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Volume 11, Number 1

January/February 2006

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Refractories are unique structural ceramics and they reveal mineralogically perfect "disequilibrium" assemblages as illustrated in front cover. The material is known to be a "patch" material used in a coreless induction furnace, which is used to melt stainless steel, carbon steel, ductile and grey cast iron. The thickness of crucible was reduced due to erosion and then cracked allowing metal into the backup lining. An alumina-magnesia plastic refractory was used to patch cracks. The CL image on front cover shows the microstructure of this plastic refractory after service. The CL image was taken from central portion of the sample. Note that large sintered magnesia (MgO) and fused alumina (FA) are used as refractory fillers. Spinel, MgAl2O4 (green CL) and forsterite, Mg2SiO4 (red CL) is formed as the ceramic bond. Interestingly forsterite is formed on magnesia while spinel is developed on alumina grains. The sample was provided by Dr. James G. Hemrick of ORNL. Musa Karakus

R AN

Front Cover

CONTENTS

Refractories Applications

and News

The Refractories Institute News . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 R. Crolius From the Editor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 W. L. Headrick UNITECR `05 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 A. Rezaie Continuous Improvement of Refractories Continues. . . . . . . . . . . . . . . . . . . . . . . . 6 C. E. Semler Industry News . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Correlations of Unhydrous Phases Present in Calcium Aluminate Cement With Its Workability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .17 M. R. Nilforoushan, M. R. Saerie, S. Otroj Historical Reprint ­ Low Cement/No Cement Monolithics ­ Their Potential for Ladle Metallurgy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22 J. L. Mendoza, R. E. Moore and C. H. Liu Directory of Products and Services . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 Buyer's Guides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34

Lock 3 Company ­ A Toll Processor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .10 M. W. Vance

ANH Refractories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 Tel: (412) 375-6600 Heidelberger Calcium Aluminate . . . . . . . . . . . . . . . . . . . . . . . . . . .inside front cover Tel: (800) 348-7070 Fax: (610) 336-7853 New Castle Refractories Company . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 Tel: (724) 654-7711 Fax: (724) 654-6322 Unimin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . inside back cover Tel: North America (800) 243-9004 Fax: (800) 243-9005 Tel: Worldwide: (203) 966-8880 Fax: (203) 972-1378 Vesuvius USA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 Tel: (217) 351-5000 Fax: (217) 351-5031

ADVERTISING INDEX

U.S. readers who would like to subscribe to this magazine should e-mail their name and address to: Mary Lee at: [email protected]

Refractories Applications and News, Volume 11, Number 1 January/February 2006 1

Refractories Applications

and News

JOINTLY SPONSORED BY THE REFRACTORIES INSTITUTE AND REFRACTORY CERAMICS DIVISION OF THE AMERICAN CERAMIC SOCIETY

Technology Bimonthly for the Global Refractories Industries

www.ranews.info

Associate Editor, William Headrick Associate Editor, Jeffrey D. Smith Associate Editor, Musa Karakus Assistant Editor/Webmaster, Mary Lee RAN Advisor, Mariano Velez Contributing Editor, Charles E. Semler Advertising Sales, Stephanie Headrick

"Refractories Applications and News" founded by Robert E. Moore in 1996. Editorial offices at University of Missouri-Rolla Materials Science and Engineering Department, 223 McNutt Hall, 1870 Miner Circle Drive, Rolla, MO 65409-0330 Phone: (573) 341-6561 Fax: (573) 341-6934 Website: www.ranews.info

E-mail: [email protected] E-mail: [email protected] E-mail: [email protected] E-mail: [email protected] E-mail: [email protected] E-mail: [email protected] E-mail: [email protected]

Phone: (573) 341-6561 Phone: (573) 341-4447 Phone: (573) 341-4120 Phone: (573) 341-6561 Phone: (573) 341-6561 Phone: (480) 895-9830 Phone: (573) 729-7628

Lou Trostel - Councilor, Refractories Ceramics Division, ACerS Rob Crolius - President, TRI Esteban Aglietti, (CETMIC, Buenos Aires, Argentina) E-mail: [email protected] Carmen Baudin, (Institute for Ceramics and Glass, Madrid, Spain) E-mail: [email protected] Richard C. Bradt, (University of Alabama) E-mail: [email protected] Elena Brandaleze, (Instituto Argentino de Siderurgia) E-mail: [email protected] Geraldo E. Gonçalves, (Magnesita, Brazil) E-mail: [email protected] Bill Lee, (University of Sheffield, England) E-mail: [email protected]

Corresponding Editors:

Refractories Applications and News, the premier technology journal for the global refractories industries, covers the latest advances in raw materials, finished products, installation and research. Refractories Applications and News is published six times a year. Printed in the United States of America. © The Refractories Institute, the Refractory Ceramics Division and the University of Missouri-Rolla, Materials Science and Engineering Department assumes no responsibility for the statements and opinions advanced by contributors to its publication.

Subscription is free upon request in the U.S. only. Please e-mail address changes to Refractories Applications and News, University of Missouri-Rolla, 223 McNutt Hall, 1870 Miner Circle Dr., Rolla, MO 65409-0330. Allow six weeks for address change. Foreign readers may receive a hard copy by sending $40.00/yr. in U.S. currency or view the current issue (free) on our website: www.ranews.info. Foreign institutes, research centers and libraries will continue to receive a free printed copy upon request.

Jose L. Mendoza-Bedolla, (Technical Consultant, Saltillo, Mexico) E-mail: [email protected] Li Nan, (Wuhan University, P.R. China) E-mail: [email protected] George Oprea, (University of British Columbia, Canada) E-mail: [email protected] Victor C. Pandolfelli, (UFSCar, Brazil) E-mail: [email protected] Michel A. Rigaud, (Ecole Polytechnique, Montreal, Canada) E-mail: [email protected] Raul Topolevsky, (Siderar, Buenos Aires, Argentina) E-mail: [email protected]

Refractories Applications and News (ISSN 1537-6443) is a bimonthly non-profit publication provided free to U.S. subscribers. Refractories Applications and News is not responsible for opinions stated by contributors to the publication. No part of this publication may be reproduced, or transmitted in any form without the written permission of the publisher. Permission is not, however, required to copy abstracts or articles on the condition that a full reference to the source is given. This consent does not extend to copying items for general distribution or for advertising or promotional purposes or to republishing items in whole or in part in any work in any format. Orders for copies of articles published in this magazine may be placed through the Refractories Applications and News office by contacting Mary Lee, [email protected], (573)341-6561.

Refractories Applications and News is being indexed by Cambridge Scientific Abstracts in Ceramic Abstracts/World Ceramics Abstracts, and by Chemical Abstracts Service, CODEN RACECN.

Instructions for the preparation of articles to be submitted for possible publication in this magazine are available from the Assistant Editor, Mary Lee, [email protected], (573)341-6561, University of Missouri-Rolla, 223 McNutt Hall, Rolla, MO 65409.

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U.S. readers who would like to subscribe to this magazine should e-mail their name and address to: Mary Lee at: [email protected]

January/February 2006

Refractories Applications and News, Volume 11, Number 1

2006

January 23-26, Thermal Solutions; The Hyatt on Sarasota Bay, Sarasota, FL; Tel: 800-636-9820; www.thermalsolutions.org

REFRACTORIES RELATED MEETINGS

Feb 27-Mar 01, Combustion Seminar, Lebanon, PA; Tel: (717) 272-3051; Fax: (717) 273-9882; E-mail: [email protected]; www.hauckburner.com March 12-16, 2006 Annual Meeting of the Minerals, Metals and Materials Society (TMS); San Antonio, TX; Contact: Jim Hwang, E-mail: [email protected]; Tel: 906-487-2600; Fax: 906/487-2921; www.imp.mtu.edu Feb 27-Mar 02, Process Plant Start-up, Amsterdam, The Netherlands; Tel: (31) 20638-2806; E-mail: [email protected]; www.cfpa.com

February 20-24, 4th Annual Refractories for Industrial Users Course, Maccauvlei Training & Conference Center, Vereeniging, South Africa. Course presented by Cannon & Hancock CC. Tel: +27 16 422 0911; Fax: +27 16 422 4514; E-mail: [email protected]; www.actchem.com.

March 26-29, 18th Industrial Minerals International Congress and Exhibition, Palace Hotel, San Francisco, CA; Contact: Mike O'Driscoll; E-mail: [email protected]; Tel: +44 (0) 20 7827 6444; www.indmin.com. March 29-30, 42nd Annual St. Louis Refractories Symposium, Hilton St. Louis Airport Hotel, St. Louis, MO; Contact: Patty Smith: Tel: (573) 341-6265, Fax: (573) 341-6151; E-mail: [email protected] Apr 17-21, 2006 MRS Spring Meeting, Moscone West Convention Center, San Francisco, CA; www.mrs.org/meetings/spring2006/

March 28, ASTM Committee C-8 Refractories, at the Hilton St. Louis Airport Hotel, St. Louis, MO.; Contact: Diane Rehiel, Manager: Tel: 610-832-9717; E-mail: [email protected]

June 4-9, International Conferences on Modern Materials Science and Technology, Acireale, Sicily, Italy; Tel: +0546 22461 / 664143; Fax: +0546 664138 / 663362; E-mail: [email protected]; www.cimtec-congress.org Jun 21-23, 4th International Workshop on Characterization of Porous Materials: From Angstroms to Millimeters, Princeton, NJ; Tel: (609) 430-4820; Fax: (609) 683-7149; E-mail: [email protected]; www.triprinceton.org/workshop2006

May 16-19, Glass and Optical Materials Meeting 2006;Call for Papers Now Available - Abstract Submission Deadline: November 7, 2005; Hyatt Regency Greenville, Greenville, SC; Contact: Matt Dejneka; Tel: 607-974-2620; [email protected]

May 7-11, 9th Annual NSTI Nanotechnology Conference and Trade Show, Hynes Convention Center, Boston, MA; Contact: Nano Science and Technology Institute, One Kendall Square, PMB 308, Cambridge, MA 02143; Email: [email protected]; Voice: (925) 901-4959; www.nsti.org/Nanotech2006

June 4-9, CIMTEC 2006, 11th International Ceramics Congress, 4th Forum on New Materials, Acireale, Sicily, Italy; Call for Papers Abstracts due by October 15, 2005. For more information: www.cimtec-congress.org June 25-29, 1st International Congress on Ceramics, The Westin Harbour Castle, Toronto, ON, CAN; www.ceramics.org, www.ecers.org, www.ceramic.or.jp July 23-28, 19th Quadrennial Meeting of the International Mineralogy Association (IMA), Kobe, Japan, Dick Hagni, IMA-CAM Chairman, E-mail: [email protected]; www.congre.co.jp/ima2006/. Abstracts and pre-registration due by February 28, 2006. (See page 21 for more information.) August 07-09, 34th Annual Conference of the North American Thermal Analysis Society (NATAS), Holiday Inn University Plaza Hotel, Bowling Green, KY; Tel: 916-922-7032; Fax: 916-922-7379; www.natasinfo.org August 21-31, 2006 TMS Fall Extraction & Processing Meeting: Sohn International Symposium; sponsored by The American Ceramic Society; Catamaran Resort; San Diego, CA; Tel: (724) 776-9000 x 243; Fax: (724) 776-3700; Email: [email protected] July 9-12, Fractography of Glasses & Ceramics V; endorsed by The American Ceramic Society; 125 E. Main St., Rochester, NY; Contact: Marlene Wightman; E-mail: [email protected]

September 24-28, Crystallization 2006 - International Symposium on Crystallization in Glasses & Liquids; Call for Papers Now Available. Abstract Deadline February 27, 2006; Snake River Lodge & Spa, Jackson Hole, WY; Contact: Mark Davis; Voice: 570-4577485 ext. 354; Fax: 570-457-3438; Email: [email protected] Fall 2006, 33rd ALAFAR Congress, Cartagena, Colombia.

September 16-29, Materials Science & Technology Conference (MS&T), Cincinnati, OH; Tel: 440-338-5151; Fax: 440-338-4634; Email: [email protected]; www.asminternational.org

October 15-19, Material Science & Technology 2006 Conference and Exhibition - MS&T06 combined with the ACerS 108th Annual Meeting, Cincinnati Convention Center, Cincinnati, OH; www.matscitech.org/ Refractories Applications and News, Volume 11, Number 1 January/February 2006

October 1-4, COM 2006 Montreal, Montréal, QC, CAN, Contact: George Demopoulos; E-mail: [email protected]; www.metsoc.org

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The Refractories Institute, 650 Smithfield St., Ste. 1160, Pittsburgh, PA 15222

News from The Refractories Institute

UNITECR 2005 SUCCESS STORY

www.refractoriesinstitute.org/

Shamu the Killer Whale made a huge splash at Seaworld the opening night of UNITECR 2005 in Orlando as did the conference itself over the four days it unfolded at the Rosen Centre Hotel. Great papers, terrific social events and entertainment, an informative Rob Crolius exhibit and good food--you really couldn't ask for more. There are many people to thank. As President of UNITECR 2005, John Turner went way beyond the call of duty. He rolled up his sleeves early on and stayed focused throughout the planning and the execution. Jeff Smith did a terrific job as Program Chair. His decision to divide the program into seminars just made a lot of sense. Tom Vert's work on the social program and in putting together the steel program and luncheon earned a lot of praise. Nancy Bunt's efforts on publicity are to be commended as is the valuable and ongoing counsel of Lou Trostel. And don't forget some of the early planning efforts. Thanks to Roy Bottjer, Charlie Semler, Michel Rigaud and others who laid the groundwork for UNITECR 2005, to include picking Orlando and the Rosen Centre as the venue. Of course, the whole thing never would have come off if it weren't for the months/years of effort of ACerS employees like Mark Mecklenborg, Dawn Sink Kennedy, and Glenn Harvey. The greatest kudos must be reserved for the guy who got it all done. Mark Stett, member of the International Executive Board and Chairman of the UNITECR 2005 Organizing Committee, led and managed the project from start to finish over a period of years and well into his retirement. His tireless and devoted commitment to ensuring a successful conference has set a standard that will be hard to beat. His election as a Distinguished Life Member of UNITECR is testimony to the excellence he brought to the table. I likely have left some people out. For that I apologize. Thanks also to the UNITECR sponsors whose financial support contributed significantly to making the meeting a memorable event.

adverse structural costs, and they have still not returned to their structural norm, according to a joint study released by the Manufacturing Institute and the Manufacturing Alliance/MAPI. The report focuses on five industries that account for over half of all manufacturing production--fabricated metal products, machinery, electrical equipment and appliances, motor vehicles and chemicals. To link to the study, go to: www.nam.org/costsqueeze.

REGULATORY EPA Amending MACT Regulation

The Environmental Protection Agency is amending the National Emission Standard for Hazardous Air Pollutants (NESHAP) for Refractory Products Manufacturing, generally know as the MACT (maximum achievable control technology) regulation for refractories. The amendments are intended to clarify certain ambiguous provisions of the rule, correct technical errors, and to make the rule consistent with the General Provisions of CFR 40 Part 63 which were also recently amended. A direct final rule and parallel proposal will be published in the Federal Register soon. There will be a sixty day comment period. You may access the proposed changes by going to: www.epa.gov/edocket. Look for docket number OAR-2020088-0447.

LEGISLATION Your Congress at Work

The House of Representatives took final action and the President is expected to sign S. 397, the Protection of Lawful Commerce in Arms Act which will prevent lawsuits against gun manufacturers and dealers for crimes committed with firearms. The House has also passed H. R. 554, the Personal Responsibility in Food Consumption Act which prevents obese people from suing fast food and other food providers. Okay. Now what about asbestos litigation reform, prohibition of lawsuits for silica exposure if there was in fact no exposure, and genuine tort R AN reform?

ALMATIS TO UNDERGO CHANGE OF OWNERSHIP

Investcorp, a global investment group, plans to acquire the Almatis Group from Rhone Capital and Ontario Teacher's Capital. The transaction is expected to close this month. Almatis has also divested its Adsorbents & Catalyst business unit to Engelhard Corporation. Both actions reflect Almatis' intention to focus and invest in its core businesses.

High Costs Undermine U.S. Manufacturing

4 January/February 2006

Manufacturing profits in five key sectors were 67% lower than they would have been from 2000 to 2003 because of

Refractories Applications and News, Volume 11, Number 1

A WORD FROM THE EDITOR

The editorial staff at Refractories Applications and News would like to thank everyone who attended UNITECR 2005. While having a wonderful time at UNITECR, I was reviewing this issue of the magazine and planning this editorial. UNITECR is a great meeting to meet other people from around the world that either work with refractories or in a related field. I enjoyed the exhibition and excellent technical papers. It William L. Headrick never ceases to amaze me that there is such a large amount of excellent research going on around the world in a field that is rapidly becoming a commodity in the U.S. This issue should reach you just in time to have a last chance to register for the 2006 42nd St. Louis Section Meeting on Refractories in St. Louis on March 29 and 30 at the Hilton airport. The topic is "Advances in Raw Materials" and this two day meeting promises

From the Editor . . .

William L. Headrick, Associate Editor, [email protected]

UNITECR `05

to once again be the premier meeting on refractories in the United States. The "Meet and Greet" Expo format is the same as before with each vendor having a six-foot table to display products and literature with an open two hour bar during the exposition for the attendees prior to dinner on Wednesday evening. Additional information is available on the REFRACTORIES RELATED MEETINGS page. This issue contains three papers regarding monolithic refractories. The first describes toll processing of monolithics from start to finish. The second compares Iranian cements with SECAR cements. This paper shows the importance of cement processing and quality control on the end properties expected for castables. The last paper is a historical article by Jose Luis Mendoza from 1987 on low cement castables. It is interesting to note the incremental changes between current technology and what was being developed in 1987. Also of interest is the lack of change. Maybe refractories are becoming a commodity. R AN

Ali Rezaie, UMR Materials Science and Engineering Department, [email protected]

The session of ultra-high temperature ceramics (UHTC) consisted of five presentations. This session was held on Thursday morning 1110-2005 in room 13/14 of Rosen Center Hotel in Orlando. The number of attendants to this session was relatively high, more than expected of about forty people. Ultra High Temperature Materials (UHTMs) are a family of compounds that are chemically and physically stable at high temperatures (e.g., above 2400°C) and in reactive atmospheres (e.g., monatomic oxygen). The characteristics of UHTMs, such as strength at high temperature and oxidation resistance, allow them to be used in extreme environments including those associated with hypersonic flight, atmospheric re-entry, and rocket propulsion. The ultra-high temperature regime is generally considered to begin at 1600°C. Some of the compounds that make up the UHTM family are the borides, carbides, and nitrides of early transition metals such as TaC, ZrB2, ZrC, HfB2, HfC, and HfN, which have melting temperatures above 3000°C. The thermal and chemical stability of UHTMs present a variety of unique scientific challenges related to processing, characterization, and evaluation of performance. Mark Opeka from Naval Surface Wafer Center, USA summarized the status of the research and development of ultra-high temperature non-oxide ceramics in the center. Silica forming materials such as SiC, Si3N4, and MoSi2 can be added to UHTCs for application in oxidizing environments. Thermodynamic calculation showed that the application of these materials is limited by the formation of high vapor pressures at the interface between the base material and the

Refractories Applications and News, Volume 11, Number 1

oxide scale. Arc heater test results showed the superior performance of boride ceramics compared to UHT carbides and nitrides of Zr and Hf. Frederic Monteverde from National Research Council, Italy, presented ZrB2 as an excellent corrosion resistant material against molten iron and non-basic slags with superb thermal shock resistance. Parts of electrical devices such as heaters or igniters made of ZrB2 are currently in use. Titanium Boride and ZrB2 can be used as molten metal crucibles or thermowell tubes for steel refining. Pressure-less densification of ZrB2 based ceramics is a barrier for processing of this ceramic. The effect of addition of sintering aids such as Ni, Si3N4, AlN, ZrN, HfN, and MoSi2 on microstructure development and properties of ZrB2 based materials was presented. Forming techniques such as isostatic pressing and machining, slip casting, or electrical discharge machining were mentioned as suitable techniques to have complex shaped components. Sylvia M. Johnson from NASA-Ames Research Center presented UHTCs as appropriate materials for application as sharp leading edges of reentry vehicles. Recent work at NASA-Ames with focus on the HfB2 system mixed with SiC was presented. William Fahrenholtz was the last speaker of the session because the last presentation by He Zhiong was canceled. The microstructure and mechanical properties of conventional ZrB2 based ceramics and ZrB2 based fibrous monolithic ceramics was presented. Strength was Continued on Page 16 January/February 2006 5

(See photo on the back cover)

20 YEARS OF CHANGE IN CHINA

China has a very long history that spans thousands of years, with many ruling dynasties. But the changes/advances since 1980 have been the most remarkable, because of their great impact in China, and worldwide. It is a rare day when we do not hear/read something about China, and see a "Made in China" label. The transformation of China over the last Charles E. Semler 20+ years has probably been the quickest and most profound of any nation in history, with so many social/lifestyle changes, as well as manufacturing and economic effects that are directly affecting the whole world. Given the greatly increased effects of China on the U.S., this article presents some of my personal observations of the changes over the last 20+ years, including specific observations about refractories.

Dr. Charles E. Semler, Semler Materials Services, Chandler, AZ 85248, [email protected]

Background

Beginning in October 1983, Prof. Dr. Xiangchong Zhong (Luoyang, and now Zhengzhou) and Prof. Li Nan (Wuhan), arranged a trip which allowed me to observe the refractories research, development, and manufacturing activities in China (Shanghai, Wuhan, Luoyang, and Beijing). At that time, the Chinese people mainly wore navy, gray, or olive-green Mao suits and bicycles were the main means of local transportation. Flights were available, but not reliable or safe, so intercity travel was mainly by steam engine-powered trains. Plant safety and environmental controls were virtually unknown. Industrial chimneys belched heavy plumes of smoke of various colors. The Chinese refractory plants had too many employees, for which they provided full services (meals, medical, school, accommodations, etc.). Support and direction came largely from the government, especially the Ministry of Metallurgy. Refractories were almost entirely formulated from natural raw materials; there was little use of beneficiated or synthetic raw materials. Friction screw presses were the dominant method of pressing bricks/shapes. One plant had 80 friction screw presses. Quality control of bricks after pressing and drying mainly involved measurement, visual inspection, and checking for cracks with a physical tapping device. Each plant had a testing lab, and appropriate Chinese standard tests were available, but frequently the labs seemed to be little used, so brick quality was always a concern. Bricks were fired in Russian-designed tunnel kiln; the kiln cars were high profile (which significantly reduced the firing capacity) and there was little insulation, so heat/energy was wasted. Also there was little use of recovered heat for drying or firing. 6 January/February 2006

Introduction

Observations from the 80's

Plant visits always began with an introductory discussion session with green tea (with floating leaves, in ceramic mugs). Coke was available for foreigners, but not for the Chinese. Foreign guests were housed in Friendship hotels, and taken to Friendship stores for shopping. There was different money, and prices, for tourists and for the Chinese. Guests were treated to banquets for lunch and dinner with large quantities of food (e.g., 20-25 different dishes), and many toasts at dinner. China held their 1st International Refractories Symposium in Hangzhou in 1988. There were opening lectures from China (Zhong), U.S., U.K., Japan, and Germany. The session topics included raw materials, metallurgical industry, cement and glass, and other general subjects. Prof. Zhong stated that "new industrial developments, especially in the steel industry, have given impetus to the refractories industry to develop sophisticated new products which have to rely upon higher quality refractory raw materials - natural, beneficiated, and synthetic".

Figure 1. Example of an older refractories plant in China producing products mostly based on natural raw materials.

Recent Observations

Since my initial visit in 1983, I have made 11 more trips to China, including 2005. Now the dress in China is generally similar to other western countries. Coke is available to everyone throughout China, but diet Coke is hard to find in rural areas. McDonalds, KFC, Pizza Hut, etc. are common throughout China. There are unlimited shopping opportunities, but there are still cases of pricing differences for Chinese and foreigners. Guests are still welcomed at plants with green tea, and are treated to large meals at lunch and dinner, with frequent toasts at dinner. The number of bicycles has decreased sharply, and the number of cars has increased greatly, with many owned by individuals (see next Refractories Applications and News, Volume 11, Number 1

paragraph). There are many new airport terminals and the jet fleet is young and reliable. Increased attention is being devoted to the environment, but chimney effluent and air pollution are still major concerns. The economy of China is robust and growing, with a GDP growth of 9.1% in 2003 and 9.5% in 2005. The government has taken steps to control/slow the economy, but there is significant momentum, which is hard to hold back. Money and modern conveniences have become powerful motivating forces for Chinese people. The "Age of Mass Car Consumption" has begun in China [1], and the annual production capacity is expected to reach 11-12 million units in 2007 [2]. In the 80's, multi-story buildings were constructed with a framework of re-bar-containing concrete beams supported by bamboo poles. Now multi-story buildings are being built with a robust steel beam structure. Cars/trucks and building construction are just two of the many new and growing markets that are increasing the demand for steel (see below). Reportedly there are still more than 2000 refractory companies in China, which fall into several general categories (1st tier, 2nd tier, and lower), based on characteristics such as attention to quality, computerization, input from foreign advisors, use of current technology and equipment, foreign business/exports, participation in international meetings, self-supporting income and profits (vs. state ownership/funding), etc. Maybe as few as 100 companies fall in the 1st tier level. Efforts are under way to reduce the number of lower tier refractories companies. This multi-level situation has resulted in severe price competition, and quality concerns, given the need for lower level companies to obtain income to maintain their viability. A large number of Chinese refractory companies are ISO-9000 certified. This means that they conform to their written guidelines, but it does not necessarily mean that their product quality will be consistent and acceptable. For foreign buyers, referee testing is still necessary to confirm and monitor the quality of production. The number of employees at refractory plants has been reduced. The use of beneficiated and synthetic raw materials has increased in refractory formulations in China, based on the need for increased service life under more severe operating conditions.

There is still widespread use of friction screw presses to form bricks/shapes, but there is increased use of imported hydraulic presses, robots, etc. Bricks/shapes are fired (up to 1850ºC) in tunnel kilns, which utilize heat recovery, and lower profile kiln cars. Some firings are still done in old style kilns (tunnel, beehive, etc.). Monolithic refractories account for only about 25% of the annual market, compared with 60+% in Japan, and 50+% in the U.S., so it can be expected that this market segment will increase.

Refractories and Steel Industries

Comparative data for the Chinese and U.S. refractories and steel industries in 1980 and 2004 are shown below, to quantize the dramatic changes: 1980 2004 %Change China - Steel, mmt 37 273 +738 U.S. ­ Steel, mmt 101 99 -1 China ­ Refractories, mmt 3.8 18.7 +492 U.S. ­ Refractories, mmt 4.9 ~2.8 -57 Because refractories are essential for the production of steel, it is not surprising that refractories production in China, which is by far the leading steel producer in the world, has increased greatly since 1980. Also, it can be seen that the U.S. led China in both steel and refractories production in 1980, but the situation is drastically different now. The U.S. refractory production peaked in 1979, with 5.85 mmt; China has far exceeded that production figure, with further production increases expected in the coming years, given their ongoing increases in steel production of >20% per year. Steel production in China in 2005 can be expected to increase >25%, to 340 mmt, or more, and the refractory production will be >20 mmt.

Summary Comments

This article provides a very brief overview of the changes that have occurred in China since 1980, including personal observations of the refractories industry. In general, there have been many significant changes/improvements, although some things have not changed much. Clearly, China is the "hotspot" for the world's refractories industry now, because of at least their raw materials, advancing technology, and business opportunities. Many foreign companies have set up successful operations in China, with very good results from both sales in China and exports. And there might possibly be further business benefits for refractory manufacturers in other countries, to help fulfill the increasing demand for high quality refractories by the commodities industries in China. So during these 20+ years, the refractories industry in China has become a major international player, changing from mainly a natural raw materials supplier, to a supplier of natural and valueadded raw materials (fused and sintered), as well as bricks/shapes. But the transformation also includes various concerns such as product quality, pricing issues, export taxes/licenses, transportation, trading company practices, etc., which are important aspects of the changing scene that also must be recognized and dealt with.

References

1. 2.

Figure 2. Example of a modern refractories plant in China producing only hightech products based on synthetic raw materials.

"Dream Machines", www.economist.com, June 2, 2005 C.H. Kwan, "China's Auto Market Slows Further ­ Automakers Revising Their Investment Plans", www.rieti.go.jp, Dec. 14, 2004. R AN

Refractories Applications and News, Volume 11, Number 1

January/February 2006

7

CHINA CERAMIC DIRECTORY 2005/06 (ENGLISH ED.) JUST PUBLISHED Business Data International Inc., the business and professional information provider, has recently announced that the English edition of the CHINA CERAMIC DIRECTORY 2005/06 has just been published. The revised and expanded edition lists about 1,400 leading ceramic and pottery enterprises, research institutes, associations, importers and exporters in China. It covers commonly used ceramics, porcelain products, sanitaryware, building ceramics, tile, electroceramics, refractories, technical and industrial ceramics, ceramic raw materials, equipment and machines, as well as publications. The directory provides information on each organization's name, address, telephone and fax numbers, e-mail addresses and websites, name of the director, registered capital, number of employees, history, production capacity and main products. The 333-page directory (ISBN:0-9733166-1-6) is available for US$199.95 plus 10% airmail postage from: Business Data International Inc., contact: May Tian, Manager, Tel: (514) 293-6146, Fax: (514) 221-3281, P. O. Box 28547, 5100 Verdun Ave., Montreal, QC H4G 3L7, Canada, [email protected], www.businessdataint.com. SCIENTIFIC DUST COLLECTORS ANNOUNCES NEW TEST RESULTS FOR ADVANCE CLEANING SYSTEM A new study shows Scientific Dust Collectors (SDC) improved cleaning system give you 9.15 times the amount of induced cleaning air and the SDC nozzle achieves a 111% increase in peak cleaning pressure capability when compared to generic baghouse cleaning systems. In addition, the nozzle geometry produces air velocities much higher than previously possible. This increased velocity allows a significantly greater volume of secondary cleaning air to be induced. In cartridge collectors, SDC improved cleaning system gives you 6.4 times the amount of induced cleaning air, the SDC nozzle achieves a 53% increase in peak cleaning pressure capability when compared to generic cartridge cleaning systems. The key is in the nozzle. SDC's problem-solving approach has allowed us to develop proprietary converging/diverging nozzles mounted on pulse pipes to induce more cleaning air for more effective cleaning. Nozzles within dust collector units process the air at orifice pressures to allow further conversion of pressure energy to velocity. In the orifice throat, the velocity is sonic, or 1,050 ft./sec. When converging/ diverging nozzles are mounted on the pulse pipe, the exit velocity from the nozzle will increase to supersonic velocity at 1,735 ft./sec., or almost MACH II sonic velocity with 90 psig in the pulse pipe. At the bag's throat orifice, we take advantage of the higher velocity to induce more air into the cleaning jet. This engineering breakthrough results in better cleaning. Collector efficiency is also improved by limiting the expansion of the air jet. This is done by stopping the induction of the induced air. Competitors use a flow-restricting venturi, which reduce overall cleaning power. Our solution is different. We employ the entire open area of the bag mouth to limit air induction. The result is that Scientific Dust Collectors systems outperform the competition in both cleaning power and filter life. 8 January/February 2006

Industry News

UNIFRAX ANNOUNCES MANAGEMENT CHANGES The Board of Directors of Unifrax Corporation, the Niagara Falls, NY based manufacturer of ceramic fiber insulation products, announces the following management changes: William P. Kelly is named Chairman of the Board for Unifrax Corporation, while continuing in his role as Chief Executive Officer. Bill joined The Carborundum Company in 1972. He held increasingly responsible positions with Carborundum and was named the first President of Unifrax in 1996 following its creation from the Fibers Division of Carborundum. He is a Fellow of the American Ceramic Society, Vice President of the Refractory Ceramic Fiber Coalition, and an Executive Committee member at The Refractories Institute. David E. Brooks is named President and Chief Operating Officer for Unifrax Corporation, and will be responsible for daily operations at the Company. David joined the Company in 1980 as a Marketing Manager. In 1995, he was promoted to President of the Monofrax fused cast refractory business. In 1998, David was hired by Unifrax as Vice Refractories Applications and News, Volume 11, Number 1

For more information contact: Steve Coffee, 4101 West 126th St., Alsip, IL 60803 USA, Tel: (708) 597.7090, Fax: (708) 597.0313, www.scientificdustcollectors.com THERMAL CERAMICS AWARDED ISO 14001 CERTIFICATION We are pleased to announce that Thermal Ceramics Inc. ­ Augusta, GA USA ­ facility has received the ISO 14001 certification. The ISO 14001 standard is the corner stone of the ISO 14000 series. It specifies a framework of control for an Environmental Management System (EMS) against which an organization can be certified by a third party. The ISO 14000 is a series of international standards on environmental management that Thermal Ceramics has chosen to implement globally. It provides a framework for the development of an environmental management system and the supporting audit program. Thermal Ceramics EMS provides a framework for managing environmental impacts in order to improve the efficiency and integration of these systems in the overall business operations. However, much more than this, our effective EMS will reduce costs, improve efficiency, and help secure a competitive advantage. Benefits of our registration to ISO 14001 include: · Demonstration of legal and regulatory compliance · Demonstration to stakeholders of our commitment to the environment · Demonstration of an innovative and forward thinking approach · Increased access to new customers and business partners · Better management of environmental risks, now and in the future · Reduction in public liability insurance risks · Cost savings For more information about our certifications please contact Sherri Pettigrew, Manager Environmental Programmer at 706.796.4200.

President of Marketing and was later promoted to Senior Vice President for the Americas. David is a graduate of Ohio State University and a past president of the Phoenix Committee, and a member of the American Ceramic Society. Unifrax Corporation is a leading global supplier of insulation products that are used in many high-temperature industrial, automotive and fire protection applications. The Company has 14 manufacturing facilities in the United States, Europe, Asia and Latin America, employing approximately 1,200 people worldwide. Unifrax Corporation is owned by American Securities Capital Partners, L.L.C. (ASCP) a New York private equity investment firm, and Unifrax management. For more information, contact: Virginia Cantara, Unifrax Corporation, 2351 Whirlpool St., Niagara Falls, NY 14305, Tel: (716) 278-3832; Email [email protected] ALMATIS ANNOUNCES GLOBAL PRICE INCREASE FOR CONTRACTS AFTER NOVEMBER 15, 2005 Effective for all new contracts placed after November 15, 2005, Almatis will increase prices 8 to 15 percent as a result of the continued and rapid increase in utility, transport and raw material costs. The global price increase covers all specialty alumina products for the refractory, ceramics and polishing markets including tabular alumina, calcined alumina, calcium aluminate cement and spinels. "In order to lessen the impact of volatile costs, we continually work to enhance our business and production processes. Our objectives are to be the high quality - low cost producer and to ensure global and secure supply of our premium alumina products", states Heide Evans, Global Vice President Commercial for Refractory, Ceramics & Polishing. "With the implementation of the SAP enterprise system and the ongoing investments in our Almatis Business System, we have a fully integrated system in place, giving us control over production, logistics and timing. We continually look to find additional ways to improve our efficiencies through our focus on productivity and quality", explains Evans. Almatis is the global leader in the development, manufacture and supply of high quality specialty alumina products. With about 800 employees in 17 locations worldwide, the company's products are used in a wide variety of industries, including steel production, cement production, non-ferrous metal production, plastics, paper, ceramics, carpet manufacturing and electronic industries. Almatis is headquartered in Frankfurt, Germany. For more information: Almatis GmbH, Andreas Pütz, Communication Officer, Phone: +49.69.95 73 41 28; [email protected]; www.almatis.com

Corning moved away from furnaces requiring traditional crowns but realizes the value that the technology still holds for other uses in the industry. GMIC anticipates that the patented composition will be used to produce a new brick that will allow the container segment to comply with clean air requirements, and have a crown material that will keep costs competitive. GMIC member, Utah Refractories Corp., has begun a program to test the composition at its manufacturing facility in Lehi, Utah. Refractory bricks are used to construct the containing vessel of a glass-melting furnace that must be able to withstand high-heat and corrosive conditions. Glass manufacturers traditionally use air furnaces to melt glass. The industry is adopting oxygen-fueled furnaces to reduce costs, enable new products, and reduce environmentally harmful emissions. In particular, oxygen fueled furnaces eliminate the emission of nitrogen oxides (NOx), which are implicated in the production of smog. However, oxygen fueled furnaces are more corrosive to their refractory bricks, which means that they must be rebuilt more frequently. The patented composition, referred to as "low-calcium", will enable glass manufacturers to use refractory bricks that are corrosion resistant, thus reducing down-time and capital expenditures. Refractory costs represent a large proportion of a glass plant's capital costs in both initial purchase and in rebuild. This patent represents an opportunity to offer a high resistance, lower cost alternative to traditional oxy-fuel furnace refractories. About the Glass Manufacturing Industry Council The GMIC is a glass industry trade association whose mission is to "facilitate, organize and promote the interests and economic growth of the U.S. glass industry through education and cooperation in the areas of technology, productivity, innovation and the environment." It includes among its members, representatives of all four sectors: Flat, Container, Fiber and Specialty. Associate members are drawn from suppliers to the glass industry, research institutes, universities, national labs and consultants. GMIC, incorporated in September of 1998, and registered in the state of Ohio as a 501(c)(6) organization, coordinates research and development activities seeking to increase the efficiency, environmental responsibility and profitability of the industry. For more information contact: Michael Greenman, Tel: 614-8189423; [email protected] IMERYS ACQUIRE DAM Following negotiations with the Nord Est Group, Imerys announce the acquisition of its subsidiary Denain-Anzin Minéraux (DAM). DAM produces kaolins, feldspars, micas and quartz from industrial facilities located mostly in France, as well as in Spain, Italy, Portugal and Germany. Active on the European markets of minerals for ceramics, floor & wall tiles, sanitaryware, tableware, fiberglass, as well as rubber and paint, DAM achieved sales of approximately Euros 85 million in 2004. This acquisition fits perfectly and is consistent with Imerys' growth strategy in industrial minerals. For further information, contact: Kevin Rowett, Head of Communications, IMERYS - Specialty Minerals Business Group, Tel: +44 (0) 1726 818113; [email protected] Industry News Continued on Page 16 9

GLASS MANUFACTURING INDUSTRY COUNCIL RECEIVES REFRACTORY COMPOSITION PATENT FROM CORNING The Glass Manufacturing Industry Council (GMIC) announced today that it received a refractory composition patent from Corning Incorporated. This patented composition, patent number 6,313,057, will enable an increase in the life cycle of refractory bricks used in oxygen fueled glass melting furnaces. Because of the more corrosive atmosphere in oxy-fuel fired furnaces, there are extra costs associated with changing from the traditional crowns (the roof) to bonded and fused cast crowns. The new material will provide a low cost alternative for container and float furnaces. Refractories Applications and News, Volume 11, Number 1

January/February 2006

LOCK 3 COMPANY ­ A TOLL PROCESSOR

ABSTRACT

The renewed demand for steel products has resulted in a stronger market for monolithic refractories. This has been aggravated by severe curtailment of American refractory production capacity over the last 20 years. It also has been worsened by the changing picture of raw materials based on calcined aluminas. Toll processing is a refractory supplier's safety valve that enables them to produce products that might be beyond their existing capacity. Raw material shortages are another issue that can greatly impact the effectiveness of meeting "Just-In-Time" customer demands. This paper describes the capabilities and technology offered by one toll processor that has effectively met these needs. Toll processing is nothing new. However, new demands placed on a greatly diminished industry can impact its ability to meet rapid demands from customers. Why, then, would a refractory company resort to toll processing? 1. There is a diminished capacity to produce specific types of refractory products. 2. New start-up companies that have recently emerged from "down-sizing" do not have the manufacturing capability to make products in sizeable quantities. 3. Initial raw materials costs have not reached the volume necessary to be competitive. 4. It is difficult for large companies to introduce new products into their existing production facilities. 5. "Just in Time" delivery is difficult because of certain raw material shortages. This paper describes the toll processing capabilities of Lock 3 Company that produces products for other companies. Lock 3 Company is located at the Mid-Mon Industrial Center on the Monongahela River, about 20 miles south of Pittsburgh, Pennsylvania. Although this once powerful steel-producing center has been greatly reduced in capacity, recent demands for products are exerting pressure, which refractory producers cannot currently meet. Generally, toll processors serve a region, which is dictated by shipping costs and the availability to rapidly meet customers' deadlines. An ideal toll-processing center is in a good location to meet customer needs, since it is near a waterway, railways and interstate highways that can effectively move raw materials and finished products economically and rapidly. The general area that this regional center can effectively cover is about 500 miles in radius. Raw materials such as Chinese and Guyanese bauxite and Chinese magnesite are brought economically in via the Ohio River to the lock systems on the Allegheny and Monongahela rivers. 10 January/February 2006

M. William Vance, President, VanceCeramics101, Inc., 23 Pheasant Run Dr., Export, PA 15632, [email protected] RAW MATERIALS STORAGE

Historically, this has made Pittsburgh an ideal commerce center for the entire region. It is important to realize that just to be able to purchase critical materials is not good enough. The ability to warehouse large quantities of raw materials is also required and it is necessary to maintain a clean, moisture-free product ready to process or ship. Figure 1 shows warehousing facilities capable of storing these large quantities of bulk materials. Additional facilities are capable of storing one-metric ton supersacks of bauxite among other raw materials. Currently, this facility has a space of 80,000 square feet for storing bulk materials and 40,000 square feet for packaged materials. Additionally, the relatively complex formulations of monolithic products processed at this facility requires a wide variety of specialized raw materials stored in readily accessible bays that can be dedicated to a specific customer.

TOLL PROCESSING CAPABILITIES ­ A REGIONAL PROCESSING CENTER

SOURCES OF MONOLITHIC RAW MATERIALS

To serve a variety of markets, Lock 3 Company stores large quantities of raw materials from a variety of sources. These consist of virgin grogs, obsolete, or used refractory brick and special shapes. Use of obsolete or used refractories obtained from manufacturers' and consumers' plants, such as steel mills, saves the cost of hauling the materials to a landfill. In addition, land filling itself often lowers environmental liability imposed by the material. Typical obsolete and/or used materials readily available include: Magnesite Tabular Alumina White Fused Alumina Fused MgO Fused-Cast AZS and Zircon Silicon Carbide Carbon and Graphite Fireclay Grog and Brick Bauxite Chrome-Magnesite

Figure 1. Raw materials are taken from barges to the Lock 3 Company warehouse by truck

Refractories Applications and News, Volume 11, Number 1

These products are sold to major integrated and mini-steel mills (stainless and carbon steel) in the United States, and glass, cement, refractory and non-ferrous producers. They include magnesitebased, magnesite-carbon, magnesite-dolomite and silicon carbide materials for slag conditioners, magnesite and bauxite back-fills and grogs for making refractories. Availability of these materials depends on location, feedstock sources and market factors.

BULK RAW MATERIAL PROCESSING

PRODUCING TOLL PROCESSED MONOLITHIC REFRACTORIES

In order to rapidly and economically produce refractory products, a regional toll processing center must have quantities of raw materials for making refractory products readily on hand. The equipment necessary is described below: · A jaw crusher that is capable of crushing bricks and shapes up to 12" x 6" x 4" size. It is directly connected via a belt system to storage hoppers for oversize and undersize grogs. This system is capable of crushing large shapes at the rate of four short tons per hour. · A modern vertical impact crusher that is capable of generating grogs of good particle size distribution for producing dry-vibratable products directly from the system with a minimum of re-blending. The system is linked with a belt system to storage hoppers for oversize and undersize grogs. It is capable of crushing up to 2-inch size coarse fractions and can operate at a rate of 50 tons per hour. Figure 2 shows the equipment. This equipment has replaced an older cone crusher unit. The advantage of this type of crusher is its ability to produce fines and cubic-shaped grog for improved particle packing efficiency. · Rare-earth magnets are attached to the belt system for removing iron contamination. · A roll crusher that can reduce grog sizes to finer fractions of 48 mesh and lower. This unit operates at a rate of five tons per hour. · A SWECO screening system capable of producing four splits at a rate of five tons per hour. A complete inventory of screens is maintained from a maximum of one-inch size to 48 mesh. The materials are fed into supersacks for direct batching into product (Figure 3). Initial Steps - Typical procedures for initiating toll producing refractory products involve reviewing a customer's recipe and raw

Figure 2. Vertical impact crusher

material specifications. Then, a process flow sheet is developed where essential processes are identified and control instructions are defined. Currently, this facility processes only dry mixed products. Equipment for preparing plastic materials is not currently installed. The following steps described below are the same as if the product were produced in the customer's own facility. Batch Sheet - Once the critical factors are identified, a batch sheet is prepared and approved by the customer. A typical batch sheet is shown in Table 1. It not only contains the product recipe, but also contains the sources of raw materials. Note that there are provisions for noting raw material lot numbers for traceability. Below the batching is a list of critical process parameters such as blend time, QA sampling, packaging and labeling. Raw Materials Procurement and Storage ­ Raw materials are specified and approved by the customer. At times, acceptable raw materials (described previously) that are in inventory at the plant are acceptable and save the time and cost of ordering materials. For repeat customers, adequate spaces for their raw materials and finished goods are set-aside in the warehouse. Preliminary Production ­ Once raw materials are in place for production, an initial plant run may be conducted to determine if process controls and raw materials will provide a satisfactory product. The batch ingredients are weighed to the nearest one-pound using platform balances. These balances are calibrated every three months by the manufacturer of the balance equipment. Normally, coarser grog materials are batched first, followed by finer constituents. For the more sophisticated castables, additives are weighed in the QA lab to a precision of 0.005 pound. The additives are dispatched to the plant in clean, sealed containers. Normally, a preliminary production run will consist of batch quantities ranging from 2000 pounds up to several thousand pounds, depending on the product. During this preliminary stage, QA sampling is performed more frequently to evaluate parameters such as raw material consistency, batch uniformity and product properties. Blending Operations ­ Blending is performed in one of two large rotary units that have capacities of up to 15 tons each (depending on the material density). At a speed of 15 to 20 RPMs, blending normally requires 5 to 10 minutes. Tests have shown that uniform blending, which is dependent on individual raw material characteristics is achieved within this time. Commitment to Production ­ This stage normally follows a successful field trial of the material produced during preliminary production. The batch sheet is finalized and QA procedures are January/February 2006 11

Figure 3. SWECO screening system

Refractories Applications and News, Volume 11, Number 1

readied for implementation. Significant quantities of raw materials are procured and stored to meet continuing customer demands. Classes of Refractories ­ A wide range of dense and lightweight castables, fibrous insulation mixes, gunning mixes, grouts, dryvibratables and backfill mixes are manufactured at this facility. Additionally, organic fibers and stainless steel fibers are routinely mixed with castable constituents. Sophisticated ultra-low cement and no-cement castable technology require products with extensive additive formulations that involve the batching of at least ten constituents. Test Sampling ­ Ample QA test materials are removed from each batch of product manufactured. This may be prior to packaging where samples are removed from the discharge stream or from packaged material. After product batch consistency is established, the samples represent a pooled sample. Samples are immediately removed to the QA laboratory for testing. Just-In-Time processing requires that testing begin immediately after production and packaging, prior to shipment. Samples of incoming raw materials are often taken for QA testing if requested by the customer. Test Protocols ­ The QA lab maintains test capabilities consistent with the requirements agreed to by the toll processor and the customer. Test procedures usually follow ASTM requirements. The primary classes of products tested are Castables ­ Vibratable and Self-Flow (Conventional, low cement, ultra-low cement and no-cement); Grouts; Dry-Vibratables and Grogs. Test temperatures are maintained within 70ºF and 90ºF. During winter months, test materials removed from the plant are warmed to at least 60ºF prior to testing. A wet lab with a sink trap for catching coarse materials that can precipitate and clog drains is required. QA Test Procedures for Castables ­ The essential properties of primary importance to customers are water demand, flow, set and strength development. At times a customer will request that more tests initially be performed to insure that the raw materials and 12 January/February 2006

QA TESTING AND REPORTING

manufacturing processes are acceptable. This includes linear dimensional change and strength as a function of firing temperature. The majority of routine testing consists of: 1. Water Demand ­ Normally, a customer has a range of water requirements associated with a castable. The goal is to use the median water level. At times, water may have to be increased or lowered depending on the castables' consistency. For example, a vibratable castable is judged by the good-ball-in-hand consistency criteria according to ASTM C-860. Water temperatures are maintained at 70ºF. 2. Mixing ­ Hobart mixers are employed that mix at a speed of 60 RPM. Normally, a mixing time of 5 to 10 minutes is required depending on the effort needed to obtain a castable with uniform consistency. Observations and notes are made that relate to the consistency of the product. Selfflow mixes should readily self-level and grouts normally will flow readily off a doctor blade. Extra water may be required (up to the product maximum) if the mix fails to achieve a uniform casting consistency. 3. Flow Tests ­ ASTM C-230 flow cones and caliper (Figure 4) are used for measuring the flow behavior of both vibratable and self-flow castables and grouts. After mixing, the castable is poured or troweled into the molds (Figure 5), completely filling them. Normally, the cones are vibrated slightly to settle the castable into the mold to eliminate fissures or voids. Procedures for Vibratable Castables ­ The ASTM C-230 flow measuring calipers and molds are used for measuring the extent of flow for vibratable products. A FMC J-50 Paper Jogger vibrating table is used to provide the energy to initiate flow for vibratables for periods ranging from 15 to 60 seconds. The tool is used to measure the flow of each quadrant of a patty that flows out. The sum of four values indicate the total flow by percent. Normally, the level of vibration is set at the lowest level (from one to two) on the vibrating table. Stiffer mixes may require a higher setting to develRefractories Applications and News, Volume 11, Number 1

Figure 6. Patty formed by self-flow castable Figure 4. ASTM C-230 flow cones and caliper

Figure 7. Set test

op enough flow to obtain an ample measurement. Figure 5 shows a castable being poured into a mold. The mold is capped top and bottom by steel sheet until it is ready to test. When the mold is placed on the table and the steel sheets removed, the patty flows at a rate depending on the castable's flowability. A steel plate is used to maintain a more consistent surface on which the patty can spread rather than the paper jogger's wooden surface. Procedures for Self-Flow Castables and Grouts ­ This test procedure is similar to that used for the vibratable castables except no tool is required for measuring flow. A circular scribed line on the steel plate representing 100 % flow is used to measure the time it takes for a patty to free-flow out to its perimeter. Figure 6 shows the patty that forms when the cone is lifted off the table and releases the castable during the test. To determine acceptable limits, acceptable times for attaining 100 % flow are determined during preliminary testing. Set and Strength Development Tests ­ Two simple field related tests have been developed that give times at which the castable hardens, followed by strengthening, to the point forms may be safely removed or a part can be removed without damage from a mold. The set test involves pouring a portion of the castable into a plastic cup of known volume (Figure 7). The set is determined by squeezing the cup, just enough to determine when hardening is Refractories Applications and News, Volume 11, Number 1

Figure 5. Castable being poured into molds

occurring. The castable is set when the cup will not deform from top to bottom. Strength development occurs when a castable patty contained in a Zip-Lock bag (Figure 8) hardens and then strengthens enough so it not readily broken by hand loading. This test can be calibrated more precisely by breaking CMOR bars at various intervals. Both of the tests are used for QA testing and during product development. Bulk Density Measurement ­ Normally, bulk density can be readily determined by weighing the specimen formed by a cup having a known volume. Bulk density measurements are determined for the cup specimen after curing, drying (230ºF) and firing at 1500ºF. QA Test Procedures for Dry-Vibratables ­ The primary tests for these products consists of performing screen analysis and a compaction test. The screens used are usually specified by the customer. At times, calibrated screens are supplied by the customer as January/February 2006 13

Figure 8. Strength development test

well. A complete inventory of screens (U.S. Standard and Tyler) and a Ro-Tap sieve shaker are maintained in the laboratory. Normally, the samples are shaken for a period of ten minutes and then retained weight percentage determined for each screen size. The compaction test uses a Humboldt soils compaction tool (No. H-4160) and mold set (No. H-4225) (Figure 9). Loose bulk density and tamped bulk density values are determined by computing the weight required for completely filling the mold and then compacting it with the tool. Rather than loose bulk density, a de-aired density can be determined by forking the mate-

rial in the mold. The data shown below for a 50% alumina dryvibratable compares densities for zero and ten tamp cycles for the same sample with and without forking. Some dry-vibratables are susceptible to moisture pick-up or could be partially calcined or de-watered. For these products, moisture on evaporation (MOE at 230ºF) and loss on ignition tests (LOI at 2000ºF) may be performed. Examples of Database ­ The QA database for a typical castable product is shown in Table 2. The lot, batch and product date codes are used to identify each batch tested. A sample of each batch is retained in the lab for six months before it is discarded. It is important to report the QA data directly to the customer immediately. This is done by emailing the database. The database calculates the average values and standard deviation. Customers usually prefer to develop their own statistical control charts and interpretation of data. Three types of packaging systems are available for bagging materials. They are an auger, a pneumatic "air-packer" (shown in Figure 10), and a gravity-fed system. The three types offer different benefits depending on the type of product. Bags are weighed to the nearest one pound during filling. Filled bags are palletized and shrinkwrapped (Figure 11). Some manufacturers provide their own brand-named bags. Products sensitive to hydration are packaged in moisture-resistant plastic lined bags that are either sewn or sealed (air-packer.) Typical bag weights are 50-pounds, 100-pounds and 25-kilograms. For lightweight products, other weights are optional. Batched and blended products are temporarily stored in supersacks until ready for shipment. Most shipments are via truck. At times, products destined for overseas shipment are loaded directly into containers (Figure 12). Dwell times in temporary storage are usually brief for justin­time delivery. Shipping is arranged either by the customer or the toll processor. Products that are shipped for large capacity applica-

PACKAGING AND SHIPPING

Figure 9. Humboldt soils compaction tool

14

January/February 2006

Refractories Applications and News, Volume 11, Number 1

Figure 10. Pneumatic "air packer"

· Changes from tabular to fused white alumina · Changes from bubble-type light-weight grog to calcined light-weight grog · Modifications in additives to lower water demand, improve set and strength development with a variety of raw material changes Some of the equipment and procedures previously mentioned in the Quality Assurance portion of this paper are useful in developing modified products. For evaluation of product performance after firing at temperatures, the laboratory is equipped with three furnaces capable of firing test bars cast into sizes from 7"x1"x1" up to 3000ºF. A bench-scale beam test machine (Figure 13) is used to determine cold-flexural strength via three-point loading. This is for evaluating a product's high temperature stability and as-fired integrity.

ACKNOWLEDGMENTS

The author acknowledges the funding provided by Lock 3 Company, which supported the publication of this paper. The guidance and assistance provided by Lock 3 Company's General Manager, Joe Montenaro and Office Manager, Jenna Laverick, are greatly appreciated.

BIOGRAPHY

Figure 11. Shrink-wrapped and palletized bags

M. W. (Bill) Vance is a native of Missouri and holds bachelor's and master's degrees in Ceramic Engineering from UMR (1965 and 1967). His first refractory engineering experience was as a ceramic technician at the A. P. Green Refractories Co. QA lab in

tions may also be packaged in plain or spouted supersacks with one metric ton or one and half metric-ton capacity.

Figure 12. Container for overseas shipment

PRODUCT RE-ENGINEERING

Constant modifications of existing toll products may be necessary because of ever-changing raw material availability, costs and the need to improve a product to meet new application demands. Often this requires the capability to re-engineer a product to meet new specifications from the customer, or to maintain existing specifications. This toll processor facility has, using its product development laboratory, the ability to develop new and re-engineered products for customers. Often, modifications have to be performed very quickly to meet market demands. Some examples of changes that have been encountered recently are: · Changes from Chinese to Guyanese bauxite. · Changes from reactive aluminas to ball-milled calcined aluminas in low and ultra-low cement castables Refractories Applications and News, Volume 11, Number 1

Figure 13. Beam testing machine

January/February 2006

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Mexico, MO. After graduation from Rolla, he spent seven years as an aerospace engineer at McDonnell-Douglas, in St. Louis. In 1974, he became a Refractory Engineer at the U.S. Steel Research Lab in Monroeville, PA. After ten years there, Bill became a Senior Refractory Engineer at the Alcoa Research Lab near New Kensington, PA. While with Alcoa, he transferred to the Industrial Chemical Division as Applications Manager-North America, followed by his retirement in 1998. Bill has a number of refractory related patents and has authored several papers related to the refractory industry. Currently, Bill is President of VanceCeramics101, Inc., with an engineering office in Export, PA. In addition, the firm operates a laboratory in Forward Township, PA. His company specializes in providing engineering and testing services for the refractory industry. For more information you may phone or fax Bill at: 724327-1680. R AN Industry News Continued from Page 9

On Saturday, October 15, 2005 of Rockville, MD. Beloved husband of 50 years to Joan Schneider; loving father of Steve Schneider (wife, Liz), Mike Schneider (wife, Mayra) and Sandy Forney (husband, Doug); grandfather of Katie, Brian and Megan Schneider, Anne and Andrea Schneider, Derek, Michelle and Nicole Forney; brother of Richard Schneider (wife, Betty). Also survived by other loving family and friends. A Memorial Service will be held at the Rockville United Church, 355 Linthicum St., Rockville, MD 20851 on Sunday, October 23, 2005 at 4 p.m. Interment private. In lieu of flowers, contributions may be made in his name to the Rockville United Church (Congregational Care Committee) at the above address or to the Alzheimer's Association of the National Capital Area, 11240 Waples Mill Rd., Suite 402, Fairfax, VA 22030. Arrangements by Pumphrey's Colonial Funeral Home, Rockville, MD. Please view and sign the family guestbook at www.pumphreyfuneralhome.com. Published in The Washington Post on 10/22/2005. Samuel J. Schneider, Jr. graduated in 1952 from MSM/UMR with a BS in Ceramic Engineering. He served as Chair of ISO/TC 206 since its formation in 1994. Mr. Schneider worked at the National Institute of Standards and Technology (NIST) for 42 years. He was a Guest Researcher at NIST in Gaithersburg, Maryland. He initiated and chaired (1988-1994) VAMAS Committee on Classification of Advanced Ceramics. Mr. Schneider was the editor of a 1100-page ceramics handbook, authored over 60 technical publications, and was a distinguished international lecturer. He received numerous awards including the US Department of Commerce Silver Medal, the ASTM Award of Merit, the ACerS Refractories Award, the NIST Rosa Award, the Japan Prize; and the ASTM Cavanaugh Memorial Award (1996). He was an Academician for the International Academy of Ceramics. Through his ISO leadership, he interacted with international standards organizations to enhance global classification efforts for advanced ceramics. Information from a 2002 ARTICLE"STATUS of ISO/TC 206 on FINE CERAMICS" R AN 16 January/February 2006

OBITUARY SAMUEL JAMES SCHNEIDER JR.

UNITECR Continued from Page 5 found to increase to 1050 MPa by SiC addition up to 30 vol%. Other properties such as fracture toughness, elastic modulus and hardness were investigated as well. Co-extrusion was employed to fabricate fibrous monolithic structures composed of weak cell boundary phases to control fracture behavior. The hydrocarbon processing session consisted of nine speakers. This session was held on Friday morning (11-11-2005) in room 13/14 of Rosen Center Hotel in Orlando. The number of attendants was about forty. Allen Jurowski from Resco Products introduced Rescobond AA22S which was originally developed and patented in 1957. This product was developed to promote longer service life in high abrasion wear areas of the Fluidized Circulating Catalytic Unit, FCCU. Lining life was reported that increased from less than one year to 15 years. Margareta Bugajski from RHI Refractories introduced a product exhibiting all the required properties to line a complete FCCU. In the past different products were to be installed in different areas depending on required properties. The product should combine the insulation properties necessary for the regenerator with the abrasion resistant behavior required for the cocker units, the reactor area, and the cyclone dip legs, as well as being able to be gunned or cast from one mix. Richard Johnson from RCJ Global introduced a new high strength, low cement castable concrete which can be effectively designed for hydrogen reformer environments. A joint free, low expansion, cost effective castable refractory system was proposed as a replacement of high alumina brick structures. The effect of physico-chemical properties and structures of catalysts corundum carrier of methane vapor reforming process was presented by V. V. Primachenko from Ukrine Research Institute of Refractories. The results of Cr2O3 refractory post-mortem failure analysis and how observations relate to gasifier service life in slagging gasifiers was discussed and presented by James Bennett from Albany Research Center. Alireza Rezaie from university of Missouri-Rolla proposed MgO and MgAl2O4 based refractories for use in high temperature low pressure black liquor gasifier in New Burn, NC. The development of chrome free silicon carbide based castables for melting zone of high reducing gasification furnace used for processing of molten ASR (Automobile Shredder Residue) was presented by Tamio Okada from Nippon Crucible Co., Ltd. ASR is generated during the final recycling process of automobile. Kyei-Sing Kwong from Albany Research Center introduced a new phosphate containing Cr2O3 refractories to be used in slagging gasifier to increase the service life by improving slag penetration resistance. James Hemrick from Oak Ridge National Laboratory presented the work going on in Oak Ridge National Lab to evaluate and develop refractory materials for containment applications in both high temperature and low temperature black liquor gasification. R AN

Refractories Applications and News, Volume 11, Number 1

CORRELATIONS OF UNHYDROUS PHASES PRESENT IN CALCIUM ALUMINATE CEMENT WITH ITS WORKABILITY

Calcium aluminates (CA) are the most important hydraulically setting cements used for preparing refractory castables because they develop early high strength. The anhydrous phases of calcium aluminate cements are CA (CaO·Al2O3), CA2 (CaO·2Al2O3), and traces of C12A7 (12CaO·7Al2O3), and -alumina. The presence and the amount of each of their phases plays an important role in hydration reactions and hence in the application properties of calcium aluminate cement in refractory castables. Sample of refractory calcium aluminate cement was produced by Isfahan Cement Company in Iran. They were taken during various production periods for investigations on the role of phase formation during firing of clinker and its effect on the hydration behavior, rheology as well as setting time of cement powder. Comparisons were made with Secar 71 and Secar 80, two types of commercial calcium aluminate cement, mostly used for preparation of high grade refractory castables. Based on the results obtained by x-ray diffraction, in the presence of CA as the major anhydrous phase, the prepared paste had reliable properties, while when CA2 forms in superior amounts during firing, the prepared slurry with water cement ratio of 0.4 revealed thixotropic behaviors and variations in setting time. Calcium aluminate cement is a group of interrelated cementious materials, with alumina contents varying from about 38% to 90%. They incorporate calcium monoaluminate (CaAl2O4 or CA) as the major constituent. Second phases are always present, but vary with the lime to alumina ratio and with the level of impurities, especially SiO2 and Fe2O3. The best known of these cements is ciment fondue, which is commonly referred to as high alumina cement. It has much higher alumina cement content than Portland cement (Al2O3 about 6%). However, the term high alumina cement is an ambiguous term since the alumina content of this type of cements is in the range

Research Article . . .

M. R. Nilforoushan, M. R. Saerie, S. Otroj, Faculty of Engineering, Department of Ceramics, University of Shahrekord, P. O. Box 115, Shahrekord, Iran, [email protected] ABSTRACT

between 38-50% and is much lower than the more refractory cements with Al2O3 contents of 70% and above. The term calcium aluminate cements is therefore, a more accurate description of this class of cements. The most refractory cements, i.e. >70% Al2O3, are usually low in SiO2 and Fe2O3. They are white in color, and are almost pure members of the CaO-Al2O3 binary system. There was at once uncertainty about the composition of the anhydrous phases in this system, but the phases are now established as C3A, C12A7, CA, CA2 and CA6. Although C3A is of major importance in Portland cement, it is absent in calcium aluminate, which consists of a mixture of CA and CA2, along with perhaps a small (but important) amount of C12A7 and unreacted -Al2O3. Cements with 80% and above Al2O3 content are not equilibrium assemblages and although they may contain a higher proportion of CA2 to CA, they often have considerably higher alphaAl2O3 content. Shown in Table 1 are general examples of the mineralogical compositions of Secar 71 and Secar 80, two types of calcium aluminate cements mostly used for preparing high-grade refractory castable in Iran. Synthetic routes for preparation of calcium aluminate cement powder as well as its pure anhydrous phases has been investigated by some workers over the years. Most of them tried it through solid state sintering while others tried chemical routes but in almost all cases people tried to investigate the hydration properties of the prepared products by XRD, FTIR, SEM, DTA, DSC and EDXS [1-8]. Once cement reacts with water a number of hydration products forms, which depends on the temperature and hydration varies and thoroughly affects the setting time of cement that has been deeply discussed in literature [9-10]. In this study, attempts by Isfahan Cement Company of Iran to produce two kinds of refractory calcium aluminate cement as replacement for the Secar group calcium aluminate cements are mentioned. The mineralogy of the unhydrous phases formed during firing was monitored by x-ray diffraction method, while its fineness and setting time were measured. A relationship was found between minerals

1. INTRODUCTION

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present and its application properties of cement. Results are summarized.

2. EXPERIMENTATION

Investigations were carried out on ESF 500 (70% Al2O3) and ESF 550 (80% Al2O3), two types of refractory calcium aluminate cement kindly supplied by Isfahan Cement Company, comparisons were made with two types of refractory cement Secar 71 and Secar 80 produced by Lafarge company in France as most available and reliable commercial cement found in the commercial market of Iran. Pastes and slurries were prepared by mixing cement powder (particle size <50 m) with boiled distilled water, which had been equilibrated at the appropriate temperature. Mixing was carried out by hand, the paste poured into molds, put into plastic bag and then into a water bath maintained at a controlled temperature. The hardened pastes were ground into powder that passed the appropriate sieve. Chemical analysis was carried out by wet chemistry and also by xray fluorescence (XRF), which was conducted on an Oxford link XR300. Mineralogical analysis was done by x-ray diffraction on an Esto-Stadi-P using a copper tube. The particle size analysis of sample was tested by a normal Blain instrument that was used in the Cement Company. The refractoriness of cement was measured by Pyrometric cone equivalent (PCE). This instrument was made by Netzsch Co. Germany model 428/410 Win-2324 working temperatures in the range between 250 and 1800ºC. For rheology test of samples, 100 gr of plain powder mixed with 40 gr of distilled water to give water cement ratio of (w/c) 0.4, the powder and water were mixed for 2 minutes by hand, then the rheology tested using a viscometer funnel that the slurry flows through, using a standard orifice. This procedure was based on standard procedure of DIN53211. The setting times of cements were measured by Vicat needle; both primary and final settings of cements were measured.

because ESF 500 cement originates directly from milling of clinker while ESF 550 contains a few percent of alpha alumina which is mixed with ESF 500 in a ball mill and lack in LOI for ESF 550 is probably due to the presence of a few percent of gibbsite (Al2O3·3H2O) in the cement. These variations in chemical compositions do not cause any harm during application of calcium aluminate cement. The amounts of silica and alkaline oxides are low in ESF 500, 550 and Secar samples as well, which is a desirable property. In the presence of these oxides, during firing of cement, low melting phases such as anortite (CaO·Al2O3·2SiO2) forms which is suspected for premature failure of castables due to rupture. The amount of SO4 is much lower in ESF 550 than in ESF 500 because of the presence of Na2SO4 in alpha-alumina. Various samples of ESF calcium aluminate cement were examined by x-ray diffraction method. The x-ray diffraction patterns of three different samples clearly showed difference in mineral formation on firing. These curves show the variations in product quality caused by production parameters such as furnace temperature, firing time and cooling schedule. Comparisons of the mineral compositions were made with Secar 71 as the reference. Its x-ray diffraction pattern is shown in Figure 1. From this peak trace, the major anhydrous phases are CA, which has its strongest peak at 2 29.2º and CA2, which has a major peak at 2 25.8º. In this x-ray pattern, the presence of minor amounts of C12A7 and corundum are also indicated with their major peaks at 2 33.4 and 43.2 respectively. From about 50 samples taken of ESF cement and examined by x-ray diffraction, three

4. MINERALOGICAL ANALYSIS

3. RESULT AND DISCUSSIONS

Chemical Analysis Samples randomly taken from different cement powders produced by Isfahan Cement Co. were mixed. Then different batches of sample were analyzed for any variations in chemical composition by wet chemical analysis and XRF. The obtained results are shown in Table 2. Based on the results, the range of variation in Al2O3 content of ESF 550 was between 79.91-81.59% while the alumina content of ESF 500 was between 69.8-72.25% which is very much comparable to the compositions of Secar 80 and Secar 71 respectively. It seems from the results that chemical analysis of ESF 500 is more stable than ESF 550 with respect to its loss on ignition (LOI). This is

Figure 1. XRD trace of Secar 71.

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different samples that showed variations in XRD peaks are shown in Figures 2-4. The XRD trace of sample N4 is shown in Figure 2. It has unhydrous phases of CA and CA2 present in relative amounts comparable to the XRD trace of Secar 71, but the amount of these phases are much higher based on the intensity of peaks. This difference might be due to the higher firing temperature or longer dwell time in the firing zone of the furnace. There is also additional phase of corundum shown in this pattern. The XRD trace of another sample (N7) is shown in Figure 3. CA2 is the predominant phase in this sample, while CA has formed in minor amount. Compared to the sample N4 in Figure 2, the relative percentage of these phases has changed. This might be due to over heating of the sample during production, presence of higher amounts of CA2 can, later on, affect the cement hydration reactions and setting time. X-ray diffraction pattern of another sample that was some how different from the routine samples is shown in Figure 4. The XRD peak of this sample revealed similarities to the unhydrous phases present in sample N7. In this pattern CA2 is still the predominant phase, the amounts of CA is higher compared to sample N7. Based on the x-ray diffraction pattern of these samples, it seems that both samples had

the same firing histories at elevated temperature, but the dwell time in the firing zone of furnace was longer in sample N7. The other important parameter which has great impact on the application properties of cement is its fineness, or the term used by cement companies, Blaine. The higher the Blaine, the better properties such as setting and mechanical strength gain through hydration reactions of cement. Blaine of a few sample of ESF 500 and 550 were examined by appropriate lab instrument, the results are shown in Table 3. Comparisons were made with the results of Secar 71 and 80, based on the data presented in the catalog by producer. The samples of ESF 500 showed some variations, but in all cases were finer than Secar 71. In the case of ESF 550, the Blaine of samples was lower compared to samples of Secar 80. The low Blaine of the ESF 550 probably relates to coarsen crushing of the calcium aluminate clinker. The Blaine of N9 was also tested which was similar to the other ESF samples.

Figure 4. XRD trace of sample N9

5. FINENESS

6. REFRACTORINESS

Figure 2. XRD trace of sample N4.

The refractoriness of calcium aluminate cement is directly related to its chemical composition. The refractoriness of the samples was measured by pyrometric cone equivalent on net cement (PCE). Results of this test conducted on a few samples are compared to commercial refractory cements are shown in Table 4. It is worth mentioning that the highest elevated temperature of PCE was up to 1730°C and any changes at higher than this temperature could not be monitored. The whole sets of samples were stable up to the temperature limit of the instrument.

Refractories Applications and News, Volume 11, Number 1

Figure 3. XRD trace of Sample N7

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the ESF and Secar 71 samples were measured by the Vicat needle technique. Using this technique to measure set time, 100 grams of cement were mixed with appropriate amount of boiled distilled water to give the water cement ratio of 0.4 which in this case was 40 gr, and after mixing for one minute, were placed in the mold. In this technique, the depth of penetration of needle in the paste was recorded. Both primary and final setting was measured and the results summarized in Table 6. According to the results comparing the primary set of S4, S7 and ESF 500 samples to Secar 71, the primary set in all cases were shorter than Secar 71 while their final set were longer. This behavior is probably due to the coarse grains of ESF samples. Based on these results the refractoriness of samples was closely comparable to the commercial cements. In this part all samples showed close correlation with the commercial samples to be replaced. The rheological properties of refractory cements are of primary importance when it is used in conventional mortars and low cement castables. It can be measured by various techniques such as the standard funnel, the flow table and the slump test. In this study, the slurry of cement introduced without aggregate, the standard drop funnel method used. Rheology of ESF and Secar samples were measured. Slurries of samples were made with water cement ratio of 0.4. A few samples of ESF formed slurries with W/C ratio of 0.35 and passed through the orifice. The average results are shown in Table 5, while some other samples of ESF 550 had the same behavior but soon after pouring into the funnel they become stiff and thixotropic so their rheology could not be evaluated. Increasing of W/C ratio to 0.4 did not do any good to the thixotropic behavior of ESF 550 samples. This behavior might be due to coarse grain size of ESF samples and also the insufficient and inappropriate amounts of additives used in this cement. In contrast, the commercial cement (Secar 71) became fluid with W/C=0.4 and had a dropping time much lower in comparison to ESF 500 samples. The rheological behavior of three previously introduced samples (N4, N7 and N9), which were equal to ESF 500 samples also tested with this method. Based on the obtained results shown in Table 5, the dropping time of N4 is longer than Secar 71 but with respect to their x-ray diffraction patterns this behavior seems to relate to its coarse grain size than to the mineralogical composition. Two other samples had both thixothrophic behaviors, which might be due to their mineralogical composition and higher amounts of CA2. The setting time of calcium aluminate cement is the only characteristic that is influenced by all other properties, including fineness, mineralogy and the presence of additives in cement. The setting time of

7. RHEOLOGY

As it has been mentioned in literature, primary set is due to nucleation of grains but growth is due to penetration of water into the cement grains and coarse grains of samples can extend the setting time of cement, which is evidenced by experimental parameters. In the case of ESF 550 samples, both primary and final setting is much longer compared to Secar 80. This behavior is due to inadequate additives and thixotropic behavior of ESF samples. In this part an extensive work is required for this type of cement to be a good and reliable replacement for Secar 80.

9. CONCLUSIONS

8. SETTING TIME

Isfahan Cement Company has tried to produce refractory calcium aluminate cement based on commercial cements normally used for making traditional refractory castables. One of the cements vastly used in Iranian market was Secar group cements. Comparisons of the prepared samples were made on mineralogical and chemical composition of Secar. The relationships of phase formation with application properties of samples of produced cements are shown in this study and the following conclusions were drawn. 1. Samples of calcium aluminate cement produced by Isfahan Cement Co. has stable chemical composition and was comparable to Secar samples.

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REFERENCES

1.

2. The amounts of minerals present in ESF samples varied, in a few cases, CA is predominant phase like Secar 71 while in the others CA2 is the predominant phase. 3. ESF 500's grain size is finer than Secar 71, while ESF 550 has coarser grains than Secar 80. 4. The refractoriness of ESF samples is similar to Secar samples when measured by pyrometric cone. 5. Correlations of mineralogical compositions with rheological properties showed that when CA is predominant phase, the cement powder has good flow property, but when CA2 is the predominant phase in samples, the slurry made by this cement showed thixotropic behavior. 6. Primary setting time of ESF 500 samples were closely comparable with Secar 71 but, final setting was longer. In case of ESF 550 samples, both primary and final setting was longer than Secar 80, which relates to inadequate additives present in ESF samples and a lot of work needs to be done in this respect. 7. Based on the obtained results in this paper people in Isfahan cement have overcome problems due to the firing schedule of their cement and mineralogical phase formation but still working on the workability of their cement by various types of additives.

T. D. Robson, "High-Alumina cements and Concretes," Wiley & Sons, New York, 1962. 2. T. D. Robson, "Refractory Concretes: Past, Present and Future, Refractory Concrete," SP-57. American Concrete Institute, Detroit, MI, 1978. 3. G. MacZura, L. D. Hart, P. Raymond and J. E. Kopanda, "Refractory Cements," Hoburn, Ceram. Eng. and Sci., 4[1/2] 4647 (1983). 4. K. M. Parker and J. H. Sharp, "Refractory Calcium Aluminate Cements," Review paper, Trans. J. Brit. Ceram. Soc., 81[2] 35 (1982). 5. A. A. Kondrashenkov, E. V. Zalizovskii and G. E. Zaldat, "Change in Properties of High-Alumina Cement Concrete with Heating," Zh. Prikl. Khim., 49[7] 767-771 (1976). 6. Tas. A. Cuneyt, "Chemical Preparation of the Binary Compounds in the CaO-Al2O3 System by Self Propagating Combustion Synthesis," J. Am. Cerm. Soc., 81[11] 2853-2863 (1998). 7. A. C. Tas, "Crystal Chemistry and Structural Characterization of Ca12Al14O33, Ceramic Congress," Proceeding book, Vol 2, pp. 419-427, Turkey Oct 1996. 8. M. R. Nilforoushan, "The Effect of Chloride Admixtures on the Setting Behavior of a Refractory CAC," Ph.D. thesis, University of Sheffield, UK 1995. 9. M. R. Nilforoushan and J. H. Sharp, "The Hydration Reactions of Refractory Calcium Aluminate Cements Investigated by DSC and SEM," Proceeding of 45th Inter. Colloquium on Refractories, Aachen Germany Nov 2002. 10. M. R. Nilforoushan and J. H. Sharp, "Investigations on the Mechanism of Early Crystallization of Refractory Calcium Aluminate Cements by TEM," Inter. Jour. of Eng. of Iran, 12[4]202-219 (2001). R AN

Dear Colleagues: This letter is to invite you to consider presenting a paper at the 19th quadrennial meeting of the International Mineralogy Association (IMA) to be held in Kobe, Japan, July 23-28, 2006. The Commission on Applied Mineralogy (CAM) of IMA is sponsoring two sessions at the meeting: 1) Crystals and Ceramics with advanced Physico-chemical properties (session 28), and 2) Process Mineralogy (session 29). The first session will include a wide range of applied mineralogy topics including applications to metallurgy, ceramics, industrial minerals, mineralogy exploration, instrumental techniques, cement, etc., and the second session will be devoted to applications to ceramic materials (and other crystals). Additional sessions on environmental and applied mineralogy, cosponsored by ICAM (the International Council for Applied Mineralogy) include: 3) clays and zeolites: natural and synthetic materials (session 27), 4) environmental and medical mineralogy (session 26), 5) mineral-water interactions: from microscopic to macroscopic aspects (session 25), and 6) Bio-Geo interface in minerals (session 24). Thirty-seven sessions and nine field trips have been organized for the meeting. The deadline for the submission of abstracts and preregistration is February 28, 2006. Abstracts must be submitted online, and authors must be pre-registered for abstract acceptance. Additional information on the meeting is available on the IMA2006 website: http://www.congre.co.jp/ima2006/. Abstract forms, abstract format instructions, registration, and housing forms are available on the website. The Commission on Applied Mineralogy (CAM) is a commission within IMA that deals with applications of mineralogy to geological, metallurgical, ceramic, and various other industrial areas. It was organized in 1986 to provide a means for reporting the results of applied mineralogical research and to emphasize the importance of mineralogical applications to a wide variety of industrial problems. CAM collaborates regularly with the International Council on Applied Mineralogy (ICAM). IMA-CAM co-sponsors portions of the quadrennial ICAM congress meetings, and ICAM co-sponsors CAM sessions at the quadrennial IMA meetings. In this manner, these two groups provide opportunities for the presentation of papers on applied mineralogy on the international level every two years. CAM does not have any financial backing, unfortunately, to help in attending the meeting. I hope that you will find that you have an interest in presenting a paper at the IMA-2006 meeting in Japan. Sincerely yours, Dick Hagni, IMA-CAM chairman E-mail: [email protected]

R AN

INTERNATIONAL MINERALOGY ASSOCIATION MEETING

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LOW CEMENT/NO CEMENT MONOLITHICS ­ THEIR POTENTIAL FOR LADLE METALLURGY

Jose Luis Mendoza, R. E. Moore and C. H. Liu, Department of Ceramic Engineering, University of Missouri-Rolla, Rolla, MO 65409

Presented at the 23rd Annual Refractories Symposium, The St. Louis Section of the American Ceramic Society, April 10, 1987 Engineers Club of St. Louis

Historical Reprint . . .

Since the beginning of the practice of substitution of refractory brick linings by monolithic refractories, such as plastics, ramming mixes and castables the major problems the users have had to face are: fabrication, bonding, heating rates, thermal spalling, and abrasion resistance. The problem most often due to fabrication is laminations or low compaction efficiency. The use of castable refractories partially solved this problem, but the high amount of water incorporated in the mix caused troubles during the curing, drying and firing of the concrete. Conventional refractory castables mixes contain 15 to 30% of cement (calcium aluminates) with water requirement of around 8 to 12%. In order to achieve the best results from these mixes it was necessary to follow very strict curing and heating schedules. Also, calcium aluminate cement based concretes exhibit low strength values between 900 to 1100ºC, due, first to the dehydration of calcium aluminate hydrates and later to calcium aluminate transformations. The apparent porosity of these type concretes over that temperature range is about 22 to 26 percent (Figures 1 to 3). The formation of the ceramic bond occurs at temperatures of at least 1200ºC with the formation of the calcium dialuminate (CA2). The final bonding mineral phase CA6 is formed by the reaction of CA2 with fine aluminas at temperatures above 1500ºC. Several investigators [1, 2] have demonstrated that

I. INTRODUCTION

Figure 2. Bulk density of refractory concretes at different firing temperature.

Figure 1. Apparent porosity of refractory concretes at different firing temperature.

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these types of refractories are susceptible to corrosion in severe environment, and they can have relatively good thermal shock resistance and high deformation under load at high temperatures [3]. Refractories Applications and News, Volume 11, Number 1

Figure 3. Modulus of rupture of refractory concretes at different firing temperature.

The tendency to reduce the cement content in castable mixes started about 20 years ago [4]. Castable mixes with cement contents as low as 5% were designed by careful adjustment of the aggregate particle size distribution (Figures 4 and 5) and by inclusion of superfine powders, especially alumina and silica. The incorporation of chemical admixtures such as water reducers, deflocculants and/or retarders contributed to the successful fabrication of high density, low porosity concretes see Table I and

Figure 6 to 8 [4, 5]. Such materials have excellent corrosion resistance and very good hot strengths at medium and high temperature. It has been reported that the gas permeability of these types of concretes is very dependent on the particle size distribution, cement and fines content, water addition and temperature. The permeability of a concrete prepared according to the ASTMC-862 and 865 showed a dramatic increase at around 800ºC. This event is due to the phase transformation of C12A7 to CA (Figure

Figure 4. Particle size distribution of refractory castable mixes.

Figure 6. Apparent porosity of low cement refractory castable mixes.

Figure 5. Particle size distribution of refractory castable mixes. Low cement and ultra-low cement compositions.

Figure 7. Bulk density of low cement refractory castable mixes.

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Figure 8. Modulus of rupture of low and ultra-low cement castable mixes.

Figure 10. Air permeability of low cement refractory concretes.

ance are required, such as in the ladle metallurgy. The additions of silica fume to low cement alumina castables have enabled the attainment of high levels of such properties. Volk [9] reported that some ultra-low cement refractories have better properties than conventional 20% cement castables. Comparatively, the ultra-low cement concrete has superior strength than that of equivalent refractory brick. The porosity of the concretes was reported to be of the order of 10% and for an equivalent super-duty brick, 13 to 17%. Figure 11 shows the permeability changes of low cement concretes with three levels of water addition compared with a conventional concrete mix [7]. The addition of other fine powders (magnesia and spinel) does not negatively affect the permeability of the cured and dried refractory concretes (Figure 12).

Figure 9. Air permeability-strength relationship of conventional refractory concrete (B) at different firing temperature.

II. HISTORICAL EVOLUTION OF MONOLITHIC REFRACTORIES FOR IRON AND STEELMAKING APPLICATIONS

9). Low cement refractory concretes have relatively lower permeability values at temperatures below 1000ºC (Figure 10). This in part is due to the high reactivity of the fine matrix system [6]. The use of chemical additives, normally organic is to activate reactive aluminas creating some kind of gel phase formation resulting in stronger concretes. Additions (magnesias, spinels, silicas, silicon carbide, graphite, chromia, etc.) to modify the mineralogical composition of the matrix do not affect the permeability at temperatures below the ceramic bond formation [7]. Such additions have the purpose to modify the matrix composition, originally formed of corundum and calcium hexa-aluminate, in order to enhance the corrosion resistance to metal attack, increase the green and fired strengths or just to reduce the open porosity. The addition of special chemical admixtures to the batch composition has made possible the design of ultra-low (up to 4 percent cement) and cement free castables [6, 8, 9]. Initially the alkali contents of the chemical additives were relatively high affecting the high temperature performance of these refractories. Because of the low porosity, high density and high strength of the low and ultra-low cement concretes they are considered especially suitable for applications where high abrasion and corrosion resist24 January/February 2006

Kappmeyer [10] presented an excellent review of the early transition from refractory bricks to monolithic linings. In his paper he analyzed the specific problems related to pouring-pit refractories. The most widely used ladle lining was the inexpensive bloating

Figure 11. Air permeability of refractory concretes after curing, and drying.

Refractories Applications and News, Volume 11, Number 1

Refractories Applications and News, Volume 11, Number 1

brick made from siliceous fireclay and had a ladle life of 15 to 20 heats. Later the steel industry had successfully used bloating high alumina ladle bricks to overcome some of the shortcomings of other ladle brick, but at increased installation cost. "The improvement of ladle brick life service has been dependent on the increases in brick density and its resistance to slag attack. Brick with a large reheat expansion will bloat sufficiently to close the joints or broken brick are present." In summary he concluded that fireclay and low alumina content refractory materials are not appropriate at all for the pouring-pit applications. Halm [11] evaluated refractories for the different sections of the casting-pit. In the case of refractories for nozzle applications, four compositions of different porosity level were evaluated for their overall performance in industrial service. It was found that the lower the porosity of the refractory (11 to 15%) the better the behavior of the nozzle. She concluded that in general the refractory requirements for casting-pit applications are: fine, homogeneous and dense texture, low permeability and low porosity compatible with good thermal shock resistance. Shultz [12] reviewed refractory candidates for slide gates applications, including high alumina, zircon, zirconia, magnesia and magnesite-chrome refractories. He reported that a 70% alumina refractory exposed to attack by manganese steel was corroded primarily due to the silicate matrix reacting to form a manganese-alumino-silicate slag. Comparatively, 90% alumina refractories with low porosity were still corroded due to the presence of large pores, which enhanced the deterioration of the matrix (silicate). The addition of small amounts of zirconia to a 90% alumina refractory did not eliminate the corrosion problem. The high porosity level and the attack by manganese of the siliceous matrix were presumed to be the reason for such failure. A high purity low porosity fused-cast alumina body showed no such failure. A high purity low porosity fusedcast alumina body showed no erosion but was very susceptible to thermal shock conditions during the test. Microstructure analysis showed the presence of cracks filled with metal, which hardly reacted with the high purity alumina matrix. For slide gate application those cracks would be unacceptable. Zirconia refractories were more chemical resistant to manganese attack. This fact is probably due to the ability of the zirconia lattice to take about 20%

Figure 12. Air permeability of a low cement refractory concrete. Effect of dopant addition.

of manganese into solution and to the high temperature at which the first liquid phase is formed. Zircon refractories, which contain some amounts of clay, experienced similar results compared with the 90% alumina. Indications were that zircon bodies with no extraneous alumino-silicate materials would be more resistant to manganese oxide than mullite bonded high alumina bodies. Kappmeyer et al. [13] reviewed the changes in refractories usage for continuous casting, focusing on those with high alumina, low porosity and on high strength brads. For nozzle applications it seems that the only functional refractories are those with high zirconia content. The movement for pouring pit materials has been toward the use of refractories with additions of graphite and or silicon carbide replacing typical fireclay refractories. As mentioned before the technology of manufacturing refractories with better characteristics is oriented to the use of high purity starting materials and improved fabrication techniques. The reduction of cement content in castable refractories has gone all the way to the zero level. The binder substitutes in most of the cases are additives of the silicate types. Kamil et al. [8] reviewed the potential uses and applications of cement free castables. As in the standard approach today, aggregate particle size distribution needed to be adjusted and the incorporation of fines (aluminas, silicas, magnesias, silicon carbide etc.), sometimes of the order of submicron size was essential. As a consequence of these changes, a more strict properties testing analysis program was necessary. Since the silicate binders in most cases contain some alkalies such as sodium and potassium oxides that may form low temperature compounds it is necessary to perform high temperature evaluations. Kamil emphasized that proper installation of low, ultra-low, and cement free castables is necessary in order to avoid catastrophic results. The heating rates during the firing of these refractories have been troublesome and the recommendation is to use the slowest heating rate schedules. Elderfield et al. [14] discussed the refractories used or potentially useful for teeming steel. He reported that highly bloating nozzles (fireclay refractories) have higher creep rates as compared with conventional bloating nozzles. Such behavior is due to the different alumina and alkali contents. Since the Flocon licensers issued the list of preferred properties for slide gates, there has been an aggressive research effort to find the refractories adequate to meet such specifications. The development of a novel thermal shock procedure ensued that consisted of passing an oxyacetylene torch along the plate under carefully controlled conditions. An 88% alumina refractory with apparent porosity of 14.8% and a bulk density of 2.95 g/cm3 with a modulus of rupture of 1900 PSI was found acceptable. Elderfield also concluded that for nozzle applications, zirconia refractories are still the strongest candidates. They reported that when using partially stabilized zirconia (3.6% CaO) better thermal shock resistance is obtained. Reeves and Payne [15] studied the performance of various refractories for mixer and ladle applications. The wide range of refractory types used in torpedo ladles, varying from dense 42% alumina firebricks to 85% alumina bauxite bricks suggest that the factors which determine economic performance of torpedo linings were not yet fully defined. The use of high alumina bricks, more January/February 2006 25

than 70% Al3O2, in metal holding vessels applies to all the applications described; steel teeming ladles, torpedo ladles and mixers. For steel teeming ladles and torpedoes it is probably correct to say that high alumina bauxite bricks are chemically resistant to the environment and their use is normally in the high wear areas. Linley [16] discussed the potential outcome of unshaped refractories as candidate to be used in the iron making and steelmaking processes. Castables and moldables including those for gun repairs have found occasional use in the hot metal transport ladles. At that time it seemed that this class of refractories created some problems in obtaining good clean surfaces. The ladle spraying process looked to be a good alternative to prolong the life of ladle linings. Lives of 50 or more heats were realized using this procedure. Jackson [17] reported that the fall of fireclay brick usage in the steel industry has been dramatic and the use of mid and high alumina bricks showed a steady rise since 1975. An interesting analysis of how important pores size and pores shape in refractories used in the steel industry was published by Carswell [18]. He correlated the pore size to erosion level in sliding gate refractories. According to him the relevance of the texture of the product in service is very important. Lee [19] compared the properties of four refractory mixes of different compositions for use in ladle linings. An alumina mix containing pyrophyllite clay, sometimes with zircon additions has been investigated first in Japan and lately in USA became an alternative for secondary steelmaking vessels. The porosity of these refractories ranged around 14.5% and a bulk density of 2.23 g/cm3 was reported. These refractories have refractoriness of around 1645ºC. Progress in obtaining consistent high quality of molten steel was reported by Lee and later by Hargreaves [20] when using these types of refractory compositions. Numerous publications [19,20,21,22,23] have updated the advances reached in the design and applications of refractories in ladles, tundishes and nozzles. The use of magnesia refractories has been increased in the last five years as was indicated by Kayworth et al. [24]. Gunning procedures gained acceptance since a wider range of seawater and ground natural magnesias became available. Others refractory materials used for this purpose are dolomite and chrome. The future of monolithic refractory materials was forecast by Spencer [25] and Benczek [26] in their respective publications. Yoshino's [27] paper on recent trends in steel ladle linings in Japan represents one of the more complete and interesting analyses of the quality of the refractories needed for such ladle lining applications. In the West German Steel industry, torpedo ladles are the standard means of transportation between blast furnace and steel plant. The common material used in the linings is bauxite bricks [28]. Due to the addition of soda into the ladle to remove sulphur, lining service life is reduced to approximately half through the formation of low melting point feldspar compounds. When calcium carbide (CaC) is used for desulphurization, the wear rate is relatively low. Andalusite refractories have become strong candidates for use in torpedo ladles. In order to protect the life of the torpedo refractory lining it is necessary that the ladle throat also has a good life, and the preferred material in this area is a high grade refractory 26 January/February 2006

concrete with tubular alumina, a 96% Al2O3 concrete, that must have high strength as the major requirement. But, in addition the creep rate, which is tested and specified as in the case of torpedo ladle bricks, is an important factor. Hardy [29] remarked on the importance of long time creep testing in blast furnace stove checkers and other refractory materials. Welburn [30] analyzed the importance of the calcium and aluminum injection ratios to ladles. If high amount of calcium compounds are injected (and particularly if the amount of sulphur in the steel after injected (and particularly if the amount of sulphur in the steel after injection is high) then casting problems can still be encountered. For situations where aluminum content is high, when insufficient calcium is added or if reoxidation reactions occur after injection, casting problems arise due to clogging of the small nozzles with alumina rich deposits. Refractory mixes containing alumina, SiC, graphite, and clay as a binder were studied in three different forms, ramming, vibration casting and dry vibration. The vibration technique was the most effective as expressed by the bulk density (3.0 g/cm3), and open porosity (12%). The vibration castables exhibited thixotropic behavior. They may be installed either by a vibrating formwork technique or by using a vibrating poker [31]. Adjusting the permeability without affecting the open porosity can minimize the risk of explosions of these refractory materials. Both chemical and physical methods can be used to increase the permeability of the material, by the creation of channels in the product, which will allow the water vapor to escape. These mixes were intended for the lining of the main runners of blast furnaces with two tapholes or more. For blast furnaces with only one taphole or where there is less than 18 hours for a major repair, the choice will be the dry vibratable mix. In most cases the expected results should be the same with castable vibration mixes. Fitzgerald [32] reported that the iron and steelmaking industries claim about 65% of the total refractory consumption in the world. Workman [33] evaluated the performance of gunning refractories in linings, and found that they were often superior to bricks. On the other hand, castables were found to be suitable for the dirty gas system of the blast furnace. Siegl [34] reviewed several magnesia refractory mixes for gunning technique application. Several aspects were considered of major importance: particle size distribution and permeability as well as high density and low porosity. Only in some special cases is high porosity desired e.g., tundish mixes with minimized heat conductivity. Miyagawa et al. [35] did similar evaluations of high alumina dense refractories, which were further protected with a magnesia-base coating, automatically spread over the entire surfaces to a desired thickness by hot gunning equipment. The gunning technique has been improved so a minimum amount of rebound results. Five castable mixes with different alumina content were evaluated by Yamamoto [36]. The study was focused on finding the conditions to avoid thermal spalling due to water vapor release during the curing of tundish linings. The improvement of permeability was experienced by the addition of organic fibers. Determinations of gas permeability of concretes with different levels of fibers additions were performed. Several other investigators [37, 38, 39] have updated the selection and uses of new refractory compositions, such as dolomite refractories. In general the goals are still the same as 20 years ago: refractory of good chemical stability, low porosity, high density and strength, good thermal shock resistance and low creep rates. Refractories Applications and News, Volume 11, Number 1

The Department of Ceramic Engineering at The University of Missouri-Rolla in coordination with the Missouri Refractories Co. has developed a series of castable compositions with cement contents ranging from 20 to 10% for conventional type of mixes. The research programs have been extended to the design and testing of low, ultra-low and zero cement content castables. Extensive research on the characterization of the rheological properties of fine powders and of these monolithic systems has been performed during the last four years. The design of the castable mixes was based on continuous size distributions. Evaluation of the flowability behavior under vibration conditions, densification factors, porosity and strength measurements are basic. Selected compositions are evaluated for high temperature creep behavior, thermal shock resistance, mineralogical composition and microstructure, etc. Several important preparation parameters have to be optimized in the development of these castable mixes: a) Water addition (quality of the water) b) Mixing time (mixing method) c) Vibration casting Selection of the amplitude Selection of the frequency Vibration time d) Curing, drying and firing schedules Table II contains data for low, ultra-low cement and cement free castables. The salient advantages of these mixes are: · Low water requirement. · Controlled setting behavior.

III. REFRACTORIES RESEARCH ACTIVITIES AT THE UNIVERSITY OF MISSOURI-ROLLA

· Prefabricated blocks or forms can easily be removed from molds after a few hours of being vibrocast. · Curing times of a few hours (less than 24 hours) can be realized. · Green densities and strengths are high (low porosity). · High abrasion resistance. · Excellent thermal shock resistance when properly fired. · Low creep strain rates (tested up to 1600ºC). · Adjustable dimensional changes. · Low risk of thermal explosive spalling. Figure 13 shows typical particle size distributions for this series of refractory castables mixes. The lognormal distribution fits a linear regression, which relates to the fact that the mix has a continuous grading.

Figure 13. Particle size distribution of an ultra-low cement castable mix.

Refractories Applications and News, Volume 11, Number 1

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Figure 14 shows the location of the evaluated mixes in the phase diagram CaO-Al2O3-SiO2. The above listed advantage of these mixes suggests their potential for ladle metallurgy. Figures 15 to 18 show different steps in a ladle lining installation. Figure 19 shows the creep behavior of refractory concrete specimens that were prefired at 1500 and 1675ºC for several hours and tested under the equivalent load of 50 psi. The testing temperatures for creep were from 1300 and 1560ºC. Figures 20 to 25 show microstructural views of fired concrete specimens of several experimental castable mixes intended for ladle applications. The same particle size distribution was used in the design of all the mixes.

Figure 14. Alumina rich section of the CaO-Al2O3-SiO2 phase diagram.

IV. SUMMARY AND CONCLUSION

As has been consistently reported by various authors, the quality of refractories needed for iron and steelmaking are: low porosity, high density and high strength, compatible level of permeability and thermal shock resistance, high temperature chemical and mechanical stability. The replacement of bricks by monolithic refractories having the requisite properties is inevitable. On the other hand the successful use of monolithic mixes (plastics, ramming mixes and castables) depends on the specific applications and very often will depend on the skills of the installer. It has been experienced that low cement and cement free, low moisture refractory concretes when properly placed will have outstanding characteristics and provide better service. Refractories Applications and News, Volume 11, Number 1

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January/February 2006

Figure 17. Finishing the installation of a ladle refractory lining.

Figure 15. Preparation of a ladle vessel and vibration equipment for refractory lining installation.

Figure 18. Refractory lining installation completed

It is very important that the users of castables mixes have good liaison with the supplier in order to eliminate misunderstandings that may result in refractory failures. This is always the case but the higher technology involved in the design and evaluation of many of the newer monolithics extends to some degree of their installation.

Figure 16. Ladle refractory lining installation in progress.

V. REFERENCES

1.

M. S. Crowley, "Refractory Problems in Coal Gasification Reactors," Amer. Cer. Soc. Bull., 54[12] 1137-1138 (1969).

Figure 19. Creep strain rates of refractory concretes at different temperatures.

Refractories Applications and News, Volume 11, Number 1

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Figure 20. Refractory concrete with 20% cement content.

50X

Figure 23. Refractory concrete with 2% cement content.

50X

Figure 21. Refractory concrete with 12% cement content

50X

Figure 24. Refractory concrete with 0% cement content.

50X

Figure 22. Refractory concrete with 6% cement content.

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January/February 2006

50X

Figure 25. Mullite-bonded refractory concrete.

Refractories Applications and News, Volume 11, Number 1

160X

2. 3. 4. 5. 6. 7. 8. 10. 11.

9.

13. 14.

12.

17. 18. 20.

16.

15.

19. 21.

22.

23.

24.

25.

26.

Refractories Applications and News, Volume 11, Number 1

G. V. Ivan, G. MacZura, R. P. Heilich and F. J. Rohr, "Thermal Shock Testing of Calcium Aluminate Bonded Refractory Concretes," Amer. Cer. Soc. Bull., 54[7] 650-653 (1975). C. H. Liu, J. L. Mendoza, "Effects of Dopants on the Creep Behavior of Low and Ultra-Low Cement Refractory Concretes," Cer. Eng. And Science Proceeding, Am. Cer. Soc., January/February 1987, pages 1-8. B. Clavaud, J. P. Kiehl, and R. D. Schmidth-Whitley, "15 Years of Low Cement Castables in Steelmaking," The First International Conference on Refractories, Tokyo, Japan, November 15-18, 1983. J. L. Mendoza, "Effect of Additives and Dopants on the Properties of Refractory Concretes," Ph.D. Dissertation (in preparation). J. L. Mendoza, "Air Permeability of Refractory Concretes," Mater Thesis, University of Missouri-Rolla, 1984. J. L. Mendoza and R. E. Moore, "Air Permeability of Refractory Concretes: Effect of Dopants and Additives," Presented at the 87th Annual Meeting of The Am. Ceram. Soc., Cincinnati, OH, May 8, 1985. Kamil B. Carr, "Cement Free Castables," Refract. J., May/June 1975, pages 12-15. R. J. Volk, "Ultra-Low Cement Castables," Iron and Steel Engineer, September 1986, pages 44-46. K. K. Kappmeyer and J. A. Lamont, "A Review of Pouring-Pit Refractories," Fourth Annual St. Louis Refractories Symposium, Amer. Ceram. Soc., March 22, 1968. L. Halm, "Problems of Casting-Pit Refractories," Trans. Brit. Ceram. Soc., [54] 507-542 (1955). R. L. Shultz, "Refractories for Slide Gates," Am. Ceram. Soc. Bull., 52[11] 833-837 (1973). K. K. Kappmeyer, C. K. Russell and D. H. Hubble, "Refractories for Continuous Casting," Am. Ceram. Soc. Bull., 53[7] 519-527 (1974). R. N. Elderfield, "Recent Advances in Refractories for Teeming Steel," Refract. J., September/October, 10-19, 1975. T. D. E. Reeves and P. Payne, "Refractories Performance in Mixers and Ladles," Refract. J., May/June, 12-19, 1976. E. G. Linley, "Unshaped Refractories," Refract. J., May 9-19, 1977 (3). B. Jackson, "Refractories Technology and Refractories OutputMore and More in Less and Less?" Refract. J., September 1225, 1977 (5). G. P. Carswell, "Pores for Thought," Refract. J., November 1119, 1977 (6). S. J. Lee, "Winds of Change in The Casting Pit," Refract. J., January/February, 13-21, 1978. J. Hargreaves, "The Evolution of Ladle Lining Refractories," Refract. J., September/October, 11-17, 1978. J. L. Evans, "Furnace Design and Operations-Key to Refractory Performance," Refract. J., July/August 9-21, 1980. G. P. Carswell, M. P. Crosby and D. R. F. Spencer, "Development of High Performance Ladle Linings," Refract. J., January/February 9-21, 1980. M. O Warman, "Ironmaking Refractories," Refract. J., November 11-20, 1979. P. M. Kayworth and G. P. Carswell, "Gunning Maintenance of BOS and Arc Furnaces," Refract. J., July/August, 11-20, 1979. D. R. F. Spencer, "Refractories in the Eighties," Refract. J., May/June, 12-28, 1979. K. Benczek, G. Mlaker and R. C. Thomas, "Dolomite Lining for Torpedo and Steel Ladles," Proceedings of the British Ceramic Society, Refractories for Ironmaking, Edited by P. T. A. Hodson and K. H. Speed, Vol. 29, 1980, pages 103-126.

27. S. Yoshino, "Recent trends in Steel Ladle Lining in Japan," Taikubutsu Overseas, 1[1] 49-55 (1981). 28. P. Artelt, "Refractory Linings of Furnaces in the West German Steel Industry," Refract. J., May/June, 10-22, 1981. 29. C. W. Hardy, "Mythology Technology and Science," Refract. J., March/April, 10-16, 1978. 30. R. W. Welburn and C. Graham, "Refractories in Continuous Casting," Refract. J., September/October, 9-10, 1982). 31. B. Clavaud, G. Landman, J. W. Marjerrison and C. Turrel, "High Performance Materials for Blast Furnace Cast-House," Refract. J., July/August, 14-21, 1983. 32. F. Fitzgerald, "Process Developments in the Iron and Steel Industry," Refract. J., September/October, 9-16, 1983. 33. G. M. Workman and J. A. C. Davidson, "Blast Furnace Castable Refractories," Blast Furnace Refractories, Publication 116 of The Iron and Steel Institute, pages 83-90, 1968. 34. W. M. Siegl, "Composition and Application of Basic Refractory Maintenance Mixes," Radex-Rundschau, [4] 706-723 (1985). 35. Y. Miyagawa, F. Hoshi, K. Fujii, T. Taniguchi, K. Koyago and T. Taniguchi, "Improvement of Surface Gunning Refractories For CC Tundish Liners," Taikubutsu Overseas, 6[3] 42-45 (1986). 36. S. Yamamoto, Y. Owada, S. Nagai, T. Yamaguti and H. Hasimoto, "Castable Refractories for Tundish Linings," Taikubutsu Overseas, 6[3] 14-21 (1986). 37. C. E. Tomazin, E. A. Upton and R. A. Wallis, "The Effect of Ladle Refractories and Practices on Steel Temperature Control," Iron and Steelmaking, June 1986. 38. J. Schruff, P. Jeschke and E. Luhrsen, "New Refractory systems for Continuous Casting Help Improve the Metallurgical Practice," Iron and Steelmaking, September 1986, pages 19-22. 39. "Refractory Materials for Steelmaking," Refract. J., 1986. R AN

To place your ad in the Buyer's Guide or the Directory of Products and Services contact Mary Lee. E-mail: [email protected] or Tel: (573) 341-6561

January/February 2006 31

PRODUCTS

DIRECTORY OF PRODUCTS AND SERVICES

MISSOURI REFRACTORIES CO. INC. 1198 Mason Circle Pevely, MO 63070 Tel: (636) 479-7770 Fax: (636) 479-7773 E-mail: [email protected] PRODUCTS

PRODUCTS

· Customized mix design and manufacturing · Central USA location · Quick response to emergency situations · Consistent products made fresh for your order

The Refractory Specialty Specialist

Christy Minerals Company 833 Booneslick High Hill, MO 63350 Tel: (636) 585-2214 Fax: (636) 585-2220 E-mail: [email protected] Website: www.christyco.com Christy Minerals mines, processes and markets a variety of clays and minerals for the refractories industry. Products include calcined MO flint clays, raw clays (including Hawthorn Bond®), bauxite, burley and diaspore. Custom calcining, grinding and packaging also available.

C-E Minerals 901 East Eight Avenue King of Prussia, PA 19406 Tel: 610-265-6880 Fax: 610-337-7163 E-mail: [email protected] Website: www.ceminerals.com

A major world supplier of quality raw materials and services to the refractory and related industries. · Mulcoa® 47, 60, 70 · Teco-Sil® · Alpha Star® · Andalusite · Spinel · Bauxite · Fused White Alumina · Brown Fused Alumina

AluChem, Inc. One Landy Lane Cincinnati, OH 45215 Tel: (513) 733-8519 Fax: (513) 733-0608 E-mail: [email protected] Website: www.aluchem.com

AluChem focuses on production and marketing of calcined, reactive, tabular, and hydrated alumina, zircon sand and flour, high purity magnesite, ground refractory grade bauxite, and toll processing are also available.

Vesuvius USA

BNZ Materials, Inc. 191 Front St., Zelienople, PA 16063 Tel: (724) 452-8650 or (800) 955-8650 Fax: (724) 452-1346 E-mail: [email protected] Website: www.bnzmaterials.com BNZ Materials, Inc. is a manufacturer of premium grade insulating firebrick, refractories, insulation materials and calciumsilicate structural insulation board products. Noted products include marinite, transite HT, transite 1000 and CS-85.

32

858 Maple Lane Waterville, OH 43566-1127 Tel: (419) 878-0001 or (800) 680-4964 Fax: (419) 878-4241 E-mail: [email protected] Website: www.matrix-ent.com Matrix Enterprises is your source for: · Silicon Carbide grain & powder · Boron Carbide powder · Borate frits for stopping the penetration of aluminum into refractory bodies · DEPA for testing elastic properties of materials · Diamond Tools for producing refractories and grinding wheels.

1404 Newton Dr. Champaign, IL 61822 Tel: (217) 351-5000 Fax: (217) 351-5031 Website: www.vesuvius.com

Steel Division: Industrial Products: Foundry Division: Glass Division: BMI:

A strong company working to serve all your refractory needs. Vesuvius has been in business since 1916 adapting to an ever-changing industry. Contact us at the following locations with your questions:

January/February 2006

Refractories Applications and News, Volume 11, Number 1

Sherrie Plummer Sherrie Anderson Pat Kuzemsky Lynn Strohecker Larry DeSantis

217-351-5000 716-825-7900 716-825-7900 412-269-6900 412-429-1800

RESCO PRODUCTS, INC.

Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 E-mail: [email protected] Website: www.rescoproducts.com Resco Products, Inc., is a leading global manufacturer and supplier of advanced high quality monolithic, formed and brick refractories for the metals producing, hydro-carbon, power, cement and lime, ceramics, mineral and general manufacturing industries.

INDUSTRY CERAMICS

PRODUCTS

DIRECTORY OF PRODUCTS AND SERVICES

ALLIED MINERAL PRODUCTS, INC. 2700 Scioto Parkway Columbus, OH 43221 Tel: (614) 876-0244 Fax: (614) 876-0981 E-mail: [email protected] Website: www.alliedmineral.com

Allied Mineral Products and its affiliate companies supply top quality: · Monolithic refractory linings for induction melting equipment · Refractory systems for blast furnace casthouse operations · Refractories for aluminum melting · Precast refractory shapes

MATERIALS

*Alumina *Cordierite *Graphite *Fireclay *Nitride SiC *SiC *Cements

PRODUCTS

PRODUCTS

Penn Center West Building 2, Suite 430 Pittsburgh, PA 15276

THE REFRACTORIES YOU NEED!

METAL PRODUCING

*Stoppers *Nozzles *Recuperator tubes *Castables *Cements *Insulating bricks and shapes

Kyanite Mining Corporation Dillwyn, VA 23936 USA Tel Sales: (434) 983-2043 E-mail: [email protected] Website: Kyanite.com Not all Kyanite and Mullite is created equal. Only Virginia Kyanite and Virginia Mullite has the highest quality, consistent purity, abundant inventories, and knowledgeable customer service enabling you to produce superior products.

Committed to producing what you need, when you need it, in any quantity. New Castle Refractories can satisfy virtually any refractory need.

*Carbide wear plates *Kiln refractories *Ceramic orifices *Kiln furniture *Composite slabs *Brooders *Burner Blocks *Setters *Abrasion *Dinnerware setters *Fiberglass furnaces *Burner Blocks *Microwave suppressors

915 Industrial Street NewCastle, PA 16102

New Castle Refractories Company

View Product Gallery: www.ncrci.com Quotes: [email protected]

Ph: 724-654-7711 Fax: 724-654-6322

Utah Refractories Corp. 2200 North 1100 West Lehi, UT 84043 Tel: (412) 851-2430 Fax: (412) 851-2425 E-mail: [email protected] Serving the primary glass industry, Utah Refractories Manufacturers Gen-Sil® A.S.T.M. type "A" silica brick.

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SERVICES

Members of the ANH Refractories Family of Companies.

Glass: 513-947-8400 EX 169 Iron & Steel: 412-375-6722 Cement and Lime: 412-375-6771 Industrial Metals: 412-375-6873 Environmental, Energy & Chemical Markets: 412-375-6873 400 Fairway Drive · Moon Township, PA 15108 website: www.anhrefractories.com

Refractories Applications and News, Volume 11, Number 1

HOTWORK-USA 223 Gold Rush Road, Lexington, KY 40503 U.S.A. Tel: (859) 276-1570 Fax: (859) 276-1583 E-mail: [email protected] Website: www.hotwork.com Hotwork provides refractory dryout and furnace heatup services to all refractory consuming industries. Our portable burner equipment and crews of highly skilled technicians are strategically located around the world to best serve the needs of our customers.

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SERVICES

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Buyer's Guide

Ads must be received by February 1st for publication in the Mar/Apr 2006 issue. Ads received after the 2nd will be placed in the next issue.

Buyer's Guide Rates:

ALUMINA-CALCINED Almatis 501 West Park Road, Leetsdale, PA 15056 Tel: (412) 630-2800 Fax: (412) 630-2810 www.almatis.com AluChem, Inc. One Landy Lane. Cincinnati, OH 45215 Tel: (513) 733-8519 Fax: (513) 733-0608 [email protected] Nabaltec GmbH Alustrasse 50-52, Schwandorf 92421 Germany Tel: ++49-9431-53 457 Fax: ++49-9431 61 551 [email protected] ALUMINA-FUSED

1700°C LAB FURNACES Zircar Zirconia, Inc. P.O. Box 287, Florida, NY 10921 Tel: (845) 651-3040 Fax: (845) 651-0074 [email protected] www.zircarzirconia.com

Suppliers please state which category you wish to be listed under or submit your own heading. Contact: Mary Lee, University of Missouri-Rolla, 223 McNutt Hall, Rolla, MO 65409, Tel: (573) 341-6561 Fax: (573) 341-6934, or E-mail: [email protected] Rates for insertion: $90 per listing in any category for 6 issues, one year. U.S. currency, Payable in advance to: Refractories Applications and News. Your company will also be listed on our website buyer's guide at no additional cost.

Almatis 501 West Park Road, Leetsdale, PA 15056 Tel: (412) 630-2800 Fax: (412) 630-2810 www.almatis.com AluChem, Inc. One Landy Lane. Cincinnati, OH 45215 Tel: (513) 733-8519 Fax: (513) 733-0608 [email protected] C-E Minerals 901 East Eight Ave., King of Prussia, PA 19406 Tel: (610) 265-6880 Fax: (610) 337-7163 [email protected] www.ceminerals.com ALUMINA - TRIHYDRATE Almatis 501 West Park Road, Leetsdale, PA 15056 Tel: (412) 630-2800 Fax: (412) 630-2810 www.almatis.com Nabaltec GmbH Alustrasse 50-52, Schwandorf 92421 Germany Tel: ++49-9431-53 457 Fax: ++49-9431 61 551 [email protected] ALUMINA-TABULAR Great Lakes Minerals, LLC 1101 Port Road, Suite B, Wurtland, KY 41144-1635 Tel: (606) 833 8383 Fax: (606) 834 1106 www.greatlakesminerals.com Electro Abrasives Corp. 701 Willet Rd., Buffalo, NY 14218 Tel: (800) 284-4748 Fax: (716) 822-2858 [email protected] Washington Mills Electro Minerals PO Box 423, Niagara Falls, NY 14302-0423 Tel: (800) 828-1666 Fax: (716) 278-6650 [email protected] Almatis 501 West Park Road, Leetsdale, PA 15056 Tel: (412) 630-2800 Fax: (412) 630-2810 www.almatis.com Gorka Cement Sp. z o.o. Street 22 Lipca 58, 32-540 Trzebinia, Poland Tel: ++48 32 758 1025 Fax: ++4832 612 1161 [email protected]rka.com.pl www.gorka.com.pl LaFarge Calcium Aluminates 1316 Priority Lane, Chesapeake, VA 23324 Tel: (757) 543-8832 Fax: (757) 545-8933 [email protected] CALCIUM SILICATE INSULATION BNZ Materials, Inc. 6901 S. Pierce St., Ste. 260 Littleton, CO 80128-7205 Tel: (724) 452-8650 Fax: (724) 452-1346 [email protected] CARBON CALCIUM ALUMINATE CEMENT BORON CARBIDE

C-E Minerals 901 East Eight Ave., King of Prussia, PA 19406 Tel: (610) 265-6880 Fax: (610) 337-7163 [email protected] www.ceminerals.com Washington Mills Electro Minerals PO Box 423, Niagara Falls, NY 14302-0423 Tel: (800) 828-1666 Fax: (716) 278-6650 [email protected] ALUMINA-REACTIVE Almatis 501 West Park Road, Leetsdale, PA 15056 Tel: (412) 630-2800 Fax: (412) 630-2810 www.almatis.com AluChem, Inc. One Landy Lane. Cincinnati, OH 45215 Tel: (513) 733-8519 Fax: (513) 733-0608 [email protected] Nabaltec GmbH Alustrasse 50-52, Schwandorf 92421 Germany Tel: ++49-9431-53 457 Fax: ++49-9431 61 551 [email protected]

BASIC BRICKS Resco Products, Inc. Penn Center West, Bldg. 2, Ste. 430 Pittsburgh, PA 15276 Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 [email protected] www.rescoproducts.com C-E Minerals 901 East Eight Ave., King of Prussia, PA 19406 Tel: (610) 265-6880 Fax: (610) 337-7163 [email protected] www.ceminerals.com Christy Minerals 833 Booneslick, High Hill, MO 63350 Tel: (636) 585-2214 Fax: (636) 585-2220 [email protected] www.christyco.com BAUXITE

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January/February 2006

Refractories Applications and News, Volume 11, Number 1

Cancarb Ltd. P.O. Box 310, 1702 Brier Park Cres. N.W. Medicine Hat, Alberta, Canada T1A 7G1 Tel: 1-(403) 527-1121 or 1-(888) 871-0077 Fax: 1-(403) 529-6093 [email protected] www.cancarb.com

CEMENT (AIR SETTING) Resco Products, Inc. Penn Center West, Bldg. 2, Ste. 430 Pittsburgh, PA 15276 Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 [email protected] www.rescoproducts.com USEM 600 Steel St., Aliquippa, PA 15001 Tel: (724) 857-9880 Fax: (724) 857-9916 [email protected] Zschimmer & Schwarz GmbH & Co KG Chemische Fabriken, Max-Schwarz-Straße 3-5 D 56112 Lahnstein, Germany Tel: 0049 (0) 2621/12-414 Fax: 0049 (0) 2621 12503 www.zschimmer-schwarz.com [email protected] Zschimmer & Schwarz Inc., US Division 70 GA Hwy 22 West, Milledgeville, GA 31061 Tel: (478) 454-1942 Fax: (478) 453-8854 [email protected] www.zs-us.com CHEMICAL ADDITIVES FOR THE REFRACTORIES INDUSTRY

FUSED MULLITE

FUSED SILICA C-E Minerals 901 East Eight Ave., King of Prussia, PA 19406 Tel: (610) 265-6880 Fax: (610) 337-7163 [email protected] www.ceminerals.com FUSED SPINEL C-E Minerals 901 East Eight Ave., King of Prussia, PA 19406 Tel: (610) 265-6880 Fax: (610) 337-7163 [email protected] www.ceminerals.com USEM 600 Steel St., Aliquippa, PA 15001 Tel: (724) 857-9880 Fax: (724) 857-9916 [email protected] Washington Mills Electro Minerals PO Box 423, Niagara Falls, NY 14302-0423 Tel: (800) 828-1666 Fax: (716) 278-6650 [email protected]

C-E Minerals 901 East Eight Ave., King of Prussia, PA 19406 Tel: (610) 265-6880 Fax: (610) 337-7163 [email protected] www.ceminerals.com USEM 600 Steel St., Aliquippa, PA 15001 Tel: (724) 857-9880 Fax: (724) 857-9916 [email protected] Washington Mills Electro Minerals PO Box 423, Niagara Falls, NY 14302-0423 Tel: (800) 828-1666 Fax: (716) 278-6650 [email protected]

KILN/FURNACE FURNITURE

New Castle Refractories Company 915 Industrial St., NewCastle, PA 16102 Tel: 724-654-7711 Fax: 724-654-6322 [email protected] www.ncrci.com Saint-Gobain Ceramics 1 New Bond St., MS 301-432 Worcester, MA 01615-0136 Tel: (508) 795-2963 Fax: (508) 795-5011 [email protected] www.refractories.saint-gobain.com

Nth Degree Products 404 Laurel Ridge Road, Hainesport, NJ 08036 Tel: (609) 518-9447 Fax: (609) 518-9445 [email protected] Saint-Gobain Ceramics 1 New Bond St., MS 301-432 Worcester, MA 01615-0136 Tel: (508) 795-2963 Fax: (508) 795-5011 [email protected] www.refractories.saint-gobain.com KYANITE Kyanite Mining Corporation Dillwyn VA 23936 USA Tel Sales: (434) 983-2043 [email protected]

CUSTOM PACKAGING/BLENDING Vessell Mineral Products Corporation P.O. Box 440, Bonne Terre, MO 63628 Tel: (573) 358-2275 Fax: (573) 358-4201

DRYING AND CURING OF REFRACTORIES Hotworks-USA 223 Gold Rush Road, Lexington, KY. 40503 Tel: (859) 276-1570 Fax: (859) 276-1583 [email protected] www.hotwork.com ELASTIC PROPERTIES ANALYZER AND TESTING SERVICES

MONOLITHIC REFRACTORIES

www.Kyanite.com

Matrix Enterprises 858 Maple Lane, Waterville, OH 43566 Tel: (419) 878-0001 Fax: (419) 878-0001 [email protected] www.matrix-ent.com FIREBRICKS AND FIRECLAYS C-E Minerals 901 East Eight Ave., King of Prussia, PA 19406 Tel: (610) 265-6880 Fax: (610) 337-7163 [email protected] www.ceminerals.com Clayburn Refractories Ltd. 33765 Pine St., Abbotsford, BC, Canada V2S 5C1 Tel: 604-859-5288 or 604-851-4556 [email protected] FIRECLAYS

GLASS FURNACE REPAIRS Magneco/Metrel, Inc. 223 Interstate Rd, Addison, IL 60101 Tel: (630) 543-6660 Fax: (630) 543-1479 [email protected] www.magneco-metrel.com HIGH ALUMINA FIREBRICKS

Christy Minerals 833 Booneslick, High Hill, MO 63350 Tel: (636) 585-2214 Fax: (636) 585-2220 [email protected] www.christyco.com FURNACE/REFRACTORY PREHEATING Hotwork-USA 223 Gold Rush Road, Lexington, KY. 40503 Tel: (859) 276-1570 Fax: (859) 276-1583 [email protected] www.hotwork.com C-E Minerals 901 East Eight Ave., King of Prussia, PA 19406 Tel: (610) 265-6880 Fax: (610) 337-7163 [email protected] www.ceminerals.com Great Lakes Minerals, LLC 1101 Port Road, Suite B Wurtland, KY 41144-1635 Tel: (606) 833 8383 Fax: (606) 834 1106 Website: www.greatlakesminerals.com USEM 600 Steel St., Aliquippa, PA 15001 Tel: (724) 857-9880 Fax: (724) 857-9916 [email protected] FUSED ALUMINA

HIGH PURITY MAGNESITE

Clayburn Refractories Ltd. 33765 Pine St., Abbotsford, BC, Canada V2S 5C1 Tel: 604-859-5288 or 604-851-4556 [email protected] Resco Products, Inc. Penn Center West, Bldg. 2, Ste. 430 Pittsburgh, PA 15276 Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 [email protected] www.rescoproducts.com Saint-Gobain Ceramics 1 New Bond St., MS 301-432 Worcester, MA 01615-0136 Tel: (508) 795-2963 Fax: (508) 795-5011 [email protected] www.refractories.saint-gobain.com

MONOLITHIC REFRACTORIES-CASTABLE

Allied Mineral Products, Inc. 2700 Scioto Pkwy., Columbus, OH 43221 Tel: (614) 876-0244 Fax: (614) 876-0981 [email protected] www.alliedmatrix.com Chicago Fire Brick Div. of Allied Mineral Products, Inc. 2700 Scioto Pkwy., Columbus, OH 43221 Tel: (614) 876-0244 Fax: (614) 876-0981 [email protected] www.chicagofirebrick.com Matrix Refractories Div. of Allied Mineral Products, Inc. 2700 Scioto Pkwy., Columbus, OH 43221 Tel: (614) 876-0244 Fax: (614) 876-0981 [email protected] www.alliedmatrix.com

INSULATING BRICKS

AluChem, Inc. One Landy Lane. Cincinnati, OH 45215 Tel: (513) 733-8519 Fax: (513) 733-0608 [email protected]

BNZ Materials, Inc. 6901 S. Pierce St., Ste. 260 Littleton, CO 80128-7205 Tel: (724) 452-8650 Fax: (724) 452-1346 [email protected]

Clayburn Refractories Ltd. 33765 Pine St., Abbotsford, BC, Canada V2S 5C1 Tel: 604-859-5288 or 604-851-4556 [email protected] Magneco/Metrel, Inc. 223 Interstate Rd, Addison, IL 60101 Tel: (630) 543-6660 Fax: (630) 543-1479 [email protected] www.magneco-metrel.com Resco Products, Inc. Penn Center West, Bldg. 2, Ste. 430 Pittsburgh, PA 15276 Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 [email protected] www.rescoproducts.com Saint-Gobain Ceramics 1 New Bond St., MS 301-432 Worcester, MA 01615-0136 Tel: (508) 795-2963 Fax: (508) 795-5011 [email protected] www.refractories.saint-gobain.com

Clayburn Refractories Ltd. 33765 Pine St., Abbotsford, BC, Canada V2S 5C1 Tel: 604-859-5288 or 604-851-4556 [email protected] IFB, Inc. 610 East Butler Rd., Butler, PA 16002 Tel: (724) 282-1012 Fax: (724) 285-7673 [email protected] www.insulatingfirebrick.com

Refractories Applications and News, Volume 11, Number 1

January/February 2006

35

MONOLITHIC REFRACTORIES GUNNING Clayburn Refractories Ltd. 33765 Pine St., Abbotsford, BC, Canada V2S 5C1 Tel: 604-859-5288 or 604-851-4556 [email protected] Resco Products, Inc. Penn Center West, Bldg. 2, Ste. 430 Pittsburgh, PA 15276 Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 [email protected] www.rescoproducts.com Saint-Gobain Ceramics 1 New Bond St., MS 301-432 Worcester, MA 01615-0136 Tel: (508) 795-2963 Fax: (508) 795-5011 [email protected] www.refractories.saint-gobain.com

MONOLITHIC REFRACTORIES PUMPABLE Magneco/Metrel, Inc. 223 Interstate Rd, Addison, IL 60101 Tel: (630) 543-6660 Fax: (630) 543-1479 [email protected] www.magneco-metrel.com Resco Products, Inc. Penn Center West, Bldg. 2, Ste. 430 Pittsburgh, PA 15276 Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 [email protected] www.rescoproducts.com MULLITE Kyanite Mining Corporation Dillwyn VA 23936 USA Tel Sales: (434) 983-2043 [email protected]

MONOLITHIC REFRACTORIES MOULDABLE Resco Products, Inc. Penn Center West, Bldg. 2, Ste. 430 Pittsburgh, PA 15276 Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 [email protected] www.rescoproducts.com

REFRACTORY AGGREGATES

PRODUCT ENGINEERING/QA SERVICES VanceCeramics101, Inc. 23 Pheasant Run Dr., Export PA 15632 Tel: or Fax: (724) 327-1680 [email protected] REFRACTORY ADDITIVES Matrix Enterprises 858 Maple Lane, Waterville, OH 43566 Tel: (419) 878-0001 Fax: (419) 878-0001 [email protected] www.matrix-ent.com C-E Minerals 901 East Eight Ave., King of Prussia, PA 19406 Tel: (610) 265-6880 Fax: (610) 337-7163 [email protected] www.ceminerals.com Maryland Refractories Company 267 Salisbury Rd., Irondale, OH 43932 Tel: (330)532-9845 Fax: (330)532-3224 [email protected] www.mrcgrog.com Resco Products, Inc. Penn Center West, Bldg. 2, Ste. 430 Pittsburgh, PA 15276 Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 [email protected] www.rescoproducts.com

PRESS TOOLING Johnson Machine Company Inc. P.O. Box 669, 290 Bigler Ave., Clearfield, PA 16830 Tel: (814) 765-9648 Fax: (814) 765-9640 [email protected]

REFRACTORY MIXERS Anchor Manufacturing Company 2922 West 26th St., Chicago, IL 60623-4127 Tel: (773) 247-2530 Fax: (773)247-4907 www.anchormxrs.com [email protected] RFI Construction Products Division of Cangro Industries, Inc. 495 Smith St., Farmingdale, NY 11735-1186 Tel: (631) 752-8899 Fax: (631) 454-9155 [email protected] www.rficonstructionproducts.com/ REFRACTORY RECYCLING A-TEN-C, Inc. P.O. Box 58184, Pittsburgh, PA 15209 Tel: (412) 821-5566 Fax: (412) 821-5577 [email protected] www.ceramicrecycling.com

REFRACTORY SHOTCRETE INSTALLATIONS Clayburn Refractories Ltd. 33765 Pine St., Abbotsford, BC, Canada V2S 5C1 Tel: 604-859-5288 or 604-851-4556 [email protected] SILICA BRICK Utah Refractories Corp. P.O. Box 12536, Pittsburgh, PA 15241 Tel: (412) 851-2430 Fax: (412) 851-2425 [email protected]

PRE-CAST REFRACTORY SHAPES American Precast Refractories, Inc. 2700 Scioto Pkwy., Columbus, OH 43221 Tel: (614) 876-8416 Fax: (614) 876-0981 [email protected] www.amprecast.com High-Temp, Inc. 14025 N. Rivergate Blvd., Portland, OR 97203 Tel: 1 (800) 325-2492 Fax: (503) 737-0771 [email protected] Magneco/Metrel, Inc. 223 Interstate Rd, Addison, IL 60101 Tel: (630) 543-6660 Fax: (630) 543-1479 [email protected] www.magneco-metrel.com Refractory Specialties, Inc. 230 W. California Ave., Sebring, OH 44672 Tel: (330) 938-2101 Fax: (330) 938-2574 [email protected] www.rsifibre.com TFL, Incorporated 14626 Chrisman, Houston, TX 77039 Tel: 281-590-8500 or 800-828-5002 Fax: 281-590-5342 [email protected] www.TFLHouston.com PRECISION REFRACTORY SHAPES Resco Products, Inc. Penn Center West, Bldg 2, Ste. 430 Pittsburgh, PA 15276 Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 [email protected] www.rescoproducts.com Saint-Gobain Ceramics 1 New Bond St., MS 301-432 Worcester, MA 01615-0136 Tel: (508) 795-2963 Fax: (508) 795-5011 [email protected] www.refractories.saint-gobain.com

www.Kyanite.com

REFRACTORY GUNNING INSTALLATIONS Clayburn Refractories Ltd. 33765 Pine St., Abbotsford, BC, Canada V2S 5C1 Tel: 604-859-5288 or 604-851-4556 [email protected] REFRACTORY GUNNING & SHOTCRETE EQUIPMENT Allentown Equipment 421 Schantz Road, Allentown, PA 18104 USA Tel: (800) 553-3414 or (610) 398-0451 Fax: (610) 391-1934 [email protected] www.AllentownEquipment.com Blastcrete Equipment Company 2505 Alexandria Rd., PO Box 1964 Anniston, AL 36202 Tel: (256) 235-2700 or 1 (800) 235-4867 Fax: (256) 236-9824 [email protected] or [email protected] REFRACTORY LANCES High-Temp, Inc. 14025 N. Rivergate Blvd., Portland, OR 97203 Tel: 1 (800) 325-2492 Fax: (503) 737-0771 [email protected]

REFRACTORY BRICKWORK INSTALLATIONS Clayburn Refractories Ltd. 33765 Pine St., Abbotsford, BC, Canada V2S 5C1 Tel: 604-859-5288 or 604-851-4556 [email protected]

REFRACTORY ANCHORS Resco Products, Inc. Penn Center West, Bldg. 2, Ste. 430 Pittsburgh, PA 15276 Tel: (412) 494-4491 or (800) 354-1211 Fax: (412) 494-4571 [email protected] www.rescoproducts.com

SILICA FUME Technical Silica Company 2250 N. Druid Hills Road, Atlanta, GA 30329 Tel: 404-321-0460 Fax: 404-633-0799 [email protected] SILICA MATERIALS BNZ Materials, Inc. 6901 S. Pierce St., Ste. 260, Littleton CO 80128-7205 Tel: (724) 452-8650 Fax: (724) 452-1346 [email protected]

SILICON CARBIDE REFRACTORY SHAPES Saint-Gobain Ceramics 1 New Bond St., MS 301-432 Worcester, MA 01615-0136 Tel: (508) 795-2963 Fax: (508) 795-5011 [email protected] www.refractories.saint-gobain.com

SILICON CARBIDE C-E Minerals 901 East Eight Ave., King of Prussia, PA 19406 Tel: (610) 265-6880 Fax: (610) 337-7163 [email protected] www.ceminerals.com Electro Abrasives Corp. 701 Willet Rd., Buffalo, NY 14218 Tel: (800) 284-4748 Fax: (716) 822-2858 [email protected] International Minerals, Inc. PO Box 1322, Coraopolis, PA 15108 Tel: (724) 857-9903 Fax: (724) 857-9917 [email protected] www.imi-minerals.com Washington Mills Electro Minerals PO Box 423, Niagara Falls, NY 14302-0423 Tel: (800) 828-1666 Fax: (716) 278-6650 [email protected]

REFRACTORY MACHINING Refractory Machining Services 610 E. Butler Road, Butler, PA 16002 Tel: (724) 285-7674 Fax: (724) 285-7673 [email protected]

SPINEL-SINTERED Almatis 501 West Park Road, Leetsdale, PA 15056 Tel: (412) 630-2800 Fax: (412) 630-2810 www.almatis.com

36

January/February 2006

Refractories Applications and News, Volume 11, Number 1

STEEL FIBERS D & C Supply Company, Inc. 335 Washington Ave., Bridgeville, PA 15017 Tel: (412) 221-1191 Fax: (412) 221-9206 www.steelfiber.com Fibercon International Inc. 100 S. Third St, Evans City, PA 16033 Tel: (724) 538-5006 Fax: (724) 538-9118 [email protected] www.fiberconfiber.com SYNTHETIC SINTERED MULLITE Nabaltec GmbH Alustrasse 50-52, Schwandorf 92421 Germany Tel: ++49-9431-53 457 Fax: ++49-9431 61 551 [email protected] TOLL CRUSHING & GRINDING AluChem, Inc. One Landy Lane. Cincinnati, OH 45215 Tel: (513) 733-8519 Fax: (513) 733-0608 [email protected] Christy Minerals 833 Booneslick, High Hill, MO 63350 Tel: (636) 585-2214 Fax: (636) 585-2220 [email protected]yco.com www.christyco.com Maryland Refractories Company 267 Salisbury Rd., Irondale, OH 43932 Tel: (330)532-9845 Fax: (330)532-3224 [email protected] www.mrcgrog.com TOLL PROCESSING AluChem, Inc. One Landy Lane. Cincinnati, OH 45215 Tel: (513) 733-8519 Fax: (513) 733-0608 [email protected]

ZIRCON SAND & FLOUR AluChem, Inc. One Landy Lane. Cincinnati, OH 45215 Tel: (513) 733-8519 Fax: (513) 733-0608 [email protected]

ZIRCONIA FIBER INSULATION Zircar Zirconia, Inc. P.O. Box 287, Florida, NY 10921 Tel: (845) 651-3040 Fax: (845) 651-0074 [email protected] www.zircarzirconia.com

ZIRCONIA Washington Mills Electro Minerals PO Box 423, Niagara Falls, NY 14302-0423 Tel: (800) 828-1666 Fax: (716) 278-6650 [email protected] Z-Tech 8 Dow Road, Bow, NH 03304 Tel: (603) 228-1305 Fax: (603) 228-5234 [email protected] www.z-techzirconia.com

This may be your last issue if you have not sent your subscription renewal card. Please send it as soon as possible or e-mail Mary Lee at: [email protected]

University of Missouri-Rolla Material Science and Engineering 223 McNutt Hall 1870 Miner Circle Drive Rolla, MO 65409-0330

PRSRT. STD. U.S. POSTAGE PAID PERMIT 170 ROLLA MO

Our future refractories expertise at the UNITECR banquet Devdutt Shukla, Ali Rezaie and Ala Moradian.

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