NATIONAL BUREAU OF STANDARDS REPORT 9879 Progress Report on AN EVALUATION OF A GALLIUM-PALLADIUM-TIN ALLOY FOR RESTORATIVE DENTISTRY U.S. DEPARTMENT OF COMMERCE NATIONAL BUREAU OF STANDARDS : NATIONAL BUREAU OF STANDARDS The National Bureau of Standards 1 was established by an act of Congress March 3, 1901. Today, in addition to serving as the Nation’s central measurement laboratory, the Bureau is a principal focal point in the Federal Government for assuring maxi- mum application of the physical and engineering sciences to the advancement of tech- nology in industry and commerce. To this end the Bureau conducts research and provides central national services in three broad program areas and provides cen- tral national services in a fourth. These are: (1) basic measurements and standards, (2) materials measurements and standards, (3) technological measurements and standards, and (4) transfer of technology. The Bureau comprises the Institute for Basic Standards, the Institute for Materials Research, the Institute for Applied Technology, and the Center for Radiation Research. THE INSTITUTE FOR BASIC STANDARDS provides the central basis within the United States of a complete and consistent system of physical measurement, coor- dinates that system with the measurement systems of other nations, and furnishes essential services leading to accurate and uniform physical measurements throughout the Nation’s scientific community, industry, and commerce. The Institute consists of an Office of Standard Reference Data and a group of divisions organized by the following areas of science and engineering: Applied Mathematics—Electricity—Metrology—Mechanics—Heat—Atomic Phy - 2 2 ics—Cryogenics 2—Radio Physics 2 —Radio Engineering —Astrophysics —Time and Frequency. 2 THE INSTITUTE FOR MATERIALS RESEARCH conducts materials research lead- ing to methods, standards of measurement, and data needed by industry, commerce, educational institutions, and government. The Institute also provides advisory and research services to other government agencies. The Institute consists of an Office of Standard Reference Materials and a group of divisions organized by the following- areas of materials research: Analytical Chemistry—Polymers—Metallurgy — Inorganic Materials — Physica; Chemistry. THE INSTITUTE FOR APPLIED TECHNOLOGY provides for the creation of appro- priate opportunities for the use and application of technology within the Federal Gov- ernment and within the civilian sector of American industry. The primary functions of the Institute may be broadly classified as programs relating to technological meas- urements and standards and techniques for the transfer of technology. The Institute consists of a Clearinghouse for Scientific and Technical Information, 3 a Center for Computer Sciences and Technology, and a group of technical divisions and offices organized by the following fields of technology Building Research—Electronic Instrumentation — Technical Analysis — Product Evaluation—Invention and Innovation— Weights and Measures — Engineering Standards—Vehicle Systems Research. THE CENTER FOR RADIATION RESEARCH engages in research, measurement, and application of radiation to the solution of Bureau mission problems and the problems of other agencies and institutions. The Center for Radiation Research con- sists of the following divisions: Reactor Radiation—Linac Radiation—Applied Radiation—Nuclear Radiation. 1 Headquarters and Laboratories at Gaithersburg, mailing Maryland, unless otherwise noted ; address Washington, D. C. 20234 2 Located at Boulder, Colorado 80302. 3 Located at 5285 Port Royal Road, Springfield, Virginia 22151. NATIONAL BUREAU OF STANDARDS REPORT NBS PROJECT NBS REPORT 311.05-11-3110560 July 17, 1968 9879 Progress Report on AN EVALUATION OF A GALLIUM-PALLADIUM-TIN ALLOY FOR RESTORATIVE DENTISTRY by R. M. Waterstrat* * Research Associate from the American Dental Association in the Dental Research Section, National Bureau of Standards, Washington, D. C. 20234. This investigation was supported in part by Research Grants D E— 00949 to the American Dental Association from the National Institute of Dental Research, and is part of the dental research program conducted by the National Bureau of Standards in coopera- tion with the Council on Dental Research of the American Dental Association; the Army Dental Corps; the Dental Sciences Division of the School of Aerospace Medicine, USAF; and the Veterans Administration. IMPORTANT NOTICE NATIONAL BUREAU OF S ess accounting documents intended Approved for public release by the to additional evaluation for use within the Government s subjected re listing of this Report, either in and review. For this reason, t Director of the National Institute of he Office of the Director, National whole or in part, is not auth Standards and Technology (NIST) agency for which Bureau of Standards, Washing by the Government on October 9, 2015 the Report has been specitical copies for its own use. U.S. DEPARTMENT OF COMMERCE NATIONAL BUREAU OF STANDARDS * 1 AN EVALUATION OF A GALLIUM-PALLADIUM-TIN ALLOY FOR RESTORATIVE DENTISTRY by R. M. Waterstrat 1. Introduction The use of gallium metal as a replacement for mercury in dental alloys was suggested at le&st as long ago as *" 4 1928* ’ but subsequent attempts to develop satisfactory alloys for this application were unsuccessful® Further re- search on gallium dental alloys was conducted by the Aluminum Company of America® and their studies led to the development of at least two promising alloys, one of which was patented in 195211 A systematic study of gallium alloys as possible dental restorative materials was begun at the National Bureau of Standards in 1952 and this study revealed several other 9 1 8 1 alloy systems with potentially useful properties® * • 0 None of these alloys have been subjected to an extensive biological and clinical investigation. They were selected primarily on the basis of their mechanical and physical properties which compared favorably with those of ordinary -2 dental amalgam. The present study summarizes research at the National Bureau of Standards and presents experimental data for one of the more promising gallium alloys. Much more work remains to be done, however, mainly in the bio- logical and clinical testing of these alloys before they can be recommended for general use. The selection of a gallium-palladium-tin alloy as offering unusual potential for use in restorative dentistry was based on an exhaustive study of many alternative binary and ternary alloys. The basis for this selection included a comparison of mechanical and physical properties together with a consideration of possible reactions with oral fluids and tissues. Alloys of nickel, for example, had been re- ®” ported as possessing some outstanding physical properties 0 but were eliminated from consideration when it was subse- quently discovered that these alloys showed a pronounced 1 3 carcinogenic behavior in soft tissue implants . -3- 2. Experimental Procedures and General Observations A primary requirement of any gallium alloy for dental application is considered to be an ability to form a plas- tic mass which hardens through a diffusion reaction similar to that which occurs in dental amalgam. The convenience of using such an alloy is largely responsible for the widespread use of dental amalgam in preference to gold foil or gold alloy castings. In order to obtain hardening by such a reac- tion it is necessary that the alloy be capable of forming an intermetallic compound at mouth temperature. The only metals^which form such compounds with gallium and have adequate resistance to corrosion in oral fluids are found within the family of transition elements or within the triad of copper, silver and gold. Each of these metals was, therefore, mixed with liquid gallium or gallium-tin eutectic alloy (gallium + 11% tin) in order to determine which metals would harden at mouth tempera- ture (37°C) . Many of these powder-liquid mixtures would not harden at this temperature but would react rapidly with considerable —4~ exothermic heating, if the mixtures were heated to about 400 °C. In these alloys, thin oxide films may prevent the diffusion reaction at mouth temperature. The metals which formed hardenable powder-liquid mixtures at 37 °C were cobalt, nickel, copper, rhodium, palladium, silver, iridium, plati- num and gold. In subsequent tests of compressive strength, however, the cobalt, rhodium, iridium and silver alloys were mechanically weak and were, therefore, eliminated from further consideration. In addition, the rhodium, iridium, and platinum alloys required far too much time to complete their respective hardening reactions. Since nickel-gallium- tin alloys had been eliminated from consideration by the aforementioned carcinogenic reactions, this reduced the remaining elements to copper, palladium and gold. These three metals formed the basis for a more extensive explora- 9 tion of possible gallium dental alloys. Gold-gallium alloys were eventually eliminated since they were generally not as strong as similar alloys of copper or palladium, and also because the gold-gallium alloys had an undesirable blue colored surface after hardening. -5 A series of tests were made using copper-gold alloy powders having compositions of 0, 35, 50, 80 and 100% Au by weight. The products of the hardening reaction in the ternary Cu-Au-Ga alloys were identified by x-ray diffraction in each case and compared with compounds reported in the 1 3 binary systems Cu-Ga and Au-Ga , In each case