Soluble Silicates - ACS Publications - American Chemical Society

1 A Short History of the Manufacture of Soluble Silicates in the United States JOHN H. WILLS

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The manufacture o f s o l u b l e silicates o f soda and potash i n the USA began i n the 1850's and received a v i g r o r o u s push when it was found to be a s a t i s f a c t o r y replacement for r o s i n i n the manufacture o f strong soaps during the war between the s t a t e s . Continuous manufacture o f the g l a s s was introduced by the E l k i n t o n family, soap and candle makers i n P h i l a d e l p h i a , PA. The a l k a l i n e crystallized products now used widely in detergents were developed i n the e a r l y 1930's, based on the patents and phase s t u d i e s of Chester L. Baker. In that decade, Dr. W i l l i a m S t e r i c k e r took the lead i n the development o f coated r o o f i n g granules and the manufacture o f b l a c k and white t e l e v i s i o n tubes using potassium silicate to bind the pigment to the g l a s s face. The manufacture o f c a t a l y s t and other g e l s and replacement o f phosphates i n detergents by s o l u b l e silicates and other a d d i t i v e s i n the 1950's overshadowed the l o s s o f the corrugated box i n d u s t r y to s t a r c h adhesives. What I want to cover i s something o f the i n d u s t r i a l beginnings o f the s o l u b l e s i l i c a t e s , how t h e i r use has grown, perhaps a f e e l i n g o f the burgeoning o p t i m i s t i c aspect o f the world i n which i t took root and o f the people who i n f l u e n c e d and l e d i t s growth. Much reference i s made to the P h i l a d e l p h i a Quartz Co. (PQ Co.) - now the PQ Corporation because t h i s company has been a major f a c t o r throughout the whole period and because i t has been able to make much more e a r l y d a t a available.(Ο Most of you know that the s o l u b l e s i l i c a t e s are p r i m a r i l y the sodium s i l i c a t e s which are a v a i l a b l e over a range o f concentrations and r a t i o s o f Si(>2:Na20, i n c l u d i n g water s o l u t i o n s , g l a s s e s , and c r y s t a l s according to the needs which i n d u s t r y has found f o r them. The s t o r y o f the i n d u s t r y began with a German p r o f e s s o r , Johann Nepomuk von Fuchs o f the German U n i v e r s i t y o f Landshut.

0097-6156/82/0194-0003$06.00/0 © 1982 A m e r i c a n C h e m i c a l Society

Falcone; Soluble Silicates ACS Symposium Series; American Chemical Society: Washington, DC, 1982.

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He became i n t e r e s t e d i n t h i s chemical about 1818 and i n the next twelve years worked out the b a s i c technology f o r production and suggested most of the p o s s i b l e uses as i n d i c a t e d by h i s study of i t s p r o p e r t i e s . Under r o y a l e d i c t , i t was used for a time to protect the stages and c u r t a i n s of theatres from c a t a s t r o p h i c d i s a s t e r s by f i r e s current at the time. Kuhlman in France for a period took up the l e a d e r s h i p i n European development, but von Fuchs i n 1855, j u s t before he died i n 1856, wrote a f u l l report on h i s work and suggestions f o r use of s o l u b l e s i l i c a t e s and t h i s was widely read.(2) One major European a p p l i c a t i o n was the replacement of animal dung i n a t e x t i l e process c a l l e d "dunging , and Gossage developed a very good soap using s o l u b l e s i l i c a t e . His company, C r o s f i e l d s , prospered and e v e n t u a l l y became the leading soap and detergent producer under the s t y l e of Unilever. Also about t h i s time, there was a s e r i e s of patents i n the USA f o r the p r e p a r a t i o n and use of waterglass, p a r t i c u l a r l y i n soap. These give us some i n s i g h t i n t o the men who began the i n d u s t r y i n the USA.(3) The p r a c t i c e of shipping s o l u b l e g l a s s as b a l l a s t seems to have been a major problem f o r would be manufacturers i n New York and Boston. Philadelphia was the center of American chemical i n d u s t r y at the time and seems to have been b e t t e r s i t u a t e d . R e l a t i o n s between the North and South were s t r a i n e d , and the expectation of war threatened the supply of colophony or r o s i n on which the many small soapers r e l i e d for the p r e p a r a t i o n of stronger laundry products.(4) Most of these soapers a l s o made candles, and kerosene lamps were r a p i d l y reducing the demand for them.


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I n d u s t r i a l development of sodium s i l i c a t e i n America begins with Dr. Lewis Feuchtwanger. He had studied about 1830 with Professer Dobereiner at Jena. The professor had been f a s c i n a t e d by Fuchs reports and was working with s o l u b l e silicates. Feuchtwanger brought h i s enthusiasm home with him and w r i t e s that i n 1832, with the permission of Admiral Perry, he c a r r i e d out some s u c c e s s f u l t e s t s at the Brooklyn Navy Yard. The cannons were protected from rust for several years by a coating of mixed sodium s i l i c a t e and asphaltum. He a l s o extended the l i f e of the wooden docks s e v e r a l times by impregnating the wood p i l e s and substructures with d i l u t e sodium s i l i c a t e . The saturated wood prevented attack by teredo worms. He probably bought t h i s s i l i c a t e from Germany and d i s s o l v e d i t here but he does c l a i m that he was manufacturing i t i n 1869.15) I have found no other evidence that he had a p l a n t , but a Mr. Sawyer of P i t t s b u r g h , Pa. reported i n 1864 that he had been buying from Feuchtwanger(1_), and i n 1867 a t r e a t i s e on soap making states that Mr. D i e t e r i c h s , chemist for the " A t l a n t i c 1



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Quartz Co. of West P h i l a d e l p h i a " had also been buying from him.(6) I have found no other reference to t h i s company i n any d i r e c t o r i e s . Feuchtwanger's f i r s t p u b l i c a t i o n seems to have been w r i t t e n out longhand, although i t i s p o s s i b l e that the manuscript I saw had been copied from h i s book, a p r a c t i c e not uncommon at the time. J.M. Ordway deserves mention i n our record for besides the patents f o r making a l k a l i s i l i c a t e s by reducing sodium s u l f a t e and preparing an e a s i l y s o l u b l e powder by coacervating the l i q u i d noted e a r l i e r , he published an a r t i c l e on the h i s t o r y and use of s o l u b l e s i l i c a t e i n S i l l i m a n ' s Journal i n 1861 and a s e r i e s of a r t i c l e s i n the American Journal of Science i n 1861, 1862, 1865 and f i n a l l y i n 1907; an a c t i v e s c i e n t i f i c l i f e o f 45 years. In h i s a r t i c l e of 1861 ( 7 ) , he gives a complete de s c r i p t i o n of the state of the a r t from melting to d i s s o l v i n g . He was already aware that the raw m a t e r i a l s should be o f the highest p u r i t y and that soda ash was e a s i e r to use. Since sodium s u l f a t e was cheaper, the r e a c t i o n was f u l l y s t u d i e d . Glass furnaces from which i t was p o s s i b l e to draw a l i t t l e fused s i l i c a t e at a time and then add more charge were used. Consistent r e s u l t s were d i f f i c u l t to o b t a i n and he recommended melting the charge completely and drawing the melt at once. He mentions furnaces with beds of 24 and 40 square f e e t . Four charges of Na 0:2.5 S i 0 could be completed i n 24 hours. The charge was drawn i n t o i r o n pots, cooled, and ground to a d e s i r e d s i z e with cast i r o n , toothed, crushing r o l l e r s . If drawn i n t o water, i t would break i n t o small fragments which were d i f f i c u l t to dry. However they were r e a d i l y d i s s o l v e d by heating the water. The d i s i l i c a t e was e a s i e r to d i s s o l v e and was recommended for the c a l i c o p r i n t e r s . With soda ash as a l k a l i source he could draw s i x charges a day. 2

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In P h i l a d e l p h i a , a young Quaker named Thomas E l k i n t o n was coming o f age. His father had gone i n t o the manufacture of soap and candles i n 1831 a f t e r 15 years of missionary work with the Seneca and Iroquois Indians at Tunessassa, N.Y. Having served h i s time and needing to support h i s family, he followed a cousin i n t o t h i s new venture which required not only manual d e x t e r i t y but b a r t e r i n g s k i l l s and f a m i l i a r i t y with ship captains. The r e l a t i o n s h i p of the E l k i n t o n family of soap makers i n P h i l a d e l p h i a with a group s t y l e d v a r i o u s l y as the New York S i l i c a t e Co. or the New York Quartz Co. or the New York L i q u i d S i l i c a t e Co. as well as with J . M. Ordway and Hodges, S i l s b e e , and Richardson of Boston encompasses the r e a l foundation of the manufacture of s o l u b l e s i l i c a t e s i n t h i s country. Thomas E l k i n t o n was a young man of 22 when i n about 1857 he became i n t e r e s t e d i n applying s i l i c a t e s to the soap made by h i s f a t h e r . Q ) A f t e r he had read van Fuch's l a s t survey and had copied Gossage's E n g l i s h patent i n t o h i s j o u r n a l , Thomas E l k i n t o n bought i r o n pans for a furnace and i n 1858 spent $2.50


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for plans for a r e v e r b r a t o r y furnace. B r i c k s were ordered i n 1861, and the f i r s t four b a r r e l s of s i l i c a t e were sold i n e a r l y 1861. His US patent #39135 f o r a continuous furnace issued i n 1863. The design included a l l the b a s i c requirements f o r a s i l i c a t e furnace. This new furnace was b u i l t i n 1863 f o r $1,100. While the f i r s t attempt was a f a i l u r e because o f inadequate or inaccurate mixing of the sand and soda ash, h i s next attempt ( a f t e r a month given to d i g g i n g out and r e p a i r ) ran f o r a month and produced 122,000 pounds o f g l a s s . His patent and perhaps h i s other a c t i v i t i e s a l e r t e d the group i n New York. G. T. Vanderburg, Secretary o f the New York Quartz Co., obtained US patent #31648 i n 1863 and assigned i t to the L i q u i d Quartz Co. o f New York. T h i s improvement covered a soap i n which the added s i l i c a t e had a r a t i o o f Si02:Na20 above 1. Vanderburg had a l s o obtained US patent #28540 i n 1860 for a process f o r reducing a s i l i c e o u s substance to a f l u i d state using superheated steam. At about the same time, Thomas bought 10 pounds o f ground s i l i c a t e o f soda from the New York Quartz Co. and he a l s o met with Vanderburg to d i s c u s s the Gossage patent, perhaps at the time the ground g l a s s was ordered.(1) He had bought l i q u i d s i l i c a t e from them i n A p r i l , 1861. So, e a r l y i n 1864, the president of New York S i l i c a t e or Quartz Co. John Graecen, J r . and the Treasurer, Samuel Booth, approached Thomas and h i s brother Joseph at t h e i r soap f a c t o r y , 783 S. 2nd S t . , t h e i r father having passed the company t o them i n 1862. The New Yorkers mentioned that they owned the Vanderburg soap patent and suggested that i t was being i n f r i n g e d . At the same time, they h i n t e d that they were a l a r g e and f i n a n c i a l l y sound company which could a f f o r d to manufacture s i l i c a t e at a p r i c e which would run the E l k i n t o n brothers out of the b u s i n e s s . They suggested a r o y a l t y of 1/4^ a pound f o r an a r t i c l e which sold f o r hi a pound, only 25% l e s s than today's bulk p r i c e o f 5.6^. The upshot was that a p a r t n e r s h i p was arranged, and the P h i l a d e l p h i a Quartz Co. came i n t o being as of February 25, 1864. The E l k i n t o n brothers were to be the a c t i v e partners and were to " c a r r y on the business i n accord with their religious principles." The New Yorkers arranged to l e a s e a property at 9th & M i f f l i n Streets from t h e i r e a r l i e r partner, a P h i l a d e l p h i a soap and candle maker with whom the brothers d e c l i n e d to be a s s o c i a t e d . This property was sold to Graecen and Booth i n 1867, and then on December 22, 1868 the E l k i n t o n brothers bought out t h e i r partners for about $23,000. In 1863-1864, Hodges, S i l s b e e , and Richardson o f I n d i a Wharf, Boston a d v e r t i s e d as agents for the New York Quartz Co. and the P h i l a d e l p h i a Quartz Co. Hodges was c u r i o u s and experimented with the production of s o l u b l e s i l i c a t e s using both ash and s a l t cake which r e q u i r e s C as a reducing agent and a l s o an o x i d i z i n g agent to get r i d of the d i s c o l o r a t i o n by the carbon. He described h i s work i n l e t t e r s to Thomas E l k i n t o n .



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In 1872, a f t e r the bankruptcy o f the New York Quartz Co., the Ordway patents were assigned f i r s t to Samuel Booth as r e c e i v e r and to Ordway and thence were assigned to Hodges and Co. Also i n 1872, the Vanderburgh patents were assigned to Booth by Ordway. F i n a l l y , i n the same year, a l l of these patents were assigned e q u a l l y to Coolidge and Hodges of Boston and the E l k i n t o n brothers o f P h i l a d e l p h i a . At about t h i s time Hodges advertised that h i s f i r m was the s o l e manufacturer i n New England at the Bayside A l k a l i Works i n South Boston. This i s r e a l l y the s t o r y of the beginning o f a l k a l i s i l i c a t e manufactured i n North America. The volume grew slowly. In 1893 Thomas wrote to C u r t i n , Hughes and Kellogg o f Boston that the commerical papers were u n l i k e l y to quote p r i c e s for a l k a l i s i l i c a t e s . He kept only small stocks f o r "outside users are so t r i v i a l that a chance order for a few g a l l o n s or b a r r e l s at a time w i l l cover the order."(1) The Centennial E x p o s i t i o n held i n P h i l a d e l p h i a i n 1876 seemed to dramatize the growth and excitement o f the times. Many companies had e x h i b i t s ; i n c l u d i n g Feuchtwanger and the Elkinton brothers. The P h i l a d e l p h i a Quartz Co. received the highest award of merit for "a most b e a u t i f u l e x h i b i t of s i l i c a t e of soda" according to one commentator. They had an a r r e s t i n g experiment i n which b l a c k , o i l y cotton rags used to wipe clean the many steam engines at the e x h i b i t i o n were washed with s i l i c a t e and turned out a l o v e l y s o f t white c o t t o n . The e a r l y development of furnaces and d i s s o l v e r s came at j u s t the r i g h t time, f o r the war between the s t a t e s i n 1861-1864 d i d cut o f f the r o s i n supply and created a demand f o r t h e i r product. The E l k i n t o n s had the advantage that they a l s o produced soap next door to the s i l i c a t e p l a n t . The s a l e o f s i l i c a t e was welcome, but e a r l y s a l e s records show only a few b a r r e l s . However, i n 1889 the P h i l a d e l p h i a Quartz Co. b u i l t a new plant at Anderson, Indiana r i g h t over a gas w e l l . It i s the oldest s i l i c a t e plant s t i l l producing and was next door to the l a r g e soap p l a n t of Peet Brothers. This e s t a b l i s h e d a custom s t i l l recognized i n the i n d u s t r y of s e l l i n g s i l i c a t e by p i p e l i n e . The F o r t v i l l e Chemical Co. was b u i l t near Anderson i n 1896 and was bought by G r a s s e l l i Chemical Co. i n 1902, as part of t h e i r expansion i n the a l k a l i business. Mechling Brothers b u i l t a plant i n Camden, NJ i n 1902 and the P h i l a d e l p h i a Quartz Co. expanded i n t o a l a r g e r plant on the Delaware River at Chester i n 1905. The Merrimac Chemical Co. at Lowell, Mass. produced s i l i c a t e i n 1890. This plant was acquired by Monsanto i n 1929. The Mechling p l a n t s , by then owned by A l l i e d Chemical Co, are now c l o s e d . One reason there i s very l i t t l e information on producers and s e l l e r s o f s i l i c a t e s i s that few people came seeking them. I assume that a drummer f o r s o l u b l e s i l i c a t e s came i n t o town, checked the l o c a l d i r e c t o r y (before phone books and yellow pages) and v i s i t e d a l l the l o c a l soap makers. In P h i l a d e l p h i a


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i n 1860 there were 45 and 22 i n New York. A s p e c i a l f a c t o r i n t h i s sales program was Charles Goudy, an Englishman with a broad background i n chemical manufacturing before c r o s s i n g the Atlantic. He s e t t l e d i n Marshalltown, Iowa for reasons having to do with h i s wife's h e a l t h and set up a very s u c c e s s f u l soap business. About 1876, he and Thomas E l k i n t o n , one or both, conceived the idea of a small machine c a r r i e d i n a s u i t c a s e which could demonstrate the use of s o l u b l e s i l i c a t e i n soap i n the would-be customer's o f f i c e . Goudy became a leading f i g u r e in PQ Co. and continued to t r a v e l u n t i l he was 80. He was t h e i r f i r s t development chemist and one of the f i r s t i n our chemical i n d u s t r y . In l a t e r years he was joined by h i s son George who had experience i n soap manufacture p r e v i o u s l y and became a leader i n PQ Co. as well as an i n d u s t r i a l statesman. The Growth of the Industry There i s a long l i s t o f companies and works b u i l t , bought, s o l d , merged, enlarged, or dismantled. The record i s not always c l e a r or exact and seems unnecessary to review. Figure 1 attempts to show the growth of production from 1850 to 1980 i n terms o f the l i q u i d s i l i c a t e which i s most common. This curve i s a composite from s e v e r a l sources, not a l l of which agree, and I have not t r i e d to show the y e a r l y ups and downs which appear when the annual census f i g u r e s are p l o t t e d . The curve follows i n a general way the growth of population as well as the gross n a t i o n a l product, but i t i s u s u a l l y hedged against depressions by the growth of the i n d u s t r i e s i t serves as well as i t s cost which makes i t a candidate for r e p l a c i n g more expensive items. The f i r s t f i f t y years are a record compiled by W.T. E l k i n t o n o f the production by the P h i l a d e l p h i a Quartz Co., p r i m a r i l y f o r the E l k i n t o n Soap Co., but f o r many other customers. I t does not include imported m a t e r i a l or the production by known competitors such as F o r t v i l l e i n 1896 or around Boston. I would suggest that the l i n e represents from 50 to 75% of the s i l i c a t e used up to 1900. This growth was p r i m a r i l y for use i n soap. James G. V a i l joined PQ Co. i n 1905 before f i n i s h i n g c o l l e g e . He then f i n i s h e d h i s formal chemical education at the I n s t i t u t e of Technology, Darmstadt, Germany, became president of the U.S. S o c i e t y of Chemical Engineers i n 1945-46 before r e t i r i n g f i n a l l y i n 1952 and wrote the major books on s o l u b l e s i l i c a t e s issued i n 1928 and i n 1952,(3) the year he d i e d . Soluble s i l i c a t e s as an adhesive had long been used i n small amounts when i n the 1890*s there began an i n t e n s i v e and continuing e f f o r t to produce paper boxes to compete with the wooden packaging then i n general use. Paperboard with a corrugated p l y between two sheets and complex machines were developed. The l a t e r development o f adhesive and cement uses


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of s o l u b l e s i l i c a t e s has been reviewed on adhesives and cements.(8)

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Hydrous S i l i c a t e s During much o f the same period there was a l e s s important but more g e n e r a l l y known a p p l i c a t i o n that i s for the p r e s e r v a t i o n o f eggs. Many people had t h e i r own chickens or were canny enough to buy eggs when they were cheap i n the s p r i n g and summer. They kept ceramic crocks i n the c e l l a r f i l l e d with d i l u t e waterglass. The excess eggs were placed i n the crocks and the s i l i c a t e reacted with the s h e l l preventing e i t h e r l o s s or increase i n the water content o f the egg, entrance o f i n f e c t i v e agents, or l o s s o f the a i r c e l l and even when kept nine months of so they were s t i l l poachable. George Goudy conceived the need for a powdered s i l i c a t e which could be r e a d i l y d i s s o l v e d at home. Using L.B. Edgerton's patents issued i n 1916 ( 9 ) , f o r atomizing l i q u i d s i l i c a t e s , a d e s i c c a t e d s i l i c a t e was produced and sold as "Goudy s Egg P r e s e r v e r " i n 56oz. packages which would make 7 g a l l o n s o f d i l u t e d waterglass, a l l f o r one d o l l a r . Demand appeared to r i s e a f t e r the war, and i n 1930 arrangements were made to i n s t a l l a spray tower imported from Germany. With the i n c r e a s i n g use o f r e f r i g e r a t i o n and l a r g e s c a l e continuous production o f eggs, the market for egg preserver evaporated, but other developments such as muds for d r i l l i n g through heaving shale areas kept the new l a r g e r d e s i c c a t i o n tower i n operation. 9

The Development of the A l k a l i n e S i l i c a t e s f o r Detergents I suppose there are s t i l l soapers who consider s o l u b l e s i l i c a t e s an a d u l t e r a n t , a derogatory word. Following World War I, many researchers c a r r i e d out vigorous programs o f i n v e s t i g a t i o n and w r i t i n g to demonstrate the s e v e r a l ways i n which s o l u b l e s i l i c a t e s act as detergents themselves and a i d as b u i l d e r s i n c l e a n i n g i n combination with soaps and other detergents. J.D. C a r t e r ' s papers published about 1930 have been considered c l a s s i c s i n the f i e l d as they set out c r i t e r i a for s o i l i n g and measuring detergency.(10) Even before the f i r s t world war, the c l e a n i n g i n d u s t r y had begun to d e s i r e more a l k a l i n e detergents. The P u r i t a n Soap Co. suggested combinations of s i l i c a t e and soda ash, but a l l such combinations seemed l i a b l e to cake i n t h e i r c o n t a i n e r s . Chester L. Baker, a f t e r an e a r l y i n d o c t r i n a t i o n i n the c r y s t a l l i z a t i o n o f commercial borax and other s a l t s of S e a r l e s Lake, CA, i n 1927, became C h i e f Chemist of the P h i l a d e l p h i a Quartz Co. of C a l i f o r n i a , an a f f i l i a t e formed i n 1917 and owned 50% by the S t a u f f e r s . Baker arid l a t e r h i s a s s i s t a n t , Ralph Jue, worked long hours developing the phase r e l a t i o n s h i p s f o r the c r y s t a l l i z a t i o n of hydrated m e t a s i l i c a t e s o f sodium over


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the range o f 0 to 90°C. They e s t a b l i s h e d the e x i s t e n c e o f and c a r e f u l l y described the p h y s i c a l c h a r a c t e r i s t i c s o f the 5, 6, 8, and 9 hydrates and the c o n d i t i o n s f o r t h e i r appearance and disappearance.(11) They a l s o found and d e s c r i b e d the s e s q u i s i l i c a t e Na3HSi04.5H 0 (3Na 0:2Si0 :11H 0). They showed that a s o l u t i o n c a r e f u l l y prepared at the composition o f Na Si03.5H 0 ( N a 0 : S i 0 : 5 H 0 , pentahydrate) could be seeded and allowed to c r y s t a l l i z e i n a soap mold and then ground and s i z e d . Since there was no excess l i q u i d s i l i c a t e , the product was s t a b l e enough to ship from San F r a n c i s c o through the humid Panama Canal to P h i l a d e l p h i a without c a k i n g . T h i s was taken as the c r u c i a l t e s t f o r a commercial product, and h i s work became the b a s i s f o r the great development o f the a l k a l i n e s i l i c a t e powders. The f i r s t sales were made i n C a l i f o r n i a i n 1928. Later he brought out the s e s q u i s i l i c a t e and l a t e r s t i l l worked out the process f o r a granulated sodium m e t a s i l i c a t e . 2

2

2

2

2


2

2

2

2

In 1980, the c a p a c i t y o f sodium m e t a s i l i c a t e as penta hydrate was about 580 m i l l i o n pounds. PQ Corporation i s s a i d to have the l a r g e s t c a p a c i t y with S t a u f f e r and Diamond-Shamrock f o l l o w i n g i n that o r d e r . By c r o s s l i c e n s e with PQ Co., Pennwalt developed a hydrated form o f o r t h o s i l i c a t e r a t i o about 1938. I t was an i n t e g r a l product made by mixing NaOH with the necessary amount o f another s i l i c a t e or s i l i c a . I f the c r y s t a l l i z e r was kept t u r n i n g , the mixture went through a higher temperature f l u i d s t a t e and g r a d u a l l y transformed i n t o p a r t i c l e s which were s t a b l e enough f o r commercial use. I know o f no phase diagrams showing the e x i s t e n c e of s t a b l e Na4Si04 ( 2 N a 0 . S i 0 ) or i t s hydrates, and the process i s no longer used. A l l s o - c a l l e d o r t h o s i l i c a t e i s now compounded and i s included i n the meta s i l i c a t e f i g u r e s . As shown i n Table I, the production o f these a l k a l i n e products not a v a i l a b l e before 1928 i s now v e r y l a r g e . 2

2

Table I USA Production i n M i l l i o n s o f Pounds o f Sodium M e t a s i l i c a t e ( C a l c u l a t e d as Pentahydrate) and o f Sodium Orthois i l i c a t e Na Si0 Year Na9Si0^:5H 0 9

1928 1929 1930 1940 1950 1955 1960 1965 1970 1976 1979 1980

0.3 e s t . 1.8 e s t . 4 est. 40 e s t . 198 314 386 502 450 378 433 336

4

4

0 1 est. 60 76 60 76 76 84 72 63 52 60 e s t .


S O L U B L E SILICATES

12


The Development of Other End Uses The chemist who bore the brunt of the i n t r o d u c t i o n o f these new detergents to the laundry and metal trades was W i l l i a m S t e r i c k e r . He always maintained that no l e a d i n g detergent or laundry soap ever held a l e a d i n g p o s i t i o n for a long period without i n c l u d i n g a good p r o p o r t i o n of sodium s i l i c a t e . From the time, 1922, when he earned h i s graduate degree at Mellon I n s t i t u t e studying the p r o p e r t i e s of sodium s i l i c a t e , he developed an uncanny sense of how to use i t i n commerical processes.(12) It was mainly h i s i n s i g h t which helped the developers of r o o f i n g granules, welding rod c o a t i n g s , o s c i l l o g r a p h c o a t i n g s , methods for preventing c o r r o s i o n i n s u s c e p t i b l e water systems, and c o a g u l a t i o n with a c t i v a t e d s i l i c a s o l s for the c l a r i f i c a t i o n of water and sewage. Just before the second World War the new detergents and non-soap compounds were appearing, and S t e r i c k e r was a leader i n working with soap and detergent a s s o c i a t i o n s to e s t a b l i s h the e f f i c a c y of s i l i c a t e s i n such systems where phosphates were g e n e r a l l y accepted. F i r s t , he demonstrated the n e c e s s i t y f o r the a n t i - c o r r o s i o n p r o p e r t i e s o f the s i l i c a t e s . This development was e s p e c i a l l y welcomed by our i n d u s t r y because the s t a r c h adhesives developed with a l k a l i and borax i n the 30*s l a r g e l y replaced the s i l i c a t e adhesives for box making i n the 50's, and t h i s l o s s caused much c o n s t e r n a t i o n among us. The g e l a t i o n of s o l u t i o n s of s o l u b l e s i l i c a t e s with a c i d s and a c i d i c s a l t s i s very o l d , but i n d u s t r i a l development began with the Wheaton patents i n England about 1922,(13) These were for base exchange g e l s f o r s o f t e n i n g water and were used through the 30's when they were g r a d u a l l y replaced with organic agents of higher c a p a c i t y . Newer v e r s i o n s are now being used i n detergents. Desiccant g e l s also began to appear i n the 30 s and Davison Chemical Co. was the c h i e f developer. The use of c a t a l y s t g e l s i n the petroleum i n d u s t r y boomed with World War II. The s i l i c a s i n f i n e l y d i v i d e d form and as s o l s came along during and a f t e r the war. Much of the s i l i c a t e production for use i n these areas i s c a p t i v e . The l i t h i u m s i l i c a t e s ( 1 4 , 15) which became a v a i l a b l e i n the 5 0 s are more expensive but are u s e f u l i n b i n d i n g c o r r o s i o n r e s i s t a n t coatings to i r o n , i n cements, and i n molds. f

The C o n t r i b u t i o n s of James V a i l James V a i l was a great p u b l i c i s t . Besides w r i t i n g many a r t i c l e s and r e p o r t s on a l l phases of s i l i c a t e technology, he put out a small monthly sheet - P's and Q*s - for over twenty years, and t h i s was known i n the chemical i n d u s t r y f a r beyond the s i l i c a t e f i e l d . In 1928, he published ACS Monograph #46 "Soluble S i l i c a t e s i n Industry" and t h i r t y years l a t e r he acceded to many requests and wrote ACS Monograph #116 "Soluble



1.

WILLS

History

of

Manufacture

in the

United

13

States

S i l i c a t e s " i n two volumes.(3) While much has happened s i n c e 1952, the book has not yet been replaced as the primary reference for s o l u b l e s i l i c a t e technology and should be reviewed f o r references and b a s i c information on processes and products I have so b r i e f l y mentioned. James V a i l was a man of great i n s i g h t , a poet, author, and above a l l a humanitarian. He c a r r i e d out s e n s i t i v e , s i g n i f i c a n t , supportive programs i n many parts of the world f o r the American Friends Service Committee of which he was Foreign Secretary f o r a long p e r i o d , about 1938 to 1948. He was i n India on such a mission when he d i e d . In h i s f i n a l paragraphs of Chapter 1 of h i s l a s t book, he notes the r i s i n g world population and the need to conserve resources not r e a d i l y r e p l a c e d . He notes there that phosphates are i r r e p l a c e a b l e and badly needed for f e r t i l i z e r i n a g r i c u l t u r e . Food resources continue to be scarce, and he p o i n t s out that a r a t i o n a l s o c i e t y would preserve phosphates both by conserving t h e i r use i n detergents and r e f u s i n g to spend energy and f e r t i l i z e r for the production of starches and p r o t e i n s for i n d u s t r i a l use which could j u s t as well be replaced by s o l u b l e s i l i c a t e s prepared from s a l t and sand, raw m a t e r i a l s abundant i n t o the foreseeable f u t u r e , " . . . s o l u b l e s i l i c a t e s now serve so wide a range o f i n d u s t r y that they are to be regarded as a fundamental part of any long range planning for the conservation of n a t u r a l resources.(3) F i n a l Comments Perhaps t h i s i s a good place to stop. Table I I shows an estimate of the c a p a c i t y f o r production o f most o f the p l a n t s i n the USA. Table I I Capacity of the Soluble S i l i c a t e Industry i n the USA i n 1981 i n B i l l i o n s of Pounds o f Sodium S i l i c a t e L i q u i d Equivalent to 3.22 Si02:Na 0 Ratio by Weight at 42° Baume 2

Producer Diamond Shamrock duPont de Nemours PQ Corp. Chemical Products Grace Chemical PG Corp. E t h y l Corp. Engelhard J.M. Huber Associated Minerals Total

Plants 7 5 12 1 1 2 1 1 2 1

Capacity, pound 1.3 0.7 2.2 0.1 0.4 1.1 0.4 0.04 0.5 0.02 6.8

(10

captive tt

u II If


SOLUBLE

14

SILICATES

Table I I I gives an idea of the amounts r e q u i r e d by major a p p l i c a t i o n s (75% of c a p a c i t y as o f 1 9 8 0 ) . 29

Table I I I Soluble S i l i c a t e Use i n 1980 i n B i l l i o n s o f Pounds of L i q u i d Product Equivalent to 3.22 S i 0 : N a 0 Weight Ratio at 1.39 S p e c i f i c G r a v i t y 2


Application C a t a l y s t s and Gels Soap and Detergents Roofing Granules, Ceramics, T e x t i l e s , Rods, Foundry, e t c . Pigments Boxboard, Adhesives Ore, Paper, Water Treatment Total

Volume, pounds

2

9

(10 )

1.3 1.2 0.7 0.6 0.3 0.3 4.4

(or

75% of c a p a c i t y

New a p p l i c a t i o n s keep cropping up and o l d ones appear i n new guise. Soluble s i l i c a t e s are u s u a l l y r e l a t i v e l y inexpensive, but t h e i r s e n s i t i v e p r o p e r t i e s have to be understood and handled competently. Many a p o t e n t i a l a p p l i c a t i o n has f a i l e d because necessary precautions were not taken e i t h e r i n the use or i n the s t o r i n g and h a n d l i n g . The manufacturers have r e p r e s e n t a t i v e s ready and able to h e l p . I have mentioned only a few o f the i n d i v i d u a l s o f the many who have helped expand the a p p l i c a t i o n o f t h i s product which has so much to recommend i t . The b a s i c raw m a t e r i a l s , water, s a l t , and pure sand are a v a i l a b l e i n e s s e n t i a l l y u n l i m i t e d q u a n t i t i e s at low c o s t . While they r e q u i r e c o n s i d e r a b l e energy in p r e p a r a t i o n , they seldom cause environmental problems and r e a d i l y r e t u r n to the s o i l . They are inorganic m a t e r i a l s which, i t seems t o me, are only at the beginning o f t h e i r development by man. Anyone who contemplates the place o f s i l i c a i n n a t u r a l organic and inorganic systems has to r e a l i z e that we have a long way to go before we r e a l i z e the f u l l p o t e n t i a l of t h i s product which e x c i t e d the imagination o f Fuchs and others 150 years ago. As we go into the l a s t twenty years o f t h i s century, I am f i l l e d with optimism, not only because o f the a p p l i c a t i o n s which now appear promising and the i n c r e a s i n g l y e f f i c i e n t operations which the computer age suggests, but because I f i r m l y b e l i e v e we have not yet discovered a l l of nature's s e c r e t s about the a b i l i t y of s i l i c a to bind or r e a c t with i t s e l f and other substances. The development of detergents, adhesives, g e l s , s o l a r heating or power systems, f i r e prevention, and the i n c r e a s i n g understanding of chemical and p h y s i c a l bonds a l l suggest to me that we can expect the production curve to continue to r i s e .


1.

WILLS

History

of Manufacture

in the United

States

15


Literature Cited 1. Historical File - T. Elkinton's Journals and W.T. Elkinton's Compilation (1931), etc., The PQ Corporation, Valley Forge, PA. 2. Von Fuchs, J.N., "Bereitung, Eigenschaften und Nutzanwendung des Wasserglasses mit Einschluss der Stereochromie"; Literarisch-artistische Anstalt: Munchen, 1857. 3. Vail, J.G. "Soluble Silicates" 1 and 2, ACS Monograph Series #116; Reinhold Publishing Corp.: New York, 1951 (Chap. 1, especially p. 4-7, gives a brief historical review). 4. Annual Record of Scientific Discovery, Wells, D.A., ed.; Gould and Lincoln: Boston, 1864. 5. Feuchtwanger, L. "Practical Treastise on Soluble of Waterglass" 3rd ed.: New York, 1875. 6 Ott, A. "The Art of Manufacturing Soap and Candles"; Lindsay and Blakiston: Philadelphia, 1867. 7. Ordway, J.M., American Journal of Science and Arts, 2nd Series, 1861 32 153-165, . 8. Wills, J.H. :"Adhesion and Adhesives", De Bruyne, N.A.; and Houwink, R., Ed.; Elsevier Publishing Co., Amsterdam, 1951. 9. Edgerton, L.B., U.S. Patent 1194827 and 1198203 (1916). 10. Carter, J.D., Ind. and Eng. Chem.18,248 1926; 23, 1289 1931. 11. Baker, C.L. and Jue, L.R. J. Physical Chem. 1938 42, 165; J. Physical and Colloid Chem. 1950 54, 208. 12. Stericker, W. in J. Alexander "Colloid Chemistry" Chemical Catalog Co., Inc.: New York, 1928p289. 13. Hilditch, F.P. and Wheaton, H.J., U.S. Patent 1717777 (1929); 1879239 (1929); 1848127 (1932). 14. Iler, R.K. U.S. Patent 2668149 (1945). 15. Cuneo, F.L. U.S. Patent 3392039 (1968). RECEIVED March 2, 1982.


Soluble Silicates - ACS Publications - American Chemical Society

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