electrodes disposed exteriorly of an electrically insulative, gas impervious envelope.
- a central passage extends into the envelope and oneelectrode is disposed in the central passage.
- the electrodes are separated at least in part by the envelope and the radio frequency signal applied to the electrodes excites the gas within the envelope to thereby generate a gaseous plasma therein.
- the gas conditions within the envelope differ from the gas conditions exteriorly thereof and the amplitude of the radio frequency signal is insufficient to generate a plasma outside the chamber defined by the envelope. Since the plasma does not contact the electrodes, efficiency is maximized and the plasma is not contaminated by the electrodes.
- the surface areas of the electrodes differ substantially thereby creating a plasma within the envelope which varies in concentration in a predetermined manner, with the concentration being greatest near the center of the envelope.
- a substrate may therefore be contacted by varying plasma concentration as it passes through the envelope and the outer wall of the envelope is not contaminated by the plasma.
- a vacuum lock for preventing gas leakage into the envelope is also disclosed.
- the present invention relates to a method and apparatus for treating substrates and specifically to a method and apparatus for more efficiently generating a plasma for the treatment of substrates and for subjecting a substrate to varying plasma concentrations during the treatment thereof.
- Various substrates have been treated in gaseous plasmas to obtain desired substrate characteristics.
- An example of one such process is disclosed and claimed in US. Pat. application Ser. No. 93,350 filed Nov. 27, 1970 by Forcap et al. for Surface Modification of Organic Polymeric Materials and assigned to the assignee of the present invention.
- an organic polymeric fiber is introduced into a gaseous plasma for modification of the surface thereof.
- a polymeric continuous filament yarn may be exposed to a gaseous plasma formed by exciting argon or other suitable gases at a pressure of about 2 mm Hg. with a 4 megahertz, 1000 watt radio frequency signal, to modify the yarn to obtain desirable surface characteristics.
- signal having a frequency of 13.6 megahertz in pulses of 100 microseconds duration at a pulse repetition rate of l kilohertz may be utilized to excite the gaseous mixture within a coating zone into which the substrate is introduced to provide a smooth, firmly adhering layer of boron l to 2 mils in thickness.
- Carbonaceous fibrous materials have been treated in plasmas as is described in United States patent application Ser.'No. 99,169 filed Dec. 17, 1970, for Surface Modification of Carbon Fibers, by KennethC. Hou and assigned to the assignee of the present invention.
- a carbonaceous fibrous material is contacted for a brief time with an excited gas species generated by applying high frequency electrical energy in pulsed form to a gaseous mixture of a monotonic inert gas and a surface modification gas.
- a carbonaceous yarn may be passed through a gaseous mixture of helium and oxygen wherein the oxygen is present in the mixture in a concentration of about 0.5 percent by weight.
- a 3 kilovolt peak-to-peak a.c. signal having a frequency of 13.56 megahertz may be utilized to excite the gaseous mixture thereby contacting the yarn with the excited gas species to modify the surface thereof.
- the excited gas species or plasma is generated by electrically exciting the gas or gaseous mixture.
- energy may be imparted to gas capacitively and a plasma thereby generated.
- the plasma is highly electrically conductive and a high conduction current flows between the capacitor plates or electrodes because of the resultant decrease in the electrical resistance of the gas between the electrodes.
- the cost of the power required to generate the plasma becomes an important factor.
- the plasma may be utilized in a more efficient manner.
- the cost of treating substrates may also be dependent upon the length of time during which a reaction chamber may be operated without shutdown for maintenance. It may be necessary to frequently change the gas within the chamber if the gas is contaminated by the electrodes. Also, the useful life of the reaction chamber may be adversely affected by material buildup on the walls thereof during the treatment operation.
- the amount of time during which the substrate is exposed to the plasma may be selectively varied to provide the desired end product. This may be accomplished through control of the speed at which the substrate passes through the plasma, assuming that other conditions remain constant.
- the substrate may, for example, be adversely affected by excess heat or the sudden exposure to high temperatures. It may therefore be desirable to expose the substrate to the plasma in a controllable manner.
- FIG. 1 is a schematic representation of a reaction chamber embodying the present invention
- FIG. 2 is a view in cross section of the reaction chamber of FIG. 1, taken along the line 2-2;
- FIG. 3 is a schematic representation of the reaction chamber of FIG. 1 with a substrate being treated therein;
- FIG. 4 is a view in cross section of the reaction chamber of FIG. 3, taken along the line 44;
- FIG. 5 is a schematic representation of a reaction chamber similar to the chamber shown in FIG. 3 with a plurality of substrates being treated therein;
- FIG. 6 is a view in partial cross section of the reaction chamber of FIG. 5 illustrating the vacuum lock of the present invention.
- FIGS. 7A and 7B are end views of the vacuum lock of FIG. 6, taken along the line 77 thereof, and illustrate two of the alternative shapes which the vacuum lock may have.
- a reaction chamber 10 is formed by a substantially gas impervious, generally electrically non-conductive or insulative envelope 12 into which a central passage 14 extends.
- An electrode 16 extends into the central passage 14 and is isolated from the chamber 10 by the radially inward wall of the envelope 12.
- An electrode 18 is disposed radially outward of the envelope 12, and is separated at least in part from the centrally disposed electrode by at least a portion of the envelope 12, thereby defining an area within the envelope 12, i.e., at least a portion of the chamber 10, which is disposed between the electrodes 16 and 18.
- a high frequency electrical potential is applied between the electrodes 16 and 18 from a suitable source such as a variable frequency and amplitude,
- radio frequency (RF) generator 20 to thereby subject the chamber as defined by the envelope 12 between the electrodes 16 and 18 to a selectable time varying electrical field.
- a suitable fill tube 22 may be provided communicating with the chamber 10 through the envelope l2 and having a valve or other suitable closure means 24 therein to selectively control the nature and pressure of the gas within the envelope 12.
- the envelope 12 defining the chamber 10 preferably comprises an outer elongated hollow glass cylindrical member 26, an inner elongated hollow glass cylindrical member 28, and apertured end plates 30 and 32 sealed therebetween in a suitable conventional manner.
- the cylindrical member 28 illustrated is substantially coextensive with the member 26 and is disposed in telescoping relationship thereto coaxially within the member 26 to define a chamber annular in cross section as is shown in FIG. 2.
- the central electrode 16 is preferably an elongated metallic cylindrical member, e.g., a wire, telescoped within the central passage 14, but may be hollow.
- the outer electrode 18 is preferably a hollow cylindrical electrically conductive member circumferentially disposed round at least a portion of the insulative member 26 and may, for example, be a metallic foil conformed to the radially outer surface of the envelope.
- the central electrode 16 preferably extends axially into the central passage 14 sufficiently so that an elongated annular portion of the chamber 10 is located between the electrodes 16 and 18.
- the application of a potential between the electrodes 16 and 18 creates an electric field between these electrodes, as is indicated by the lines 34 in FIG. 2.
- the electrode configuration i.e., the relative positions of the electrodes and the relative dimensions thereof, cause the electric field to be more concentrated or dense in the vicinity of the central electrode 16 near the axis of the annular chamber 10.
- the gas in the chamber 10 will be excited sufficiently to create a gaseous plasma in the chamber.
- the plasma generally comprises highly reactive species such as ions, electrons and neutral fragmented particles in highly excited states. Since the exciting of the gas by the electric field creates the plasma, the plasma concentration or density generally conforms to the electric field concentration or density. Thus, the concentration or density of the plasma generated within the gas impervious envelope 12 varies between the outer cylindrical member 26 and the inner cylindrical member 28 in a manner related to the electric field concentration of density.
- the plasma is thereby concentrated around the inner cylindrical member 28 rather than being dispersed evenly throughout the chamber 10.
- This central concentration permits more efficient utilization of the plasma for treating substrates and permits selective exposure of the substrate to the plasma as will hereinafter be described.
- this central concentration of the plasma prevents excessive buildup of material on the inner wall of the outer cylindrical member 26.
- the relationship between the gas conditions within the envelope l2 and the gas conditions exteriorly thereof is desirably such that the plasma may be confined to the chamber 10.
- the electric potential applied to the electrodes 16 and 18 may thus be lower and the current density will be correspondingly less.
- This desirable relationship may be obtained by utilizing selected gases at predetermined pressures within the chamber 10, while exposing the electrodes outside the envelope 12 to the atmosphere.
- a monatomic inert gas such as argon or helium at atmospheric or slightly less than atmospheric pressure may be utilized in the chamber 10.
- a plasma will be more readily generated within the chamber than exteriorly thereof.
- the potential of the RF signal applied to the electrodes set at a value corresponding to the potential required to generate a plasma within the chamber 10, but below the potential required to generate a plasma in the vicinity of the electrodes 16 and 118 externally of the chamber 10, the current which flows between the electrodes 16 and 18 will not be appreciably affected by the ion flow within the highly electrically conductive plasma since these electrodes are electrically isolated from the plasma.
- the plasma within the chamber 10 is not contacted by the electrodes 16 and 18 and therefore not contaminated by the electrodes.
- a substrate 36 to be treated within the generated plasma may be introduced into the chamber 10 through a vacuum lock 38 subsequently described in greater detail in connection with FIGS. 6 and 7.
- the substrate 36 may be passed through the chamber 10 in contact with the plasma therein at a rate determined by the particular treatment process to which the substrate is being subjected.
- the substrate 36 may be an organic polymeric fiber, such as a thermoplastic or thermosetting polyester, polyamide, cellulosic or polyolefin material, the surface of which is to be treated in the plasma to obtain a particular surface modification as is described in greater detail in the previously discussed US. Pat. application Ser. No. 93,350, by Fortent et al.
- the substrate 36 may alternatively be a carbonaceous fibrous material to be treated in the plasma within the chamber 10 as is described in greater detail in the previously discussed US. Pat. application Ser. No. 99,169, by Kenneth C. Hou.
- a coating may be deposited on a suitable substrate by generating a suitable gaseous plasma and contacting the substrate with this plasma.
- a more detailed description of the substrate and gases utilized in one such coating technique may be had by reference to the previously discussed US. Pat. application Ser. No. 88,358, by Kenneth C. I-Iou. The above referenced Fortress and Hon patent applications are hereby incorporated herein by reference.
- the substrate 36 may be introduced into the chamber 10 at an a angle with respect to the central electrode 16 as is illustrated in FIG. 3.
- the substrate 36 might thereby follow a path generally indicated at 40 which subjects the substrate 36 to varying concentrations of the plasma as it passes through the chamber 10.
- one or more substrates 36 may be passed through the chamber 10'substantially parallel to the electrodes 16 at a selected radial distance therefrom, thereby permitting the exposure of the substrates 36 to a selected plasma concentration.
- a hollow tube 40 sealed to the end plate 30 of the envelope I2 communicates interiorly with the chamber 10 and provides a passage through which the substrate 36 may be introduced into the chamber 10.
- the substrate 36 may be, for example, a loosely packed fiber bundle through which air leakage ordinarily occurs during the passage thereof between chambers at different pressures.
- the tube 40 generally conforms in cross-section to the shape of the substrate, i.e., the bundle of fibers, but is slightly smaller in cross-section than the bundle causing the fibers to be inwardly compressed against each other and against the internal wall of the tube 40.
- the tube 40 may also be circular in cross-section with a slightly smaller diameter than that of the bundle.
- the tube 40 preferably conforms to that shape and is scaled down to slightly smaller dimensions.
- One end 42 of the tube 40 is flared or funnel-shaped providing a transition zone for gently compressing the fiber bundle without damage thereto. If desired, the tube 40 may also narrow slightly along the length thereofto further compress the fiber bundle during the introduction thereof into the chamber 10. It should be noted that when the substrate is a tightly packed fiber bundle or a single filament substrate, the diameter of the tube 40 may be the same or slightly larger than the substrate to prevent damage thereto.
- At least two fluid passages 44 and 46 are spaced along the length of the tube 40 and communicate with the interior thereof. Each of the passages 44 and 46 is connected to associated pressure sources 48 and 50, respectively.
- the gas pressure applied to the passage 46 preferably approximates the pressure in the chamber 10, while the pressure applied through the passage 44 is preferably slightly higher than the pressure in the chamber 10, thereby creating a pressure differential along the interior of the tube 40.
- This pressure differential together with the mechanical compression of the substrate, prevents gas leakage into the chamber 10 when, for example, the pressure in the chamber 10 is less than the pressure outside the chamber 110.
- the electrodes are isolated from the highly conductive plasma created within the envelope, resulting in greater efficiency as well as greater current control and eliminating contamination of the plasma by the electrodes.
- Control of the substrate treatment process is facilitated by the controlled plasma concentration achieved in the present invention.
- the substrate may be selectively contacted by the proper concentration of plasma by selecting the path which the substrate follows through the generated plasma. Additionally, the plasma is concentrated in one location within the chamber resulting in more efficient substrate treatment and less material buildup on the interior walls of the envelope.
- continuous substrates may be treated without adverse effects on the conditions within the reaction chamber since isolation is provided between the interior and exterior of the envelope.
- the substrate may pass from an area at one pressure, into the envelope which may be at another pressure, and then into an area at yet a different pressure without any substantial gas leakage.
- Apparatus comprising:
- electrically insulative means defining a gas impervious envelope having a central passage extending thereinto;
- a first electrode disposed exteriorly of said envelope and within said central passage
- a second electrode disposed exteriorly of said envelope and separated at least in part from said first electrode by a portion of said envelope;
- the apparatus of claim 1 including means for introducing a substrate into said envelope for exposure of the substrate to the plasma generated therein.
- said means for introducing a substrate into said envelope includes means defining an elongated passage interiorly communicating at one end with said envelope, said elongated passage being larger in cross-section at the other end thereof than at said one end whereby said plurality of fibers are inwardly compressed against each other and against the internal walls of said elongated passage sufficiently to substantially preserve the gas imperviousness of said envelope during introduction of said substrate into said chamber through said elongated passage.
- said means for introducing a substrate into said envelope further includes a plurality of pressure sources communicating with said elongated passage at spaced points along the length thereof.
- said means for introducing a substrate into said envelope includes a first means for supplying a first pressure and a second means for applying a second pressure, said first and 5 second means communicating with said elongated passage at spaced points along the length thereof.
- radio frequency electrical signal has a potential sufficient to generate a plasma between said electrodes within said envelope but insufficient to generate a plasma between said electrodes externally of said envelope.
- the apparatus of claim 7 including means for introducing a substrate into said envelope for exposure of said substrate to the plasma generated therein.
- said second member is a hollow cylinder substantially coextensive and coaxial with said first member
- said second electrode is a hollow cylinder only slightly larger in diameter than said first member.
- said second electrode is a thin layer of metal conformed to the radially outer, external surface of said first member.
- Apparatus for treating a substrate comprising:
- electrically insulative means defining a gastight chamber
- first and second electrodes disposed exteriorly of said chamber for generating a high frequency induced plasma in said chamber
- Apparatus for treating a substrate comprising:
- Apparatus for treating a substrate without expo- 5 sure to a high current density comprising:
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- Analytical Chemistry (AREA)
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- Plasma & Fusion (AREA)
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Abstract
Description
Claims (18)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17128271A | 1971-08-12 | 1971-08-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3723289A true US3723289A (en) | 1973-03-27 |
Family
ID=22623196
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US00171282A Expired - Lifetime US3723289A (en) | 1971-08-12 | 1971-08-12 | Method and apparatus for plasma treatment of substrates |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3853657A (en) * | 1972-02-14 | 1974-12-10 | Monsanto Co | Bonding of poly(ethylene terephthalate) induced by low-temperature plasmas |
US3974750A (en) * | 1974-03-16 | 1976-08-17 | Hauni-Werke Korber & Co., Kg | Method and apparatus for neutralizing electrostatic charges of filter material for smokers' products |
US3992495A (en) * | 1973-09-07 | 1976-11-16 | Sumitomo Chemical Company, Limited | Method of manufacturing a semipermeable membrane from a water-soluble polymeric resin |
US4145101A (en) * | 1975-04-18 | 1979-03-20 | Hitachi, Ltd. | Method for manufacturing gas insulated electrical apparatus |
US4980196A (en) * | 1990-02-14 | 1990-12-25 | E. I. Du Pont De Nemours And Company | Method of coating steel substrate using low temperature plasma processes and priming |
US4981713A (en) * | 1990-02-14 | 1991-01-01 | E. I. Du Pont De Nemours And Company | Low temperature plasma technology for corrosion protection of steel |
US5716877A (en) * | 1996-02-08 | 1998-02-10 | Applied Materials, Inc. | Process gas delivery system |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1710155A (en) * | 1922-07-20 | 1929-04-23 | Universal Oil Prod Co | Process and apparatus for forming oxidation products of hydrocarbon oils |
US1845670A (en) * | 1929-05-18 | 1932-02-16 | Lebrun Paul Francois Joseph | Ozonizer |
US2468173A (en) * | 1949-04-26 | cotton | ||
US2822327A (en) * | 1955-03-31 | 1958-02-04 | Gen Electric | Method of generating ozone |
US2955998A (en) * | 1953-02-17 | 1960-10-11 | Berghaus Bernhard | Process for carrying out technical operations in a glow discharge |
-
1971
- 1971-08-12 US US00171282A patent/US3723289A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2468173A (en) * | 1949-04-26 | cotton | ||
US1710155A (en) * | 1922-07-20 | 1929-04-23 | Universal Oil Prod Co | Process and apparatus for forming oxidation products of hydrocarbon oils |
US1845670A (en) * | 1929-05-18 | 1932-02-16 | Lebrun Paul Francois Joseph | Ozonizer |
US2955998A (en) * | 1953-02-17 | 1960-10-11 | Berghaus Bernhard | Process for carrying out technical operations in a glow discharge |
US2822327A (en) * | 1955-03-31 | 1958-02-04 | Gen Electric | Method of generating ozone |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3853657A (en) * | 1972-02-14 | 1974-12-10 | Monsanto Co | Bonding of poly(ethylene terephthalate) induced by low-temperature plasmas |
US3992495A (en) * | 1973-09-07 | 1976-11-16 | Sumitomo Chemical Company, Limited | Method of manufacturing a semipermeable membrane from a water-soluble polymeric resin |
US3974750A (en) * | 1974-03-16 | 1976-08-17 | Hauni-Werke Korber & Co., Kg | Method and apparatus for neutralizing electrostatic charges of filter material for smokers' products |
US4145101A (en) * | 1975-04-18 | 1979-03-20 | Hitachi, Ltd. | Method for manufacturing gas insulated electrical apparatus |
US4980196A (en) * | 1990-02-14 | 1990-12-25 | E. I. Du Pont De Nemours And Company | Method of coating steel substrate using low temperature plasma processes and priming |
US4981713A (en) * | 1990-02-14 | 1991-01-01 | E. I. Du Pont De Nemours And Company | Low temperature plasma technology for corrosion protection of steel |
US5716877A (en) * | 1996-02-08 | 1998-02-10 | Applied Materials, Inc. | Process gas delivery system |
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