US3914143A - Photoflash lamp primer composition - Google Patents

Photoflash lamp primer composition Download PDF

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US3914143A
US3914143A US487776A US48777674A US3914143A US 3914143 A US3914143 A US 3914143A US 487776 A US487776 A US 487776A US 48777674 A US48777674 A US 48777674A US 3914143 A US3914143 A US 3914143A
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primer
primer material
lamp
polyvinyl pyrrolidone
zirconium
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US487776A
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Vaughn C Sterling
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General Electric Co
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General Electric Co
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Priority claimed from US315663A external-priority patent/US3893798A/en
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21KNON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
    • F21K5/00Light sources using charges of combustible material, e.g. illuminating flash devices
    • F21K5/02Light sources using charges of combustible material, e.g. illuminating flash devices ignited in a non-disrupting container, e.g. photo-flash bulb
    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
    • C06B33/06Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being an inorganic oxygen-halogen salt

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  • ABSTRACT A miniature high performance flashlamp is disclosed which includes an improved primer material that is more stable in handling during lamp manufacture and further improves performance of the lamp in operation.
  • Said primer material comprises a mixture in percentages by weight of l-5% sodium chlorate, 1-6% sodium perchlorate, and the balance being zirconium, which mixture can be bonded to form a unitary mass with a polyvinyl pyrrolidone binder.
  • An aqueous solution of the primer material which includes the polyvinyl pyrrolidone binder remains substantially gel-free for long time periods and provides a tough and adherent coating in the lamp.
  • a known primer material comprises a mixture in percentages by weight of 4-50% phosphorus, 3-8% potassium chlorate, 630% potassium perchlorate, and
  • Schupp and assigned to the assignee of the present incomprises a mixture in percentages by weight of 4-50% phosphorus 10 2570 potassium chlorate, 4-l0% sodium chlorate, and the remaining being titanium which is described and claimed in pending application, Ser. No. 198,587, filed Nov. 15, 1971 in the name of the same inventor and also assigned to the assignee of the present invention.
  • the solid primer coating can also be applied from an aqueous suspension containing the polyvinyl alcohol binder.
  • An improved flashlamp construction of the present invention thereby comprises a hermetically sealed light-transmitting envelope, a quantity of filamentary combustible material distributed within said envelope, a filling of combustion-supporting gas in said envelope, and an electrical ignition system in communication with the interior of said envelope, said electricalignition system including a quantity of primer material which comprises an adhesively bonded solid mixture in percentages by weight of l-5% sodium chlorate, l-6% sodium perchlorate, and the balance being zirconium.
  • the combined weight percent of sodium chlorate and sodium perchlorate in the primer mixture does not exceed ten percent in the preferred compositions so that a water-base coating composition can be used in applying the primer material having all of said oxidizer substances completely dissolved in the coating composition.
  • the present primer mixture is adhesively bonded to the envelope member with a polyvinyl pyrrolidone binder instead of the polyvinyl alcohol binder employed in the referenced primer formulations.
  • a polyvinyl pyrrolidone binder substituted for polyvinyl alcohol.
  • the coating compositions for the primer material of the present invention comprises a suspension of the aforementioned solid mixture in an aqueous solution of commercially available polyvinyl pyrrolidone which can have an average molecular weight in the range from 40,000-160,000. Certain optional materials such as dispersants and preservatives can be added to the coating compositions in minor amount including polyvinyl alcohol which improves the toughness and chip resistance of the final solid coating.
  • the powered zirconium fuel is suspended by mixing with a colloidal silica suspending agent in an aqueous solution containing up to approximately 1% polyvinyl alcohol binder until a uniform smooth dispersion has been obtained.
  • the sodium chlo rate and sodium perchlorate oxidizers are separately dissolved with a fungicide in an aqueous solution containing up to 20% polyvinyl pyrrolidone binder which provides safe handling of the ,oxidi'zer substances prior to mixing with the liquid fuel suspension when the final coating composition is to be applied.
  • a fungicide in an aqueous solution containing up to 20% polyvinyl pyrrolidone binder which provides safe handling of the ,oxidi'zer substances prior to mixing with the liquid fuel suspension when the final coating composition is to be applied.
  • One part of said oxidizer solution can be added to about 56 parts of said fuel suspension to provide the final coating composition.
  • FIGURE is a crosssectional view partly in elevation of a preferred flashlamp of the present invention.
  • a preferred flashlamp comprises a glass bulb or envelope 1 which, as shown, may be formed of a short length of glass tubing, for example, about one-fourth outside diameter, which is constricted and rounded off at one end as indicated at 2 and closed off thereat by an exhaust tip 3 and is formed at the other or base end 4 with a stem press base.
  • the lead-in wires 6 are sealed in opposite corners 7 of the stem press base which provides a longer path length for the in-leads through the lamp envelope and less likelihood of leakage and loss of the hermetic seal.
  • the envelope 1 is preferable made of a borosilicate hard glass which is capable of forming a good hermetic seal to the preferred iron-nickel cobalt alloys employed for the in-leads 6.
  • the preferred glass compositions consist essentially of the following constituents in about the range stated by weight: 60 to 75% SiO 10 to 25% B 1 to 10% A1 0 4 to 10% total alkali oxides, and 0 to BaO except for incidental impurities and residual fluxes and refining agents, and having a mean coefficient of linear thermal expansion between 0 and 300C about in the range of 40 to 50 X per C.
  • the preferred alloys for at least one electrical in-lead being hermetically sealed through said glass wall include commercial products known by the names Kovar, Rodar, Therlo, Fernico I, Fernico II, Nicoseal, Nilok, Sealvac A and others. Generally, these are allows predominantly of iron, nickel and cobalt, and optionally contain manganese in amounts generally less than 1 percent preferably less than 0.5 percent, along with incidental impurities.
  • the general range of composition for such alloys is 27 to 32% Ni, -14 to 19% Co, less than 1.0Mn, the balance iron, except for incidental impurities.
  • the composition of Kovar, a suitable lead material is about 54% Fe, 29% Ni, 17% Co; 0.5% Mn, O.2% Si, and 0.06% C.
  • the inner ends of the leads are coated with the primer material 8 and have an electrical filament 9 connecting them.
  • This filament may be a fine tungsten wire or preferably constructed of a 97% tungsten 3% rhenium alloy.
  • a quantity of filamentary combustible material 10 such as a shredded foil of zirconium or hafnium, for example, is distributed within the interior space of the envelope 1 which also contains a filling of a suitable combustion-supporting gas such as oxygen generally at high pressure in excess of several atmospheres.
  • the solid coating of primer material in the above embodiment can be applied to the in-lead members as a stabilized aqueous suspension of the present invention in various known ways.
  • the in-lead members can be dipped into the aqueous slurry followed by drying in the air or with heat to remove the liquid and produce a solid adhered coating having the desired characteristics previously described.
  • the aqueous slurry can be sprayed on the in-lead members and thereafter processed to provide a solid coating exhibiting comparable performance.
  • the oxidizer solution can be added to about 56 parts of the liquid fuel suspension in the manufacturing plant by conventional means to provide the primer coating composition.
  • the individual por tions After mixing the individual por tions to produce a smooth even blend of the constituents, there is obtained a liquid coating composition which is stable in storage up to one week.
  • the zirconium fuel material should have a particle range from a fine mesh size to a micron size to provide the final smooth and uniform primer coating.
  • a stabilized liquid suspension of primer material which comprises an aqueous solution of polyvinyl pyrcontaining in weight percent 68-80% zirconium, 20-35% water, O-5% colloidal silica and 0-2% polyvinyl alcohol with a liquid solution containing in weight percent 45-75% water, 5-25% sodium chlorate, 5-30% sodium perchlorate, and 5-20% polyvinyl pyrrolidone dissolved in said solution.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Paints Or Removers (AREA)

Abstract

A miniature high performance flashlamp is disclosed which includes an improved primer material that is more stable in handling during lamp manufacture and further improves performance of the lamp in operation. Said primer material comprises a mixture in percentages by weight of 1-5% sodium chlorate, 1-6% sodium perchlorate, and the balance being zirconium, which mixture can be bonded to form a unitary mass with a polyvinyl pyrrolidone binder. An aqueous solution of the primer material which includes the polyvinyl pyrrolidone binder remains substantially gel-free for long time periods and provides a tough and adherent coating in the lamp.

Description

[ Oct. 21, 1975 PHOTOFLASH LAMP PRIMER COMPOSITION- [75] Inventor: Vaughn C. Sterling, Cleveland, Ohio [73] Assignee: General Electric Company,
Schenectady, NY.
[22] Filed: July 11, 1974 [21] Appl. No.2 487,776
Related US. Application Data [62] Division of Ser. No. 315,663, Dec. 15, I972.
[52] US. Cl. 149/40; 149/42; 149/44;
149/83; 149/85 [51] Int. Cl. C06B 33/12 [58] Field of Search 149/40, 42, 44, 85, 83
[56] References Cited UNITED STATES PATENTS 3,724,990 4/l973 Schupp 149/40 X Primary Examiner-Stephen J. Lechert, Jr. Attorney, Agent, or Firm-John F. McDevitt; Lawrence R. Kempton; Frank L. Neuhauser [57] ABSTRACT A miniature high performance flashlamp is disclosed which includes an improved primer material that is more stable in handling during lamp manufacture and further improves performance of the lamp in operation. Said primer material comprises a mixture in percentages by weight of l-5% sodium chlorate, 1-6% sodium perchlorate, and the balance being zirconium, which mixture can be bonded to form a unitary mass with a polyvinyl pyrrolidone binder. An aqueous solution of the primer material which includes the polyvinyl pyrrolidone binder remains substantially gel-free for long time periods and provides a tough and adherent coating in the lamp.
2 Claims, 1 Drawing Figure US. Patent Oct. 21, 1975 BACKGROUND OF THE INVENTION velope to form a hermetic seal with a pair of electrical lead-in wires having a metal resistance filament connected therebetween. In such electrical-ignition type photoflash lamps in general use at present, the inner ends of these lead-in wires are coated with a charge of heat sensitive primer material so that when electrical current is passed through the resistance filament there will be deflagration of the primer material causing the shredded combustible foil in the lamp envelope to burn rapidly with incandescence.
With increasing miniaturization of a photoflash lamp such as that disclosed and claimed in U.S. Pat. No. 3,506,385 to Weber et al, and assigned to the assignee of the present invention, more difficulties are encountered with the primer material of the electrical-ignition system both as affects lamp manufacture and the lamp operation. More particularly, a smaller bead size of the I oxidizing materials are also generally not very soluble in the liquid coating compositions used to obtain the primer coatingon the in-leads, it further became neces-- sary to increase the oxidizer concentration even more so that enough oxidizer was present throughout the v primer coating to cause complete combustion of the available fuel. The. percussion-sensitive nature of these oxidizer substances makeshandling them hazardous so that it would be desirable to reduce their concentration in the solid primer material.
, Certain primer materials are already known which can be applied as coatings from a water-base suspension to reduce the hazards of handling the primer solids. A known primer material comprises a mixture in percentages by weight of 4-50% phosphorus, 3-8% potassium chlorate, 630% potassium perchlorate, and
V the remainder beingtitanium which is described and claimed in copending patent application, Ser. No.
198,547 tiled Nov. 15,. 1971 in the name of Lewis J,
Schupp and assigned to the assignee of the present incomprises a mixture in percentages by weight of 4-50% phosphorus 10 2570 potassium chlorate, 4-l0% sodium chlorate, and the remaining being titanium which is described and claimed in pending application, Ser. No. 198,587, filed Nov. 15, 1971 in the name of the same inventor and also assigned to the assignee of the present invention. The solid primer coating can also be applied from an aqueous suspension containing the polyvinyl alcohol binder.
SUMMARY OF THE INVENTION An improved primer material has now been discovered which can be applied reliably as a coating for the in-lead members of an electrical-ignition type flashlamp from a waterbase suspension wherein all oxidizer constituents of the primer'material are dissolved in the liquid suspension. The present primer material exhibits proper ignition sensitivity along with low blast characteristics upon actuation which makes it especially suitable for miniaturized photoflash lamps of the all-glass type which are described in the aforementioned U.S. Pat. No. 3,506,385. In such lamps having an internal volume of approximately 0.3-0.4 cubic centimeters it becomes possible to flash the lamps reliably with a high constant light output by using the present primer material at a primer weight range between 0.5 and 2.5 milligrams. Additionally, the lower ratio of oxidizer to fuel in the present primer material reduced the hazards of handling the primer solids.
An improved flashlamp construction of the present invention thereby comprises a hermetically sealed light-transmitting envelope, a quantity of filamentary combustible material distributed within said envelope, a filling of combustion-supporting gas in said envelope, and an electrical ignition system in communication with the interior of said envelope, said electricalignition system including a quantity of primer material which comprises an adhesively bonded solid mixture in percentages by weight of l-5% sodium chlorate, l-6% sodium perchlorate, and the balance being zirconium. The combined weight percent of sodium chlorate and sodium perchlorate in the primer mixture does not exceed ten percent in the preferred compositions so that a water-base coating composition can be used in applying the primer material having all of said oxidizer substances completely dissolved in the coating composition. By having the oxidizer constituents fully dissolved in the coating composition there are a number of benefits which include eliminating oxidizer segregation, reducing any flocculation and lumping tendency in the coating composition, and maintaining constancy of the oxidizer-fuel proportions throughout the life of the liquid coating composition. The present primer mixture is adhesively bonded to the envelope member with a polyvinyl pyrrolidone binder instead of the polyvinyl alcohol binder employed in the referenced primer formulations. Substitution of a polyvinyl pyrrolidone binder provides additional advantages of lesser foam tendency, a more rewettable nature, and higher tolerance to the dissolved oxidizers in the coating composition than was experienced with polyvinyl alcohol.
The coating compositions for the primer material of the present invention comprises a suspension of the aforementioned solid mixture in an aqueous solution of commercially available polyvinyl pyrrolidone which can have an average molecular weight in the range from 40,000-160,000. Certain optional materials such as dispersants and preservatives can be added to the coating compositions in minor amount including polyvinyl alcohol which improves the toughness and chip resistance of the final solid coating. In a preferred coating composition, the powered zirconium fuel is suspended by mixing with a colloidal silica suspending agent in an aqueous solution containing up to approximately 1% polyvinyl alcohol binder until a uniform smooth dispersion has been obtained. The sodium chlo rate and sodium perchlorate oxidizers are separately dissolved with a fungicide in an aqueous solution containing up to 20% polyvinyl pyrrolidone binder which provides safe handling of the ,oxidi'zer substances prior to mixing with the liquid fuel suspension when the final coating composition is to be applied. One part of said oxidizer solution can be added to about 56 parts of said fuel suspension to provide the final coating composition.
BRIEF DESCRIPTION OF THE DRAWING 1 In the drawing, the single FIGURE is a crosssectional view partly in elevation of a preferred flashlamp of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring to the drawing, a preferred flashlamp, according to the invention comprises a glass bulb or envelope 1 which, as shown, may be formed of a short length of glass tubing, for example, about one-fourth outside diameter, which is constricted and rounded off at one end as indicated at 2 and closed off thereat by an exhaust tip 3 and is formed at the other or base end 4 with a stem press base. The lead-in wires 6 are sealed in opposite corners 7 of the stem press base which provides a longer path length for the in-leads through the lamp envelope and less likelihood of leakage and loss of the hermetic seal. The envelope 1 is preferable made of a borosilicate hard glass which is capable of forming a good hermetic seal to the preferred iron-nickel cobalt alloys employed for the in-leads 6. The preferred glass compositions consist essentially of the following constituents in about the range stated by weight: 60 to 75% SiO 10 to 25% B 1 to 10% A1 0 4 to 10% total alkali oxides, and 0 to BaO except for incidental impurities and residual fluxes and refining agents, and having a mean coefficient of linear thermal expansion between 0 and 300C about in the range of 40 to 50 X per C. The preferred alloys for at least one electrical in-lead being hermetically sealed through said glass wall include commercial products known by the names Kovar, Rodar, Therlo, Fernico I, Fernico II, Nicoseal, Nilok, Sealvac A and others. Generally, these are allows predominantly of iron, nickel and cobalt, and optionally contain manganese in amounts generally less than 1 percent preferably less than 0.5 percent, along with incidental impurities. The general range of composition for such alloys is 27 to 32% Ni, -14 to 19% Co, less than 1.0Mn, the balance iron, except for incidental impurities. The composition of Kovar, a suitable lead material is about 54% Fe, 29% Ni, 17% Co; 0.5% Mn, O.2% Si, and 0.06% C. The inner ends of the leads are coated with the primer material 8 and have an electrical filament 9 connecting them. This filament may be a fine tungsten wire or preferably constructed of a 97% tungsten 3% rhenium alloy. A quantity of filamentary combustible material 10 such as a shredded foil of zirconium or hafnium, for example, is distributed within the interior space of the envelope 1 which also contains a filling of a suitable combustion-supporting gas such as oxygen generally at high pressure in excess of several atmospheres.
The solid coating of primer material in the above embodiment can be applied to the in-lead members as a stabilized aqueous suspension of the present invention in various known ways. For example, the in-lead members can be dipped into the aqueous slurry followed by drying in the air or with heat to remove the liquid and produce a solid adhered coating having the desired characteristics previously described. Alternately, the aqueous slurry can be sprayed on the in-lead members and thereafter processed to provide a solid coating exhibiting comparable performance.
As an example of suitable coating compositions which are prepared as generally above described in two portions so as to maintain the oxidizer and fuel constituents separately until the final coating composition is to be applied, there is listed below a typical formulation together with permissible variation in the individual constituents as follows:
For the above coating compositions approximately one part of the oxidizer solution can be added to about 56 parts of the liquid fuel suspension in the manufacturing plant by conventional means to provide the primer coating composition. After mixing the individual por tions to produce a smooth even blend of the constituents, there is obtained a liquid coating composition which is stable in storage up to one week. The zirconium fuel material should have a particle range from a fine mesh size to a micron size to provide the final smooth and uniform primer coating.
While the best mode of carrying out the present invention has been set forth above, it will be understood that additions, changes and modifications may be made thereto without departing from the spirit and scope of the invention as defined in the appended claims. For example, it will be apparent that still other optional constituents can be added to the liquid coating compositions if desired so long as in minor amount to modify the film-forming characteristics of the final solid coating when necessary for a particular lamp construction. Likewise, it will be apparent that other electricalignition type flashlamp constructions other than herein specifically disclosed can employ the primer materials of the present invention. It is intended to limit the present invention, therefore, only the scope of the following claims.
What I claim as new and desire by Letters Patent of the United States is:
1. A stabilized liquid suspension of primer material which comprises an aqueous solution of polyvinyl pyrcontaining in weight percent 68-80% zirconium, 20-35% water, O-5% colloidal silica and 0-2% polyvinyl alcohol with a liquid solution containing in weight percent 45-75% water, 5-25% sodium chlorate, 5-30% sodium perchlorate, and 5-20% polyvinyl pyrrolidone dissolved in said solution.

Claims (2)

1. A STABILIZED LIQUID SUSPENSION OF PRIMER MATERIAL WHICH COMPRISES AN AQUEOUS SOLUTION OF POLYVINYL PYRROLIDONE BINDER HAVING SUSPENDED THEREIN A SOLID MIXTURE CONTAINING 1-5% SODIUM CHLORATE AND 1-6% SODIUM PERCHLORATE AS DISSOLVED SOLIDS IN SAID SOLUTION, AND THE BALANCE BEING ZIRCONIUM BY WEIGHT OG SAID SOLID MIXTURE.
2. A PRIMER COATING COMPOSITION FOR A FLASH LAMP WHICH COMPRISES AN ADMIXTURE OF A LIQUID SUSPENSION CONTAINING IN WEIGHT PERCENT 68-80% ZIRCONIUM, 20-35% WATER, 0-5% COLLOIDAL SILICA AND 0-2% POLYVINYL ALCOHOL WITH A LIQUID SOLUTION CONTAINING IN WEIGHT PERCENT 45-75% WATER, 5-25% SODIUM CHLORATE, 5-30% SODIUM PERCHLORATE, AND 5-20% POLYVINYL PYRROLIDONE DISSOLVED IN SAID SOLUTION.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2372377A1 (en) * 1976-11-24 1978-06-23 Gte Sylvania Inc
EP0061751A1 (en) * 1981-03-27 1982-10-06 GTE Products Corporation Filament-type photoflash lamp, process for fabricating the same, and primer material
US4522665A (en) * 1984-03-08 1985-06-11 Geo Vann, Inc. Primer mix, percussion primer and method for initiating combustion
GB2320493A (en) * 1996-12-19 1998-06-24 Eastman Kodak Co Photoflash particle mixture

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3724990A (en) * 1971-11-15 1973-04-03 Gen Electric Photoflash lamp

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3724990A (en) * 1971-11-15 1973-04-03 Gen Electric Photoflash lamp

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2372377A1 (en) * 1976-11-24 1978-06-23 Gte Sylvania Inc
US4369028A (en) * 1976-11-24 1983-01-18 Gte Products Corporation Photoflash lamp
EP0061751A1 (en) * 1981-03-27 1982-10-06 GTE Products Corporation Filament-type photoflash lamp, process for fabricating the same, and primer material
US4522665A (en) * 1984-03-08 1985-06-11 Geo Vann, Inc. Primer mix, percussion primer and method for initiating combustion
GB2320493A (en) * 1996-12-19 1998-06-24 Eastman Kodak Co Photoflash particle mixture
US5821451A (en) * 1996-12-19 1998-10-13 Eastman Kodak Company Photoflash particle mixture
GB2320493B (en) * 1996-12-19 2000-12-20 Eastman Kodak Co Photoflash particle mixture

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