EP0107308A2 - Elektrolytisches Palladium-Bad und Verfahren zu seiner Herstellung und seiner Verwendung - Google Patents

Elektrolytisches Palladium-Bad und Verfahren zu seiner Herstellung und seiner Verwendung Download PDF

Info

Publication number
EP0107308A2
EP0107308A2 EP83305242A EP83305242A EP0107308A2 EP 0107308 A2 EP0107308 A2 EP 0107308A2 EP 83305242 A EP83305242 A EP 83305242A EP 83305242 A EP83305242 A EP 83305242A EP 0107308 A2 EP0107308 A2 EP 0107308A2
Authority
EP
European Patent Office
Prior art keywords
bath
palladium
ammonium
cations
anions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP83305242A
Other languages
English (en)
French (fr)
Other versions
EP0107308A3 (de
Inventor
Jeannine Wilcox
George Karustis
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Catalysts LLC
Original Assignee
Engelhard Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Engelhard Corp filed Critical Engelhard Corp
Publication of EP0107308A2 publication Critical patent/EP0107308A2/de
Publication of EP0107308A3 publication Critical patent/EP0107308A3/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals

Definitions

  • the present invention concerns an acidic, aqueous palladium electrolytic plating bath and methods of making and using the same for the electrolytic deposition of palladium.
  • Electrolytic deposition of palladium on base metal and other conductive substrates is well known in the art and the resulting plated products have numerous applications, including the preparation of electrical contact materials for switches and the like. Electrodeposited palladium coatings are typically utilized on low pressure electrical contacts such as those employed in conjunction with printed circuit boards. The low' voltages and low contact pressures usually employed for such switches require a corrosion-resistant, and therefore precious metal-coated, contact material.
  • Palladium plating baths of various types are known, including those prepared from halogenated palladium derivatives such as palladium tetraammine halides and palladium dichloro diammine hydroxide.
  • palladium plating baths from complexes of palladium with organic cvmpounds, for example, palladium cyclohexanediammine tetraacetate, palladium ethylenediammine chloride and the corresponding sulfate, as well as palladium urea salts.
  • Palladium nitrate baths are also known, including palladium diamminodinitrite containing baths.
  • an electroplating bath comprising (1) a bath soluble source of palladium, which may be any palladium amine complex, including the nitrite, chloride or sulfate, (2) an ammonium conducting salt, which may be, e.g., ammonium sulfate or ammonium chloride, and (3) ammonium hydroxide in an amount sufficient to maintain a pH of about 8 to 10.
  • an electroplating bath of a preferred pH of 9 to 9.5 includes palladium diamminodinitrite, a conducting salt such as dibasic ammonium phosphate, ammonium hydroxide and, optionally a pH buffer.
  • British application 2,090,868 A discloses an embodiment in which, in addition to the source of palladium and an ammonium conductivity salt, chloride ions and organic and/or inorganic brighteners are utilized, and in which the use of ammonium hydroxide is optional.
  • a p H range of about 5 - 10 is disclosed and ammonium hydroxide is used when an alkaline bath within the disclosed range is required
  • a bath for electroplating palladium comprising a substantially halide-free aqueous solution of: (a) a palladium tetraammine compound obtained by reacting Pd(R) 2 (N0 2 ) 2 wherein R is ammonium or an amine with ammonium hydroxide and present in at least an amount sufficient to electrodeposit palladium upon a workpiece in the bath; (b) anions selected from the group consisting essentially of sulfamate, sulfate, or mixtures thereof; (c) ammonium cations; and (d) optionally alkali metal cations; the bath having a pH from about 5 to 7, preferably 5.5 to 7.0, more preferably 6 to 7.
  • the anions and cations are present in an amount at least sufficient to enhance the ductility of the palladium electrodeposited from the bath.
  • the bath includes both sulfamate and sulfate anions in solution.
  • At least about 25% of the cations preferably at least 50%, more preferably at least 80%, and most preferably 100%, are ammonium.
  • the balance of the cations may be any noninterfering species, generally alkali metal cations.
  • the palladium tetraammine compound is present in an amount sufficient to provide from about 1 to 30 pa in the bath and the anions and cations are present in an aggregate amount of from about 10 to 200 g/l, though higher amounts may be used without deleteriously effecting the bath.
  • the weight ratio of sulfate anions to sulfamate anions is generally not more than about 4:1, preferably from about 4:1 to 2:3.
  • a method of electroplating a palladium deposit upon a workpiece comprising the steps of: A. immersing a workpiece having an electrically conductive surface into an aqueous bath having a pH of from about 5 to 7, the bath comprising: (1) the palladium tetraammine compound as defined herein and present in an amount at least sufficient to electrodeposit palladium upon a workpiece in the bath; and (2) anions selected from sulfate, sulfamate, or mixtures thereof; (3) ammonium cations; and (4) optionally alkali metal cations; B.
  • the bath includes both sulfamate and sulfate anions in solution. Most preferably all of the cations are ammonium.
  • the palladium utilized in the present invention is obtained by reacting a known material Pd(R) 2 (NO 2 ) 2 wherein R is NH 3 or an amine such as an alkyl C l-8 amine, an alkanol C l-8 amine, substituted alkyl or alkanol amines, and the like; or the two R groups are derived from a polyamine such as ethylene diamine, propylene diamine, diethylenetriamine, and the like, with ammonium hydroxide to form the palladium tetraammine compound.
  • the palladium dinitrite starting compounds are not soluble in water, but the tetraammine is.
  • the reaction of the palladium dinitrite compound with ammonia in aqueous solution may be repre-sented by the following equation, which shows the formation of the palladium tetraammine dihydroxide:
  • nitrite radical may react to form a nitrite salt or the like.
  • a part or all of the hydroxyl moiety of the resultant tetraammine compound may be replaced by other species.
  • X may represent a hydroxyl group, a nitrite group, a sulfate group or a sulfamate group
  • the bath the present invention may contain any suitable concentration of thew palla dium tetraammine compound which is sufficient to provide a suitable electroplating rate. At very low palladium content of the bath, the rate of deposition of palladium becomes unsatisfactorily low. While, theoretically, any very small amounts of palladium contained in the bath could be plated, as a practical matter, the amount of the tetraammine compound present should be such as to provide at least about 1 gram per liter (g/1) in the bath. Lower levels of palladium could be utilized. On the other hand, the plating bath could theoretically -the palladium tetraammine compound as could be maintained in solution, but there is a practical upper limit which is also determined largely by economic factors.
  • the amount of tetraammine compound in the bath be not more than that sufficient to provide about 30 g/l palladium in the bath, preferably not more than about 20 g/l palladium.
  • a Pd content of 4 to 20 g/l is preferred.
  • the bath of the invention is a simple formulation and essentially comprises sulfamate and/or sulfate anions, ammonium and optionally other cations in the solution together with the palladium compound.
  • the bath may also contain a pH adjuster, such as one or more of sulfamic acid, sulfuric acid, and ammonium hydroxide in amounts as required to adjust the pH of the bath to within the specified pH range.
  • the ion component of the plating bath of the invention serves both as an electrolyte to enhance electrical conductivity of the bath and as an additive to provide enhanced ductility of the palladium electrodeposit.
  • concentration of the ion component in the bath has been found to be operative in the practice of the invention. Generally, from about 10 to 200 grams per liter (g/1) of total ion content has been found to be satisfactory.
  • g/1 grams per liter
  • the cation component at least 25%, preferably 50%, more preferably 80%, and most preferably 100% of the cations should be ammonium.
  • the balance, if any, may be any noninterfering species, preferably alkali metal cations. For example, about 38 g/l ammonium sulfamate and 25 g/l ammonium sulfate is a preferred content of total electrolyte salts.
  • the aggregate amount of the electrolyte ions present should be substantially the same as that when either anion is utilized in the absence of the other. This is, the aggregate amount of electrolyte ions present in the bath composition should be from about 10 to 200 g/1.
  • the aggregate amount of electrolyte ions present in the bath composition should be from about 10 to 200 g/1.
  • at least one fifth by weight of the total weight of anions should be comprised by the sulfamate in order to assure sufficient ductility of the resultant palladium deposit.
  • the weight ratio of the sulfate to sulfamate should be not greater than about 4:1.
  • the sulfamate may comprise up to about three fifths by weight of the total of sulfate present, i.e., the weight ratio of sulfate to sulfamate may be up to 2:3.
  • the sulfamate and sulfate may be present in equal weight proportions in one embodiment.
  • the bath of the present invention is prepared simply by dissolving required amounts of the palladium tetraammine compound, ammonium or alkali metal sulfamate and/or ammonium or alkali metal sulfate, in water.
  • the palladium tetraammine compound may be obtained by solublizing the appropriate palladium dinitrite compound with ammonium hydroxide. It is immaterial whether the palladium tetraammine compound is prepared in advance and the electrolyte salt or salts added to a solution of the tetraammine compound, or if the electrolyte salt or salts are already in solution when the tetraammine compound or the precursor palladium salt and ammonium hydroxide are added thereto.
  • the palladium tetraammine compound need not be freshly prepared in preparing the plating bath of the invention, since it has exhibited shelf-life stability of over six months.
  • Any suitable ingredient or ingredients to adjust the pH of the bath to the desired level may be utilized, so long as it does not adversely affect or interfere with the operation of the palladium bath.
  • Sulfuric acid is preferred for acidifying the bath, although sulfamic acid may also be employed for this purpose, and ammonium hydroxide is preferred for alkalizing the bath.
  • One of the advantages of the present invention is the simplicity and stability of the halide-free palladium plating bath provided.
  • other additives of the type normally utilized in palladium plating baths such as pH buffers, brighteners, surfactants and the like may be incorporated.
  • pH buffers such as sodium bicarbonate
  • brighteners such as sodium bicarbonate
  • surfactants such as sodium bicarbonate
  • an amine or imine type brightener such as polyethyleneimine and such brightener (or other conventional additives) may be utilized.
  • amine or imine type brightener such as polyethyleneimine and such brightener (or other conventional additives)
  • the bath of the present invention may be operated within a moderately acid pH range, is quite stable at such acid pH levels and gives excellent plating results even at extraordinarily high plating rates.
  • the bath of the present invention may be usefully operated over a pH range of from about 5 to 7. At a pH level lower than about 5, problems of poor adherence of the palladium electrodeposit to the workpiece or substrate may occur.
  • Both the operating temperature and the pH level of the bath affect the plating efficiency, which may be defined as the weight percent of palladium in the bath which is ultimately deposited on the workpiece per unit of current compared to that which could be deposited if all the current were consumed by the deposition process.
  • palladium is an excellent absorbent for hydrogen and, generally, deposition efficiency varies inversely with the rate of hydrogen generated in the electroplating reaction. Hydrogen absorbed in the palladium electrodeposit tends to evolve after deposition, resulting in the formation of cracks and fissures in the palladium electrodeposit. Higher plating efficiency is therefore desirable as not only providing a more economic operation, but in providing a better quality palladium deposit because of the reduction in hydrogen absorption.
  • the palladium plating bath of the present invention is utilized by immersing the workpiece to be plated within the bath, together with a plating anode, and applying an electrical potential across the workpiece and the anode to provide a desired level of current density at the surfaces of the workpiece.
  • Any suitable workpiece may be electroplated with palladium.
  • At least the surface of the workpiece must be electrically conductive and the workpiece may be prepared by known techniques to provide a surface on which the palladium electrodeposit will adhere in the desired thickness, which typically may be from about 2 millionths of one inch, up to several mils. Depending upon the nature of the substrate to be plated, it may be prepared, for example, by depositing a thin nickel strike prior to application of the palladium electrodeposit thereover.
  • a wide range of current densities at the workpiece surface may be employed and, generally, the higher the current density, the higher is the rate of deposition of palladium.
  • the palladium acidic plating bath of the present invention has demonstrated the ability to be plated at surprisingly high plating rates with good efficiency.
  • plating current densities of as high as 80 amperes per square foot have been employed to attain very high speed plating of adherent, bright deposits.
  • current densities up to about 500 amperes per square foot may be used.
  • the bath of the invention may readily be replenished simply by additions of electrolyte salts and the palladiun tetraammine compound, as required. Any pH adjustments needed are attained by additions of such as sulfuric or sulfamic acids or ammonium hydroxide.
  • the moderately acidic and substantially halide-free plating baths of the invention are simple, stable and provide surprisingly high plating efficiencies and bright low-stress palladium deposits without the need for auxilliary brighteners. Further, they can be operated with substantially lower concentrations of conducting salts than can alkaline baths, usually only about one-half the amount of conducting salts needed for alkaline baths being required for comparable operation of otherwise identical acid baths.
  • an alkaline version of the bath of Example 1 is made by following the procedure of Example 1, except that the amounts of electrolyte salts are adjusted to provide a total of 125 g/1 electrolyte salts in solution, the ammonium sulfate and ammonium sulfamate being in the same weight proportion as in the bath of Example 1, and ammonium hydroxide or dilute (10%) sulfuric acid is added as required to adjust the finished plating bath to a pH of 8.0.
  • Example 1 The acidic bath of Example 1 is utilized to plate palladium on brass workpieces comprising brass tabs measuring 3 by 1 by 0.012 inches.
  • the brass tabs were cleaned with an alkaline cleaning solution comprising trisodium phosphate and a suitable detergent in water, thoroughly rinsed and then dipped in a 10% H 2 S0 4 solution and rinsed in order to provide bright, clean surfaces on them.
  • the brass tabs and a suitable plating anode are immersed in the bath, the tabs are reciprocated parallel to the anode at a rate of about 20 times per minute, and an electrical potential is applied across the anode and the tabs in the conventional manner.
  • Example 2 The alkaline comparison bath of Example 2 is utilized to plate palladium on brass tabs as in Example 3. As indicated in the following table, one of current density,
  • Example 4 shows adequate plating efficiencies for an alkaline bath, they are significantly lower than those attained by the acid bath of this invention shown in Example 3. Bright, adherent palladium electrodeposits were also attained by the bath of Example 4. Temperature was not varied for the alkaline baths does not provide any significant benefit and results in a higher rate of evolution of noxious fumes.
  • ammonium sulfamate and ammonium sulfate employed as the electrolyte salt system provides, with the palladium tetraammine compound, a highly efficient, simple and stable moderately acidic palladium plating bath which yields bright, adherent, ductile, low stress palladium deposits.
  • compositions expressed in grams/liter, plating conditions, and results were as follows:
  • Example 1 The procedures of Examples 1 and 3 were repeated except varying the anions and cations and their amounts in the bath.
  • the compositions all contained 10 g/l palladium; the plating was done at a temperature of 40-45°C, a current density of 10 amperes per square foot, and a pH of 6.5.
  • the ion content and the results were as follows:
  • Example 1 The procedures of Examples 1 and 3 were repeated except that the palladium tetraamine compound (218 g) was reacted with monoethanolamine (12.5g) by gentle heating prior to formation of the plating bath.
  • the electrolyte was a 50/50 mixture of ammonium sulfate and ammonium sulfamate, and sulfamic acid was used to adjust the pH to 6.0.
  • Deposits were produced at 10 and 20 amperes per square foot at temperatures of 25, 35, 45 and 55° C. All were bright, stress free, and had an efficiency of 60-70%.
  • Example 9 The procedure of Example 9 was repeated except that the monoethanolamine was replaced with diethanolamine. Similar plating results occured.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
EP83305242A 1982-09-09 1983-09-08 Elektrolytisches Palladium-Bad und Verfahren zu seiner Herstellung und seiner Verwendung Withdrawn EP0107308A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US41641282A 1982-09-09 1982-09-09
US416412 1982-09-09

Publications (2)

Publication Number Publication Date
EP0107308A2 true EP0107308A2 (de) 1984-05-02
EP0107308A3 EP0107308A3 (de) 1985-07-03

Family

ID=23649865

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83305242A Withdrawn EP0107308A3 (de) 1982-09-09 1983-09-08 Elektrolytisches Palladium-Bad und Verfahren zu seiner Herstellung und seiner Verwendung

Country Status (5)

Country Link
EP (1) EP0107308A3 (de)
JP (1) JPS5967388A (de)
KR (1) KR840006022A (de)
BR (1) BR8304883A (de)
ES (1) ES525483A0 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358375A1 (de) * 1988-09-07 1990-03-14 Johnson Matthey Public Limited Company Platin- oder Platinlegierung-Plattierungsbad
EP0545586A1 (de) * 1991-12-02 1993-06-09 AT&T Corp. Synthese von Palladium-Hydroxid-Verbindungen
FR2807422A1 (fr) * 2000-04-06 2001-10-12 Engelhard Clal Sas Sel complexe de palladium et son utilisation pour ajuster la concentration en palladium d'un bain electrolytique destine au depot de palladium ou d'un de ses alliages
US9435046B2 (en) 2007-07-20 2016-09-06 Rohm And Haas Electronics Llc High speed method for plating palladium and palladium alloys
CN116043290A (zh) * 2022-12-01 2023-05-02 崇辉半导体(深圳)有限公司 一种提升led灯珠寿命的电镀工艺
WO2024105359A1 (en) 2022-11-18 2024-05-23 Johnson Matthey Public Limited Company High efficiency platinum electroplating solutions

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4570213B2 (ja) * 2000-01-12 2010-10-27 古河電気工業株式会社 パラジウムめっき液
KR100797731B1 (ko) * 2002-11-25 2008-01-24 삼성전자주식회사 합금 패턴 형성을 위한 유기 금속화합물의 조성물 및 이를이용한 합금 패턴 형성방법

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB348919A (en) * 1930-06-13 1931-05-21 Baker & Co Improvements in and relating to the electro deposition of metals and alloys of the platinum group
US3925170A (en) * 1974-01-23 1975-12-09 American Chem & Refining Co Method and composition for producing bright palladium electrodepositions

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358375A1 (de) * 1988-09-07 1990-03-14 Johnson Matthey Public Limited Company Platin- oder Platinlegierung-Plattierungsbad
EP0545586A1 (de) * 1991-12-02 1993-06-09 AT&T Corp. Synthese von Palladium-Hydroxid-Verbindungen
CN1092537C (zh) * 1991-12-02 2002-10-16 美国电话及电报公司 氢氧化氨合钯化合物的制备方法
FR2807422A1 (fr) * 2000-04-06 2001-10-12 Engelhard Clal Sas Sel complexe de palladium et son utilisation pour ajuster la concentration en palladium d'un bain electrolytique destine au depot de palladium ou d'un de ses alliages
WO2001077025A1 (fr) * 2000-04-06 2001-10-18 Metalor Technologies France Sas Sel complexe de palladium et son utilisation pour ajuster la concentration en palladium d'un bain electrolytique destine au depot du palladium ou d'un de ses alliages
US6743950B2 (en) 2000-04-06 2004-06-01 Metalor Technologies France Sas Palladium complex salt and use thereof for adjusting palladium concentration of an electrolytic solution for deposit of palladium or one of its alloys
US9435046B2 (en) 2007-07-20 2016-09-06 Rohm And Haas Electronics Llc High speed method for plating palladium and palladium alloys
WO2024105359A1 (en) 2022-11-18 2024-05-23 Johnson Matthey Public Limited Company High efficiency platinum electroplating solutions
CN116043290A (zh) * 2022-12-01 2023-05-02 崇辉半导体(深圳)有限公司 一种提升led灯珠寿命的电镀工艺
CN116043290B (zh) * 2022-12-01 2025-07-22 崇辉半导体(深圳)有限公司 一种提升led灯珠寿命的电镀工艺

Also Published As

Publication number Publication date
EP0107308A3 (de) 1985-07-03
JPS5967388A (ja) 1984-04-17
ES8407118A1 (es) 1984-09-01
KR840006022A (ko) 1984-11-21
BR8304883A (pt) 1984-04-24
ES525483A0 (es) 1984-09-01

Similar Documents

Publication Publication Date Title
EP1009869B1 (de) Cyanidfreie, monovalente kupferelektrobeschichtungslösung
US6251249B1 (en) Precious metal deposition composition and process
US4428802A (en) Palladium-nickel alloy electroplating and solutions therefor
KR101502804B1 (ko) Ｐｄ 및 Ｐｄ-Ｎｉ 전해질 욕조
US5552031A (en) Palladium alloy plating compositions
US20090038950A1 (en) High speed method for plating palladium and palladium alloys
JP2609349B2 (ja) 電気メッキ方法
US6743346B2 (en) Electrolytic solution for electrochemical deposit of palladium or its alloys
US4552628A (en) Palladium electroplating and bath thereof
EP0304315B1 (de) Bad für das Elektroplattieren einer Gold-Kupfer-Zink-Legierung
KR20030033034A (ko) 치환 무전해 금 도금액, 및 상기 도금액 제조용 첨가제
US3637474A (en) Electrodeposition of palladium
JP2012112004A (ja) 金めっき液
EP0107308A2 (de) Elektrolytisches Palladium-Bad und Verfahren zu seiner Herstellung und seiner Verwendung
US3879270A (en) Compositions and process for the electrodeposition of metals
EP0663460A1 (de) Elektroplattierungsbad zum Aufbringen einer Zinn-Zink Legierung und Verfahren zur Elektroplattierung unter Verwendung desselben
JPH0270084A (ja) 金めっき浴及び金めっき方法
JPS609116B2 (ja) パラジウム及びパラジウム合金の電着方法
JPH02305971A (ja) ホルムアルデヒドを含まない無電解銅めっき液
GB2046794A (en) Silver and gold/silver alloy plating bath and method
US4265715A (en) Silver electrodeposition process
US4468296A (en) Process for electroplating palladium
JPS6250560B2 (de)
US4297179A (en) Palladium electroplating bath and process
US4778574A (en) Amine-containing bath for electroplating palladium

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB IT LI LU NL SE

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 19860304

RIN1 Information on inventor provided before grant (corrected)

Inventor name: WILCOX, JEANNINE

Inventor name: KARUSTIS, GEORGE