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By James S. Browning

The Bureau of Mines conducted laboratory and small--scale continuous tests of weathered mica pegmatite ores from Hart County, Ga., to determine the technical feasibility of recovering commercial-grade mica concentrates by flotation. Two modifications of the Bureau-developed anionic-cationic method were used. In one method, sodium carbonate and calcium lignin sulfonate were used for pH control and quartz depression; this method yielded mica concentrates containing 98.5 percent mica with a recovery of 91.4 percent. In the other modification, lime and sodium silicate were used with the calcium lignin sulfonate; concentrates containing 98.9 percent mica with a recovery of 86 percent were obtained.

Jan 1, 1966

By Reginald E. Hore

I. INTRODUCTION. SINCE the discovery of silver at Cobalt, Ontario, in 1903 more than 100,000,000 oz. of silver have been produced b: the mines in the Nipissing district, and there is reason to believe that at least as much more will be produced in the next five years. The estimated value of the aggregate output o ore to the end of 1910 is $48,327,280. The ore yielded 93,977,833, oz. of silver and was mined at a net profit of about $26,000,000. For 1910 the production was 30,558,825 oz. valued at $15,436,894, and yielding a profit of about $9,000',000 The details of the production of the Cobalt district for the years 1904 to 1909, inclusive, are given in Table I. TABLE I.-Silver-Production of the Cobalt District, 1904 to 1909 SMELTING-ORE. Production. Value. Silver-Content. Value Per Ton Ounces. Oz. Per Ton. 1904 206,875 $111,887 1,309 $708 1905.:.... 2,451,356 1,360,503 1,143 634 1906 5,401,766 3,667,551 1,013 687 1907 10,023,311 6,155,391 677 416 1908 18,022,480 8,468,293 736 363 1909 22,436,355 10,809,872 809 389 CONCENTRATES. 1908 1,415,395 $665,085 1,240 585 1909 3,461,470 1,651,704 1,174 559 The shipments from Cobalt are in the form of smelting-ore, concentrates from milling-ore, and bullion. The smelting-or( is largely high grade, averaging about 3,000 oz. per ton- A

May 1, 1911

By Robert G. Bottge

The Bureau of Mines has engaged m a program to determine the availability of land for mineral exploration and development in Alaska. Land availability, based on ownership and Federal and State laws and policies, is compared with mineral terranes and mineral deposits. This is the fifth of six regional studies, which cover the State with a comprehensive set of maps and data compilations. This study covers an area of 112.3 million acres in western Alaska. In July 1986, 41.0 million acres, 37% of the study area, were available for mineral exploration and development; 14.6 million acres, 13%, were available with restrictions; and 56.7 million acres, 50%, were unavailable. Nearly 65% of the unavailable land is classified as national parks, preserves, wildlife refuges, and wild and scenic rivers. Of the 34.0 million acres of mineral terranes that underlie the study area, 12.9 million acres, 38%, are available for exploration and development; 3.6 million acres, 11%, are available with restrictions; and 17.5 million acres, 51%, are unavailable.

Jan 1, 1988

By C. M. Lesher, R. R. Keays

"The komatnte-associated Fe-Ni-Cu sulphide mineralization at Kanihalda, Western Australia, is generally believed to be magmatic in origin, but a number of postmagmatic processes significantly modified the original distribution, structure, texture, mineralogy and chemistry of the ores. Two important types of mobilized magmatic sulphides are interpillow/interbreccia sulphides and hydrothermal vein-type sulphides. Interpillow and interbreccia sulphides occur interstitial to pillowed or volcaniclastic footwall metabasalts beneath or adjacent to the stratiform contact ore horizons. They are mineralogically and compositionally similar to massive ores (and are similarly depleted in PGE relative to the compositions of bulk samples of mined ores), but normally do not contain the distinctive chalco-phile ferrochromites characteristic of contact ores. They are interpreted as magmatic sulphides that have been mobilized from the overlying or adjacent massive sulphide layer during peak tectono-nietamorphism.Hydrothermal sulphide-quartz + albite veins also occur in the footwall metabasalt and contain unannealed deformation fabrics indicative of emplacement during retrograde metamorphism. The high Ni and Pd contents of these sulphides (7-13% Ni, up to 70 ppm Pd) indicate that the metals have been derived from the spatially associated komatiites and/or contact ores, consistent with the Pd depletion previously inferred for massive ores. Very low Ir contents and high Pd/Ir ratios of the vein-type sulphides confirm an aqueous transportation-deposition mechanism; hydrothermal transfer of PGE results in strong decoupling of Pd from Ir.There appears to be a complete continuum of sulphide mobilization at Kambalda ranging from whole-scale phy sical dislocation (fault offset ores) and selective mobilization (stringer sulphides) through nietamorphie replacement (interpillow/interbrec- cia sulphides) to jiydrothermal dissolution and redeposition (vein-type sulphides)."

Jan 1, 1984

By David B. Reger

Wildcat drilling for new supplies of gas and the expansion of previously discovered oil and gas pools were the principal petroleum activities in West Virginia .during 1942. Much of the new gas exploration is still uncompleted and still indecisive but various wildcats made substantial extensions to existing pools. Out of 53 wildcats drilled 27 resulted in commercial gas and 6 in commercial oil. Four of the oil discoveries also had commercial gas. No strictly new pools of oil or gas can safely be described as discovered but several scattered oil and gas wells previously drilled have been confirmed as the openers of definite pools; also, various completions closed wide gaps between apparent gas pools already discovered. The proved oil territory of the state was increased about 4850 acres and the proved gas territory about 51,000 acres. The new proved oil reserves should about balance withdrawals and the new gas may represent a substantial increase. Aside from the drilling in four rather lively pools, oil activity was slight because of unfavorable operating conditions and prices. Gas drilling also declined for reasons beyond the control of the operators. The account of operations, as gathered from trade journals and other reporting services, shows that 797 new wells were drilled, providing 119 new oil wells with 2762 bbl. of daily new production; 536 new gas wells with 1,228,501,000 CU. ft. of daily open flow: and 142 dry holes. Also... 76 old wells were drilled to deeper sands, with 71 bbl. and 26,034,000 cu, ft. of added production. On the new wells the oil average was 23.21 bbl. per well per day; and the gas average was 2,270,406 CU. ft. per well per day. On new wells the ratio of dry holes to completions was 17.82 per cent. On deeper drilling the ratio of failures was 21.05 per cent. Production of oil for the year was estimated by the Oil ad Gas Journal as 3,492,000 bbl., as compared with 3,378,000 bbl. in 1941. Production of natural gas for the year is estimated by the author as 220,000,000,000 cu. ft., as compared with the U. S. Bureau of Mines final figures of 207,000,000,000 cu. ft.* in 1941. General State op Industry Leasing of wildcat acreage increased considerably. The total land of all classes under lease may now exceed 5,000,000 acres. Taking into consideration completions, abandonments and corrected figures or estimates, Table I shows cumulative and late annual statistics. New Pools and Extensions Table 2 shows the principal areas of drilling activity during 1942. Various consolidations of territory, hitherto treated as separate pools, have been made. in addition to these active pools, extensive drilling was done in numerous other areas where pool boundaries can hardly be defined. Summary or Exploration Table 3 gives a summary of important wildcat or exploratory wells drilled during

Jan 1, 1943

By David B. Reger

Wildcat drilling for new supplies of gas and the expansion of previously discovered oil and gas pools were the principal petroleum activities in West Virginia .during 1942. Much of the new gas exploration is still uncompleted and still indecisive but various wildcats made substantial extensions to existing pools. Out of 53 wildcats drilled 27 resulted in commercial gas and 6 in commercial oil. Four of the oil discoveries also had commercial gas. No strictly new pools of oil or gas can safely be described as discovered but several scattered oil and gas wells previously drilled have been confirmed as the openers of definite pools; also, various completions closed wide gaps between apparent gas pools already discovered. The proved oil territory of the state was increased about 4850 acres and the proved gas territory about 51,000 acres. The new proved oil reserves should about balance withdrawals and the new gas may represent a substantial increase. Aside from the drilling in four rather lively pools, oil activity was slight because of unfavorable operating conditions and prices. Gas drilling also declined for reasons beyond the control of the operators. The account of operations, as gathered from trade journals and other reporting services, shows that 797 new wells were drilled, providing 119 new oil wells with 2762 bbl. of daily new production; 536 new gas wells with 1,228,501,000 CU. ft. of daily open flow: and 142 dry holes. Also... 76 old wells were drilled to deeper sands, with 71 bbl. and 26,034,000 cu, ft. of added production. On the new wells the oil average was 23.21 bbl. per well per day; and the gas average was 2,270,406 CU. ft. per well per day. On new wells the ratio of dry holes to completions was 17.82 per cent. On deeper drilling the ratio of failures was 21.05 per cent. Production of oil for the year was estimated by the Oil ad Gas Journal as 3,492,000 bbl., as compared with 3,378,000 bbl. in 1941. Production of natural gas for the year is estimated by the author as 220,000,000,000 cu. ft., as compared with the U. S. Bureau of Mines final figures of 207,000,000,000 cu. ft.* in 1941. General State op Industry Leasing of wildcat acreage increased considerably. The total land of all classes under lease may now exceed 5,000,000 acres. Taking into consideration completions, abandonments and corrected figures or estimates, Table I shows cumulative and late annual statistics. New Pools and Extensions Table 2 shows the principal areas of drilling activity during 1942. Various consolidations of territory, hitherto treated as separate pools, have been made. in addition to these active pools, extensive drilling was done in numerous other areas where pool boundaries can hardly be defined. Summary or Exploration Table 3 gives a summary of important wildcat or exploratory wells drilled during

Jan 1, 1943

By W. C. Holliman

This second of a series of reports on the characteristics of commercial aviation gasolines presents inspection test data furni8hed on their products by 15 manufacturers of commercial grades of aviation gasoline and special data obtained in Bureau of Mines laboratories on samples of these gasolines. Data on 18 grade-80, 20 grade-91/98, 20 grade-100/130, and 9 grade-115/145 aviation fuels are presented. These gasolines represent July 1947 production.

Jan 1, 1948

By Brian Gettinger, Jim Schlaman, Alston Noronha

"INTRODUCTION The public understanding of green solutions today is based on the definition of sustainability adopted by the Brundtland Commission (World Commission on Environment and Development) in 1987: “development that meets the needs of the present without compromising the ability of future generations to meet their own needs.” Over time this initial definition evolved to identify three distinct factors impacting sustainability that are often referred to as the “Triple Bottom Line”: Economic, Environmental and Social. The triple bottom line approach seeks to drive outcomes that create maximum value for all stakeholders. In the last ten years purveyors of water and wastewater tunnel solutions have found themselves on the wrong side of a politically polarizing issue in the crosshairs of politicians, environmental activists and community groups branding tunnels as expensive, “gray” and not-sustainable. Tunnels under design were stopped and large planned tunnel programs were delayed or canceled. Therefore being sustainable and “green” is not simply using natural vegetation, but creating an asset that meets current and future needs and will not become a future liability. As this paper will discuss, tunnel projects embody a sustainable triple bottom line project well, are equally sustainable as green infrastructure, and have begun to gain awareness for their sustainability. GREEN INFRASTRUCTURE CHANGES TUNNELING LANDSCAPE The green movement quickly swept across the nation in the mid to late 2000’s and was a hot topic in the media and at all the local, regional and national industry conferences. Politicians espoused the benefit of green infrastructure including job creation, urban renewal, aesthetics, property values economics and sustainability. The political microscope was focused the closest on stormwater and wastewater management, particularly in communities responding to combined sewer overflow (CSO) consent decrees from the Environmental Protection Agency (EPA). As communities with CSO problems evaluated their long term control program (LTCP), local government officials and planners began to balk at the huge price tag required for compliance and began looking for alternatives. “Green” infrastructure was proposed as lower cost solution that could be used to offset capital-intensive “gray” infrastructure like new sewers, storage tanks, tunnels, and treatment facilities. In addition, including green infrastructure in a previously negotiated LTCP required a reset on the entire planning process, additional studies and more planning which would push capital investment further off into the future, subsequently delaying unpopular user rate increases. As a result, tunnel projects as well as trenched conveyance and treatment plant projects that had not yet started construction were stopped, delayed or substantially changed."

Jan 1, 2016

By M. M. Tilman

As part of ongoing research to improve mine safety, the Bureau of Mines conducted research on the corrosion of friction rock stabilizer steels in five Missouri lead and iron mine waters. Electrochemical corrosion tests, including evaluation of pitting tendency, were performed on two types of high-strength, low-alloy (HSLA) steels and galvanized steel in four Missouri lead mine waters and one Missouri iron mine water. The tests were conducted at in-mine water temperatures in both air-saturated and deaerated waters. Static, weight-loss corrosion tests were also conducted on HSLA steel specimens in the five Missouri mine waters for 2,900-h duration at average in-mine water temperatures and air-dissolved oxygen contents of 6 to 7 ppm. Corrosion rates determined by the weight-loss tests were roughly comparable with rates determined electrochemically in deaerated waters containing 0.3 to 0.5 ppm dissolved oxygen content. Passivation of specimen (nongalvanized) surfaces in air-saturated waters resulted in very low electrochemically deter- mined corrosion rates. Pitting-tendency was generally higher for both HSLA steels in air-saturated waters than in deaerated waters. Galvanized steel generally exhibited higher tendency to pitting in the deaerated waters than in the aerated mine waters.

Jan 1, 1985

By D. M. Carris

Since the Buffalo Creek incident in February, 1972, Federal and state environmental agencies have had the pressure on the coal industry in the Appalachian area to close the coal processing plant water circuits. In an attempt to comply with this requirement, Eastern .Associated Coal Corp. decided to install a vacuum disc filter system at its Kopperston plant to eliminate the tailings pond and reduce the amount of plant make-up water. It was recognized at the time that the plant static thickener tailings would be a very difficult slurry to dewater because of its unusually high clay content. The following is a case history of the Kopperston installation and the refinements Eastern has made in its vacuum disc filter operation to increase efficiency.

Jan 1, 1979

President Howe : It is not so clear to me that the facts which Dr. Waldo brings forward really argue that the nature of the combination between copper and aluminum differs from that of the combination between copper and zinc or copper and tin. As regards electric conductivity, I suppose that the fact, which he thinks points to a special intimate kind of union between aluminum and copper, is that the line in his Fig. 1 is neither straight nor uniformly curved, but that its curvature varies rapidly, not to say abruptly. But we find just such variation in like curves for the copper-zinc and copper-tin alloys. Thus, a slight addition of zinc or tin to copper causes a change in color wholly out of proportion to the quantity added; and, as we add zinc or tin to copper, the tenacity rises very greatly, only to fall off abruptly with further additions of either of these metals. Dr. Waldo : My curve related only to electrical conductivity. The President : If irregularity in one physical property argues

Jan 1, 1895

By CIM Mineral Resource, Mineral Reserve Committee

These Leading Practice Guidelines for Mineral Processing (LPGMP) were prepared by the Sub-Committee on Leading Practice Guidelines for Mineral Processing. The Sub-Committee reports to the Executive Committee of the Canadian Mineral Processors (CMP) which is a Technical Society of the Canadian Institute of Mining, Metallurgy, and Petroleum (CIM) and incorporates those members of the CIM who are concerned with the processing of mineral deposits. The LPGMP covers the involvement of mineral processing professionals, referred to as Practitioners in this document, in providing inputs to the estimation of Mineral Resources and Mineral Reserves and providing technical content for internal reports as well as public reports on mineral projects as required under National Instrument 43-101 Standards of Disclosure for Mineral Projects (NI 43-101). The LPGMP supplement the CIM Exploration Practice Guidelines (2018) and the CIM Estimation of Mineral Resources and Mineral Reserves Practice Guidelines (2019) which are referenced in Companion Policy 43-101CP to NI 43-101 and recognized internationally. The LPGMP consist of 3 sections: • Principles of Process Support in Mineral Resources and Mineral Reserves Estimation; • Appendix A – Use of Supporting Studies in Process Evaluation and Assessment for NI 43-101 Documentation; • Appendix B – Glossary of Terms Relevant to the LPGMP. The LPGMP deal primarily with the description of leading practice as it applies to the mineral processing and extraction of base metals, precious metals, and other mineral products by the application of mineral processing technology. Other commodities may be considered with future updates of these guidelines. It is expected that this is a ‘living’ document and that these guidelines will develop in the future to address the requirements of the mining industry, investing public, and mining professionals involved. Clarifications and changes to these guidelines will be done under the guidance of the Executive Committee of the CMP.

Nov 25, 2022

By B. K. Cantrell, K. L. Rubow

"The US Bureau of Mines and the University of Minnesota have developed design and performance criteria for a personal diesel exhaust aerosol sampler for underground coal mines. These are based on the premise that size can be used to separate diesel exhaust aerosol, which is mostly submicron in size, from coal dust aerosol, which is mostly greater than a micron in size. The sampler has three stages: a respirable aerosol preclassifier, a 0.8-um aerodynamic diameter inertial impactor to collect mineral dust and a final filter to collect the diesel aerosol. Using a sample flow rate of 2 L/min and gravimetric analysis to within 0.1 mg, the measure sub-0.8 um diesel aerosol has an a-priori limit of detection of 0.3 mg/m3.A miner working in an underground coal mine with diesel equipment is exposed to a wide array of pollutants from the diesel exhaust. These include CO, CO2. NO, NO2, SO2, diesel exhaust aerosol, and a variety of hydrocarbon compounds. A quantitative definition of the health risk resulting from these exposures remains elusive. During the past several years, though, progress has been made in defining the problem.Results from epidemiological studies by Garshick et al. (1988 ), animal inhalation studies by Mauderly eta). (1986), Iwai et al. (1986), and Brightwell et al. (1986) and in vitro studies by Lewtas et al. (1986) have provided sufficient data for the National Institute of Occupational Safety and Health (NOSH) to recommend that ""whole diesel exhaust be regarded as a 'potential occupational carcinogen,' as defined in the Cancer Policy of the Occupational Safety and Health Administration"" (NIOSH, 1988). NIOSH further stated that ""though the excess risk of cancer in diesel-exhaust-exposed workers has not been quantitatively estimated, it is logical to assume that reduction in exposure to diesel exhaust in the workplace would reduce the excess risk.""The Mine Safety and Health Administration (MSHA) has also been directed by an advisory committee to establish a diesel exhaust aerosol standard and to establish regulations to minimize exposure to diesel pollutants in underground coal mines (MSHA,1988). Both reports point out the need for development of measurement techniques for respirable diesel aerosol.In the past four years, the US Bureau of Mines (Cantrell,1987 and Cantrell, et al. 1987), in cooperation with Marple, et al. (1986), at the University of Minnesota's Particle TechnologyLaboratory (PTL), have studied the use of size-selective sampling techniques to measure the mass concentration of diesel aerosol in underground coal mines. Results from these studies have been used to develop design and performance criteria for a personal diesel exhaust aerosol sampler for use in underground coal mines.These criteria are based on the premise that size-selectivesampling techniques,can be used to separate diesel exhaust aerosol, which is predominantly submicron in size, from coal dust aerosol, which is mostly greater than a micron in size. In addition to the performance criteria, this paper discusses the laboratory and field test data used to develop the criteria."

Mar 1, 1992

The Australasian Institute of Mining and Metallurgy (AusIMM) is a professional society for all those associated with the activities of the mineral industry. Differences of opinion exist within the membership of the AusIMM on the role it should play in the future as a professional society in a changing industry and world environment. This same dilemma is concerning other professional societies of which the author is a member. Some of the activities and priorities of the AusIMM are reviewed in order to clarify a frequently expressed opinion that it identifies with and supports industry at the expense of representing the interests of its individual members. By definition and by action this is certainly not the case and it is concluded that all activities whether seen to be industry or member orientated serve to benefit both. The AusIMM plays a most important role in integrating and promoting the interests of all sections of the mineral industry whether corporate or individual and the Presidential activities in education this year provide an excellent example of this.

Jan 1, 1997

By Frank D. Lamb

"INTRODUCTION The use of beryllium and its alloys has come into prominence in the last 15 years and increased considerably during the war. In contrast to other light metals, such as aluminum and magnesium, beryllium is relatively hard, has a high melting point (1,285° C.), and other properties that make it resemble steel in many respects. It has a specific gravity of 1.85, is only slightly heavier than magnesium (specific gravity 1.74), and is appreciably lighter than aluminum (specific gravity 2.7). Its lack of ductility prevents its use as a structural material, but this difficulty may be overcome in the future by the use of various alloy forms. The only important commercial alloy in which beryllium is used today is with copper. The addition of small percentages (1/2 to 2 percent) of beryllium to copper imparts properties to the alloy that make it desirable for use in springs carrying electrical current, particularly at high temperature. Many other uses of berylliam are known, and new uses are being found constantly that make the metal of increasing interest.Possibly the main factor preventing the use of more beryllium is the lack of a large source of beryllium ore. Many beryllium minerals are found as minor constituents of natural deposits, some of the more common ones being beryl (Be3Al2(Si03)6), chrysoheryl (Be A1204), helvite (3(Mn, Fe) Be Si04. MnS), and phenacite (Be2Si04). Of the known beryllium minerals, beryl is by far the most common and has been found distributed rather widely throughout the world. It usually occurs associated with granitic rocks and is commonly found as a constituent of granitic pegmatite."

Mar 1, 1947

By Douglas R. Shaw

Normal dodecyl mercaptan was evaluated as a collector for flotation of sulfide minerals and precious metals. The reagent is from the class of normal mercaptoalkanes (n-alkyl thiols), and is commercially available in the form of a mixture of n-dodecyl mercaptan and a dispersant, under the trade name Pennfloat(TM)3. Reported are results of bench-scale flotation experiments on many commercially treated base metal and precious metal sulfide ores. Dosages, points of addition, and flotation pH were among the uariables studied. Most notable results were increased copper, molybdenum, and precious metals recoveries. Dosages of dodecyl mercaptan on some ores were considerably lower than required for conventional collectors.

Jan 1, 1979

By Maria I. De Rosa

The U.S. Bureau of Mines conducted experiments for predicting materials' ease of combustion (smoldering onset, smoldering, flaming, and decomposition rates) by means of submicrometer smoke particle characteristics for the development of a simple test method. The experiments were carried out in an approximately 20-L furnace, with a 10-L/min airflow through the furnace for a 14-min duration, at set furnace temperatures of 150°, 250°, and 1,000° C. The variables studied as a function of time were the onset time of smoke particles, time and duration of maximum smoke particle generation, average concentration of smoke particles, and particles' average diameter, mass weight loss, and furnace temperatures. Results show that the onset time of smoke particles is predictive of materials' ease of smoldering, and the time of maximum smoke particle generation and its duration, coupled with mass weight loss, are predictive of materials' ease of smoldering and flaming (depending on the experimental temperatures), and decomposition rates.

Jan 1, 2010

By J. G. Craig

This paper initially was to be on the design, construction and operation of the Lucky Friday mill. However, this subject has been pretty well covered in some of the mining publications in the past few years - specifically Mining Congress Journal for April, 1961 and Mining World for March, 1962- : In order to avoid too much repetition, we decided to present in this paper a comparison of the Lucky Friday mill constructed in 1959, and the Mayflower mill built by us in 1962. During the past three years Hecla Mining Company has constructed two relatively small mills: The Lucky Friday mill at Mullan, Idaho 750 T/day; and the Mayflower mill at Heber, Utah - 450 T/day. These mills were engineered, designed and constructed by Hecla, using principally our own personnel, with very little outside (contractor) labor employed. This paper presents a comparison of some of the interesting features of these mills, and where differences occur, it discusses the reasons for the various differences. It compares such points as the testing program, physical layout of the plant, construction costs, the grinding section, the flotation section, tailings disposal, metallurgy, recovery, grades, operating costs, etc. To help illustrate, and to compare these features, we will project pairs of slides showing each of the two mills. First a little background and history on the properties ---

Jan 1, 1964

By Clinton C. Knox

During the latter part of 1943, a magnetometric survey was conducted by the Geophysical Division of the Bureau of Mines at the Mahopac magnetite mine, Putnam County, N. Y., in an endeavor to locate a segment of the ore body that reports state was cut off by a fault. The Mahopac mine was abandoned about 1895 after producing nearly 1,000,000 tons of high-grade magnetite iron ore. The results of the investigation indicate the termination of the ore body by "pinching", or a displacement of such magnitude as to place any extension at a considerable distance from the original are body. This report describes the work done on the project and presents the data obtained.

Jan 1, 1948

By M. S. Seehra, R. S. Pandurangi

"The interaction of amorphous silica particles with several hydrogen bonding agents (H2O,, C2H,OH, C,H,NO) was investigated by monitoring the changes in the bulk and surface IR vibrational modes of silica using photoacoustic spectroscopy, It is argued that the intensity of the silanol band at 3747 cm-1 provides (an inverse) quantitative measure of the interaction of surface groups, along with the shift in the broad hydroxyl band, the interaction following the order C,H,NO > C2H2OH > H2O.The use of IR spectroscopy to study the adsorption on solid surfaces is well documented in the literature,"" For example, hydroxylation of a clean silica surface results in the formation of the free silanol group Si-OH, with a sharp IR band near 3747 cm-1. Further hydroxylation produces a broad band near 3500 cm-1, which is believed to result from various hydrogen-bonded silanol bands leading to a multilayered surface structure of few nm.3-6 Earlier studies had indicated a relationship between the surface silanol band and various chemical activities of silica such as cytotoxicity,7-9 catalysis,10-12 and others.13 Recent studies from our group14-in which the intensity of the silanol band and cytotoxicity of silica, heat-treated at various temperatures up to 1095°C, were investigated-have provided a strong correlation between cytotoxicity and intensity of the silanol band.Coating of silica by PVPNO (polyvinyl-2-pyridine N-oxide with the empirical formula C7H8N0), a strong hydrogen bonding agent, is known to reduce the cytotoxicity of silica, presumably by chemically blocking the silanol groups from phospholipids.15 This interaction of the hydrogen bonding agents with the silica can be studied by IR spectroscopy, and Knozinger16 and Rouxlet and Semples17 have used transmission IR spectroscopy to study the effect of various chemicals on the surface IR modes of silica. However, one of the major disadvantages of transmission IR spectroscopy is that the sample preparation (grinding and mixing with KBr and pelletizing) usually distorts the surface modes (see, e.g., Ref. 14) and there is always a doubt about the effect of the sample preparation on the measured properties, In recent years, photoacoustic (PA) spectroscopy has become the technique of choice for studying the IR spectra of samples in their natural state, since no sample preparation is necessary.18,19 Moreover, according to a recent paper,20 the relative intensity of the surface modes in PA spectroscopy of silica particles is much higher than that in transmission FT-IR spectroscopy. Consequently PA spectroscopy is ideal for studying the surface chemistry, In this work, we have used PA spectroscopy to investigate the interaction of three hydrogen bonding agents (C7H8NO, C2H5OH, and H20) with the silica surface by monitoring changes in the surface IR modes, Our results show that the surface IR modes get perturbed to a larger extent than the bulk IR modes in interaction with the hydrogen bonding agents, Moreover, whereas in the earlier studies, the shift of the broad silanol band near 3500 cm-1 was used as a measure of the interaction with hydrogen bonding agents,16,17 here we show that the relative decrease in the intensity of the sharp silanol band near 3747 cm-1 also serves as a quantitative parameter for the relative surface coverage and surface modification, Details of this work are given below,The Cab-O-Sil samples of silica used here were obtained from the Cabot Corporation of Tuscola, IL, In our earlier studies,14,20 we have shown these particles to be amorphous and about 0.05 am in size, For coverage of these particles with H20 and C2H50H, the following procedure was employed. About 5 mg of silica was mixed with 50 mL of the liquid (H2O or C2H5OH) and refluxed for one hour, The remaining liquid was allowed to evap¬orate to dryness and 1 mg of the treated sample was used to collect the PA spectra. In the case of PVPNO, the amount that binds to Cab-O-Sil is taken from the data on quar"

Mar 1, 1992