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A flexible metal-film laminate can comprise a layered film structure having a metal layer securely bonded to a film layer. The laminate contains a unique metal-oxide attachment structure between the film and metal layer comprising randomly distributed regions of metal-oxide. After the metal/metal-oxide layer, a chromium metal or chromium alloy layer is formed before subsequent layers of copper, gold, etc. The peel strength of such a laminate is significantly improved over prior laminates and is resistant to peel strength reduction due to environmental stress. The preferred metal-film laminates made with polyester or polyimide can be used in the manufacture of high-quality, low cost, flexible printed circuit boards.
1. A metal-film laminate, resistant to the delamination of the metal from the film, which laminate comprises:
(a) a polyimide film layer having at least one surface bearing a non-continuous random distribution of metal-oxide, said metal-oxide selected from the group consisting of oxides of iron, chromium, nickel, molybdenum, manganese, zirconium or mixtures thereof; and
(b) a metal surface adhered to the film through the random distribution, said metal surface comprising:
(b) a metal surface adhered to the film through the random distribution, said metal surface comprising:
(i) a sputtered first metal layer comprising a chromium metal composition having a thickness of about 10 to 100 Å;
(ii) a second metal layer, formed on the first metal layer by vapor metallization, having a thickness of about 50 to 5000 Å; and
(iii) a third metal layer having a thickness of 0.1 to 40 μm formed on the second layer;
wherein the peel strength of the metal-film laminate is at least 3 pounds per inch.
2. The laminate of claim 1 wherein the metal-oxide distribution results from a film treatment with a plasma comprising ionized oxygen, produced from a metallic electrode comprising a metal selected from the group consisting of manganese, chromium, nickel, iron, molybdenum or mixtures thereof.
3. The laminate of claim 1 wherein the first metal layer comprises chromium metal and has a thickness of about 20 to 100 Å.
4. The laminate of claim 1 wherein the second metal layer is copper and is formed by metal vaporization.
5. The laminate of claim 1 wherein the third metal layer is a copper layer formed by electrodeposition.
6. The laminate of claim 5 wherein a further metal layer comprising gold, silver, palladium, nickel or mixtures thereof is formed using electroless techniques.
7. A metal-film laminate, resistant to delamination of the metal from the film, which laminate comprises:
(a) a polyimide film layer having at least one surface bearing a non-continuous random distribution of metal-oxide, said metal-oxide selected from the group consisting of oxides of iron, chromium, nickel, molybdenum, manganese, zirconium, or mixtures thereof, said distribution less than 20 atomic layers in thickness; and
(b) a metallic surface adhered to the film through the random distribution, said surface comprising:
(i) a sputtered first metal layer comprising an alloy comprising nickel and chromium having a thickness of 10 to 100 Å;
(ii) a second metal layer formed on the first layer by vapor metallization, having a thickness of about 50-5000 Å; and
(iii) a third layer comprising copper having a thickness of 0.1 to 40 μm formed on the second metal layer;
wherein the peel strength of the metal-film laminate is at least 3 pounds per inch.
8. The laminate of claim 7 wherein the first metal layer comprises about 5-25% chromium and 55-75% nickel and has a thickness of about 20 to 100 Å.
9. The laminate of claim 7 wherein the third layer is formed by electro-deposition.
10. The laminate of claim 7, wherein the polyimide film comprises a polyetherimide.
11. A metal-film laminate, resistant to delamination of the metal from the film, which laminate comprises:
(a) a polyimide film layer having at least one surface bearing a non-continuous random distribution of a metal and an oxide of a metal selected from the group consisting of iron, chromium, nickel, molybdenum, manganese, zirconium or mixtures thereof; and
(b) a metal surface adhered to the film through the random distribution, said metal surface comprising:
(i) a sputtered first metal layer comprising an alloy of chromium and nickel having a thickness of about 10 to 100 Å;
(ii) a first copper layer, formed on the first metal layer by vapor metallization, having a thickness of about 50 to 5000 Å; and
(iii) a second copper layer having a thickness of 0.1 to 40 μm formed on the first copper layer;
wherein the laminate is free of a metal tie-coat and the peel strength of the metal-film laminate is at least 3 pounds per inch.
12. The laminate of claim 11 wherein the first metal layer has a thickness of about 20 to 100 Å.
13. The laminate of claim 11 wherein the second copper layer is formed by electrodeposition.
14. A metal-film laminate, resistant to the delamination of the metal from the film, which laminate comprises:
(a) a polyimide film layer having at least one through hole, said layer and through hole bearing a non-continuous random distribution of metal-oxide, said metal-oxide selected from the group consisting of oxides of iron, chromium, nickel, molybdenum, manganese, zirconium and mixtures thereof, said distribution less than 20 atomic layers in thickness; and
(b) a metal surface adhered to the film and through-hole through the random distribution, said metal surface comprising:
(i) a first metal layer comprising a chromium metal composition, formed on the metal-oxide regions by sputtering, having a thickness of about 10 to 100 Å; and
(ii) a copper metallized vapor layer having a thickness of 10 to 1800 Å formed on the first metal layer;
wherein the peel strength of the metal-film laminate is at least 3 pounds per inch.
15. The laminate of claim 14 wherein the metal-oxide regions result from a film treatment with a plasma comprising ionized oxygen, produced from a metallic electrode comprising a metal selected from the group consisting of manganese, chromium, nickel, iron, molybdenum or mixtures thereof.
16. A metal-film laminate, resistant to the delamination of the metal from the film, which laminate comprises:
(a) a polyimide film having at least one through-hole;
(b) a non-continuous random distribution on the polyimide film, said distribution comprising a metal-oxide, said metal-oxide selected from the group consisting of oxides of chromium, iron, nickel, manganese, molybdenum, zirconium and mixtures thereof; and
(c) a metal surface adhered to the film through the random distribution, said surface comprising:
(i) a sputtered first metal layer comprising an alloy comprising nickel and chromium having a thickness of 10 to 100 Å;
(ii) a metal layer comprising copper formed on the first metal layer by vapor metallization having a thickness of about 50 to 1800 Å; and
(iii) a second copper layer having a thickness of 0.1 to 40 μm formed on the metallized layer; wherein the peel strength of the metal-film laminate is at least 3 pounds per inch.
17. The laminate of claim 16 wherein the metal-oxide regions result from an oxygen plasma produced from a metallic electrode.
18. The laminate of claim 16 wherein the second copper layer is formed by electrodeposition.
19. The laminate of claim 16 wherein the random distribution comprises a chromium-oxide in a thickness of less than 5 atom monolayers.
20. The laminate of claim 16 wherein the polyimide film comprises a polyetherimide.
This is a Continuation of application Ser. No. 08/578,152, filed Dec. 29, 1995, now abandoned, which is a Continuation-in-Part of application Ser. No. 08/339,029 filed Nov. 14, 1994, which is now Swisher, U.S. Pat. No. 5,480,730, which is a Continuation of application Ser. No. 07/909,058, filed Aug. 4, 1992, which is now Swisher, U.S. Pat. No. 5,364,707, which is a Divisional of application Ser. No. 07/681,073, filed Apr. 5, 1991, which is now Swisher, U.S. Pat. No. 5,137,791, which is a Divisional of application Ser. No. 07/580,505, filed Sep. 13, 1990, which is now Swisher, U.S. Pat. No. 5,112,462.
The invention relates to a flexible metal-film laminate having a metal layer securely bonded to a film. The metal layer can be made resistant to delamination as measured by a 90� peel strength of at least 3 preferably 4 or more pounds per inch width measured at a speed of about two inches per minute. Such metal-film laminates are ideal for many uses including packaging, flexible printed wiring boards, insulation, labels, decorative layers, anti-static films, reflective layers, antennas, heaters, etc. Such laminates can be subjected to environmental stress, mechanical stress and chemical treatment without significant delamination.
A. Film Treatment and Metal Forming Process
Flexible metal-film laminate materials have become the focus of great interest in recent years. A variety of techniques including film pre-treatment processes and metal layer forming processes have been studied to improve the properties of laminates. Such processes include film etching, organic coatings, the sputtering of metal, the adhesive lamination of pre-formed metal foil to film, electroless plating, electroplating, and others. Such metal-film laminate products each have different characteristics including metal thickness, metal tensile strength, laminate flexibility, delamination tendency, etc.
One useful metal forming method involves producing a "tie coat" of chromium typically on a polyimide surface. Such tie coats are equal to or greater than 50 nanometers, greater than 100 atomic layers, of chromium atoms, in thickness and aid in bonding a electroplated copper layer to polyimide. We are aware that a successful film laminate comprises a film having a greater than 50 nanometer thickness (more than 100 atom monolayers) chromium tie coat and a plated copper layer having a thickness of greater than 0.1 μm. Such laminates are inconvenient to process into wiring boards because they generally require two etch steps, one basic etch for copper and a second acid etch for chromium. Polyimide laminates with a "tie coat" have acceptable peel strength but can be expensive to produce and use in applications requiring low cost materials.
Kennedy, U.S. Pat. No. 3,700,538 discloses an adhesive used to bond copper foil to resin impregnated fiber glass cloth using a polyimide resin adhesive. The use of an adhesion promoter to bond metal to an insulating base material is known. For example, Soukup, U.S. Pat. Nos. 3,477,900 and 3,149,021 disclose that when the insulating base material comprises methylmethacrylate resin, an unsaturated polyester may be added to the resin as an adhesion promoter to bond a copper foil. However, these patents disclose that an increase in the proportion of polyester is generally accompanied by a decrease in an adhesion of the copper foil to the resinous base. U.S. Pat. No. 4,420,509 to Barrell et al. and U.S. Pat. No. 4,093,768 to Cordts et al. disclose procedures for preparing polyester resin copper clad laminates. These processes require several steps or expensive continuously operating equipment.
Van Essen, U.S. Pat. Nos. 4,081,578; 4,189,517 and 4,414,173 are directed to in-mold coating processes which are substantially different from the present process in that a preform substrate is either made or placed in a mold and cured. The mold is opened and a small amount of resin is placed on the molded substrate sufficient to form a coating up to about 20 mils. in thickness. The mold is then closed over the polymerizing resin to apply pressure.
Japanese Pat. No. 57083-427 discloses a process where an insulation material is mounted on an inner surface of an injection mold and a metal foil is overlaid on the insulated surface and fixed. A thermoplastic resin is melt-injected into the mold to provide a resin product laminated firmly with the metal foil.
Bristowe et al, U.S. Pat. No. 4,916,016 also teaches injection molded metal-thermoset laminates.
Kawakami et al, U.S. Pat. No. 4,913,938 teaches coating a resin substrate with a copper solution and heating in a non-oxidizing atmosphere to increase copper laminate adhesion.
Pinch et al, U.S. Pat. No. 4,772,488 teaches the use of a carbon dioxide plasma to treat and clean dielectric layers.
Haque et al, U.S. Pat. No. 4,524,089 uses a three step plasma treatment of copper foils.
U.S. Pat. No. 4,482,998 to Marouf et al. and U.S. Pat. No. 4,582,564 to Shanefield et al. teach a sputter etching of a rubber modified epoxy surface or coating.
Holmes et al, U.S. Pat. No. 4,153,518 teaches treating a refractory metal oxide layer to improve adhesion of oxide forming metals.
Toth et al, U.S. Pat. No. 4,568,413 teaches forming a releasable metallic layer on a polymeric carrier, adhering the releasable metal onto a substrate and peeling the carrier.
Sato, U.S. Pat. No. 4,193,849 teaches conventional pre-treatments of plastic prior to electro-chemical deposition of metal surfaces.
Hogge, Jr. et al, U.S. Pat. No. 4,724,401 teaches heating a film substrate to a temperature between 0.6 and 0.8 of the curing temperature (Tc) of the substrate material, commonly an elevated temperature exceeding 200� C. (often 240-280� C.) and evaporating or sputtering metal ions such that a metal ion can interact with the heated substrate layer and penetrate into the interior of the heated substrate. The processes in Ho et al are done in an inert atmosphere and produce no metal oxide.
Fronz et al, Plasma Pretreatment of Polyimide Films, a paper presented at the August 24-28 meeting of the Soc. of Vacuum Coaters, teach many of the drawbacks of copper-polyimide laminates. Fronz et al teaches that surface cleaning of the polyimide film will increase peel strength. Fronz et al does not discuss the importance of metal-oxide adhesion structures nor uses metallic methods in the film treatment.
One pre-treatment technique used with films called "corona discharge" has been found to aid in surface cleaning but not helpful in introducing binding structures to promote the peel strength of laminates. Corona discharge uses ceramic elements or other types of non metallic electrode and an ambient atmosphere temperature/pressure discharge to generate UV radiation and ozone (O3). This treatment apparently produces no new metal/film metal-oxide/film structure on the surface of the film and does not appear to promote film-laminate bonding.
While film treatment steps and metal forming processes are known, a fully satisfactory laminate has not been prepared. In particular, no fully satisfactory polyimide laminate is known for use in printed circuit board manufacture.
B. Delamination Tendency of Laminates
In general, metal-film laminates, which can be formed by forming (plating) metal onto the film or onto treated film, have a tendency to delaminate during and after the formation of a plated metal layer having a thickness of about 0.1 to 35 μm. The peel strength of many such laminates currently in use is generally felt to be insufficient for many end uses because any delamination can cause the failure of the laminate to operate in its intended use. However, even the peel strength currently achievable in many films can be still further decreased by exposure of the film to processing chemicals (etchants, cleaners, coatings, etc.) and environmental stress (such as humidity in the case of polyimide) and can be reduced to much less than 3 pounds per inch and in certain instance, can be much less than 1 pound per inch. Delamination of the metal layer can result in the failure of the material to be reflective, insulating, an adequate packaging material or to function in a useful circuit assembled on a printed wiring board made from the laminate.
A variety of other influences can promote the delamination of metal poorly bonded to film substrate. First, the strength of the laminate bond is an important characteristic. Higher strength bonds reduce delamination tendency. Further, the mechanical stresses (soldering, film flex during processing, etc.) involved in first forming the metal on the flexible film and in subsequent processing steps can cause the film to distort or flex and can cause the poorly bonded metal to leave the film.
Additionally, a number of polymer surfaces are known to be less likely to maintain an integral laminate structure. Fluorocarbon resins, polyethylene, polypropylene, and polyvinylidiene chloride or polyvinylidiene-fluoride films tend to be difficult surfaces for metal bonding.
Flexible printed circuit boards are currently one preferred circuit manufacturing format used in a variety of electronic devices. These boards are fabricated from flexible plastic substrates having a thin copper metal laminate layer and can have conductive metal on one or both surfaces with through-hole interconnections. During circuit fabrication, copper is selectively removed by chemical etching or is pattern plated to leave a pattern of the desired interconnecting circuitry between various components in an electronic circuit. With improvements in etching technology, intercircuit line spacings approaching two-thousandths of an inch can be achieved. Narrow line spacing is one of the current technical innovations that permit continued miniaturization of complex circuitry. However, a narrow line width can promote delamination.
As a result of the problems in laminate preparations and the rigors of the laminate use, an increase in the bond strength of the metal layer to the film polymer substrate is a highly desirable end in the production of inexpensive delamination resistant metal-film laminates. Further, production of low cost polyester laminate and low cost polyimide laminate, free of a "tie coat", has not been achieved despite a long felt need.
Accordingly, a substantial need exists for delamination resistant metal-film laminates and for processes for the preparation of such laminate materials from the film materials including polyester and polyimide. A further need exists to form delamination resistant metal-film laminates on hard to bond films. The preferred laminates are substantially resistant to delamination caused by either chemical treatments or mechanical stresses.
We have found in the manufacturing of metal-film laminates, that a laminate resistant to delamination can be made by a process comprising (1) treating a film with a plasma, comprising ionized oxygen produced from a metallic electrode, to form a metal or metal-oxide treated film, (2) forming a first sputtered chromium metal or chromium alloy layer with a thickness of about 5 to 100 Å, preferably 10 to 100 Å, (3) followed by a second metal layer preferably by vacuum metallization of copper, onto the chromium-alloy layer. Such films have many uses and can be used in the manufacture of thicker laminate by forming a electroplated metal layer with a thickness of 0.1 to 35 μm on the metallized layer. Such a layer can be followed by electroless deposits of noble metals without reduction in peel strength. Swisher, U.S. Pat. Nos. 5,112,462; 5,137,791; 5,364,707 and 5,480,780 teach certain aspects of this process.
The plasma pretreated film surface, the metal-oxide, the sputtered layer, the vacuum metallized layer and the electroplated metal layer cooperate to ensure that the formed metal surface is securely bonded to the film and is delamination resistant. The peel strength of the resulting laminate can be greater than about 3 pounds per inch, and can under ideal conditions be in excess of 10 pounds per inch. Unlike laminates made by other processes, the peel strength of the laminate of the invention, and in particular polyimide laminate, can be substantially resistant to change when exposed to heat, chemical treatment, mechanical stress or environmental stress.
In the production of a plasma comprising ionized oxygen, an electric field is established across the plasma producing gas. The electric field exhibits a potential difference across the gas which can maintain a suitable plasma supporting ionizing current. In the production of the plasma, conductive rods are introduced into the plasma chamber and act as source or drain electrodes for the current. Such electrodes can be either positively or negatively biased and are typically made of plasma resistant or corrosion resistant metals such as copper, titanium, stainless steel, aluminum, etc. The rods can contain a large variety of metals. We have found in the production of plasmas useful in manufacturing the treated films of the invention, that the plasma production is preferably conducted with sufficient current flow such that metal atoms or clusters, are driven from the metal electrodes, are partially or completely oxidized to metal-oxide and interact with and bond to the surface of the film forming a novel structure. We have found that the metal-oxide or metal-oxide clusters, which are embedded in the polymeric film, in a random discontinuous fashion cooperative with subsequent layers and are characteristic of the high peel strength produced in the invention. This structure retains high peel characteristics even if electrolessly plated.
We have further found that this process and product is suitable for the fabrication of a variety of products and is particularly suited to the production of flexible printed wiring (printed circuit) boards made by pattern plating metal or by selectively etching or removing metal from the laminate leaving a wiring pattern on the surface of the film. Unlike many laminates which need both acidic and basic etchants, a printed wiring board can be made from the laminate of the invention with a single basic chemical etching step. Further, the process and product of the invention can be used in the manufacture of double sided printed wiring boards with through hole interconnections. Further, the flexible laminates of the invention can be adhered to more rigid support materials such as cardboard, epoxy prepreg, corrugated board, polymer sheets, engineering plastic sheets, etc. The printed wiring boards made using the laminate of this invention can be plated, etched, cut, drilled, assembled, soldered and used under usual operating conditions with no significant delamination caused by such environmental stress, mechanical stresses or chemical treatment steps. In copper-polyimide laminate manufacturing, after the plasma treatment step, but before the vacuum metallization step, a metal sputtering, preferably a chromium metal or chromium alloy sputtering step can be practiced to further improve peel strength.
By the term "ionized oxygen" we mean a material that, when placed in the heated, reduced pressure, electric field conditions that form an ionized plasma, forms an oxygen plasma or oxygen ions through the ionization of single atoms or molecules of oxygen or by the disruption of molecules containing oxygen atoms.
FIG. 1 is a cross-sectional representation of a low pressure single unit vacuum treatment chamber including stations for a film roll, plasma metal/metal-oxide treatment, chromium metal or chromium alloy sputtering, vacuum metallizing with copper or other metal and a treated film take-up roll. The unit contains regions that can vary in pressure from area to area.
FIG. 2 is a graphical representation of the relationships between ionized oxygen plasma input power and final 90� peel strength.
We have found a novel metal-film laminate structure exhibiting a substantial increase in peel strength between metal and film polymer surface when compared to prior art metal-film laminates. The novel structure comprises a random distribution of metal-oxide or clusters of metal-oxides of metals including Cr, Ti, Fe, Ni, Mo, Mn, Zr, Al, or other metals common to metallic electrode rod materials, e.g., stainless steels etc., on the surface of the polymer film which aid in bonding the metallized layer to the film. Such atoms are introduced into the surface of the polymeric film in an initial oxygen plasma treatment of the polymer surface and are believed to be less than 20, more likely less than 5 atomic layers in thickness. Such randomly located metal-oxide regions are preferably noncontiguous and act as anchoring sites binding the metallized layer to the film. The metal atoms or oxide clusters are deposited on the polymer film during plasma treatment. The potential difference and resulting ion current between metal electrodes causes metal to leave the plasma generating electrode and to deposit on and bond to the film polymer surface as a metal or metal oxide cluster.
After the oxygen plasma treatment, a metal sputtering step can be used to form a metal layer having a thickness of about 5 to 100 Å, preferably 20 to 100 Å. Following such steps, a thin conductive metal layer, preferably copper, can be formed, preferably by vacuum metallization. The conductive layer can comprise copper, silver, gold, aluminum, polymeric conductive layers, etc. Preferably, a copper vacuum metallization step is used. The step forming the conductive layer results in a layer having a minimum thickness of about less than 2000 Å, typically having a thickness of 10 to 1800 Å, repeated vacuum metallization treatment can increase the thickness to greater than 500 nanometers if needed.
The laminate comprising the plasma treated film and a first metallized layer has a variety of end uses. Metal thicknesses greater than about 300 nanometers can be used in the manufacture of printed circuits having current densities below about 4000 amps per square centimeter. Such films can be used in the formation of printed circuits using a variety of etching modes including printing a resist using laser jet printer technology supported by circuit design software. If large current flows are planned, thicker conductors can be made by forming a second layer on the metallized layer. Onto the metallized layer can be formed an electroplated layer having a thickness of at least 0.1 μm and typically having a thickness of about 2 to 50 μm.
After fabrication of the metal film laminate, no clear distinction with respect to origin can be drawn between any arbitrary atom in contact with the film surface through the metallization layer into the second layer formed. The metal layer appears to be unitary, even though its formation is step-wise.
The process of the invention is performed by passing a film through a plasma chamber containing metal electrodes. After evacuation of the chamber to a desired pressure, a gaseous material producing ionized oxygen is passed into the chamber at a flow rate to maintain an ionized oxygen plasma with a desired pressure and purity. Power is applied to the working electrodes at a useful current with a steady or pulsed D.C. potential and power level sufficient to create the oxygen plasma. The laminate film material is passed through the oxygen plasma at a distance from the electrode such that the film surface is fully contacted with the plasma and metal-oxide driven from the electrode can impact and bond to the polymer film surface. The plasma treatment can also cause the film material to be dried or cleaned of materials that can interfere in the vacuum metallization or later formation of metal coatings onto the film surface. The temperatures and pressures common in plasma treatment remove surface water, volatile hydrocarbon material and unreacted monomer. After plasma treatment, the film can be vacuum metallized. A second conductive or metal layer then can be formed.
Films that can be used for forming the metal film laminates of the invention are commonly organic film-forming compositions that can be formed from a variety of common polymeric films including addition polymers, condensation polymers, natural polymers, treated films, thermosetting or thermoplastic resins.
Useful thermosetting resins include phenolic resins, phenol-aldehyde resins, furan resins, amino-plast resins, alkyd resins, allyl resins, epoxy resins, epoxy prepregs, polyurethane resins, thermosetting polyester resins, polyimide bis-maleimide resin, polymaleimide-epoxy resin, polymaleimide-isocyanate resin, silicone resins, cyanate resins, a cyanate-epoxy resins, a cyanate-polymaleimide resins, and a cyanate-epoxy-polymaleimide resin; thermosetting so-called "IPN" as obtained by compounding the above thermosetting resins and engineering plastics such as polyamide (Nylon), aromatic polyester, polyetherimide, polyetherether ketone, polysulfone, and polyphenyleneether, and further adding a catalyst; crosslinkable resins obtained by compounding an organic peroxide as a crosslinking agent and a radical polymerizable polyfunctional compound, a thermosetting resin and the like to resins. Because of the nature of thermosetting resins, they cannot be further heat processed without severe distortion or destruction.
Polyimide film can be used in the preferred film laminate. Preferred polyimides are typically made by a two step reaction involving contacting a tetrabasic acid dianhydride with an aromatic diamine giving first a polyamic acid which is then converted by heat or catalyst into a high molecular weight, linear polyimide. Such polyimides are easily produced as film or sheet.
An infinite number of polyimide structures are possible limited only by the number of available dianhydrides and diamines. An example of a commercially important polyimide is a polypyromellitimide that is available as one of a series of films manufactured by duPont prepared by the condensation polymerization of pyromellitic anhydride and 4,4-diamino-diphenyl ether. Polyimides having excellent thermal and thermal-oxidated stability (with higher costs) can be obtained from fluorinated dianhydrides especially 6F-dianhydride. Fluorinated diamines can also be used such as 2,2-bis[4-(4-amino phenoxy) phenol]-hexafluoropropane. Similar poly(amide/imide) and polyether imide can be used using more flexible aromatic groups such as aromatic ethers and amides. Other dianhydride compounds that can be used include biphenyl dianhydride, benzophenone dianhydride, 1,2,4,5-benzene tetracarboxylic acid dianhydride (3,3',4,4'-benzophenone-tetracarboxylic acid dianhydride (BDTA). Other useful diamines include para-phenylene diamine, 4,4'-oxybisbenzeneamine, meta-phenylene diamine, and others. Such materials can be treated to improved their anti-slip properties, and can be made using improved tin catalytic materials resulting in materials having high heat stability, metal adhesion, and aging properties. Depending on end use, storage environment, processing, and other variables, different films may have useful properties depending on monomer solution, preparation, treatment, etc. A variety of preferred polyimide films are available from duPont.
After electroplating the metal, preferably an electroplated copper layer, the formed circuit layers then can be electrolessly coated with a variety of corrosion resistant or noble metals. Such metals include gold, silver, platinum, paladium, nickel, etc. and alloys thereof. Electroless plating is the controlled auto-catalytic deposition of the continuous film binding interaction in typically aqueous solution of a metal salt and a chemical reducing agent. Electroless deposition can give films with metal alloy compounds, and composites on both conductive and non-conductive surfaces. The area of practice of electroless plating parallels that of electrolytic plating. The main difference between electroless and electrolytic plating is the source of electrons used for metal reduction forming the metal coating. In electroless plating electrons used in reduction are supplied from a chemical reducing agent present in solution or suspended in an aqueous medium. Electroless solutions are not thermodynamically stable because the reducing agent and the metal salt are always present and ready to react to form the metal coating. Preferred electroless solutions contain a metal salt, reducing agent, pH adjuster or buffer agents, completing agents and one or more additives to control stability, improve film properties, control deposition rates, etc. Only a few metals (nickel, copper, gold, silver, platinum, paladium) are use on any significant scale. Plating tanks are preferably plastic or are lined with plastic or rubber coatings. Tanks linings must be stripped with metal deposits using acid solutions periodically. In using electroless plating in the manufacture of printed circuits or printed wiring boards both as a flexible or rigid substrates, a diverse field of electroless plating is known. Numerous variations exist in solution processes and techniques.
Thermoplastic resins are also useful in the laminate films of the invention. Useful addition polymers include poly alpha-olefins, polyethylene, polypropylene, poly 4-methyl-pentene-1, ethylene/vinyl copolymers, ethylene vinyl acetate copolymers, ethylene acrylic acid copolymers, ethylene methacrylate copolymers, ethyl-methylacrylate copolymers, etc.; thermoplastic propylene polymers such as polypropylene, ethylene-propylene copolymers, etc.; vinyl chloride polymers and copolymers; vinylidene chloride polymers and copolymers; polyvinyl alcohols, acrylic polymers made from acrylic acid, methacrylic acid, methylacrylate, methacrylate, acrylamide and others. Fluorocarbon resins such as polytetrafluoroethylene, polyvinylidiene fluoride, and fluorinated ethylene-propylene resins. Styrene resins such as a polystyrene, alpha-methylstyrene, high impact polystyrene acrylonitrile-butadiene-styrene polymers and others and reinforced materials obtained by compounding glass, carbon, alumina, other fibers, fiber cloth, powder and other fillers to the above polymers of these, those having a glass transition temperature of at least 160� C. are preferred. In particular, polymers having a glass transition temperature of at least 140� C. and preferably a Tg of 180� C. or more is preferred in that the metal treatment or forming conditions used during the formation of the copper film can be chosen from a wider range.
A variety of condensation polymers can also be used in the manufacture of the laminates of the invention including nylon (polyamide) resins such as nylon 6, nylon 66, nylon 10, nylon 11, nylon 12, etc. A variety of polyester materials can be made from dibasic aliphatic and aromatic carboxylic acids and di or triols. Representative examples include polyethylene-teraphthlate, polybutylene teraphthlate and others.
Polycarbonates can also be used in the manufacture of the invention. Such polycarbonates are long chained linear polyesters of carbonic acid and dihydric phenols typically made by reacting phosgene (COCl2) with bisphenol A materials resulting in transparent, tough, dimensionally stable plastics. A variety of other condensation polymers are used including polyetherimide, polysulfone, polyethersulfone, polybenzazoles, aromatic polysulfones, polyphenylene oxides, polyether ether ketone and others.
Preferred material for use in the laminate of the invention are polyester film materials such as poly-ethylene-teraphthlate, polybutylene teraphthlate and polyimide materials. These film materials are sold by duPont, Allied-Apical, Teijin, Kanega-fuchi, as Mylar�, Kapton�, Apical�, Upilex�, etc., films. The duPont Kapton� film series are most preferred.
The metals useful in forming the metal film laminate of the invention are metals commonly found in the laminate film applications of the invention including packaging insulation, labels, decorative layers, anti-static films or reflective layers, etc. Such layers are often shiny, metallic layers not subject to substantial corrosion from atmospheric conditions and have substantial electrical conductivity. Preferred metals for use in forming the laminate structures of the invention include aluminum, copper, gold, silver, chromium alloys including chromium and a second metal, chromium and two or more alloy metals, etc.
Preferred chrome alloys include chrome nickel alloys, chrome-nickel-iron alloys, chromium-molybdenum alloys, chrome-cobalt alloys, chrome-copper alloys. Preferred chromium alloys include Inconel� (about 75/15/5--Ni/Cr/Fe), Nichrome� (nickel and about 1-25 parts be weight chromium per each 100 parts of alloy), Permalloy�, and constantan.
Although gases normally act as electrical insulators, at sufficiently high temperature or current densities a gas can become a conductor. A plasma generated under such conditions contains free electrons and free positively charged ions. At sufficiently high electron densities, an ionized gas becomes a plasma. The basic property of a plasma is a substantial electrical neutrality. In other words, the numbers of negative charges and positive charges free in volume are approximately equal. The ionization energy of the gas forming the plasma typically is supplied by applying an electric field to the gas to accelerate and scatter ionized electrons and positive ions. For plasma formation to occur, a sufficiently high electric field must be applied. The strength of the electric field depends on the geometry of the plasma chamber and the pressure of the gas. Basic variables of concern in the production of plasma are number densities of electrons and positive ions, plasma pressure, temperature, electric and magnetic field strength and particle velocity.
The electric field through the gas to be ionized to form a plasma is established by applying a potential difference across electrodes inserted in the plasma chamber. Such electrodes for use in this invention are typically manufactured from corrosion and plasma resistant metals such as copper, stainless steel, titanium, aluminum, etc.
Current flows through the plasma from electrode to electrode. The biased current flow in the rods can cause metal to be transferred from electrode to film surface. We have found that in the operation of the plasmas of the invention, that a thin, random, preferably noncontinuous distribution of metal-oxide occurs across the film surface. Such metal-oxide typically comprise oxides of chromium, titanium, iron, nickel, etc., or mixtures thereof. We believe these scattered noncontinuous atoms are characteristic of the formation of the delamination resistant metal layers formed by the subsequent metallization and metal layer formation.
We have found that the 90� peel strength of metal laminates formed in the process of the invention, varies directly with the power used in the plasma generation assuming a constant plasma geometry and throughput of a film. Treatment of a film having a width of 60 to 70 cm and a thickness of 1 to 5 thousandths of an inch in a plasma, we have found that plasmas generated with greater than about 400 watts produce finished film laminates having a peel strength of greater than 3 pounds per inch and at about 800 watts or greater, peel strengths can be on the order of 5 pounds and greater. The increasing power of the plasma appears to increase the peel strength of the laminate.
We have also found that the metal layers formed using the process of this invention are layers having little internal stress. Prior art metallized layers often are higher stressed resulting in curling or surface distortion.
The plasma volume can take any convenient geometrical size or shape if sufficient time of contact between the high energy plasma and the polymer film occurs. Further, the film can be passed through the plasma volume at any speed ensuring substantial contact. However, we have found that the preferred mode of passing the film through the plasma volume is by a repeated passage of the film past multiple plasma generating electrodes. Often the plasma treatment is conducted in a continuous process in which a long continuous film web is passed through a treatment plasma volume. Such webs can be of substantial length and can require significant process times. Such plasma zones operated at low pressure require low gas leakage from any entrance and exit for the film web. Pressures common in the plasma chamber are less than about 150 mTorr and are preferably between 20 to 80 mTorr. Since substantial gas leakage can occur at the entrance and exit, substantial effort must be directed to the maintenance of proper gas mixture within the chamber and the proper pressure.
Sputtering is a material transportation phenomenon caused by energetic ions striking a cathode causing the material making up the cathode to be transferred to a different surface through a momentum transfer mechanism. In the performance of a sputtering technique, the substrate to be coated is placed adjacent to a cathode made of the substance which will form the coating. The cathode is subject to a high negative voltage and is placed in an inert gas atmosphere at low pressure. Under the influence of the high voltage potential difference, atmospheric ions are accelerated against the surface of the cathode wherein the momentum of the ions is transferred to atoms on the surface of the cathode, ejecting the atoms from the surface of the cathode and causing them to contact and adhere to the adjacent substrate. Such sputtering process parameters which affect the sputtering rate include mass and energy (accelerating voltage) of the impinging ions; gas temperature; electrode spacing; material and crystalographic orientation of the cathode; cathode surface (containment layers) and cathode shape and shielding. Inert gases useful for such sputtering techniques include helium, neon, argon, krypton, xenon, nitrogen, etc. Preferably, a chromium metal or chromium alloy is sputtered to a layer having a thickness of 2-100 Å, preferably 2-100 Å.
We have found in many films, preferably in polyimide films, that a sputtering step, performed after the metal oxide/plasma step, can also significantly increase laminate properties.
The plasma treatment, sputtering and metallization steps are each carried out at relatively low pressure, typically less than 200 mTorr. These processes can be carried out in a single chamber which is divided into sections operated at a pressure that is optimized for each step. Typically, the metallization occurs at pressures less than 0.5 mTorr, the sputtering occurs at pressures less than 30 mTorr, while the plasma treatment occurs at pressures between 30 and 200 mTorr.
The plasma treated film is then contacted with a source of a conductive layer. Preferably, a source of metal vapor is used to form a metallized layer on the plasma treated film. Vapor metallization is a low pressure, high temperature (energy) process in which metal vapor is formed. A variety of other layers can be used including carbon, conductive polymers, etc.
Vapor metallization occurs in three basic modes. First, metal wire can be directed into a hot boat or other container at high temperatures and low pressures wherein the metal melt formed in the boat is converted into vapor. Secondly, electron beam excitation of a metal held at low pressure and approximately ambient temperature can cause the production of a pool of molten metal and a metal vapor. Thirdly, the induction heating of metal in a susceptor vessel can result in the production of useful quantities of metal vapor at low pressure.
In common vapor metallization processes, metal is vaporized at a rate sufficient to maintain the substantial quantity of vapor in the treating area. At pressures common in a vapor metallization chamber, metal deposits can be formed at a rate of about 100,000 to 300,000 angstroms per minute. The high energy metal vapor when contacted by organic film layers often condenses and bonds to the substrate forming a thin metallized layer with a characteristic thickness of about 2 to 2000 Å, preferably about 10 to 1800 Å, most preferably about 1000-1750 Å. Pressures common in vapor metallization chambers are less than about 0.6 mTorr and are preferably about 0.1 to 0.3 mTorr or less.
The chamber can optionally contain a metal sputtering station used to sputter a second metal layer on the plasma treated surface prior to metallization.
The plasma treated, metallized film is particularly suited for the subsequent formation of thick metal layers such as those useful in the end uses discussed above. Such layers can be formed in a variety of techniques, however, electro-plating and electroless plating are the most commonly used metal layer formation techniques.
Electro-plating is the electrodeposition of an adherent metallic coating on an electrode surface to form a metal deposit. The electrode surface being treated is made the cathode in an electroplating solution or bath. Such baths are typically aqueous solutions from which metal is reduced by the flow of an electric current through a solution of the metal salt. In performing electro-plating of metal on a conductive electrode, the electrode or substrate is often cleaned, rinsed, dipped in acid or is subject to other pretreatment or substrate preparation. In operating electro-plating techniques, the substrate is immersed into a solution and necessary DC power is applied typically from metallic anodes to the substrate cathode. The solutions are often agitated and the temperature current metal concentration and other variables are closely controlled using well known principles.
In the preparation of metal laminates of the invention, the laminate metal is typically copper plated onto a substrate having a metal layer prepared using the copper metallization techniques.
Useful copper layers, can also be formed using electroless plating which is the controlled autocatalytic deposition of a continuous film by the interaction, in a solution of metal salt between a metal and a chemical reducing agent. Electroless deposition can give films of metals, alloys, metallic compounds, and composites on both conductive and non-conductive surfaces. Electroless solutions contain a metal salt, reducing agent, a pH adjuster or buffer, a complexing agent and one or more additives to control solution stability, film properties, deposition rates, etc. Primarily, nickel, copper, gold, paladium and silver are plated using electroless techniques. The advantage of electroless plating is the ability to plate metal on non-conductive or poorly conductive surfaces.
Once the metal layer(s) are formed, a printed wiring board can be made by forming the circuit pattern in metal on the film. The pattern can be formed by an etching process or by a semi-additive pattern plating process. In an etching process, a resist and basic etchant baths are used to selectively remove copper leaving the pattern. Alternatively, a conductive circuit pattern can be formed on the laminate of the invention using a semi-additive technique. In such a technique, the circuit pattern is formed in a way to significantly reduce the amount of metal removed through an etching step. In the semi-additive technique, after the first metal layer is formed using metallization, a resist is formed on the first layer. The resist leaves revealed, the first metal layer in the pattern of the desired circuit. Onto the revealed pattern is plated a thick, 0.1 to 40 μm layer of copper using commonly electroplating or electroless techniques. After the second metal layer in the desired pattern is complete, the resist can be removed leaving the thick metal pattern and in the areas revealed by the removal of resist, the thin metallized layer. The remaining revealed metallized areas are then removed using a light etch. The metallized layers are thin and require brief etching and it substantially reduces the amount of metal removed, the amount of etchant consumed and substantially reduces the amounts of waste materials.
FIG. 1 is a cross-sectional representation of a single unit treatment chamber containing plasma treatment, metal sputtering and vacuum metallizing stations, each station having a different operating pressure. Film to be treated is provided by a film roll 10 which delivers film 10a to the plasma treatment station 11. Plasma treatment station 11 is operated at a pressure of about 30 to 150 mTorr and contains stainless steel glow rods 13 fixed in position to treat surface of the film as it passes through the plasma treatment station 11. The rods are fixed in a frame 14 maintained by supports 14a. The film passes over a series of rollers 12 for a multiple passes near the treatment rods 13. The film passes from the plasma treating station and re-enters the upper vacuum chamber 16 maintained at a pressure of about 3 to 30 mTorr and can be treated by a sputtering station 15 for a chromium metal or chromium alloy coating. The film then passes to a coating roll 17 wherein the surface of the film can be exposed to a metallic vapor in a lower chamber 18 having a residual gas pressure of about 0.1 to 0.4 mTorr. Copper wire is introduced into heated boats 19 at a temperature of about 1600� C. At this temperature and pressure, substantial quantities of copper vapor are created which condense and adhere to the film in a uniform low stress metal coating. After vacuum metallization is complete in chamber 18, the film 10a is introduced into a take-up mechanism 20 where on the film 10a is wound on a roll.
FIG. 2 is a graphical representation of the relationship between plasma input power and the 90� peel strength of electro-plated films made using the treatment of the invention. The figure shows that the increase in peel strength is directly proportional to the increase in plasma input power which is related to the ability of the plasma to form a random distribution of metal-oxide on the cleaned-treated film surface. These randomly distributed metal-oxide regions cooperate in bonding first the vacuum metallized layer and secondly, the second metal layer formed on the film and act as an important part of the novel attachment structure.
An experiment was conducted to determine the properties of laminate made according to the invention involving an oxygen plasma treatment, and a copper vapor metallization of polyester film. The film is treated in the treatment mechanism of FIG. 1 with no subsequent metal sputtering (except for Example 2) at sputter station 15 (see FIG. 1). The goal of the polyester treatment experiment was to find important parameters affecting single pass treatment of film and copper deposition. An initial goal was to obtain greater than 1 pound per peel strength on 1 ounce copper plated on the polyester film. We have monitored the variables in the test including coating drum temperature, fraction of water vapor in oxygen gas treatment, rod current at set voltage, gas pressure, film speed, film thickness, etc. We have found the only statistically significant variable in obtaining high peel strength are film speed through the treatment unit and current in the treatment unit at a fixed voltage. Both these variables indicate that the production and treatment of film with metal-oxide in the plasma unit is a major contributor to increase peel strengths. Increasing the film rate through the treatment would tend to reduce the effects of the plasma treatment on the film. Varying the current in the treatment unit would also vary the amount of treatment occurring on the film surface. We have found that by increasing the power input to the plasma treatment unit and maintaining the film speed at certain controlled rates, that a fully treated film can be prepared having high peel strengths after plating.
TABLE I__________________________________________________________________________The results of this experiment and similar experiments are shown graphically as FIG. 2 which relates plasma power against 90� peel strengthlb/in. Polyester Film Plating 1/2"- Thick- O2 Sput- Step 90� ness Gas Flow Press tered Thick- Peel Ex. (mils) (cc/min) mTorr Volts Amps Rod Cu Metal ness Strength__________________________________________________________________________1 3 14 31 2000 0.46 S.S.304 No Cu 35 μM 5.00 2 3 14 31 2000 0.46 S.S.304 Yes Cu 35 μM 4.60 3 5 28 50 650 0.10 S.S.304 No Cu 35 μM 0.77 4 3 32 50 1100 0.46 S.S.304 No Cu 35 μM 2.35 5 3 36 100 700 0.46 S.S.304 No Cu 35 μM 3.60 6 3 25 100 700 0.46 S.S.304 No Cu 35 μM 3.50__________________________________________________________________________
An experiment was conducted to determine the nature of the surface of a polyester film made according to the invention involving the oxygen plasma treatment produced by metal electrodes. The film was treated in a plasma treatment mechanism of FIG. 1 with no metal sputtering step. The goal of the polyester treatment experiment was to discover how the plasma treatment changed the nature of the treated polyester surface. In the experiment, large rolls of PET film were copper vacuum metallized at speeds ranging from 10 to 100 feet per minute in the mechanism of FIG. 1. The films were treated in a large plasma treatment chamber.
Several of the treated PET films were submitted for evaluation of the nature of the metal on the surface of the PET film. Samples were analyzed by ESCA and ISS under identical conditions. Angle resolved ESCA analysis was performed to enhance surface sensitivity. In the conventional or "normal" mode of ESCA data collection, electron detectors oriented to view the sample along a perpendicular to the sample surface. For the angle resolved or "tilted" mode, the sample was tilted so that only electrons escaping in an angle approximately 12� from the surface are detected. Normal ESCA spectra represent sampling depth of 82-100 Å wherein the tilted spectra represent a depth of 20-30 Å. Additional data were obtained by scanning narrow energy regions of the spectrum at higher resolutions to determine the relative amounts of specific elements in various bonding states such as carbon bonded as carbon to carbon, carbon-oxygen, carbon-carbonyl and carboxy. ISS (Ion Scattering Spectroscopy) and SIM (Secondary Ion Mass Spectroscopy) analysis were done on the selected samples. Comparing the elemental depth profile for information from ISS on the raw and on the plasma-treated polymer, chromium and copper are detected on the film surface. Neither copper or chromium is detected on raw untreated polymer. The chromium on the film is derived from the stainless steel components of the plasma generating mechanism and is believed to be in the form of chromium-oxide regions. Copper is derived from the vacuum metallizing station. In performing the analysis, a small proportion of each sample approximately 1/2 in2 was cut and mounted on a stainless steel stub with double faced adhesive tape. All samples for analysis were analyzed with a Kratos X-San 800 combined scanning auger microprobe ESCA (Electron Spectroscopy for Chemical Analysis also termed X-Ray Photo Electron Spectroscopy) equipped with a turbo molecular pump sample introduction system and DEC micro PDP-11 computer data acquisition system with a Tektronic color terminal and color printed. System and base pressures normally maintained below 2�10-10 Torr using a 300 liter per second ion pump and titanium sublimators to minimize contributions from vacuum contaminants. The sample is excited by a dual anode x-ray source with a choice of aluminum or magnesium anodes.
The presence of chromium in such copper layers and on the surface of the products of the invention indicates that the metal plasma generating electrodes used in the plasma treatment station introduces metal atoms onto the surface of the treated polyester film. The chromium atoms embedded in the film act in concert with subsequent metal layers as a structured attachment layer that significantly increases 90� peel strength.
An experiment was conducted to determine the properties of a polyimide film-copper laminate made according to the invention involving an oxygen plasma treatment using a variety of metal electrodes, a copper sputtering treatment in an inert atmosphere, a copper metallization step which was then plated with copper to a thickness of from about 0.85 to 3.5 thousandths of an inch in thickness which was then tested for peel strength under wet and dry conditions. The thickness of the film ranged from 1 to 5 thousandths of an inch. The plasma treatment was done in an oxygen atmosphere. Copper was sputtered in an inert atmosphere on to the polyimide film and a thin layer of a copper was then metallized under typical conditions. The data summarized on the table below show that the treatment of the polyimide materials using such techniques result in very high peel strengths attained in the absence of a chromium "tie coat". Further, surprisingly, the peel strengths of the polyimide laminate material remains high in the presence of substantial humidity. In the past, polyimide laminates, when exposed to high humidity, could lose as much as 80% of the peel strength. The data below show that while the peel strength in certain experiments drops some, the percentage loss of peel strength due to humidity is significantly improved.
TABLE II__________________________________________________________________________Laminate Preparation Plasma Treater Sputtering PlatingFilm Thk. Rod Pressure Vapor Dep. Thickness Example Type (�0.001 in) Gas Type Metal millitorr Volts Amps Metal (�0.001 in)__________________________________________________________________________8 Kapton 2 O2 S.S. Cu 10.4 500 6.0 Cu 2.00 Lamtech 9210 2 O2 S.S. Cu Cu 10 Apical NP 2 O2 Cu. Cu 8.8 460 5.2 Cu 3.30 Kapton 2 O2 S.S. Cu 10.4 500 6.0 Cu 1.90 Apical NP 2 O2 Ti. Cu 8.8 460 5.2 Cu 1.50 Apical NP 2 O2 Al. Cu 8.9 480 4.4 Cu 1.50 Apical NP 2 O2 S.S. Cu 10.4 500 6.0 Cu 0.85 15 Apical NP 2 O2 Cr. Cu 8.5 500 4.3 Cu 2.30 Apical NP 2 O2 S.S. Cu 6.6 480 2.2 Cu 1.70 Apical NP 2 O2 S.S. Cu 6.6 480 2.2 Cu 3.13 Apical NP 2 O2 S.S. Cu 6.6 480 1.0 Cu Apical NP 2 O2 S.S. Cu 6.3 480 5.0 Cu 1.15 20 Apical NP 2 O2 S.S. Cu 10.5 460 4.0 Cu 1.47 Apical NP 2 O2 S.S. Cu 10.4 500 6.0 Cu 1.70 Apical NP 2 O2 S.S. Cu 6.6 480 1.0 Cu Apical NP 2 O2 S.S. Cu 6.6 480 1.0 Cu 1.70 24 Apical NP 2 O2 S.S. Cu 6.6 480 1.0 Cu 25 Apical NP 2 O2 S.S. Cu 6.6 480 1.0 Cu 1.10 Apical NP 2 O2 S.S. Cu 6.6 480 1.0 Cu Kapton VN 2 O2 S.S. Cu Cu 3.20 Apical NP 2 O2 S.S. Cu 6.6 480 1.0 Cu Apical NP 2 O2 S.S. Cu 10.4 500 6.0 Cu 1.67 30 Upilex R 1 O2 Cr. Cu 8.5 500 4.3 Cu 2.47 Upilex R 1 O2 Cu. Cu 8.8 460 5.2 Cu 1.70 Kapton VN 2 O2 Cr. Cu 8.5 500 4.3 Cu 2.85 Apical NP 2 O2 S.S. Cu 6.6 480 2.2 Cu 1.60 Kapton H 2 O2 S.S. Cu 10.5 460 4.0 Cu 1.85 35 Kapton VN 2 O2 Al. Cu 8.9 480 4.4 Cu 1.30 Kapton H 2 O2 Al. Cu 8.9 480 4.4 Cu 1.25 Upilex R 1 O2 Al. Cu 8.9 480 4.4 Cu 1.44 Kapton H 2 O2 Cr. Cu 8.5 500 4.3 Cu 1.50 Kapton VN 2 O2 S.S. Cu 10.5 460 4.0 Cu 1.73 40 Kapton H 2 O2 Cu. Cu 8.8 460 5.2 Cu 2.30 Upilex R 1 O2 Ti. Cu 8.8 460 5.2 Cu 1.50 Kapton H 2 O2 Ti. Cu 8.8 460 5.2 Cu 1.00 Apical NP 2 O2 S.S. Cu 7.3 520 6.0 Cu 1.07 Apical NP 2 O2 S.S. Cu 6.3 540 5.5 Cu 0.60 45 Apical NP 2 O2 S.S. Cu 6.4 530 5.0 Cu Upilex R 1 O2 S.S. Cu 10.5 460 4.0 Cu 1.00 Apical NP 2 O2 S.S. Cu 6.4 530 5.0 Cu 0.90 Kapton VN 2 O2 Cu. Cu 8.8 460 5.2 Cu 1.58 Apical NP 2 O2 S.S. Cu 12.8 480 5.0 Cu 0.90 50 Upilex S 1 O2 Cr. Cu 8.5 500 4.3 Cu 1.40 Upilex S 1 O2 Ti. Cu 8.8 460 5.2 Cu 0.80 Upilex S 1 O2 Al. Cu 8.9 480 4.4 Cu 0.90 ICI Upilex 2 O2 S.S. Cu 10.5 460 4.0 Cu 1.00 ICI Upilex 2 O2 Ti. Cu 8.8 460 5.2 Cu 1.50 55 Upilex S 1 O2 S.S. Cu 10.5 460 4.0 Cu 1.10 Upilex S 1 O2 Cu. Cu 8.8 460 5.2 Cu 1.23 ICI Upilex 2 O2 Cr. Cu 8.5 500 4.3 Cu 1.25 ICI Upilex 2 O2 Cu. Cu 8.8 460 5.2 Cu 1.46 59 ICI Upilex 2 O2 Al. Cu 8.9 480 4.4 Cu 2.47__________________________________________________________________________
TABLE III______________________________________Peel Strength Testing of the Materials in Table II Units: lbs/in width Example 90� 90� (wet)______________________________________8 11.2 10.9 10.0 10 8.0 6.4 7.3 7.2 7.0 6.4 6.9 7.3 6.8 6.8 7.3 6.6 6.5 6.5 6.2 5.7 20 5.7 5.5 5.6 5.8 5.6 5.6 4.2 5.6 5.6 5.5 5.4 28 5.4 29 5.3 5.2 5.3 5.7 5.2 4.4 5.1 5.7 5.1 3.8 5.1 5.3 4.9 6.2 3.8 5.6 4.7 3.9 4.7 5.2 4.6 5.8 40 4.6 4.7 4.4 3.6 4.2 4.3 3.8 3.6 45 3.6 3.5 3.6 3.4 48 3.4 3.4 49 3.3 2.4 1.9 1.4 1.8 1.6 1.7 2.4 1.6 1.2 1.6 1.3 1.6 2.2 1.6 1.7 1.3 1.2 1.2 1.2 59 1.1 2.1______________________________________
An experiment was conducted to determine the properties of a laminate made with polyester, polyethylene, polypropylene, poly-4-methyl-pentene-1, etc., according to the invention involving an oxygen plasma metal-oxide treatment and a copper vapor metallization of various films. In this experiment, a variety of poly films having a thickness of from about 1 to about 5 thousandths of an inch were treated in a plasma chamber using oxygen gas or water vapor using a variety of electrode types, including stainless steel, aluminum, chromium, titanium, and copper. After the plasma treatment, which created metal oxide regions on the film surface, the treated film surface was then metallized with copper using common copper vapor metallization techniques. After metallization was complete, the film was plated with copper to a thickness of from about 0.9 to about 2.2 thousandths of an inch and tested for peel strength. The results of these experiments are set forth in the table below showing substantial, reliable peel strengths for the copper film laminate material.
TABLE IV__________________________________________________________________________Laminate Preparation and Peel Strength Plasma Treater Plating Peel Thickness Rod Vapor Dep. Thickness Testing Example Film (�0.001 in) Gas Type Metal (�0.001 in) 90�__________________________________________________________________________60 Teijin SL 3 O2 S.S. Cu 5.00 Teijin SL 3 O2 S.S Cu 4.60 Teijin s1 3 O2 S.S. Cu 1.63 3.87 AH 4600 2 O2 S.S. Cu 3.6 ICI 377 3 O2 S.S Cu 3.5 AH 4660 3 O2 Al. Cu 1.5 3.08 AH 4660 3 O2 S.S Cu 1.00 3.05 Teijin s1 3 O2 Cr. Cu 0.90 2.81 Teijin s1 3 O2 Al. Cu 1.13 2.73 TPX 88 2 O2 Cr. Cu 0.90 2.65 70 Mylar D 2 O2 S.S. Cu 1.00 2.60 Mylar D 2 O2 Ti. Cu 2.00 2.56 Teijin SL 3 O2 S.S. Cu 2.35 Teijin SL 3 O2 S.S. Cu 1.40 2.10 TPX 22 2 O2 Cu. Cu 1.40 2.04 AH 3000 2 O2 S.S. Cu 2.00 ICI 343 2 O2 S.S. Cu 2.00 Teijin SL 3 H2 O S.S. Cu 1.95 Teijin SL 3 O2 Ti. Cu 1.00 1.94 Teijin SL 2 S.S. Cu 1.90 80 Teijin SL O2 SS Cu 1.50 1.90 Teijin SL 3 O2 S.S. Cu 1.40 1.80 AH RN 2 O2 S.S. Cu 1.70 Teijin SL 5 O2 S.S. Cu 1.69 Teijin s1 O2 SS Cu 1.5 1.64 TPX 22 2 O2 Al. Cu 1.50 1.62 Teijin SL 5 H2 O S.S. Cu 1.41 Teijin s1 O2 SS Cu 1.50 1.40 Teijin SL 5 H2 O S.S. Cu 1.37 89 AH 4660 3 O2 Cr. Cu 0.90 1.33 90 Teijin SL 3 O2 S.S. Cu 1.10 ICI 505 5 O2 S.S. Cu 1.10 1.10 SKC SN81 2 S.S Cu 1.10 Teijin SL 3 H2 O S.S Cu 1.05 AH WN 2 O2 S.S. Cu 1.00 AH 4660 3 O2 Ti. Cu 1.17 0.95 Teijin SL 5 O2 S.S. Cu 0.77 100 Polyethlene 1 O2 Cu. Cu 1.50 0.76 AH 440 2 O2 S.S. Cu 0.72 Teijin SL 3 O2 S.S. Cu 0.70 TPX 88 2 O2 S.S. Cu 1.40 0.62 Teijin SP2 2 S.S. Cu 0.60 Polypropylene 1 O2 Cr. Cu 1.30 0.60 Polyethylene 1 O2 Al. Cu 2.01 0.57 Polyethylene 1 O2 Ti. Cu 1.60 0.57 Polypropylene 1 O2 S.S. Cu 0.50 0.55 Polypropylene 1 O2 Al. Cu 0.95 0.53 Polyethylene 1 O2 Cr. Cu 1.50 o.51 TPX 88 2 O2 Al. Cu 1.30 0.43 Teijin SL 3 O2 Cu. Cu 2.00 0.30 110 AH 4660 3 O2 Cu. Cu 2.20 0.30 Polypropylene 1 O2 Cu. Cu 1.50 0.28 AH 4500 2 O2 S.S. Cu 0.21 Teinjin SP 2 S.S. Cu 0.20 Teijin HP7 2 S.S. Cu 0.20 SKC SH82 2 S.S. Cu 0.20 SKC SH92 2 S.S. Cu 0.12 ICI 505ST 5 O2 S.S. Cu 0.10 ICI 561 3 O2 S.S. Cu 0.10 119 TPX 22 2 O2 Ti. Cu NA 121 TPX 88 2 O2 Ti. Cu NA TPX 88 2 O2 Cu. Cu NA NA Mylar D 2 O2 Cr. Cu 1.03 no start* Mylar D 2 O2 Al. Cu 1.80 no start 124 TPX 22 2 O2 Cr. Cu 2.50 no start__________________________________________________________________________ *No start indicates a very high peel strength, i.e., greater than 5 pound per inch.
Two samples (10" each) of a 62" width double sided copper laminates formed on Apical NP (A) and Kapton VN film (B) with 1 oz. copper, were tested for dimensional stability (Methods B and C), chemical stability and moisture resistance.
Dimensional Stability Results
______________________________________ Method B Method CSample M.D. T.D. M.D. T.D.______________________________________A-side 1* -0.0319% +0.0201% -0.0437% +0.0361% A-side 2** -0.0409% +0.0362% -0.0469% +0.0357% B-side 1* +0.0163% +0.0517% -0.0198% +0.0415% B-side 2** +0.0090% +0.0351% -0.0126% +0.0384%______________________________________ *Two samples were tested, results were average. **One sample of side 2 was tested.
Using the apparatus set forth in FIG. 1 and generally using the conditions set forth in Example 1, a laminated film was made. The film was made from a duPont Kapton� polyimide having a first metal/metal oxide layer followed by a sputtered chromium layer followed by a vaporized copper layer prepared using metal vaporization followed by electroplating. The metal/metal oxide layer was produced in an oxygen atmosphere at 20 mTorr. The treater power was 2 kW. The chromium layer was about 80 Å and was formed using a sputter power of 8.2 kW in an argon atmosphere at 4 mTorr. Lastly, the vapor deposited copper layer had a thickness of about 1500 Å. Film was run through the chamber at 38 meter/minute.
Example 128 was repeated exactly except that the initial metal/metal oxide layer was formed using power at 2.5 kW and using a nichrome alloy (80/20 Ni/Cr) in the sputter step forming a layer of 70-100 Å in thickness.
The materials prepared in Examples 128 and 129 were tested for peel strength. Test films were made having 5 mil wide 15 μm thick conductors. The conductors were electrolessly plated with 4 μm nickel followed by 1 μm gold. The copper conductors and the electrolessly plated conductors have the following peel strength properties:
______________________________________As Plated with Cu, Ni and Au 5 lb/in After 10 sec/288� C. Solder Dip 4.8 After 24 hr/120� C. Steam (Pressure Cooker) 4 After 30 day/85� C./85% RH exposure 4.9______________________________________
Clearly, the materials made using the chromium metal or chromium alloy metal layers are superior in peel strength even after electroless treatment.
The above specification provides a complete description of the use and construction of the invention. Since many embodiments of the invention can be made without departing from the spirit and scope of the invention, the invention resides in the claims hereinafter appended.
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with 46.9 to go. Indiana's Briann January made two free throws with 12 ..... the ball on the other end, but January missed a jumper before the buzzer ..... to tie it with 1 second left. January missed a jumper as time expired
Fever-Sky Preview
third time in six years, but guard Briann January realizes that earning that victory ..... really well on their home court," January said. "We have to make our adjustments ..... to close it out in Chicago.'' January and Shavonte Zellous look to continue
Sylvia Fowles leads Sky past Fever in two OT to even series
triumphed in Game 2. Indiana's Briann January had eight points after scoring ..... Catchings, she stole the ball, but January missed a jumper before the buzzer. In the second overtime, January made two free throws with 12
Sky headed to WNBA Finals after beating Fever
begin the second half. Even with Delle Donne on the bench, Indiana's struggles continued. Trailing 39-33, Briann January committed a foul that lead to two Tamera Young free throws with 4:09 left in the third, stalling the momentum Indiana
Allie Quigley scores 24 as Sky eliminate Fever from WNBA playoffs
begin the second half. Even with Delle Donne on the bench, Indiana's struggles continued. Trailing 39-33, Briann January committed a foul that lead to two Tamera Young free throws with 4:09 left in the third, stalling the momentum Indiana
Fever hold off Sky, 77-70
INDIANAPOLIS (AP) Briann January scored 19 points and Shavonte Zellous added 18 to help the Indiana Fever beat the Chicago Sky 77-70 on Saturday night in the
Fever-Sun Preview
missing their leading scorer. With Briann January potentially back in the mix, Saturday ..... victory at Washington came without January - the team's leading scorer with ..... And that's all we focus on." January , who suffered her injury in practice
Sparks-Fever Preview
be even tougher if point guard Briann January is unable to play. Third on the ..... while averaging 4.3 assists, January left in the third quarter Saturday ..... with Atlanta's Shoni Schimmel. January totaled 23 points against the Sparks
Catchings' 21 points lead Fever past Sun 72-68
led Indiana with 21 points and Briann January added 13 to lift the Fever past ..... 11 from Catchings and eight from January . ''Once we got the energy and ..... cut the lead to single digits. January ' 3-pointer to open the fourth
Fever-Liberty Preview
minutes. Tamika Catchings finished with 25 points and Briann January added 14 for the Fever, who have won three straight ..... with Thursday's 76-63 home victory as Catchings and January combined for 31. The Liberty will miss the playoffs


text:
Posts Tagged 'Dick Clark's New Year's Rockin' Eve Ratings'
November 28th, 2012 at 7:44 am
Taylor Swift, Carly Rae Jepsen, Neon Trees, Fergie, Brandy, Flo Rida, Karmin, One Republic & Pitbull to Perform on 'Dick Clark's New Year's Rockin' Eve With Ryan Seacrest'
Ryan Seacrest hosts the year's biggest celebration at the crossroads of the world when Carly Rae Jepsen and Neon Trees join headliner[Read-More]
November 5th, 2012 at 1:05 pm
ABC Announces Holiday Movies and Specials Including Four Episodes of 'Extreme Makeover: Home Edition'
Begins Monday November 26[Read-More]
January 6th, 2012 at 9:48 am
ABC's "Dick Clark's New Year's Rockin' Eve with Ryan Seacrest 2012-Part 1" Outdraws its Combined NBC and Fox Competition by an Astounding 94%
Drawing 22.7 Million Viewers, "New Year's Rockin' Eve-Part 1" Scores an 11-Year High, Representing its 2nd-Largest Audience in the Last 2 Decades[Read-More]
January 1st, 2012 at 12:51 pm
Attracting 22.6 Million Viewers, ABC's Late-Night New Year's Rockin' Eve Hits an 11-Year High
11:35p-12:32 a segment averaged 22.6 million.[Read-More]
January 1st, 2012 at 9:13 am
TV Ratings Saturday: Dick Clark Rocks the New Year's Eve Competition
Happy New Year![Read-More]
December 6th, 2011 at 10:50 am
The Band Perry, blink-182, Christina Perri, Florence + The Machine, Gym Class Heroes, LMFAO, OneRepublic, Nicki Minaj, Taio Cruz And will.i.am to Perform on "Dick Clark's New Year's Rockin' Eve with Ryan Seacrest 2012"
Dick Clark and Ryan Seacrest will celebrate 40 years of history as they host "Dick Clark's New Year's Rockin' Eve with Ryan[Read-More]
September 8th, 2011 at 9:29 am
Lady Gaga To Perform Live From Times Square On "Dick Clark's New Year's Rockin' Eve With Ryan Seacrest 2012," December 31
40th Anniversary of "NYRE" to Begin at 8:00 p.m., ET with New Two-Hour Special[Read-More]
January 1st, 2011 at 10:21 am
ABC Dominates with 'Dick Clark's Primetime New Year's Rockin' Eve'
primetime portion draws biggest audience in 3 years.[Read-More]


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Learning science research and practical experience highlight the importance of interaction and engagement to successful learning. Active and collaborative learning environments are particularly effective for Net Generation learners. Games, simulations, group projects, and undergraduate research are among a number of models for interaction and engagement being explored.
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- Setting the Stage for Digital Engagement: A Five-Step Approach, EDUCAUSE Review, September/October 2014. The practical, pedagogical, and privacy implications of a smart, connected digital campus engaged with its constituents have yet to play out. To handle whatever comes next, colleges and universities must be well positioned today, with effective strategies in place.
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- Podcast: WMU's "Broncoland" is a Video Game for Student Success, This podcast features an interview with Kevin Abbott, project lead for 3D and interactive media at Western Michigan University, August 2013
- Continuous Improvement in Teaching and Learning: Open Learning Initiative (OLI) and Open Learning Net (OLnet), ELI Web Seminar, January 11, 2010
- Clickers and Peer Instruction: A Powerful Way to Improve Student Engagement and Learning, but Only If You Do It Right ELI Web Seminar, October 05, 2009
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- View "IT Accessibility: What Campus Leaders Have to Say"
November 13, 2012
Just prior to the EDUCAUSE 2012 Annual Conference , I noted that the AccessComputing project at the University of Washington would premier a video at the conference on technology accessibi…
- ECPA Reform Letter in Support of Leahy Amendment
September 17, 2012
The Senate Judiciary Committee will take action on September 20, 2012 on an update of the Video Privacy Protection Act (H.R. 2471), which the House passed in December 2011, and attach provisions …
- The Importance of Doing Enterprise (and Infrastructure)
October 17, 2012
...as Oscar Wilde well might have titled an essay about campus-wide IT, had there been such a thing back then. Enterprise IT it accounts for the lion's share of campus IT staffing, expenditu…
- A Comparison of the 2012 Republican and Democratic Platforms on Internet, Broadband, and Information Technology Policies
September 11, 2012
This document provides a summary of the 2012 Republican and Democratic Platforms, starting with a look at their overall approach to these areas, and then looking more closely at specific issues r…
- Ex Parte Contact in USF Contribution Methodology
August 30, 2012
On Wednesday, August 29, 2012, Greg Jackson (Vice President, EDUCAUSE) and John Windhausen (Telepoly Consulting), on behalf of EDUCAUSE, met with Vickie Robinson, Ernesto Beckford and Charles Ebe…
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October 5, 2012
Earlier this year, EDUCAUSE participated in a task force of higher education associations and organizations that have e-learning as a significant part of their strategic agenda. Supported by a gr…
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August 6, 2012
Reply comments sent by EDUCAUSE to the Federal Communications Commission on August 6, 2012 in the matter of the Universal Service Contribution Methodology (WC Docket No. 06-122), A National Broad…
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July 31, 2012
In this letter sent to Senate Majority Leader Reid and Minority Leader McConnell, EDUCAUSE joined with the Association of Research Libraries, businesses, and other trade associations to support …
- Free Digital Textbooks, More For-Profit Accountability Coming to California
September 28, 2012
As reported by Inside Higher Ed , new laws enacted in California will have significant impacts on higher education in the state. The Los Angeles Times reports that two companion pi…
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September 26, 2012
The National Association of College and University Business Officers (NACUBO) has provided a concise overview of the implications for federal student aid and research programs if the pending …


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Drunken man run over by own truck in road rage incident, Gainesville police say
An intoxicated man was run over by his own pickup truck after he got into a road rage incident during a rainstorm, according to police.
The incident happened Tuesday evening in Gainesville.
The Gainesville Sun reports 48-year-old Joseph Carl drove into a vehicle stopped at a red light. He got out of his truck without putting it in park and began banging on the window of a woman's car.
When the frightened woman drove away, there was nothing holding his truck in place, and the truck rolled into Carl, police say. A police report says he was taken to the hospital where he was treated for fractures in his hand and foot.
Carl faces charges of DUI and DUI property damage.
Copyright 2014 by Graham Media Group. All rights reserved. This material may not be published, broadcast, rewritten or redistributed.
The views expressed below are not those of News4Jax or its affiliated companies. By clicking on "Post," you acknowledge that you have read the Terms of Service and your comment is in compliance with such terms. Readers, please help keep this discussion respectful and on topic by flagging comments that are offensive or inappropriate (hover over the commenter's name and you'll see the flag option appear on right side of that line). And remember, respect goes both ways: Tolerance of others' opinions is important in a free discourse. If you're easily offended by strong opinions, you might skip reading comments entirely.


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Video interviews
June 2013
Restoring confidence in the world of work
17 June 2013
How to reconnect and restore confidence in jobs and growth as instruments of social progress was the topic of debate during a high-level panel discussion of the International Labour Conference.
African Union: Job creation key to achieve prosperity
17 June 2013
Addressing the 102nd International Labour Conference, African Union Commission's Chair, Dr. Nkosazana Dlamini Zuma has echoed African leaders' vision that job creation is among the most important factors to achieve growth and prosperity. Dr. Dlamini Zuma also highlighted that Africa is a continent of young people and called for more investment to promote employment and the provision of entrepreneurial skills for youth.
Employment and social protection in the new demographic context
14 June 2013
Demographic change including population ageing is a universal trend in all countries. Delegates at the 102nd International Labour Conference are discussing the implications of this new demographic context on the labour market and social security systems.
6 Steps to a job-friendly recovery
03 June 2013
Globally, investment as a share of GDP is close to 1 percentage point below the pre-crisis level. Yet emerging economies accounted for 47 per cent of global investment as opposed to advanced economies who represented just over one-third. What does this mean? Investment patterns mirror employment trends. Less investment means less employment and this is what we are seeing in developing and advanced economies. So how do we get back on track to creating jobs? Raymond Torres, Director of the ILO's International Institute for Labour Studies, and lead author of the World of Work Report 2013 presents six steps that countries should follow to enjoy a sustainable job recovery.
May 2013
Policies for youth employment: A global framework to tackle the youth jobs crisis
08 May 2013
The current jobs crisis has hit young people especially hard. The ILO urges policy makers to work together with social partners to address this alarming situation. The 2013 edition of the ILO's Global Employment Trends for Youth report analyses a number of key policies and action that can be taken. Gianni Rosas, coordinator of the ILO Youth Employment Programme and co-author of the Report, calls for "a strong focus on growth and jobs, including through a more coordinated macroeconomic response at national and global levels".
Global employment trends for youth 2013 - A generation at risk
08 May 2013
An estimated 73.4 million young people - 12.6 per cent – are expected to be out of work in 2013, and the picture is only set to get worse say Sara Elder and Theo Sparreboom, authors of the Global Employment Trends for Youth 2013 report. Youth face persistent unemployment, a proliferation of temporary jobs and growing discouragement in advanced economies; and poor quality, informal, subsistence jobs in developing countries. There is no one-size-fits-all solution, but as Sara Elder and Theo Sparreboom explain, there are measures that governments - as well as trade unions and employers - can take to boost youth employment.
March 2013
"Confidential, concrete and in consensus" - the work of the ILO's Committee on Freedom of Association
27 March 2013
The right of workers and employers to create and join organisations of their own choice freely and without fear of reprisal or interference - to freely associate with whomever they choose - is a fundamental right that the ILO's Declaration of Philadelphia calls "essential for sustained progress of societies worldwide". For over 60 years, the ILO Committee on Freedom of Association (CFA) has examined more than 3,000 complaints about violations of this right. Paul van der Heijden, Chair of the CFA since 2002, discusses the work of the Committee and the special role it plays in the ILO's supervisory procedures.
January 2013
Emerging middle classes fuel new global growth engines
22 January 2013
Global economic growth slowed sharply in 2012 and its impact on jobs and labour productivity is being felt in every region. Unemployment has gone up the most in the developed economies, such as the European Union. However a strong middle class now emerging in East Asia and elsewhere in the developing world could become a new global growth engine, says ILO Labour Economist, Steven Kapsos.
New skills for new jobs
22 January 2013
With high unemployment workers are increasingly finding themselves looking for work in new occupations where they lack the skills employers are looking for. This skills mismatch means unemployed people are taking longer to find a new job, and this is driving up long-term unemployment rates, says ILO Labour Economist Theo Sparreboom, especially for young people.
Wanted: Productive jobs for the developing world
22 January 2013
In the developing world an important route to economic growth is through increased opportunities for workers to move from lower to higher productive jobs, for example from subsistence farming to work in industry and service sectors. This process, called "structural change", has slowed down in recent years as job creation in productive sectors has stalled, says ILO Labour Economist Christian Viegelahn.


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Arts Beat
London Calls Mary J. Blige11/21/14
Jon Caramanica and Ben Ratliff discuss Mary J. Blige and her new album, "The London Sessions."
How Bobby Shmurda Danced Into the Hot 100
The 20-year-old East Flatbush rapper Bobby Shmurda has just jumped from No. 8 to No. 6 on the Billboard chart.
Dave Grohl's 'Sonic Highways'
Ben Ratliff and Jon Caramanica discuss "Sonic Highways," the new album and HBO mini-series by Dave Grohl and the Foo Fighters.
Listening to Taylor Swift's '1989'
Jon Caramanica and Ben Ratliff discuss Taylor Swift's poppy new album.
The Myth of Scott Walker
Jon Caramanica and Ben Ratliff discuss Scott Walker and "Soused," his new album with the drone-metal band Sunn O))).
Tinashe, FKA Twigs and the Semantics of R&B
Ben Ratliff and Jon Caramanica discuss the singers Tinashe and FKA twigs, and whether they point toward a new conception of R&B.
Parsing Steve Coleman's Genius
Ben Ratliff and Nate Chinen discuss the jazz saxophonist, a recent winner of a MacArthur "genius" grant.
What We Talk About When We Talk About Chris Brown
Jon Caramanica and Ben Ratliff discuss the challenges of appraising Chris Brown.
U2's 'Songs of Innocence': Gift or Spam?
Ben Ratliff and Jon Pareles discuss the new U2 album, released this week for free in iTunes.
Our Vacations with Ariana Grande and Kate Bush
Ben Ratliff and Jon Caramanica discuss new projects by Ms. Grande and Ms. Bush.
The Alchemist
Ben Ratliff talks to Jennifer Herrema of the band Black Bananas.
Songs of the Summer
Jon Caramanica and Ben Ratliff discuss some of the most popular songs of the summer.
Arto Lindsay's Ecstatic Procession
The singer and guitarist Arto Lindsay discusses his work and career, including a new album, "Encyclopedia of Arto."
Can Hip-Hop Thrive on Broadway?
Jon Caramanica and Charles Isherwood discuss the failure of "Holler if Ya Hear Me," the musical based on the work of Tupac Shakur.
Sia's Path from Victim to Victory
Jon Pareles and Ben Ratliff discuss Sia Furler, the Australian singer-songwriter, and her new album, "1000 Forms of Fear."
Metal, Poetry and Satan
Ben Ratliff and the poet Michael Robbins discuss the current state of metal and the music's perhaps surprising similarities with poetry.
Lana Del Rey, Downcast Superstar
Jon Pareles and Ben Ratliff discuss Lana Del Rey and her new record, "Ultraviolence."
Ed Sheeran and Sam Smith, British Pop Imports
Jon Caramanica and Ben Ratliff discuss the young English singers.
Among the Rediscovered: Jimmy Giuffre and Eric Dolphy
Ben Ratliff and Nate Chinen discuss two underappreciated jazz artists.
Outkast Returns
With Outkast is coming to New York this weekend to perform at the Governors Ball festival, Ben Ratliff and Rachel Kaadzi Ghansah discuss the duo and its legacy.
- New York, NY
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- Visit the station website Email the show Update show info


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WestCoast Entertainment will announce its 2011-2012 season at an event on April 21, 4 p.m. at the INB Performing Arts Center.
No, I have no inside information about the season. However, the WestCoast people say that they are "flying in a lead actress to perform a selection from one of the productions."
The last time they flew in a performer for a season announcement was in 2008 — and that was to announce the return of "Phantom of the Opera."
So I suspect the season might include a show of that magnitude..
Anybody have any guesses about what's coming?
Please keep it civil. Don't post comments that are obscene, defamatory, threatening, off-topic, an infringement of copyright or an invasion of privacy. Read our forum standards and community guidelines.
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Budget News
Realty: 6 issues that Jaitley left unanswered in Budget
17 Jul 2014, 11.44 am | Source: Moneycontrol.com
The increase in the limit of home loan interest deduction is helpful and provides some additional disposable income in the hands of home-owners. Howev...
Budget proposals neither bold, nor clear: Lupin
17 Jul 2014, 10.39 am | Source: Moneycontrol.com
The Budget is unequivocally positive for the infrastructure, manufacturing and banking sectors; however, no incentives were given to the pharma indust...
Budget modestly credit positive for India: Moody's
17 Jul 2014, 10.37 am | Source: PTI
"Unless the budget is followed by a more specific implementation plan, as well as additional measures to address macroeconomic imbalances, its credit ...
To gain from RBI norms over medium-long term: Gammon Infra
17 Jul 2014, 7.58 am | Source: CNBC-TV18
Finance minister Arun Jaitely in Union Budget on July 10 had underlined his government's focus to revive Indian economy by giving an impetus to the ...
'Job creation to meet population growth a daunting task'
16 Jul 2014, 6.41 pm | Source: CNBC-TV18
In an exclusive interview with CNBC-TV18's Malvika Jain on July 02, 2014, SP Kothari, Deputy Dean, MIT Sloan School of Management gave his take on t...
Just why is IDFC riding on relaxed infra lending norms?
16 Jul 2014, 2.48 pm | Source: CNBC-TV18
Banks will now be exempted from statutory liquidity ratio (SLR) and cash reserve ratio (CRR) requirements for long-term infrastructure bonds. However...
Budget 2014 has brought clarity in tax policies: FinMin
16 Jul 2014, 2.36 pm | Source: PTI
In his maiden Budget presented in Parliament on July 10, Finance Minister Arun Jaitley has tried to provide relief to the middle class by increasing t...
How you can get maximum out of Budget 2014
16 Jul 2014, 12.48 pm | Source: CNBC-TV18
The Budget has brought a lot of joy to retail investors along with a lot of benefits....
Budget 2014: Govt plans to revive SEZs, but question mark on tax sops
16 Jul 2014, 12.48 pm | Source: CNBC-TV18
The issue of exemption of SEZs from MAT is still under consideration according to commerce secretary Rajeev Kher. Both the finance and the commerce mi...
Hiking FDI limit in insurance to 49% a big positive
16 Jul 2014, 11.30 am | Source: Moneycontrol.com
Move towards "Health for All", the creation of a free drug service and free diagnostic service for people who cannot afford medical aid is commendable...
The Unbearable Lightness of BJP's Tax Policy!
16 Jul 2014, 10.30 am | Source: CNBC-TV18
The Unbearable Lightness of BJP's Tax Policy!...
CRISIL lists out 4 big positives from Union Budget 2014
16 Jul 2014, 10.30 am | Source: CNBC-TV18
Roopa Kudva, MD & CEO, CRISIL says long-term GDP growth is dependent on investment pick up, which is under threat from poor monsoon season. "The Bud...
Budget proposals: MFs fear outflows; seek Sebi help
15 Jul 2014, 8.46 pm | Source: PTI
The fund houses have also appealed for restricting the new rules to close-ended debt schemes as against all non equity MF schemes as proposed, as per ...
RBI move to give infra financing a boost: Andhra Bank
15 Jul 2014, 8.44 pm | Source: CNBC-TV18
According to the RBI circular infra status will be awarded for home loans up to Rs 50 lakh, of course with certain riders. The minimum maturity period...
FDI: Big bet of Union Budget 2014-15
15 Jul 2014, 8.35 pm | Source: Moneycontrol.com
With the increase in FDI in his maiden budget speech, the finance minister has also made it clear that the NDA government would not be surrounded by a...
Budget 2014-15: Impact on personal finance planning
15 Jul 2014, 8.35 pm | Source: Moneycontrol.com
In an attempt to boost household savings, the finance minster has announced an increase in exemption limit for investments under Section 80C of the in...
How will Budget 2014 impact you?
15 Jul 2014, 8.35 pm | Source: Moneycontrol.com
Tax slab increased to Rs. 2.5 Lakhs for citizen and Rs 3 lakhs for senior citizen. Income earned by an individual is chargeable to tax as per the slab...
Is PPP the cure for India's infrastructure woes?
15 Jul 2014, 4.35 pm | Source: Moneycontrol.com
From developing highways and railway networks to gas grids and seaports, all in state partnership with the private sector, Finance Minister Arun Jaitl...
Autonomy for PSU banks tough; capital needs huge: Experts
15 Jul 2014, 4.35 pm | Source: CNBC-TV18
The Union Budget has proposed has PSU banks offer shares to retail investors to raise money. Experts feel retail alone cannot satisy PSU banks' huge c...
PM meets Chinese President Xi Jinping ahead of BRICS Summit
15 Jul 2014, 4.35 pm | Source: PTI
The two leaders appeared well prepared for the meeting as both of them referred to the statements made by the other before they assumed power. "When I...
India Budget 2014: Slum Rehabilitation won't be part of CSR for co, says HDIL
15 Jul 2014, 3.59 pm | Source: CNBC-TV18
Hariprakash Pandey of HDIL believes plan to incentivize development of low cost housing, raising of I-T exemption limit, deduction of interest on self...
Modi's Union Budget mix bag of opportunities: 99acres.com
15 Jul 2014, 3.13 pm | Source: Moneycontrol.com
Setting up of modified REITs and infrastructure investment trusts will help create more liquidity for the sector. There is some reason to celebrate fo...
Caution! Mkt to fall further; like ICICI, TCS: Dipan Mehta
15 Jul 2014, 2.49 pm | Source: CNBC-TV18
According to Dipan Mehta, given the pickup in the earnings season is still two weeks away and in the absence of any positive news flow, technical corr...
Modi meets Chinese Prez, calls for solution to border issue
15 Jul 2014, 1.32 pm | Source: IBNLive.com
The two discussed the contentious boundary issue with the PM pushing for a resolution of the dispute. Prime Minister Modi said that the border dispute...
Budget 2014: Start of a new journey, says Angel Commodities
15 Jul 2014, 12.59 pm | Source: Moneycontrol.com
Angel Commodities has come out with its analysis on Budget 2014-15. "The budget charisma is now done with and investors focus should move towards the ...
Union Budget 2014: India on the path of MODIfication, says Microsec
15 Jul 2014, 12.59 pm | Source: Moneycontrol.com
Microsec has come out with its analysis on Budget 2014-15. "Its a growth oriented Budget and India is on the path of MODIfication", says the research ...
Govt may achieve Fiscal Deficit of 4.1% in FY15: GEPL Cap
15 Jul 2014, 12.59 pm | Source: Moneycontrol.com
According to GEPL Capital, the budget was positive & showed the Government's intent to achieve the Fiscal Deficit target of 4.1% in FY15 & control e...
Dolat Capital suggests add your portfolio on correction
15 Jul 2014, 12.59 pm | Source: Moneycontrol.com
Dolat Capital has maintained its positive stance on the markets though near term consolidation will be most likely scenario. Valuations at 14.6xFY16E ...
Budget fails to fuel oil & gas sector; time to book-out?
15 Jul 2014, 12.49 pm | Source: Moneycontrol.com
Translation of this reduction to company earnings depends on government's policy decisions and its willingness to share savings. ...
Budget 2014: Here's how realty sector will be impacted
15 Jul 2014, 12.26 pm | Source: Moneycontrol.com
"Tax rebates like increase in housing loan exemption from INR 1.5 lakhs to INR 2 lakhs will encourage property seekers to finalise their pending prope...
video of the day
Be careful while betting on midcaps; like Kotak: Dimensions
- Rail Budget Of India
- Budget 2014 2014
- Budget News 2014
- Financial Budget
- Indian Union Budget
- Union Budget 2014 Highlight
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- Latest Updates On India Budget
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- India Rail Budget
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- Union Budget Of India


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Location: Fort Lauderdale, FL
Tickets: 0
Sorry, tickets are no longer available for this event.
Carnival Cruise Line - Carnival Freedom
Fort Lauderdale, FL
Adelaide Oval, Adelaide, Australia
Simon Cross
October 25, 2014 |
The Arena At Gwinnett Center, Duluth, Ga.
Chris McKay / WireImage.com
October 28, 2014 |
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Power steering is noisy and hard to turn steering wheel UNTIL engine warms up. Then it is fine. What's happening? I have sucked old old fluid and put in new but wife says it still doing the above but not as bad. Once engine warms up, steers like it came out of showroom.
Thanks for your help.
BTW, I did replace with Dextron II ATF per manufacturers specs.