Патент USA US3077461код для вставки
Sates Patent " 3,077,456 ” 1C6 Patented Feb. 12, 1953 1 2 ‘ EXAMPLE III 3,077,456 The procedure of Example I was repeated with the PHOSPHORESCENT GLASSES AND METHOD OF MAKING SAME Carroll J. Biliian, Perrys’ourg, Ohio, assignor to Owens Illinois Glass Company, a corporation of Ohio same results except that 8 parts of ZnS were used and a proportionate lesser amount (92 parts) of B203, ZnO, , No Drawing. Filed Aug. 10, 1959, Ser. No. 832,423 9 Claims. (Cl. 252—301.6) This invention relates to phosphorescent glasses and EXAMPLE IV Phosphorescent Solder Glass (Conducting) the method of making the same. More particularly this 10 invention relates to conducting and non-conducting solder glasses which exhibit phosphorescence and to the method Ingredients: Parts I B203 ___ ___ __ __ _ _ . __ ZnO _________________________________ _._ 7.7 11.7 ' PbO _________________________________ __ 70.0 of preparing such solder glasses. Si02 ._ The use of zinc sul?de and cadmium sul?de including complexes thereof as phosphorescent material is well F known. Moreover, methods for the incorporation of these 10‘ phosphors in porcelain enamels are also well known; ZnS ___ 1.8 _________________________________ __ Ag ____ 3.8 __ 5.0 However, the use of a phosphor such as zinc sul?de in Patties, which were formed as in Example I above and ?red at_380° C. for 20 minutes, had an electrical resistance ground solder glass, whether conductive or non-conductive of about 1/2 ohm using silver paint for contact spots. and then ?ring the same at such a low temperature as to 20 Using three different current sources for excitation, name4 ly, a DC. source (20 ampere limit), a 60 cycle A.C. source leave the zinc sul?de unreacted is believed to be new. The resulting ?red solder glass containing zinc sul?de exhibits (6 ampere limit), and 60-6000 cycle A.C. source (2 phosphorescence and can be used as a sealing material or ampere limit), it was noted that a visible glow occurred a decorative medium for illuminating clock dials and in strument panels. I at 2 amperes. Higher current intensities gave brighter, 25 glows providing the amperage did not exceed 8-10 amperes, when melting of the patties or samples occurred. Accordingly it is an object of this invention to provide a novel solder glass which exhibits luminescent properties when under the in?uence of radiant and electrical energy and‘ to provide a method of making the same. ' EXAMPLE V Phosphorescent Solder Glass (Conducting) , _It is. a further object of this invention to provide phos 30 The procedure of Example IV was repeated with the ' phorescent solder glasses as sealing and decorating media; same results of phosphorescence but the following com ‘It is a further object of this invention to provide con-‘ position was used. ducting and non-conducting solder glasses having phos phorescent properties. It is a still further object of this invention to conduct the ?ring at low temperatures so as to prevent disintegra Ingredients: 35 , Parts B203 _________________________________ __ , 7.4 ZnO _________________________________ __ 11.2 tion of the phosphor. Additional objects will be apparent PbO _ 67.1 ' from the description which follows. SiOz ZnS . The novel process of this invention comprises ?ring a mixture of ground solder glass and a phosphor such as zinc sul?de at temperatures under 400° C. whereby the 40 1.7 7.6 ‘I , _____________ -;- ------------------- _.-.> 5-0 EXAMPLE VI glass resulting therefrom possesses phosphorescent prop erties. _____ Phosphorescent Solder Glass (Conducting) ' The present invention will be more completely underl .The procedure of Example IV was repeated with‘the stood by reference to the following examples in which all 45 same results of conductive phosphorescence but the fol-p parts and percentages are by weight unless otherwise ’ speci?ed. . ‘50 ‘ ____ __ _ _ ___ 12.31 PbO _______________ __-_____-_ _________ __ 73.67 SiOz _______________________ __>___.._e____. 1.92 ZnS 4.0 > -' _____ ' Parts _ PbO _ _‘ ~ _ ' 66.4 1.7 ZnS ________________________________ _V__ ' Ag 55 ' 7.3 _ __, 11.0v ‘ S102 8.10 ZnO __ ' ‘ ZnO, Parts B203 ________________________________ __ ’ a B203 ____________ _‘___,________________ _.__.. Phosphorescent Solder Glass . _ Ingredients: EXAMPLE I Ingredients: lowing was used. ‘ _..__ ' . ___ 3.6v I 110.0, , EXAMPLE VII , Phosphorescent Solder Gloss (Conducting) 1A ‘glass in powder‘ form consisting of the above ingredie " 'The' procedure 'o'f'Example IV' was‘ repeated withthe'~ ents, namely, B203, ZnO, PhD and SiOz in the proportions same results of phosphorescence but the following compo by weight set forth, was mixed with the aforementioned 60 sition was used. weight of the phosphor, 2115, and shaped into patties of Ingredients: Parts 1 mm. thick and 1 inch in diameter using a binder of 1.5% nitrocellulose in amyl acetate and fired at 380° C. for 20 minutes. The resulting solder glass exhibited phosphorescence and was suitable for clock dials, instru 65 ment panels, and the like. EXAMPLE II The procedure of Example I was repeated with the B203 _ 7.0 ZnO PbO 10.6 ____ 63.5 sio2 _-__ 1.7 ZnS 7.2 Ag _____ __ 10.0 The above examples are merely by way of illustration same results except that 1 part of ZnS was used and a 70 and variations apparent to one skilled in the art may proportionate larger amount (99 parts) of B203, ZnO, PhD, and SiOZ. be made without departing from the spirit of the inven tion disclosed. For example, other phospors such as ‘3,077,456 3 4 CdS may be employed. In addition other solder-glass selected from the class consisting of zinc sul?de and cad compositions may be employed such as the following. mium sul?de. Ingredients: 3. A method of preparing phosphorescent solder glasses comprising ?ring at a temperature of about 380 400" C. and for a period of about 4 to 20 minutes, a Parts ZnO B203 ________________________________ -’ .._ __ 12.83 PbO 76.22 SiO'z " ' _-_ " -._ - - .'__' __________ __'____‘ ____ __'___’____ __ powdered glass mixture of the following composition: 75 to 80% PbO; 7 to 10% B203; 7 to 14% ZnO; and 1.5 to 3% SiO2 and which has added to said mixture (a) from 1 to 10% of a phosphor selected from the class 2.0 In general it has been found that ground glass composi— consisting of ,zinc sul?de and cadmium sul?de and ,(b) tions which consist of about 75-80% PbO; of about 7-14% ZnO; of about 7-1'0% B203; and of about 1.5-3% SiOz to which has been added from 1-10% of a phospor such as ZnS provide not only the properties of a low from 5 to 10% of a conducting material selected from the class consisting of silver, gold and platinum. , 4. A method of preparing phosphorescent solder glasses comprising ?ring at a temperature of about 380° and contraction but phosphorescence. However, the and for a period of about 20 minutes, a powdered glass preferred range of phospor in the above composition mixture 'of the following composition; 75 to 80% PbO; is from v4--8,%. Where conductance is also desired, the 7 to 10% B203; 7 to 14% ZnO; and 1.5 to 3% SiO,,, further addition of 5—10% of a conductor such as silver and which has added to said mixture (11) from 1 to 10% may be employed with excellent results. Although the of a phosphor selected from the class consisting of zinc above ground glass and phosphor-silver mixture may be 20 sul?de and cadmium sul?de .and (b) from 5 to 10% heated from 4 to 40 minutes and ‘from 360-440° C., the of a conducting material selected from the class con preferred ‘heating period is 4 to '20 minutes and the pre sisting of silver, gold and platinum. ferred temperature range is 380-400° C. Care must 5. The method of claim 4 in which the phosphor is zinc sul?de and the conducting material is silver. be taken not to heatthe glass mixture for an unduly softening temperature and satisfactory thermal expansion long ‘period of time even at the lower temperatures since 25 6.I A method of preparing phosphorescent solder the phosphor willlose its phosphorescent properties. glasses comprising ?ring at a temperature of about 360 However, the duration of the heating period for a given temperature ‘can be readily determined for each glass to 440° C. and for a period of about 4 to '40 minutes, a ‘powdered glass mixture of the following ‘composition: 75 to 80% PbO; 7 1O 14% ZnO; 7 to 10% B203; and It is obvious that various modi?cations may be made 30 1.5 to 3% SIiO2 to which has been added from I to, 10% in the above formulations which would still come within of a phosphor selected from the class consisting of zinc the scope of the present invention. For example other sul?de and cadmium sul?de. conducting materials ‘such as ‘gold and platinum may be 7. A Imethod of preparing phosphorescent solder composition by routine testing. I I I employed with equally good results. Morever, organic glasses comprising ?ring at a temperature of about 360 binders other than nitrocellulose in amyl acetate may to 440° C. and for a period of about '4 to 40 minutes, - be used without departing from the spirit vof the invention a powdered glass mixture of the, following composition: herein disclosed. 75 to 80% PbO; 7 to 14% Zn(); 7 to 10% B203; and 1.5 to 3% sio2 10 which has been added from 1 ‘to 10% of a phosphor selected from the class consisting of ‘zinc sul?de and cadmium sul?de and from 5 to 10% of a’con Organic binders which I have found satisfactory include gelatin dissolved in water, camphor with cellulose nitrate, 'dibutyl phthalate with cellulose acetate, a'myl and butyl alcohols, paraffin, biphenyl, etc. ducting material. As indicated by the modi?cations given above, it is to be understood that within the scope of the appended claims, ‘the invention may be practiced otherwise than as speci?cally described. 8. The product produced by the method of claim 6. 9. The product produced by ‘the method of claim 7. I The term ?ring as employed herein means heating the 45 composition until it is sintered or fused. I claim: I I I References Cited in the ?le of this patent UNITED STATES PATENTS : III.II A method of preparing phosphorescent ‘solder 2,130,215 2,643,020 glasses comprising ?ring at a temperature of about 380 Young ‘..; _____ _-_ _____ “Sept. 13, 1938 Dalton c___>__-_ _______ __ June 23, 1953 4009 C. and for a period of about 4-20 minutes, a pow 60 2,837,487 Huttar~ ____ __'..__' ______ __ June a, 1958 deIredIglass mixture of the following range in composi tion: 75I_Ito 80% _Pb_O; 7 to,14% ZnO; 7 to_,10% B203; 2,866,117 2,924,540 Walker et a1. ________ __ Dec. 23, 1958 D’Andrea ____________ __ Feb. 9, 1960 and 1.5 to 3I%I§iQ2IIto which has been added from 1 to 2,945,128 Kuan-Han Sun et al. ..___ July 12, 1960 10% or; phosphorselected from the class consisting of zinc sul?de and cadmium sul?de._ Aminethod of preparing phosphorescent solder glasses I_coIrnIpIrIi_svinI'g_ firing at a temperature of about 380" CI. for a period of about 20 minutes, a powdered glass mixture of the following composition: 75 to 80% PbO; 7 to 14%_ ZnO; 7 to 10% B203; and-1.5 to 3% Slog to which has been added from 1 to 10% of a phosphor FOREIGN PATENTS 55 625,466 Great Britain ________ __ June 28, 1949 OTHER ‘REFERENCES Egelstaff: “Glass ‘Scintillators for Prompt Detection of Intermediate Energy Neutrons,” Nuclear Instruments 1 (1957), 197-199; North Holland Publ. Co., Amsterdam.