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Triboluminescence and Triboelectrification by the Motion of Mercury Over Glass Coated with Scintillator Dyes

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Triboluminescence and Triboelectrification by the Motion of Mercury Over Glass Coated with Scintillator Dyes 1726 J. Electrochem. Soc.: SOLID-STATE SCIENCE AND TECHNOLOGY December 1973 Acknowledgment 2. J. R. Brown and J. H. O'Donnell, Macromolecules, 5, 109 (1972). The authors would like to recognize R. D. Heiden- 3. M. J. Bowden and L. F. Thompson, J. Appl. Poly- reich and E. D. Feit for helpful discussions and C. M. mer Sci., In press. Melliar-Smith for supplying the tungsten substrate. 4. R. Glang and L. V. Gregor, in "Handbook of Thin Film Technology," L. I. Maissel and R. Glang, Manuscript submitted March 8, 1973; revised manu- Editors, Chap. 7, McGraw-Hill, Book Company, script received July 25, 1973. New York (1970). 5. M. Hatzakis, This Journal, 116, 1033 (1971). Any discussion of this paper will appear in a Discus- 6. J. M. Shaw and J. A. Amick, RCA Rev., 31, 306 sion Section to be published in the June 1974 JOURNAL. (1970). 7. L. F. Thompson, E. D. Feit, C. M. Melliar-Smith, REFERENCES and R. D. Heidenreich, J. Appl. Phys., In press. 1. S. Magdo, M. Hatzakis, and Ch. Ting, IBM J. Res. 8. R. D. Heidenreich, E. D. Felt, L. F. Thompson, and Develop., 15, 446 (1970). C. M. Melliar-Smith, ibid., In press. Triboluminescence and Triboelectrification by the Motion of Mercury Over Glass Coated with Scintillator Dyes Csaba P. Keszthelyi* and Allen J. Bard** Department of Chemistry, The University o] Texas at Austin, Austin, Texas 78712 ABSTRACT The conversion of mechanical energy into electrical energy and light (triboelectrification and triboluminescence) by the movement of mercury over glass surfaces coated with scintillator compounds was investigated. The motion of mercury over the coated glass involves the build-up of potential differ- ences in excess of 20V; the nature of these triboelectric potentials differs sig- nificantly from those observed in the absence of scintillator coating. Twelve scintillator compounds were investigated with the observed luminescence being characteristic of the coating material. Interracial processes can generate potentials of duce excited states of the inert gases, mercury and varying magnitude, and from a fundamental aspect, even of the silicon and boron of the glass, and to these voltage-producing interracial processes involve cause decomposition of such molecules as methane. energy conversion. Scintillator compounds are charac- We report here that coating the glass surface with a terized by a relatively efficient conversion of one form scintillator compound results in intense luminescence of energy into another; that is, in the usual experi- that is color-specific to the coating during movement mental situation, the kinetic energy of high energy of mercury over the surface and that this light emis- particles is converted into light energy. The study was sion is localized at the scintillator coating and does not concerned with the electrification, i.e. the separation of extend into the interior volume as has been reported electrical charges, which occurs upon rubbing together when only mercury and glass are involved (6). Other dissimilar materials, a process termed "triboelectrifi- significant differences that can be attributed to the cation" or sometimes "static electrification." The re- scintillator coating and potential difference measure- lated optical phenomenon is called triboluminescence ments are also discussed. (1), the emission of light when certain materials are rubbed or certain crystals are crushed. It has been Experimental known for a long time that triboelectrification and The structures and fluorescence maxima of the scin- triboluminescence occurs when mercury moves over tillator compounds that we used as coating with posi- a glass surface in the presence of inert gases. For tive results are shown in Fig. 1. In our previous work example, Picard (2) in 1675 observed a "whitish glow" involving scintillator compounds (9) we found that in a Torricelli barometer. He attributed this to some the commercially available samples are of a high "phosphors" ostensibly present as impurities. The ex- quality and required no further purification. The FTD, planation that is in general agreement with present ATD, APD, and BTD samples were sent to us by Prof. thinking, namely, that a static electric charge builds Richard L. Taber, Colorado College, who reported up, was first put forth by Huksbee (2) in 1705. Recent them to be extensively purified by column chromatog- workers in this field have observed chemical reactions raphy; these were used as received. The purity of the in a triboelectric discharge (3, 4) and have studied the other compounds that were used as coatings (rubrene, spectra of light generated by the relative motion of phthalocyanine, ~,~,~,5-tetraphenylporphin) was ascer- contiguous surfaces of mercury and glass (5-7). In tained as described previously (9). related experiments, contact electrification potentials The glass surface to be coated was always cleaned as high as 100V have been measured (8). While many first by rinsing with reagent CH2C12, hydrochloric acid, details of the basic mechanism remain obscure, the distilled water, ethanol, and methylene chloride (spec- process involves charge separation at the mercury- troscopy grade) several times. The last CH2C12 rinse glass interface with the subsequent charge recombina- was checked using an Aminco-Bowman speetrophoto- tion reaction being energetic enough (>20 eV) to pro- fluorometer and a quartz cuvette to make sure that * Electrochemical Society Student Member. no traces of luminescent impurities, especially those ** Electrochemical Society Active Member. from a previous coating, were still evident. The glass Key words: luminescence, static electrification, scintillator com- pounds. was almost always coated by contacting it with a Downloaded 19 Feb 2009 to 146.6.143.190. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp VoL 120, No. 12 TRIBOLUMINESCENCE AND TRIBOELECTRIFICATION 1727 NIN N~N O ocN3 FTD TH APD 0 0 o 3510 A 4340 A 3620 A N~N N~N NIN 3 OCH3 C~3~'CH3 ATD PPD BTD O o 0 3590 A 3420 A 3500 A (TH3 ~H3 PTP PPO BBOT 0 o o 3800 A 4350 A 3460 A =-NPO POPOP DPA 0 O 4050 A 4200 ~ 4280 A Fig. i. Structures of the scintillator compounds that were used as coating. [Principal fluorescence or scintillation emission is indicated CH2C12 solution saturated with the compound being coated tube. It was found impossible to achieve a investigated; using approximately 0.5 ml solution for steady rate of rise under our experimental setup, and the length of the tube indicated in Fig. 3; the liquid recorded measurements were confined to the falling was slowly rocked back and forth in the horizontally Hg column. The He, Ne, and Ar were a high purity, held tube that was slowly rotated until all the commercially available, grade, used as received. The CH2C12 had evaporated. Vapor deposition was also imbedded electrodes (cf. Fig. 3) were of platinum wire. employed as a coating technique. By use of a "heat gun," it was possible to make the coating more homo- Results and Discussion geneous, melting the coating at either specific spots For a preliminary investigation of the tribolumines- or along the entire surface. The observations were cence, the hermetically sealed cell arrangements shown made either in hermetically sealed cells (Fig. 2) or in in Fig. 2 were employed. These were coated tubes con- a detachable vacuum-line type arrangement using taining a small amount of mercury sealed under "Swagelock" couplings. vacuum which produced light emission upon moving Potentials were measured in an arrangement re- or shaking the mercury. Such closed cells functioned sembling Debeu's (8) by using either an electrometer essentially without change over a period of several (General Radio Company, Type 1230-A) or a solid months when used intermittently. For a continuous state operational amplifier (Philbrick-Nexus) in a test, a glass wheel, scintillator coated, and containing voltage follower arrangement yielding an input re- mercury, was rotated by connection to a motor re- sistance >10 TM ohms. A Moseley 7005-A XY recorder volving at 0.5-5 rpm; emission was observed for 48 hr was used to obtain the potential-time plots shown in in this arrangement before the test was terminated. Fig. 4 and 5. The electrometer could measure voltages In these cells, even the slightest movement of the Hg in up to 10V, the Philbrick operation amplifier limits the coated tube produced the characteristic lumines- ,~20V. cence. The rate of the rise and fall of the distilled Hg We have made quantitative measurements of the tri- column could be controlled by the arrangement shown boe~ectric potentials generated at the scintillator in- on the top of Fig. 3, whereby the vacuum pump or a terface by the movement of the mercury using the noble gas source was alternately connected to the main arrangement indicated in Fig. 3. In this apparatus, Downloaded 19 Feb 2009 to 146.6.143.190. Redistribution subject to ECS license or copyright; see http://www.ecsdl.org/terms_use.jsp 1728 J. EIectrochem. Soc.: SOLID-STATE SCIENCE AND TECHNOLOGY December 1973 vacuum to the inlet, is allowed to fall by slow addi- tion of inert gas. Flashes of light are observed at the mercury-coated glass interface. The potential-time be- havior (termed here a "potentiogram") between the platinum contacts taken at various ohmic resistance settings of the electrometer is shown in Fig. 4. While the two electrodes remain shorted by the descending Hg column, the reading on the electrometer (or from the operational amplifier in the voltage follower ar- rangement) is, naturally, zero. There is a sudden in- coated crease in potential as the Hg level moves below the top platinum lead (with the lead contacting the mer- glass wheel J cury positive with respect to the upper glass lead); subsequent variations and the detailed shape of the potentiogram are highly reproducible for a given coat- ing, but vary from coating to coating.
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