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ti' - T' v--eV:-'-^6-' "':..' 1 -f * ',*.. . `M .sje CONFIDENTIAL FOR INTERNAL USE ONLY tr I > ,, -4 ?: \t : *"1- ; Vi :v" * V t \ A * It ' >-A. '-.v-i'. .t ri -*.,/ ^ ' "riTA . > l: r /.,:i,. > ....... >. *4,iW- ..! -* i vta -.A#,'. *V v :i.^` i itl'/mfiAte ?i:?* 1fr ;;v- ':\.a .' :. . ,... . ' : " '> s;*r.-.va 4 * ^ y,\ 'i- ^:">v ya CHRYS0T3LE ASBESTOS V (if/ tl/' /ti*'t# .' y.A' ":|: i.- . 'A 4 Kl'V.-:/". ST: ~ - ir'*!" k*! `**>*.Sy5vA^V* ' !>: r-"*,' si>v:.-t< ^-4 -'vf i'a'-f 5 V GROUP 7 (SHORTS) MARKET ANALYSIS UCC 004053 Morgan Guaranty Trust Company or York w>jii r'f/i rt. ,.4V b The Morgan Bank Mr. William C. Thurber Vice President & General Manager of Tungsten S Asbestos Union Carbide Corporation Old Ridgebury Road Danbury, Connecticut 06317 Dear Bill: Enclosed is the market analysis of Chrysotile Asbestos. Please let me take this opportunity to ciiank you for the use o f this material and all your other ass is canoe during the project. You and your colleagues were very helpful in working with us :o complete the project. Yours tru Iv. // j/ ( K. /db 1 n h l d H. Cj r o to ?. c d' s Ld can i: rr^HSur UCC 004054 CHKYSOTIIjE asbestos MARKETS AND FORECASTS For Group 7 March 197^ G. J. Weihs UCC 004055. CONTENTS Summary ................................. .......... ................................. Conclusions .......... ............................. ....... Recommendations . . ............................................... The Product The Market (General) ............................. . ........... Captive Fiber Sources & Product Mfgrs. .......... Asbestos Manufacturers and Plant Locations ........ Domestic Markets by End Use ...... . ......... Floor Tile ................................................................................................... Oil Well Drilling Muds........................................... ....................... w/B Joint Tape Muds ............................................................. . . . Paints & Miscellaneous Coatings ........................ ................... Adhesives & Sealants ............................................................. Ceiling Tile ................................................................................ . . . Paper . ............................................... ........................................................ Export (Floor and Sealing Tile & Paper) ....... Asbestos Filled Phenolic Compounds ..... ................... New Developments .............................................................................................. Elastomers (Shoes and Mechanical) ........................ .... Oil Well Drilling Muds .................................................... .... . . . Water Treatments........................ .... ..................................... . . . . Synthetic Wood .......................................................................................... Plastic Reinforcement . ............................. .................................. Sources . .................................................... ................................ . . . Exhibit I - UCC Asbestos Sales - 1973 ............................. Appendix I - Oil Well, Rig, and Refining Activity Appendix II - Asbestos Reinforced Plastics Technology Page 2 3 3 h 5 6 9 10 16 18 19 19 19 20 21 22 25 25 26 26 27 29 30 UCC ..004056 -2- SUMMAKY U. S. consumption of asbestos fiber. Group 7 (short) is estimated at 143,800 tons for 1973- We anticipate a growth rate of about 4 l/2 - 5# per year to 1980, when domestic demand should exceed 202,500 tons. Some of this growth will depend on new uses, such as reinforced plastics and mechanical rubber goods. It appears that Chrysotile asbestos is expected to remain in short supply.* Our sources indicate that many suppliers are planning to increase their prices by about 10# in 197^- 9/ f ^^ b ^ s We have not'considered the negative effects of possible federal re gulations and consumer attitudes toward asbestos since there is independent monitoring of that aspect by UCC and the industry. An exception is in the areas of paints, where restraints by that industry are already in force. , CONCLUSIONS 1. Floor tile, currently the leading consuming.product, will remain dominant to 1980. 2. Drilling muds application will grow at a healthy rate - mostly after 1975* This appears to be the best opportunity for UCC. 3* Wall board tape joint muds should continue to grow, pacing the increase in housing starts and, to some extent, commercial and * The "White House" phoned the Bureau of Mines (in ny presence) to inquire if the U. S. could become self-sufficient in asbestos. The answer was "probably not." We understand from U. S. Government sources that Russia, a major supplier of asbestos, has not been honoring its customer commitments. Therefore, the coming shortage may be world-wide. UCC . 004057 -3- 4. Paper Use of Asbestos appears to require a concentrated effort in the areas of both market research and development. 5* Best opportunity for nev markets are: reinforced plastics, _\ and elastomers for the shoe industry.; / _ ' 6. Best (and obvious) opportunity for growth is to Inherit the market segment now held by Johns ManvlUe. 7. Best opportunity for growth in established markets is oil drilling muds. RECOMMENDATION 1. From a market research viewpoint, plant expansion is justified, the extent of which to be determined by technology, engineering, toxicological and marketing considerations. 2. A market study of the possible use of Calldria asbestos in vinyl roll goods, and extended use in paper, should be undertaken. THE PRODUCT . Asbestos is actually a group name that refers to fiberous minerals having different chemical compositions, but similar characteristics. The most widely used type is chrysotile. These fibers are graded according to length with longer fibers priced at 10 - 20 times higher than the shortest grades. UCC's interest focuses on group 7 - one of tbr shorter fibers. UCC 004058 Asbestos - group 7, included in the U.S. Bureau of Mines Designa tion BMIII, is usually combined with other materials and loses identity in the final product. For the purpose of this study we are omitting statis tics on asbestos/cement, packing and gaskets, textiles and other uses for long fiber where UCC does not compete. THE MARKETS - General Domestic production of asbestos during 1973 was approximately 151,000 short tons with an average value of $109 per ton. This total value ($l6, 390,000) was 22$ over 1972. California was the principal producing state (72$); Vermont ranked second. (For producers, plants and mine locations, see Tables 1, 2, & 3)* Apparent U.S. consumption, according to the U. S. Bureau of Mines, of all chrysotile asbestos was 871,000 tons, up 8$ from 1972. Canada continues to be the major supplier. As we continue to make inroads into the market segments served by Canadian asbestos, the total market shrinks,since that portion of product shipped which is rock, is eliminated or greatly reduced. UCC's product is approximately 96$ (average) purity. ;, Some group 7 applications have also been excluded on the basis of inability to compete. UCC's experience in selling the various markets is summarized.is Exhibit ! Continued after Tables-on Page 11 UCC 004059 -5 TABLE 1 CAPTIVE FIBER SOURCES FOR THE major asbestos products manufacturing firms ..... ............................ .................................... ' U. S. & CANADA ^Company The Flintkote -Co. GAF Corp. ASARCO (through CAPO, 40^ owned by ASARCO) JohnB-Mansville ^ Products Corp. National Gypsum Co. Jim Walter Corp. H. K. Porter Co., Inc. Raybestos-Manhattan, Inc. General Dynamics Corp. Union Carbide Corp. Atlas Asbestos Corp. Bell Asbestos Mines, Ltd. Advocate Mines, Ltd. Jaquays Mining Co. Captive Mine(s) Fiber-Producing Capacity (short tons/year) Flintkote Mines, Ltd. Quebec (wholly owned subsidiary) 33,000 . 1 Lovell Mine Orleans, Vermont . 40,000 Lake Asbestos of Quebec Ltd. 130-150,000 Canadian Johns-Manville Co., Ltd. Coallnga As bestos Corp., Calif. (80S( interest) 835,000 15,000 National Asbestos Mines, Ltd. 60,000 Carey-Canadian Mines, Ltd. 250,000 Pacific Asbestos Corp. 40-50,000 Cassiar Asbestos Corp. (Partial Interest) 110,000 Asbestos Corp., Ltd. (54^t interest) 350-500,000 Union Carbide Mines San Benito, Calif. 35,000 Santa Cruz, California 10-20,000 Quebec, Canada 60,000 Baie Verte, Newfoundland Gila, Arizona 70,000 3,000 (1) J. M, may cease operations in California in 197^* . UCC 004060 1' -6TABLE 2 THE MAJOR ASBESTOS MANUFACTURING FIRMS AND PLANTS IN THE UNITED STATES 1 UCC 004061 Company American Biltrite Rubber Corp. Armstrong Cork Co. Certain-Teed Products Corp. The Flintkote Co. GAF Corporation ;\ 1u \ Total Number of Employees Estimated Annual Sales ($000,000) About 4,500; 20# involved in as bestos products 161.0 21,000; about 80$ involved in asbes tos products 550-600 7,600 332.0 11,300 441.0 20,000 It's subsidiary, Ruberoid, is pro bably the sole producer of asbes tos products 768.0 Principal AsbestosBased Products Manufactured Floor tiles Gaskets % insula ting materials; vinyl asbestos tileB Roofing products Asbestos-cement pipe; vinyl as bestos tiles; roofing products Asbestos-cement products; vinyl asbestos tiles; roofing products; asbestos paper Plants-Establishments Manufacturing Asbestos Products 14 plants involved to some degree in ashes , tos manufacturing Fulton, N. Y. Jackson, Miss. Kankakee, 111. Lancaster, Pa* South Gate, Cal. Santa Clara> Cal* Riverside, Cal* Ambler, Pa. Hillsboro, Texas St. Louis, Mo, Los Angeles, Cal. Chicago Heights, 111. New Orleans, La, Ravenna, Olio Chillicothe, Ohio Mobile, Ala. Long Beach, Cal, Joliet, 111. Millis, Mass. St. Louis, Mo* So. Bound Brook, N.J. Vailis Gate, N* Y. Erie, Pa. (two plants) Whitehall, Fa. Houston, Texas $ of Line Related to Asbestos 5 50 75 20 5 -7- Company Jim Walter Corp. Johns-Manville Products Corp. Hlcolet Indus tries, Inc. National Gypsum Co. Raybestos Man hattan I TABLE 2 (cont'd) Total Number of Employees 1,000 in asbestos products manufac ture - (also own Celotex) Estimated Annual Sales ($000,000) 882.0 Principal AsbestosBased Products Manufactured Roofing materials 4 Plants-Establishments Manufacturing Asbestos Products Perth Amboy, N. J. Linden, N. J. Memphis, Tenn. Lockland, Ohio Miamisburg, Ohio Wilmington, Del. Houston, Texas Tampa, Fla. Cincinnati, Ohio # of Line Related to Asbestos 12 25,000 796.0 Asbestos-cement products; asbestos roofing; asbestos insulating materials; millboard Nashua, N* H. Manville, N, J. Pittsburg, Cal. Stockton, Cal. Waukegan, 111. Marrero, La. Long Beach, Cal. Los Angeles, Cal. Green Cove Springs, Fla. Savannah, Ga. Billerica, Mass. Tilton, N. H. Denison, Texas Forth Worth, Texas 30 350 15.0 Asbestos paper; Ambler, Pa* 100 asbestos millboard Norristown, Pa. Hamilton, Ohio 14,500 6,500 519.0 165 Asbestos-cement pro ducts; asbestos roofing; insulating board New Orleans, La* Millington, N. J, Mobile, Ala. ./ Brake linings & blocks Bridgeport, Cfc. (Heme Office ) & asbestos products - -8- TABLE 3 'TRENDS IN THE HUMBER OF U. S. ASBESTOS PRODUCTS MANUFACTURING COMPANIES PRODUCT Asbestos Products YEAR 19^7 195^ 1958 1963 1967 1973 NUMBER OF COMPANIES 85 7^ 69 73 81 80 Sources: 19^7-1967 1967-1973 1967 U. S. Census of Manufacturers Industry Estimates / ' UCC 004063 -9- TABLE if DOMESTIC MARKET FOR CHRYSOTIUE ASBESTOS (Primarilly Group 7) USE (1) Floor Tile 1973 ~ 105,000 (2) Oil Prilling Muds (3) Elastomers (Shoe) Mechanical Rubbers Adhesives & Sealants (if) Reinforced Plastics ------ ^(^henolics}. Paints (Incl. Misc. coatings) 10,000 Keg. .> Filled Plastics (Fhenolics) 11,000 V/B Tape Joint Muds 9,000 (5) Ceiling Tile 1,200 Paper w ' 2,000 Annual # Growth 3* 7* 33t 3* Keg. Keg. (6) Total lif3,800 short tons % 1980 202,500 short tons (1) Excluding "long 7's" used in roll vinyls. This area should be explored. (2) Based on world-vide sale of U. S. production. Expect less than average growth until 1976 and over average to 1980. (3) Based totally on acceptance in shoe industry - not incl. in 1980 totnl. (if) Based solely on acceptance in thermoplastics, thermosets are future possibility which could greatly increase markets. (5) Totally dependent on 1 customer where prospects are uncertain. (6) Kot allowing for possible restrictive actions by 0SHA or EPA, .UCC 004064 -10- THE MABKETS (Cont'd) ' The market break-down and estimated future consumption shown In Table 4 does not consider the probability that OSHA and/or EPA will force regulations on the asbestos mining and consuming industries which may hinder growth or actually eliminate some existing markets - e.g. paint. FLOOR TILE 1973 production of vinyl-asbestos floor tile required about 105,000 tons of asbestos. The remaining portion of a typical vinyl-asbestos floor tile consists of vinyl resin, plasticizer, lubricants, stabilizer, limestone and TiOg. Limestone contributes over 55$ "to the average formulation. Natur ally, variations exist depending on manufacturer. The industry suggested growth rate for vinyl asbestos floor tile is 5$ per year to 1980,but reBin suppliers place increasing rresin demand at about 2$ with less growth anticipated during 1974. This 197*+ slackening of demand is attributed mostly to the shortage of raw materials. Some of the differences between estimates may be attributed to the desire of tile manu facturers to decrease scarce, esqpensive resin and Increase filler whenever possible. ' We believe an average annual growth of 3$ can be envisioned based on the following assumptions: 1. Resurgence of residential soft (carpet) floor coveiing may hinder ^ vinyl/asbestos tile growth. UCC 004065 -11- 2. Decline in housing starts. 3. Acceptance of soft floor coverings in business and commercial *' establishments. 4. Trend to smaller homes and apartments. 5. Gradual replacement of asphalt tile by vinyl asbestos. TABLE 5 ESTIMATED 1973 ASBESTOS CONSUMPTION IK FLOOR TILE COMPANY . GAP Corp. Uvalde Rock Asphalt Co. Kentile, Inc. Armstrong Cork Co. American Biltrite Rubber Corp. Flint^ote Co. Others CONSUMPTION (short tons) 20,000 5,000 12,000 20,000 10,000 (e> O $ 20,000 18,000 00 U. S. Total 105,000 . r-> !"''i >J 'j--' " Source: UCC - Mining & Metals Division UCC 004066 -12- TABLE 6 "CALISRIA" ASBESTOS SALES FOR FLOOR TILE TEAR 1964 AMER. BILT Tons |M OAF Tons $M 1965 1966 1967 1968 1969 1970 1878 1721 97 88 00 260 12 1971 1972 2139 109 1760 88 3490 2618 157 126 1973 1107 197^ est. 720 62 44 4695 3000 225 159 KEHTILE Tons IP 3190 3228 2600 160 168 122 3845 180 2641 1590 127 82 Uvalde Tons $M Total Tons $M l4l 8 972 54 (1)7524 376 1380 69 n4o 57 1680 84 7082 355 5630 28o 6448 326 6349 325 9909 472 2732 136 10955 530 5227 230 (2)13678 644 4800 238 (2)10680 533 (1) UCC,` -announced decision to "go out" of floor tile market and sell all plant production to HP markets. Ibis did not materialize. (2) Sales limited by production capacity. UCC 004067 FIGURE I f UCC.004068 GEOGRAPHICAL LOCATION OF THE MAJOR VINYL - ASBESTOS FLOOR TILE PLANTS IN THE UNITED STATES -lk- COMPETITION: A mmiher of companies are engaged in the mining and marketing of asbestos to the floor tile manufacturer. These companies^located in both the United States and Canada,are listed in Table 1-2. Competition from chemically different substances is emerging, and the tempo increasing as directives from OSHA and EPA precipitate uncertainty. Among these are: ' . An inorganic fiber, available in development quantities in the form of ftiuminft or zerconla fiber - from ICI. UCC Group I, Chemicals,is working under a secrecy agreement with GAP end Flintcote to develop an asbestos substitute specifically for floor tile. This development material is reported to be a "unique resin with a polycaprolactone (family) compound." It is claimed to handle in the forming equipment equally as well as asbestos. Additional information can be obtained on a secrecy basis, if necessary. UCC 004069 -15- Hev Developments in Floor Tile Marketing Developments in the industry include an announcement "by Congoleum's resilient flooring group of a stepped-up program for the company's vinyl asbestos floor tile. They have instituted a number of field and management changes to support this policy. It would appear that at Congoleum, there is little fear of product use legislation at the "ultimate consumer" level. Another new activity involves GAF, which has announced introduction of a vinyl/asbestos "do it yourself" wall tile. Heavy Fall T.V. coverage is planned. (See Figure I - Floor tile plant location.)* TABLE 7 WORLD-WIDE ASBESTOS IN FLOCK TILE Argentina Eyi^ope (w. Germany) S. Africa Viet Ham Brazil Taiwan Colombia. Chile Tons 5,000 20,000 2,500 11,000 3,000 4,000 1,300 1,700 45,500 Tons Source Canada Canada S. Africa Unknown Canada - JM Taiwan Atlas (AZ-20) JM Coalinga * Known Markets UCC 004070 (** <,' AO tv -16- eJ.1 - -/ ~ 7' ' /l- OIL WELL DRILLING MUDS Asbestos is used as a viscosity control agent in drilling muds mostly for aqueous systems but also for non-aqueous (oil) systems.* U. S. asbestos demand was about 7000 short tons in 1973 and U. S. export amounted to an additional 3>000 short tons. Although we forecast growth at 756 per year to 1980,, we believe the greater portion of growth will be realized after 1975- z OOO ~hsy* r Short term growth is hindered by lack of equipment such as rig availability in the' U. S. which, during the early 196Q's, stood at 2,000 units and today, at approximately 1,370** It may take 2-4 years to build rig capacity to meet demands and by 1980,there could be 2,200 rigs avail able. There is also a shortage of pipe and other parts, and a shortage of skilled personnel which could require 2-3 year to completely overcome. However, as prices for oil products increase, the attraction of investors (money suppliers) may solve the equipment problem in a shorter period of time. Government intervention and priorities may also help. * Oil systems are used where it has been pre-determined that the subterreanean rock formations would be degraded by water. ** Rigs in operation in Canada * 258 as of 3/74. See Appendix I for additional data on rigs and wells - world-wide. UCC 004071 -17- TABLE 8 UNION CARBIDE ASBESTOS (Short Tons) SALES TO MONTELLO FOR DRILLING MUD APPLICATIONS Product Designations 1970 CSV 677 NGSV 0 IMC/Visquifc 120 Visbestos 1242 Total 2039 1971 1671 0 0 750 2421 1972 1175 0 0 642 1817 1973 1319 469 999 249 3036 1974 (Budget) 1440 360 l44o 360 3600* \%o a.yoo Th^c. * Sales limited by plant capacity Problems: Problems currently facing asbestos drilling muds are: . Possible restraints by Federal government agencies . Shortages of asbestos may entice customers and prospects to formulate around the product. Competition on the horizon in cludes biodegradable r long chain polymer systems. However, these are high priced and, along with other chemicals r may continue in short supply. * Connietition from Johns Manvllle's "Flosal" asbestos. This may soon end which will strengthen our position in the market place UCC 004072 -18- . Order of priorities - some of tiie monies made available through increased prices may be ear-maxIced for refinery capacity rather than for drilling. There is now reported to be a short fall of ever 2 million barrels per day of refining capacity. . Continuing competition from Bentonite. (See Appendix I for the number ana location of drilling operations - world-wide) WALL BOARD "JOINT" TAPE MUDS U. S. production of gypsum wall board during 1973 vas approximately 14 billion square feet. Assuming a requirement of 5 gallons of (3$ con tained asbestos) mud per 900 sq. ft..of wall, we estimate a current demand of 9000 tons of asbestos for this purpose. Growth of gypsum wall board depends largely on housing starts as well as, other business and commercial construction. We accept a Jfh average annual growth rate td 1980. Projected, this would mean a market for as bestos of about 11,000 tons in 1980. According to the Gypsum Wallboard Association and our own internal information, there is an alleged hazard in the use of asbestos in this application due to sanding of the semi-finished job. This "dusting" is considered unacceptable by the trade in view of OSHA attitudes. Warning Labels may be required. UCC 004073 MINOR ASBESTOS APPLICATIONS PAINTS The industry estimates approximately jOO tons of asbestos were consumed in textured paint during 1973 and an additional 300 tons in allied applications. Although the market for textured paint is increasing, manufacturers, fearing restrictions by OSHA, are substituting 7 asbestos with talc and inert pigments. According to one source, some development work is still being done. We therefore, hesitate to eliminate asbestos paint from our future market picture and elect to carry the volume over on a "no growth" basis. ADHESIVES AND SEALANTS According to information received from the Adhesives and Sealants Council and others knowledgeable in the field, there is a current demand for asbestos of about 5,000 tons per year. This requirement is based on the use of asbestos in mastic adhesives, vinyl and rubber based sealants, caulks & putty. Growth is expected to approximate 5-6$/year to 1980. CEILING THE / Conwed Corporation, Cloquet, Minn, is the only U. S. ceiling tile manufacturer known to be using asbestos. 1973 consumption was 1200 tons ai1 uCC's "Calidria". Demand for 197^ is 1000 tons and maximum requirement by I960 is put at 1^00 tons. Since this is a "one customer" market, every thing depends on the whim of the single company - Conwed. Other ceiling tile manufacturers such as Kaiser Gypsum and Armstrong Cork do not use asbestos. UCC 004074 -20 Use of asbestos improves tensile strength in board formation, and clay and starch retention. However, major ceiling tile manufacturers can and do obtain satisfactory product substituting various organic chemicals. The contribution of asbestos - "to supply the positive charge necessary to keep it and other ingredients clinging to the wire on the Fourdrinier - is inportant for older but apparently, not never equipment. Continued domestic use and growth depends substantially on the out come of a legal suit by the Federal government against Reserve Mining Co. for allegedly dumping asbestos-like waste into the Great Lakes. If the government's case stands up, it would have an adverse effect on our future domestic ceiling tile business.*1 (See Table 9 for UCC exports.) PAPER: m i' Three known uses for asbestos in the paper industry are: 1. Add to "furniBh" for pitch control. 2. Retaining agent for such paper additives as clay. 3. Ti02 Extender In some cases, the use of asbestos can have dual purpose. There are reported to be technical problems precluding asbestos use at the newer millB. In these operations, the asbestos must be added to the ''furnish" in slurry form, which in many instances, results in lumping. This, the mill can not tolerate. It appears the problem can be overcome, but by costly methods. In the older mills, it is satisfactory to add the as bestos as a dry powder and lumping does not occur. Talc has been suggested to be as good as asbestos and at a cheaper price. Future for foreign shipments still looks bright. UCC 004075 -21- A relatively new use is Tor electric paper. Stevens, Westfield., Mass, is the only known asbestos customer. The remaining two manu- #' facturers are Crocker Burbank, Fittsburg, Maine and P. J. Schwetzer, Lee, Main. We believe that this use vill remain relatively small. The 1973 domestic demand for asbestos in paper is about 2000 tons per year sold to four customers: Longview (pitch control); Boise Cascade (TiOg Extender); Kimberly Clark (control of sheet porosity); and Prairie States (contaminant dispersion and pitch control). See Table 9 for UCC exports. TABLE 9 ESTIMATES OF UCC EXPORTS pJQCT Tons) 1971 Floor Tile - Japan 0 (1) Europe 0 0 1977 4,000 5,000 9,000 Paper - Japan Europe Ceiling Tile Japan 1,000 100 1,100 3,4oo 2,300 600 3,100 7,900 1980 8,000 10,000 18,000 2,600 1,400 4,000 9,600 Source: Internal (UCC, KF) Assumes capture cu zjQFj of market by 1980 which W.R. Grace estimates to be currently 20,000 tons/year.1 (1) No material avialable UCC 004076 -22- Asbestos Filled Phenolic Molding Compounds; According to an internal report are categorized by seven market areas: phenolic molding materials % of Total Production 1) Applaince parts - toaster handles, electrical control knobs, etc. 25 2) Automotive-transmission parts, brake parts, distributor caps, etc. 16 3) Electric^. - switch gear, high voltage circuit breakers, etc. 30 h) Wiring devices - electrical parts 110V switches, plugs, etc. 12 5) Closures - bottle caps, etc. ^ 6) Communications - switch terminal blocks, etc. 7 7) General industrial parts - knobs, ash trays, etc. 6 Asbestos is used largely in appliances and automotive phenolic ap plications which account for approximately kOjo of phenolic molding materials. Some asbestos is used in electrical wiring devices and general industrial applications for specialty high-temperature resistance items, hut usage is relatively small compared to the forementioned areas. Asbestos is not normally used in closures or communications parts. (See Table 10)1 (1) B. L. Engalls 1-11-lk UCC 004077 -23- Union Carbide requires approximately 1,000 tons/year of asbestos "7 RF9" purchased from Carey. (1) There are 3 stated reasons for not using UCC's "Calidria": 1) Since both materials are shipped FOB to distination, the ' freight costs from California exceed those from Carey's oper ation in Canada. 2) Although Calidria pellets are easier to handle in bulk, they are more difficult to disperse. 3) UCC's equipment is set up to handle the compound as received from Carey and it would require production and formulation changes to convert to "Calidria." General Electric Co. recently announced intention to formulate away from asbestos and have changed to a combination of other fillers. This asbestos free formulation has so far, received mixed acceptance. While the substitute may be satisfactory for some items, asbestos filled phenolics are the best performers in high temperature applications. Such items as household appliances, which operate at temperatures above 250F, still require asbestos. We understand that 3E is purchasing asbestos filled phenolics for their dissatisfied customers. G.E. is also considered to be very public relations conscious and for this reason, will promote "non asbestos" to the trade as an "environmental asset." ^ The loss of asbestos business to this company has been estimated at over 1,000 tons/year. Note: There is a use for asbestos in other thermosets such as urea and melamine but this is small.(l) (l) Carey's total annual sale of asbestos for all applications is approx imately 235,000 TFT. UCC 004078 -24- YEAR I960 1972 1973 1974 1975 1976 1977 1978 1979 1980 TABLE 10 PHENOLIC MOLDING COMPOUNDS (1) ASBESTOS POTENTIAL DEMAND 1973-1960 PRODUCTION (OOP Tons) ESTIMATEDPRODUCTION CONTAINING ASBESTOS (25$) 100 25 170 42*. 5 190 47.5 195 204 48.7 51.0 210 220 230 240 52.5 55 57-5 60.0 250 62.5 ASBESTOS DEMAND @ (23$) AVERAGE CONTENT (Rounded) 5*8 .9.8 11.0 .11.2 11.7 12.0 12.6 13.2 13.8 14.3 Competition is also coming from less expensive materials such as talc. vhich recently replaced asbestos in the auto fan shroud. This was about a 1,500-2,000 ton per year outlet. /- (1) UCC had, in 1913> approximately 11$ of the phenolic molding compounds market. UCC 004079 -25- NEW EEVELOPMEHTS RUBBER (Elastomers) Due to the shortage and Increasing price of "high" styrene resins, there is a possibility of an impending market for 5,000 tons of asbestos by the shoe industry. Interested, prospective customers include EndicottJohnson and Thom McAn (J. F. McEllvin). Present market for asbestos in the shoe industry is about 500-1,000 tons per year. UCC's "Calidria" does not now compete. Advantages of "Calidria" asbestos are price and expected availability. Again, there could be an environmental problem;and since ve believe its use will be a "go or no go" situation (either all or nothing), ve have not added the market potential to our estimated total demand in I960. This application must be watched closely to determine outcome. UCC should have more definitive information within the next few months. MECHANICAL RUBBER GOODS Including rubber rollers, shock mounts and belting,hold a potential market of 5,000 tons/year for asbestos by 1980-81. Use In rubber tiles will also add another 1,000 tons. OIL WELL DRILLING During 1973 a new development occurred which could markedly increase Union Carbide Corporation's participating in the oil well drilling business. Dresser Industries has developed, and we believe have a patent application on, a silane treated asbestos (UCC silane). UCC 004080 -26- OIL WELL DRILLING (cont'd) Technical details are meager but the nev product appears to be intended for oil based systems and increases their useful operating range from about 250F to 350F, Dresser has ashed for 1,000 tons in 1975,and dis cussions are in progress to determine economics and business relationships WATER TREATMENT A licensing and distribution agreement has been negotiated with the Perrautit Company covering the use of High Purity Asbestos in, the treat ment of certain types of waste water. Sales in 197^ are estimated at 300 tons. It is too early to make firm predictions;but sales in the order of 5,000-10,000 tons/year for this application are quite possible by 1980. SYNTHETIC WOOD A small inventor, Holman Construction of Anderson, South Carolina has been working for about 3 years on a "synthetic wood." Fiberglass strands are pulled through a die while a filled plastic is simultaneously extruded. SG-130 at a loading of 5-10$ is a hey ingredient for a flow con trol in the extruder. Owens-Corning, as a fiberglass supplier, has become increasingly involved with the project and has recently taken a two year option on Phe pilot plant. If the project becomes commercial,the asbestos potential could be very large. UCC 004081 -27- PLASTIC REINFORCEMENTS Union Carbide's chrysotile asbestos pellets, treated with our proprietary phenolic coupling agent, is being offered to the trade as a reinforcing fiber in thermoplastic resin systems. This fiber Is designed as a substitute for glass at an approximate ratio of 1:1. Our offering is designated "RG600." See Appendix II for technical information. Market potential for RG600 is based on a reasonable share of cur rent consumption of, and growth expectations for, glass fiber reinforcement in polypropylene, nylon, HDPE,^) styrenics, acetateB and other thermoplastics During 1973, thermoplastics were consumed in the amounts shown in Table 11. TABLE 11 CONSUMPTION OF THERMOPLASTICS IN 1973 RESINS Polypropylene Nylon Engineering Plastics Polyethylene Styrenics TOTAL OR MM IBS 1*0 23 3^ 13 20 130 MM LBS. (65,000 TONS) E3T. GLASS FIBER 10 6 3 3 5 32 MM LBS. (16,000 TONS) (1) RG660 is 2.5 microns in length - fully liberated. (2) It should be noted that RG600 and other grade "7" asbestos can be used to convert low density polyethylene to high density, as well as substitute for a portion of high priced, scarce, styrene monomer.in some formulations. ' UCC 004082 --28- Aseioming a 25% penetration potential, we see a current available market for approximately 8,000,000 lbB. or 4,000 tons. Our present commer eial penetration iB nil. Market available in i960 (assuming no growth for 197%) is about 15,000 tons. UCC's ability to penetrate this market, in view of the entrenchment of glass, and ecological considerations, is highly problematic. Besides overcoming the negative publicity which surrounds asbestos, it will be necessary to sell at a reasonably lower price to entice those users now * wed to glass and glass reinforcing technology. ' We have avoided a discussion of reinforced thermoset resin reinforce ment because, as of this analysis, there is no satisfactory coupling agent for asbestos in this system. However, work is proceeding with thermoset/ asbestos at USC - Bound Brook and future developments are possible. If * successful, a market potential for UCC's RG600 is 8-10 times greater than that for thermoplastics alone. UCC 004083 CODE: 11 3 5 1 8 8 11 6 k k 2 6 3 11 -29SOURCES External Asbestos Magazine N- L. Industries (Market Research) N. L. Industries (Research & Development) Gypsum Wall Board Assoc. Oil and Gas Journal Montello Bureau of Mines (U.S.) Rubber Age Ma* *g*azine Adhesives and Sealant Council Fluid Sealing Assoc. Resilient Tile Institute PPG Industries Glidden U.S.R.C. \ Internal UCC Chemicals & Plastics 2 A. Constantine 6 R. Lindberg 6 D. Barry 8 J. Madden 7 M. Ranney 10 G. Shipston 10 P. Potter 10 W. DeFaber UCC Asbestos Group 11 Marketing & Development Personnel * Rev York, Niagara Falls, Chicago and Atlanta UCC Group I R & D . 7 F. Ancker - Bound Brook 8 T. Foster - South Chas. 8 S. Livengood - Tarrytovn CODES: 1) Wallboard 2) Floor Tile 3) Paints k) Adhesives & Sealants 5) Paper 6) Elastomers 7) Plastics Reinforcement 8) Oil Drilling Muds 9) Ceiling Tile 10) Plastic-Filled Phenolics 11) General UCC 004084 1 EXHIBIT I 30 "CAL I DR 1 A" ASBESTOS SALES- ...... (Domestic & Export) Product Add!ications ! 970 Tonnage i 5/3 1974(Budget) St-iQX Floor Tile .. 3G-130 ' 3G-200 Mastics Res In filler '. . A5-200 Cei-I.i ng Tile.. . -. " ^ij--21 0 Tape Joint Compounds, Mastics, Sealants HDP Ceiling Tile, Paper, Rubber . ... -F0 Resin filler. Waste Water Treatment . HPO-J Dri11ing Fluid .. ,.. T- 1 35-F T-135-0 'Paper Coatings .' ' ' CG-I35-P Coatings j. RG-100 Resin filler RG-1 10 Undercoat, Mastics, etc. ' RG-i44 Adhesives, Sealants, etc. SX-14 Same as RG-144 - 'RG-^44 )___ xThixotrope cO v -- . SX-24 Same as RG-244.W 2L_;--------' ....... .. ' Ttto ' . Visbes+os Dr i 1 ] i ng fHtXfd . irncobe5t Dri11ing F1uid CSV Dr I1 1Ing F1uid XG5V Drilling Fluid . Other 5400 ! 3495 190 . 278 0 100 . 0 750 917 5512 3946 5151 602 35! 'o' 55 - 438 587 419 13 .13. 0 ' 106 650 754 407 6 i 6 33 50 185 803 34 I 18 1032 254 0 999 663 1 344 0 53 127 55 10680 360 1000 1400 4800 5900 360 240 430 230 75 100 1030 700 1 15 882 230 360 1440 1440 350 0 TOTAL 17,303 50,725 32,232 1 ................................................... ; UCC 004085 JIM 3/26/74 . ...................... - - - APPENDIX I Rotary-rig activity by states Peak No. Low No. ' 1973 1972 Average rig activity-- 1971 1970 1969 1968 1967 Alabama ......... ............... . Alaska . . ................. .. Inland ....................... Offshore ....... . Arkansas ......................... Arizona ......................... .. California ......... ........... Inland ....................... . Offshore ..................... . Colorado ....................... . Florida ........................... . Georgia ......................... Idaho ............................ . Illinois ........................... . Indiana --................. Iowa .............................. Kansas ............. ............. . Kentucky ..................... Louisiana ..................... 18 10 S 3 23 5 68 65 4 58 15 2 2 11 2 1 45 3 253 North ........... ......... inland waters ......... South ................-- Offshore Maryland................... Michigan . . . . 31 66 76 97 1 26 Mississippi . 44 Missouri ..................... Montana ..................... 1 28 Nebraska ......... 10 Nevada ................. 2 New Mexico................... 86 New York....................... 6 North Carolina ............... 0 North Dakota.................... 17 Ohio .............................. .. 48 Oklahoma ....................... . 150 Oregon ........................... .. 1 Pennsylvania 19 South Dakota ............... . 3 Tennessee ....................... . 2 Texas ............................. .. 454 Gulf Coast 143 Offshore . . 18 North ......................... Panhandle ................... East ........... West Central West ........... Utah ............. Virginia........... Washington..................... West Virginia Wyoming ........... 29 29 37 104 115 49 3 0 32 105 Total U.S. 1,440 Canada West................... 272 Canada East ..................... 9 7 13 15 055 044 01 1 8 15 15 02 1 34 51 46 33 49 45 02 1 23 42 35 5 9 19 010 010 1 6 14 00 1 01 0 8 28 24 01 2 161 205 214 15 23 19 43 55 54 37 56 59 56 71 82 001 10 20 17 23 29 37 01 0 9 19 20 156 00 0 40 62 55 010 00 0 5 10 7 21 36 22 SO 115 90 000 6 11 8 01 1 00 0 328 376 322 82 109 91 696 14 22 15 23 15 30 73 82 82 101 29 38 01 00 6 20 33 70 16 22 26 71 SO 34 0 0 16 60 970 1,194 1,087 70 175 148 04 4 87 E3 2 5 14 28 20 21 5 12 18 3 5 0 2 10 17 16 15 13 16 7 8 1 0213 46 52 78 87 . 83 40 42 61 65 67 6 10 17 22 16 30 25 23 17 16 11 4 1 1 2 00000 00000 13 14 17 22 30 11 1 23 1 0000 29 30 38 35 41 21259 194 204 230 233 235 16 12 19 19 20 50 57 57 64 66 54 56 69 59 58 74 79 85 91 91 001 10 12 11 10 10 10 39 43 40 36 33 00000 17 17 31 3* 22 5 6 10 5 5 1 002 1 47 40 64 68 56 1001 1 00000 9 9 12 13 11 17 24 22 22 18 90 98 120 106 101 00 0 00 99757 12110 121 01 291 302 322 329 340 79 73 71 88 90 5 6 10 6 7 15 17 25 25 28 16 19 19 20 21 23 25 37 34 36 76 77 74 67 67 77 85 80 89 91 17 ' 12 12 12 15 1 I000 00001 17 16 18 16 15 45 71 SI 56 44 976 1,028 1,194 1,150 1,134 120 131 149 150 144 432 1 1 Grand Total 1,627 1,043 1,373 1,239 1,100 1.162 1,345 uoi 1,279 Source: Hughes Tool Co. Note. Peak and low fibres may not add to totals 1966 2 13 5 8 10 1 79 70 9 16 2 0 0 30 5 1 55 13 256 23 72 63 98 4 9 34 1 24 8 1 60 1 0 12 14 141 1 10 o 1 387 103 8 31 23 38 82 102 14 0 1 19 48 1,273 156 1 1,430 1935 1 6 3 3 11 1 89 83 6 19 4 0 0 24 5 0 70 12 270 30 72 73 95 2 11 35 0 26 10 2 65 1 0 12 22 163 1 9 2 0 425 112 5 34 25 40 102 107 14 1 0 24 50 1,387 163 2 1,552 1964 2 5 3 2 9 2 93 87 6 21 1 0 0 20 6 0 87 8 282 27 83 81 91 2 13 39 0 21 11 1 79 1 0 14 56 158 0 11 1 0 477 135 2 42 31 43 121 103 17 l G 16 48 1,502 149 11 1.652 UCC 004086 A F P E K D I X J ( Con't) Worldwide oil at a glance COUNTRY ASIA-PACIFIC Afghanistan Australis BanglaOesh Brunei-Malaysia Burma . China Rep. (Taiwan) Guam .... India Indonesia Japan Khmer Republic . Korea, South . New Zealand Okinawa (R.i.) . Pakistan . Philippines ___ Singapore .. Sri Lanka . Thailand Total Asia-Pacific TCondensate RESERVES 1-1-74 Oil (I.OOObbl] Gas (hiIlian cu ft) WELLS OIL PRODUCTION Producing fij! 7-1-73 Drilling 12-1-73 i Estimated 1 % change 1973 ! from (1,D0D b/d; | 1972 Refin eries REFINING Capacity (I.DOOb/ed) 1-1-74 Crude Cracking Ketorm ing +89,840 2.300.000 1,600.000 67,800 14,000 779,000 10,500,000 19,000 +224,000 31,200 10,200 15,6351740 4,900 37,700 8,000 20,000 200 400 2,000 15,000 700 15,000 10,120 180 114,200 13 394 126 700 50 1,500 2,567 1,084 4 7 1 5 7 .2 _. 9 25 11 0.2 420.0 325.0 23.0 0.2 150.0 1,300.0 15.0 23.3 17.7 15.0 - 0.5 22.6 41 16 5 3 3.6 33.0 8.0 -11.1 25 6,479 2 03 82 2,245.2 20.0 10 6B0.9 1 30.6 3 123.2 2 Zb.3 2 210.0 1 29.5 10 499.1 E 427.7 45 4,939.8 1 12.5 3 420.0 1 54.0 3 212.0 .3 80.5 4 283.8 4 699.6 1 38.0 4 366.2 106 .932.7 144.7 9.0 36.1 19.5 277.4 21.7 7.0 515.4 156.7 1.6 5.7 20.0 21.8 7.0 486.0 1.8 27.6 18.0 12.0 2.5 42.6 20.0 35 23.5 8503 EUROPE Austria Belgium Cyprus Denmark Finland France Germany, West Greece! .. Ireland! . Italy-Sicily Netherlands Norway Poland* . Portugal Romania* . Spain Sweden Switzerland United Kingdom Yugoslavia Total Europe 157,000 248,500 80.000 544,000 212,000 251300 4,000,000 589 1,800 6,500 12308 5,300 92,000 23,000 1,250 4 284 2,782 125 319 4 5 1 5 6 7 9 G 60,000 10,000,000 **438,000 500 50,000 1,800 26 63 1,012 4 is 8 50J) 3.1 26.3 133.0 -11.4 -12.6 - 3.4 22.3 3.7 28.6 - 8.6 37.5 13.6 222 788.0 1.5 -11.7 71.0 9.7 1 220.0 8 816.7 1 15.0 3 226.5 2 196.0 23 3,140.0 33 2.825.7 4 313.6 1 58.0 34 3.882.0 7 1,825.5 3 168.0 6 145.8 2 110.0 10 320.0 9 1,163.0 5 248.0 2 140.0 20 2,762.1 15,990,500 793,797 5,869 69 395.5 5.5 15G 18,110.1 ed but not developed. *Not inc luded in non-commui! 1st total. ** Government estimate djusted. 16.5 553 18.0 32.0 182.4 126.1 304.7 75.0 133 12.0 188.6 24.0 903 2.7 193 25.8 389.6 332,9 21.5 133 374.6 163.9 18.5 10.8 15.6 138.5 47.8 23.0 386.2 1,010.0 2.0883 .\l ~ , Vunh t. MIDDLE EAST Abu Dhabi Bahrain Dubai Iran IraQ Israel 21,500,000 12,500 142 4 1,285.5 '360.000 4,000 215 63.7 2,500.000 1,000 39 2 223.0 60,000,000 270,000 350 9 6,000.0 31,500,000 22.000 133 9 1,888.2 2,500 25 29 1 +100.0 Jordan Kuwait 64,000,000 32,500 692 1 2,890.2 Lebanon . Neutral Zone Oman Qatar Saudi Arabia Sharjah 17,500,000 8,000 362 1 507.5 5,250,000 2,000 97 2 271.9 6,500,000 8,000 92 3 555.5 132.000.000 50,900 627 3 7,417.9 1,500,000 1,500 * 2 South Yemen (Aden) Syria Turkey . 7,100,000 450,000 700 123 1 105.7 200 286 6 65.0 Total Middle East 350,162,500 413,325 3,187 44 21,374.1 c tlnciudss captured Sinai fields. 'Not yet producing, ttlncluded in Kuwaiti figures. 22.5 - 8.7 45.8 19.5 30.5 - 7.0 . - 3.6 -11.2 - 3.5 15.2 29.4 -12.1 18.1 1 5 6 2 1 5 2 A 2 1 1 4 31 250.0 660.0 98.5 212.0 14.1 646.0 53.5 tt 1.0 4283 162.0 513 305.5 2,882.2 342 36.0 23 12 28.6 108.3 143 41.3 5.0 27.0 1.0 204 7.3 15.1 8X 283 1683 UCC 004087 APPENDIX if ConH ) COUNTRY RESERVES 1-1-74 Oil (1,000 bill) Gas (billion cu ft) WELLS OIL PRODUCTION Producing Drilling Estimated % change ______ oil 12-1-73 1973 from j Refin- 7-1-73 n ,ooob/in 1972 REFINING ""N Capacity (1.000 b./cd' 1-1-74 [ Retorm- Crudt Craeking [ ing AFRICA Algeria Angola-Cabinda Congo Brazzaville Dahomey! ......... Egypt Ethiopia! . Gabon Ghana! ............. ivory Coast Kenya . Liberia Libya Malagasay ........... Morocco Mozambique! Nigeria Rhodesia Senegal ... Sierre Leone ........... Sudan ........... Tanzania ............... Tunisia ................. Union of South Africa! Zaire!! ................... Zambia....................... '7,640.000 1,500.009 4.888.000 5,125,000 1,500,000 25,500,000 `750 20,000,000 950,000 200,000 105,945 1,500 1,000 4,200 6,500 27,000 25 40,000 .... 1,500 50 574 10 169 5 19 3 261 4 . 122 4 895 9 22 2 898 28 56 4 Total Africa 87903,750 187,720 3,016 69 'Revised. !Oil or gas discovered but not developed. ttTo go on production 1,035.4 160.0 39.0 180.0 145.6 2,116.6 0.9 ,2 000.0 87.0 5,763.9 - 2.6 14,7 490.9 -15.0 15.4 - 4.5 4.2 10.0 4.6 1.8 115.3 24.5 30.5 1.9 4 1809 1 14.4 1.9 1 179 2.0 1 25.3 9.4 1 44.2 59 1 48.0 4.0 1 10.0 29 5 16.4 19 1 1.5 09 2 58.5 3.6 7.6 1 17.0 2.5 1 609 6.0 I (hot operating- -not included in total) 1 189 2.0 1 10.0 1 22.0 . 2.0 1 179 2.6 1 21.4 39 5 3319 55.9 46.1 1 16.1 2.7 1 24.6 5.6 39 1,092.2 59.5 13B.6 WESTERN HEMISPHERE Antiqua Argentina . . Bahamas . Barbados! ......... Bolivia............... Brazil............. Chile............. Colombia Costa Ricat Cuba .... Dominican Republic! Ecuador ............... El Salvador ............. Guatemala! ............. Honduras ............ Jamaica ............. Martinique ... Mexico................. .. Netherlands Antilles Nicaragua ............. Panama ................... Paraguay ................. Peru ....................... Puerto Rico ....... Trinidad & Tobago Uruguay ................... Venezuela Virgin Islands United States Canada Total W. Hemisphere 2.500.000 250 260,000 799.000 124.000 1.432.000 5,675,000 3,600,000 1.050.000 2.200.000 14,000,000 `34,700,249 9,424.170 75.764,669 8,000 4,096 30 442.0 10,000 253 4 47.0 921 1,265 25 170.0 3,400 466 6 30.0 2,500 2,023 8 186.0 5,000 829 197.0 11,000 4,345 45 4789 3,500 5,000 42,000. 247,310 "50,299 388.930 2*499 im 12,461 503,505 22,996 557,670 13 15 20 1,411 171 1,754 689 1599 3,3709 9.225.0 2.750.0 16,122.0 29 79 3.0 -12.8 - 5.8 148.1 8.4 19 12.4 4.7 -- 2.4 14.0 2.0 1 17.3 1.9 14 623.6 101.2 51.4 1 500.0 1 39 5 25.5 10 791.8 168.6 20.8 3 123.5 26.3 109 6 166.1 49.5 2.0 1 7.6 1.1 3 1229 14.6 11.7 2 46.0 7.0 3 35.2 1 13.7 2.1 2 26.0 69 1 14.0 1.8 1 33.0 2.3 1 14.0 29 6 6259 1099 56.3 2 945.0 35.0 159 1 13.2 2.6 1 75.0 79 1 5.0 5 106.6 6.7 1.8 3 307.8 47.8 759 3 4619 269 27.0 1 43.0 4.0 3.0 12 1,531.6 46.6 19.8 1 590.0 247 13 383.0 4,5129 3,278.1 41 1,788.1 427.6 290.0 380 22,43 6.B 5,575.9 3,897.2 tOil or gas discovered but not developed. "Does not include Arctic gas. 'Includes Alaska 10 biII ion. Total Nee-Communist 524,856,459 1297,972 576221 2,018 45,990.7 9.8 714 33,454.0 7269.1 7,142.4 CMMinist Werid `103,000,000 7735,400 9,3129 49 Total World 627,856.459 2.033.372 55212.7 8.8 'including Russia with 80 billion, Red China 20 billion, and others 3 billion. Tlncludmg Russia 706 trillion. Red China 20 trillion, Hungary 3 trillion, and others 6.4 trillion. "J/ UCC 004088 ' * APPENDIX II COUPLED CHRYSOTILE ASBESTOS REINFORCED THERMOPLASTICS F. H. Ancker, R. G. Azrak and U. D. Bertolucci Union Carbide Corporation Chemicals and Plastics Division Bound Brook, New Jersey UCC 004089 2. Introduction '' Chrysotile asbestos Cl) is a serpentine mineral occurring in nature as macroscopic bundles of colloidal-size fibers. Union Carbide's 'Calidria' asbestos is a domestic chrysotile asbestos which by specially developed wet process.beneficiation techniques has been highly purified and liberated into individual fibers having diameters of 250-300A and average lengths of 2-Sp., i.e. aspects ratios in the range of 65-200., `Calidria1 asbestos is commercially available as 1/8" diameter pellets which can be readily handled and processed with a minimum of dust generation. A new grade of 'Calidria' asbestos has recently been introduced (RG 600) where the asbestos surface has been pretreated with a : novel, proprietary coupling agent. The coupling agent treatment has markedly increased the reinforcing efficiency of chrysotile. asbestos in thermoplastic resins, especially in the polyolefins, and has also enabled dramatic improvements in process heat sta bility and heat aging of polypropylene (PP) and poly (vinyl chloride) `{PVO composites. The new `Calidria * grade RG 500 provides the fcrm.ulator and molder of thermoplastic composites with a highly . cost-effective reinforcing agent which can be used to obtain unique combinations of material properties. ' Mechanisms of Reinforcement .. Colloidal chrysotile asbestos has many inherent properties which make it interesting as a reinforcement for plastics; a) the stiffness is more than twice that of E-glass; b) the tensile . strength is at least equivalent to E-glass; c) the surface of ex truded or molded `Calidria' composites is smooth in contrast to fiberglass composites which have a rough and abrasive surface texture; d) the `Calidria' compounds can be processed ana repro cessed without fiber attrition, i.e.'without deterioration of mechanical properties whereas glass fibers undergo severe break age during normal extrusion and molding processes. On the negative side, e) the practical reinforcement efficiency attainable with chrysotile fibrils has been very much below theoretical ex pectations, especially in polyolefins; and f) the thermal and oxidative stability of labile polymers such as polypropylene and ?VC are adversely affected" by incorporation of natural chrysotile fibers. The micromechanics theories of short fiber composites have been utilized to help identify the principal causes of the low practical reinforcement efficiency of chrysotile fibrils in thermo plastic resins. These studies have shown that two principal causes are low fiber/matrix adhesion and difficulties in achieving satisfactory fiber dispersion at the colloidal level during normal compounding processes. In retrospect, it is perhaps not too sur prising that these two phenomena have such large effects on the> UCC 004090 reinforcing efficiency of colloidal asbestos fibers. * Chrysotile 'asbestos has a Brucite (magnesium hydroxide) surface with poor wetting characteristics for non-polar polymers. Due to the colloidal dimensions of liberated chrysotile fibrils, it has not been possible to determine experimentally the adhesion (interfacial shear strength) between various matrix resins and . chrysotile fibrils. However, even for the case of perfect fiber/ matrix adhesion, the critical fiber length is of the order of the average actual fiber length of 'Calidria' fibrils. For lower levels . of adhesion, the critical fiber length will be much longer which ' means that the reinforcement efficiency is in the range of extreme sensitivity to interfacial adhesion. Similarly, low levels of fiber dispersion on the colloidal levelhave the effect of reducing the apparent aspect ratio of the fibrils which again will have a ' pronounced negative effect on the reinforcement efficiency in this fiber length range. A novel class of proprietary coupling and dispersing agents has now been developed which conveniently can be applied di rectly to the chrysotile asbestos prior to pelletizing. The coupling agent used in RG600 was designed specifically to pro mote adhesion between the Brucite surface of chrysotile and poly olefins, especially polypropylene, but it has beneficial effects in thermoplastic resins in general. The establishment of true interfacial activity of the coupling agent is presented in Table I. It is seen that the coupiing agent in and of itself does not signi ficantly alter the tensile strength, modulus or heat distortion temperature (HDT) of a thermoplastic resin such as HDFE. How ever, when the coupling agent is present in chrysotile reinforced composites, improvements over uncoupled chrysotile of 53% in tensile strength, 79% in tensile modulus and 52% in HDT are found. Figure 1 illustrates the approximate concentration depen dence of mechanical properties with weight percent fiber surface coverage. An abrupt change in slope of plots comparing tensile strength, tensile modulus and HDT with % coupling agents based on the total composite weight is found at approximately 1.8% addi tive. Assuming--60 m^/g surface area for well liberated chrysotile fibers, this value corresponds quite closely to monolayer coverage of the fibrils. little improvement in mechanical properties or further reductions in mold shrinkage are observed at levels of additive above 2%. These results are classic illustrations of . interfacial activity. The improvement in dispersibility of chrysotile fibers effec ted by the coupling agent- is shown in Figure 2. Chrysotile/polystyrene composites were prepared from natural (RG144) and . modified chrysotile (RG600) with identical compounding conditions UCC .004091 and shear history. The electron micrographs show clearly the in crease in apparent fiber aspect ratios caused by the coupling ager.t treatment, - The. relative efficiency of the coupling agent in various ther moplastic polymers is shown in Table II. The tensile strength of a composite (CTc) can be expressed by the rule of mixtures I e'hfVf + Prr.d-Vj) -c where Or and Grm are tensile strengths of fiber and matrix, re- . spectively, is the fiber volume fraction and e is an over-all efficiency factor. The coupling agent efficiency (00 is -defined as (X c i.e . the efficiency factor ratio between samples with (ec) and ' without (e0) coupling agent. TableII shows that the coupling agent is highly effective in the polyolefins, exceptionally so in polypropylene, but marked effects are attained in a broad range of thermoplastics. . . RG 500 Composite Properties The following ASTM test methods were used to evaluate the composite materials: tensile properties (D-638-64T), flexure properties (D-790-66), HDT (D-64S-56), specific gravity (D-79264T), coefficient of linear thermal expansion (D-635-44), notched Izod impact strength (D-256-56). The thermal stability of chrysotile/PP blends is a particularly important property; therefore special attention was given to its determination. Sinc subjective tests such as the time to 10% or 25% crazing of the surface of a composite are a dubious measure of thermal stability, we report the induction time for a calcrimetric response to the onset of oxidative degradation as measured by a differential scanning calorimeter (DSC). Tests of thermal oxidative stability were performed on 10 mil films pressed from injection molded bars. A Perkin Elmer Model 1-3 DSC was used throughout. The stability at 230C in air was measured. Tables III and IV show that at all levels of filler, be tween 18 and 3 6% marked improvement? in tensile and flexure strengths are obtained in ?ID?E and PP resins reinforced with RG600 over natural well liberated chrysotile fibers. At the optimum loading of approximately 30% by weight, use of RGSOCtc reinforces standard grade polypropylene yields, as shown in Table V, substantial im provements in all mechanical end thermal properties when com pared to commercially available asbestos reinforced polypropylene composites. Table VI compares improvements in mechanical prop erties between coupled and uncoupled asbestos and glass poly propylene composites, respectively. Coupled asbestos/PP is close to standard glass reinforced PP in overall properties and in UCC 004092 general will compare favorably with all glass/PP composites on a cost/performance basis. Figures 3 and 4 respectively illustrate the improvements ob tained with RG600 in HDT and flexure modulus compared with unfilled PP and a RG.144/PP blend. It is clear that RG600 at the 13% level has superior properties compared with unmodified chrysotile at twice the fiber loading. At the optimum level of 30% RG600, improvements of 112% in HDT and-275% in flexure modu lus are obtained over the base resin. . Tables VII and VIII show the properties of .Nylon 6 reinforced with RG600 vs RG144 and other commonly used inorganic rein-, forcements. The superior combination .of high moduli, .strength and heat distortion at low loadings is evident. Unlike fiberglass reinforcement, chrysotile fibers have been long known to accelerate the thermally induced oxidative degrada tion of thermally, labile polymers such as PP end ?VC. The coupling agent present in RG600 inhibits.this tendency as shown in Figure 5 where at chrysotile loadings of 40% improvement cf 635% in the thermal stability under accelerated conditions are attained. With the surface modification present in RG600, as is shown in Figure 6, adequate thermal stability of chrysotile/P? blends can be achieved with reasonable levels of standard antioxidants. Formulations of RG600 at the 30% level in PPwith 0.7% hindered phenol foased on the composite wt.) and showing stabilities of 55 mtn.230C by DSC retain their mechanical strengths in excess of 703 hrs at 150C in an air circulating oven. At times approaching 2000 hrs similar composites show no sign of surface craning in a I50C oven aging test. ' The improvements attained in RG600 reinforced tnermaily labile polymers are particularly striking the the case of PVC com posites where oxidative'degradation of the matrix during hot com pounding in the presence of natural chrysotile .is 5 severe problem. A 2 00% increase in the time to significant thermal oxidative degra dation has been found in comparisons between uncreated and sur face modified chrysotile filled rigid PVC blends by a high speed mill test. At a milling speed of 110 ft/min and roll temperatures of 13DC significant discoloration and evolution of volatile chlorides occurred only after 9 minutes for 20% RG6GC blends as compared to 3 minutes for 2 0% RG144 blends. The stability of the asbestos blends under standard milling conditions is therefore significantly improved - RG600/polyolefin composites have exceptional wet strength retention, far exceeding those attainable with fiberglas reinforce ments. The data in Table IX show that even after 2 and 7 days immersion in boiling water, there is no decrease but an actual increase in the mechanical and heat distortion properties of the UCC 004093 composites. This is a singularly important advantage in a number of practical applications, Another important property in formulating reinforced .thermo plastics is impact strength. Often practical requirements will dictate a certain minimum impact strength combined with high modulus and strength. As is well known, short reinforcing fibers generally contribute little and often even detract from the impact properties of a polymer . However, unique composite properties are often attainable by the proper choice of base resin. For example, impact modified PVC and high impact polyolefins com- ^ bined with RG600 enable formulation of PVC and polyolefin base composites having overall property combinations similar to those of impact polystyrene and ABS. In general, RG 600 in the hands of skilled formulators of 'the plastics industry should open up .many unique and novel applications for reinforced thermoplastics. References: . ' (1) R. E. Byrne: `Asbestos Fibers'* Modern Plastics Encyclopedia, 386-390, 1969-1970. {2) L. Ongchin, W. K. Olender, F, H. Ancker: 'Piber/Matrix Adhesion and the Fracture Behavior of Glass Reinforced'High Density Polyethylene* 27th Annual Techn. Conf., Reinforced Plastics/Composite Institute, Soc.Plastics Ind., 1972. UCC. 004094 |T\* FIGURE 1 ' 7. INTERFACIAL ACTIVITY OF COUPLING AGENT (20% wt. Chrysotile-HDPE Composites}1 t s o ii s 11 e s t r e rtg th t p r, 1) M o ld S h rin k a g e (%) 1) Resin supplied by Union Carbide (Grade DMDJ-70GS) - ram injection molded test specimens. * Calculated wt. % coupling agent for monolayer coverage cf asbestos. FIGURE 2 ELECTRON MICROGRAPHS OF CKRYS OTILE/POIY5 TYRE NS COMPOSITE (Magnification 14,000 times) a) 30% wt. RG144 b) 30% wt. RG600 UCC .004095 .......... ...... . . 'T"' 8, UCC. 004096 HEAT DISTORTION TEMPERATURE OT PH KYSO TH E REINfORCED POLYPROPYLENE . ttOr CHRYSOTILT. R C IN IORC E p POI,Yt'ROPYU~NE o U O' c oc o oo N ifl O CO co o WO TH3I xo R* 51 li -- o C tr> cm C1O0 i to! TCJ JZ s! o cuzl\ B o -*[ -o 2 ^ < i <Cav* = * -- =S' K - CC t--r -sh=*. J>I_Z 5 O ^ u u o. u 6< # ^ ** * NC 3N -= w *'Co o n oo rsi r*c-rTJ> c >e X= o- fl1 O in 4/1 M 9 uo .fct> & o ft * NS< S ft is wt. ( t) Ram In lfc tir m m olded bars (2) H igh D ensity ro lye th ylo n o (llCC - DMDJ-700B) (3) P olypropyleno (S h e ll 5S24S) o sh c- C EU Xf0 3j o9j i=i! T--^*Jj CTi 01 i! l a 3 Si 3. Hi 3 5i O! jr --5ii XW u*.{j a 5ft?53ftr oCe S3* figr* Ixs O31. ;'gQ 0 1 ? C 3 Oo * * S$A 5>0sSS'"s ^Wo *a7 ""P-iffl=r 2c c* ~!) t--S sC e0 --4e coS.| ; *c s rao a I? s i " & C2 3 ^,,SI)i--n *emn ee A.i oOh Li U i! 3 a! S --n O 2MU3 i i vl 1 n\ *sr r> XI ul No tnf NoOn Oof|t e*vi0?r o(i(fA0t oor40t |; o^ seM tnfi ei Md] oO oOv oOnt ^ tff> O o o to 9* C O^ ** ft* S irt o go -T > cs S 5 ,Lw 6^2.- 2f,Dl ctt) s -1 So I ill z0 w 00. >1 g s k! Si lAi 2u w Ia e* ^iO ? UCC 004097 t TABU VI REINFORCED POLYPROPYLENE Reinforcement Tensile (osl) Strenoth Modulus 27% RG144 (1) * 3 * 5 5,900 27% RGC00 {1) 7,300 30% Gloss 6,100 30% Glass 14,000 460,000 580,000 735,000 800,000 Flexure (dsI) Strenath Modulus 10,400 12,900 14,000 24,000. 580,000 992,000 850.000 900,000 (1) Polypropylene supplied by Shell (S524S) (2) Modified polypropylene supplied by Hercules (PC072) HDT (C) (264 DSi) 87 123 124 153 TABLE VII CHRYSOT1LE REINFORCED NYLO.KL6 Reinforcement^) Tensile (psP Strength Modulus Flexure (pi)) Strength Modulus HDT tC) Notched leod <7 6* Mi) tft-lbs/in) 15% RG144 12,400 725,000 22,000 754,000 151 0.94 15% RG600 14,000 620,000 24,600 634,000 164 1,01 (1) Nylon 6 supplied by Tire stone (Grade 200-001) - Ram injection molded test specimens. (2) Samples contain 0.31% polyamide stabilisers based on the resin content. IAP1J5 Vllt NYLON 6 REINFORCEMENT*0 Pr*treeted Mineral Flllera Unfilled^ 15% RG600 30% WoHastoalte0) 18% Glass*** 30% Glass flexure Strength (psi) Modulus b 10*7 psi) Tensile Strength (pit) Moduli! ft ix 10' psi) NOTCHED IZOD (ft-lb/in. notch) HPT PC) 264 psi 12.000 290 8,400 330 1.31 74 24,800 834 14,000 820 1.01 ' 164 16,800 660 9,900 634 1.04 86 18.900 455 11,800 812 1.29 187 25,900 990 15.700 976 1.81 198 (1) Ram injection molded bars (2) Nylon 5 suppllad by Firestone - 200-001 <31 Wollastonite F-l pretreeted with 1% wt. amtnosllene ." . - (4) Silane treated glass relnlorcad nylon suppllad by Firestone - 415-001 end 430-001 table IX DRY-WET.MICHAN1CAIS FOR CHPYSOtILE/THERMOPIASTIC COMPOSITES^ Semple Y/t.% Fil'.er 30% RG144 30% *3600 Reftin pp(3) " 13% RG144 20% RG600 33% R350C * * Test121 fi 100C (deysi 7 7 2 2 2 ... Tensile (osl)*^ Streneth (3) 4160 6310 3990 5510 5540 Strer.cth (A) 4010 6500 3730 5560 6860 Tensile (osl x 10~3) Mod. (B) Mod. (A) 29.S 258 507 545 264 406 536 ' 215 426 589 HDT (C> Ml (A) 62 58 95 106 58 45 81 99 96 no (1) Rs.t, imecuon molded test specimens (2} Tc:J. immersion in boiling water (3) P? * Polypropylene supplied by Shell (S524S) (4i HOPE High Density Polyethylene supplied by Union Carbide (DMDJ-7Q0B) (5) Before test " (3); Alter test - (A1 ............................................................ UCC 0Q4O98_____ 10