Laser fusion of glass electrodes
United States Patent Sangermano et al. 1 Apr. 8, 1975 [54] LASER FUSION OF GLASS ELECTRODES 3.471.392 10/l9b9 Kansky (iS/DIGw 6 [75] lnventnrs: Lawrence David Sangermano;  
  William Lester Mowrey, both of Burnt Hills, NY. Primary Evaminer-Arthur D. Kellogg Alrorne Agent, or Firm-M0rgan, Finnegan. Durham [73] Assignee: General Electrlc Company, &amp; p  
 Milwaukee, Wis.  
 [22] Filed: Nov. 15, 1972 [2]] Appl. No.: 306,904  
 [57] ABSTRACT [52] US. Cl. 65/40; 65/57; 65/27];  
  65/0166 A novel method of affixing a glass membrane to a 15: Int. Cl .Q C03b 23/20 glass electrode is described which p y a laser 53 yield f Search U 5 3 40 57 27; mg 6 beam. The method is especially useful in the manufacture of glass pH electrodes and i0n-selective elec- [56] References Cited nudes general UNITED STATES PATENTS 3.217.088 H/l965 Steierman 65/40 X 6 Claims, 1 Drawing Figure LASER FUSION ()F GLASS ELECTRODES??? BACKGROUND OF THE INVEN&#39;IIGN Glass electrodes are commonly employed to measure pH on the principle that an electric tension exists be tween one surface of the glass and an aqueous solution which varies as a function of the pH of the solution. The glass electrode comprises a glass membrane which is shaped in the form of a closed vessel containing a comparison electrode immersed in a solution of constant hydrogen ion concentration and containing an ion that is reversible with said comparison electrode These vessels are assembled by skilled gas blowers by flame sealing a glass membrane to the end of a tube of glass wherein the comparison electrode and the electrolylte are contained. These membranes are either flat, slightly concave or slightly convex. Particular difficulty is en countered in assembling the flat type ofglass electrodes because these tend to warp or otherwise become distorted under the influence of the glass blowers torch.  
  Accordingly, it is one object ofthis invention to pro vide an improved method of affixing the glass membrane of a glass electrode. the method providing a sealed membrane with an undistorted surface.  
  It is also an object of this invention to provide an in expensive, reproducible technique for fabricating glass electrodes.  
 DESCRIPTION OF THE DRAWING The drawing is a partial cross-section of an elevation of an electrode assembly in a preferred form of work holder that is used to relatively position the electrode in the path of the laser beam.  
 DESCRIPTION OF THE INvENTION According to the present invention. there is provided a method of affixing a glass membrane to a glass eiec trode which comprises fusion sealing said glass membrane to the glass casing of the electrode sub-assembly using a focused beam of a laser to provide the means for fusion. In the practice oftlie invention. any particu Iar laser may be employed so long as it has an effective wave length; and sufficient power and efficiency to fuse the interface between the glass membrane and the glass casing of the electrode.  
  It is preferred to employ a molecular gas laser for this purpose and especially preferred to employ a carbon dioxide laser for this purpose.  
  Among the glass membrane electrodes provided herein are those which are being employed, for example, to measure H Na Li Ag K&#34;. Rb*. (Is NH? Tl Mg, Ca Sr and Ba i The criteria for the selection of suitable glass membranes for particular purposes is detailed in the literature and those skilled in the art may select appropriate glass compositions to achieve the desired cation selectivity.  
  In a preferred embodiment. fusion sealing ofthe glass membrane to the glass casing of the electrode is effected by mounting said membrane and said casing in a suitable work holder and cs i ecially preferably. a Workholder adapter to rotate the sub asscmbly through an arc of 360 tor a multiple thereof): in the path of a focused laser beam during at least the fusion step. it is preferred during the fusion step also to hold the niernbrane in contact with the casing by means ofa vacuum which is applied to the glass casing through a rotatable workholder.  
 Lit  
  The rotatable workholder is provided with a motordriven base which is capable of low speed (e.g., l-200 rpm) operation so that the glass membrane glass tubing assembly will be rotated through the focused laser beam at a uniform rate of speed. This procedure insures uniform contact time and results in a continuous glass to glass seal without membrane distortion.  
  The glass membrane surface may be either flat or curved. In particular, the laser technique is highly advantageous as it results in a seal without distortion of the preformed membrane surface.  
 DESCRIPTION OF THE PREFERRED EMBODIMENT A pH selective electrode was made from the following materials:  
 Membrane Corning 015 glass SiO 72 mol CaO 6 mol It Na O 22 mol Sb O l.0 mol &#34;fr Tubing Corning 0120 glass SiO 56-64 mol 7( PbO 25 30 mol &#34;/0 AI O l mol 7( Na O -8 mol &#34;/r K 0 6-8 mol 2? With reference to the drawing, a 3/16 inch diamter glass tubing which forms glass casing I0 in the finished electrode was placed in receiving element 12 of vacuum chuck 22. Vacuum collar 14, of brass or any other suitable material is placed around vacuum chuck 22 and vacuum line 16 is connected thereto at port I8. Thereafter, vacuum chuck 22 and vacuum collar I4 are placed on rotatable motor driven mount 20. Glass membrane 24 is then positioned on the upper, open end of glass casing and a partial vacuum is applied by aspirating or pumping through vacuum line 16 to hold the glass parts of the sub-assembly together. Thereafter the assembly is positioned in the path of the laser beam and the laser beam 28 is adjusted so that it impinges on the joint area at an angle that is orthogonal to the glass casing. The rotatable motor driven mount 20 is rotated at rpm by a Bodine type KYC-23RB motor in motor housing 26 while a power of [0 watts is applied at an effective wave length to fuse the glass. In this arrangement, the rotatable motor driven mount is the motor shaft. As the membrane and casing are fused together. the partial vacuum is gradually released so to prevent rupture of the membrane 24 or casing 10.  
  In one embodiment. a Na selective membrane, NAS 11-18 is fused to a GSC No. 3 (GE. Co.) tubing by a procedure analogous to that employed hereinabove.  
  It is to be understood that other changes may be made in the particular embodiment of the invention in the light of the above-teachings, but that these will be within the full scope of the invention as defined by the appended claims.  
 What is claimed is:  
  I. A method of affixing a glass membrane to a glass electrode which comprises fusion sealing said glass membrane to the glass casing of said glass electrode by means of a focused beam of laser, applying a partial vacuum to hold said glass membrane in contact with said glass electrode. during fusion sealing, and gradually releasing said partial vacuum as the fusion sealing NHJ, Tlfl Mg, Ca, Sr and 821*? 5. A method as defined in claim 1 wherein said glass membrane is flat.  
 6. A method as defined in claim 1 wherein said fusion sealing is effected by rotating the glass membrane and glass casing through an arc of at least 360 in the path of said focused laser beam.