John Mercer and Mercerization, 1844 SISTER VIRGINIA HEINES Nazareth College, Nazareth, Kentucky and got a little of all kinds of stuffs the dyers used, wilh ihe names w r i l f a on each. Weavers at this time having plenty of cotton fents, I was thus well provided with all that was required, and by ringing changes and labelling all the results I was able to dye all the colors then in use. Kot having convenience where I lived, I took a man to join with me, who had a sufficient building for a dyehouse, with water near, and we dyed for the inhabitants of Great Harwaod and the surrounding villages (I).
NE hundred years ago marked the discoveryof a process very important to the textile industry. The man who made it was a self-taught one, without the advantage of a technical education, but by indomitable energy and perseverance he has left behind him a name that will always be known and revered in the dyeing and printing trade. John Mercer was born on February 21, 1791, at Great Harwood near the town of Blackburn in Lancashire, England. His father had owned a small spinning mill but lost it through financial reverses and turned to farming. The failure of his crops in 1799 left him a broken-hearted man and left his family in poverty. His death followed in a few months. To help his widowed mother support the little family, nine-year-old John went to work as a tenter for ahand-loom weaver, and in a few years became a weaver himself. Very little is known about his early education beyond the fact that a t the age of nine he was receiving private instruction in the three R's from one of the workers in a local print shop. He became interested in the dyeing of cloth and spent the few pence he could spare each week for coloring materials. In 1806 while on a visit to his mother, who had married a second time, he was especially attracted to the bright orange color of his stepbrother's dress and fded with the burning desire to learn the art of dyeing. In an outline drawn up by Mercer for his son, he says:
His success with dyes attracted the attention of the proprietors of the Oakenshaw Print Works, near Manchester, and they offered him in 1809 an apprenticeship in their color shop. A year later the great depression in the English printing trade forced his employers to release the apprentices and Mercer went back to handloom weaving with regret. Probably he would not have soreadily given up the work, but "obstacles had been constantly thrown in his way by his superiors, the men of mysteries and jealousies, a type which existed in those days and which unfortunately are not yet extant, men of few receipts, little knowledge and less common sense" ( 2 ) . For three years he worked a t his loom and saved enough money to buy a weaving business of his own. I t is related that on his way to get his marriage license he stopped at a stall to purchase a few books. One of these was a used copy of the "Chemical Pocket Book" arranged in a "Compendium of Chemistry" by James Parkinson of Hoxton (3). His marriage to Mary Wohlstenholme on April 14, 1814, was a happy one, and his description of their long years together is deeply stirring. The book of chemistry introduced Mercer to a new field of knowledge. He readily saw the need of it to interpret his failures and adopt other methods of experimentation. This led to his first important discovery in 1817 of a new orange dye, produced by passing calico through a solution of antimony sulfide dissolved in sodium sulfide, followed by passage through a dilute solution of sulfuric acid. The orange was of much hrighter hue than had been made before with annotto. While on his way to show his new color to Hargreaves, Dngdale & Co., proprietors of the Broad Oak Print Works, Accrington, he met John Fort of the Oakenshaw Print Works. Fort offeredMercer a situation as experimental chemist in the color shop for five years at 30 shillings a week. He accepted and remained with the firm for about 25 years, entering the partnership in 1825. During this time he contributed many important discoveries to the calico-printing trade and the Oakenshaw Print Works enjoyed a long period of prosperity (22).
How to begin was my difficulty. There was no fancy dyer in our village; I had no acquaintance with anyone who knew anything of dyeing, and I had no books that would help me. The villagers wore mostly dyed cotton at that time, and got them dyed at Rlackhurn. I therefore went to a druggist at Blackburn,
The foundation of the mercerizing process seems to have been laid in Mercer's preoccupation with substances capable of forming definite hydrates in solution.
0
MERCERIZATION
He made a number of viscosity experiments with the hope of finding a variation in flow that would indicate the extent of chemical hydration. He thought to bring about a partial separation of the different hydrates by fractional filtration and while engaged in filtering alkali-makers' red liquor (4) observed that the cloth contracted in the wetted portions. In his own words: For this purpose I made a filter composed of six folds of strong cotton cambric passed three times through the calendar to make it compact and poured upon it a solution of caustic soda of 60"Tw. The filtration was very slow; the liquor passed through was of 53O Tw (as well as I remember). But I found my filtering cloth had undergo& an extraordinary change; it had become semi-transparent, contracted both in length and breadth, and thickened or "fulled" as I then termed it. I then spotted bleached cambric with single drops of caustic soda of 60" Tw and 50" Tw, and noticed that the central portion of ezch drop (about the size of a shilling) became semi-transparent and contracted; around this was a rim of a quarter of s n inch, neither semi-transparent nor contracted, which evidently contained little soda ( 3 ) .
This preparation of "fulled cloth" took place in 1844, but it was not until 1848 when Mercer dissolved the partnership of the Print Works that he had sufficient time to devote to his discovery. He found that the alkali could be removed by washing with water, but a change in strength of the caustic on filtering led him to believe that a definite compound was formed by the cotton retaining some of the alkali, but that it broke down leaving a molecule of water attached to the cotton. I t was a t this time that Robert Hargreaves of the Broad Oak Print Works Accrington, offered him assistance in return for a share in the mercerizing patent. He accepted and the patent was filed in the year 1850. The principal part of his process is thus described in it: The mode I adopt of carrying into operation my invention to cloth made wholly or partially from any vegetable fibres and bleached is as follows: I pass the cloth through a padding machine charged with caustic soda or caustic potash a t sixty or seventy degrees Twaddles' hydrometer. a t the common temperature, a t , say, sixty degrees Fahrenheit, or under, and without drying the cloth wash i t in water, then pass through dilute sulphuric acid, and wash again, or I run the cloth over and under a series of rollers in a ci tern with caustic soda or caustic potashat from forty t o fifty degrees of Twaddels' hydrometer, a t the common temperature of the atmosphere, the last two rollers being set so as to squeeze the excess soda or potash back into the cistern; the cloth then passes over and under rollers placed in a series of cisterns charged a t the commencement of the operation with water only, so that a t the LaJ cistern the alkali has nearly been all washed out of the cloth; when the cloth has either gone through the padding machine or through the cisternsabove described, I wash thecloth in water, pass it through dilute sulphuric acid, and wash again in water (5).
I t is interesting to read a contemporary comment on the discovery. Gladstone in his article, "On the compounds of cotton with alkalies," says: The beautiful effects produced by Mr. Mercer through treated cotton with a cold solution of caustic soda, are well known not only to the scientific world, but through the medium of the Great Exposition, to the public in general. Yet, I believe the chemical c o m ~ o u n ditself has not hitherto been investigated (6).
After a series of experiments, Gladstone came to the conclusion That the combination of the soda with the cotton has effected permanent change upon it is certain; when regained, it is contracted, and takes dyes better; but the question arises: Is this merely a physical alteration or has a real chemical change of the lignine taken place? I am inclined to view the "mercerized" cotton as chemically identical with the original substance.
The change that takes place in the physical condition of the cotton is best observed under the microscope. The fibres in their ordinary state appear as flattened twisted ribands; but the moment they are treated with the alkaline ley [sic lye] they untwist themselves, and contract in length, as they swell out, assuming a rounded solid form; and their circular appearance (7) they retain after the soda is removed from the water. Thus the shrinking is explained, and I think also the superior character of the colours which mercerized cotton is capable of exhibiting. Far the substance of the fibre itself is of a porous nature and will of course absorb a larger quantity of the dye when expanded, than when compressed into a flat twisted band, and as this takes place in the same space, a greater intensity of colour must be the result. From the observations it appears that lignine is capable of forming a combination with soda, the proportion of the alkali varying with the strength of the solution employed, but in no instance exceeding one atom, and that this compound is decomposed by water, being resolved into its original compounds (6).
In one of our modem texts we read this explanation of the above as it is interpreted today: In this process the cotton is passed through a 30 per cent NaOH Eath in the cold to give a sodium cellulose and then washed well with hot and cold water to give a hydrocellulose. The surface fibers are changed slightly in composition resulting in a product with a greater sheen. By this treatment the flat cotton fibers become cylindrical and thicker and increase in weight from 8-10 per cent. They also become smooth and translucent and possess a luster similar to that of silk (8).
and in another: The cause of the mercerizing effect is not yet clear. I t seems that the difference between native and mercerized cellulose depends on various physical and ciystallographic changer. Their x-ray diagrams are different( 9 ) .
Mercer had not mentioned the art of crimping in his patent, but he quickly devised a method for craping cotton and exhibited samples of various patterns at the London Exhibition. Arthur Morris in his "Mercer and Mercerization" gives us a clear idea of how this was done: If part of the cloth is protected from the action of the lye, for instance, by printing an i t a strong gum paste in parallel strips, the "unreserved" portion of the fabric alone contracts. Therefore, when the gum is removed by steaming, the contracted part draws with it the non-mercerized fibres, and as they have more space to fill, they crinkle up, producing a crepe effect. Specimens of all these applications were shown a t the Great Exhibition of 1851. Doctor Lyon Playfair, the elder, perhaps the leading scientist of the day, declared these samples to he one of the two most remarkable exhibits in the building. Her majesty, who prudently declined the numerous presents pressed upon her by the exhibitors, made two exceptions. She accepted with gratification a handkerchief of "contracted cloth" prepared by the process of Mr. John Mercer (10).
Dr. Playfair lectured upon the invention before the
British Association, saying that Mercer had his attention drawn to the subject as early as the year 1844. He displayed stockings of open weave and showed that the mercerization process made them appear of a much finer texture besides taking colors better and increasing the strength and brilliancy (11). Mercer's reputation as a research chemist was now well established but several factors prevented, the commercial success of his discovery. A keen competition of the calico-printing trade necessitated low prices for cloth, and the cost of sodium hydroxide a t £26 per ton was too high. There was much objection to the loss of material due to shrinkage. This contraction of cloth by the mercerization process amounted to about 25 per cent in each direction (12). However, despite these drawbacks its future possibilities as a commercial product may have been foreseen by some, as he was offered £40,000 for his patent but could not obtain the consent of his partner to sell. Tension in the crimping and craping of cloth was not used by Mercer, yet it is strange he did not notice that the uneven tension of the cloth between the rollers of the roller-cistern dyeing machine produced a kind of luster. Possibly it was due to the fact that only fabrics made from short cottons lacking natural luster were used (13). It was not until 1890, when H. A. Lowe, a Manchester chemist, took out a patent for mercerizing under tension, that the foundation of the modem mercerizing industry was laid (14). Lowe's patent was declared void by the English courts in 1897, but the real commercial tension process dates from this time, and in 1921 the Society of Dyers and Colonrists awarded Lowe its highest honor, the Perkin Medal for the production of a permanent luster on cotton (12). The enterprising Fremh dyers, Richard Thomas and Emanuel Prevost, located in Crefeld, Germany, definitely established the value of mercerization under tension, and men identified with the industry began to realize its possibilities. Thomas and Prevost tried to patent a method to prevent shrinkage, and a production of luster, but their patents were declared invalid by English, German, and American courts because of Mercer's and Lowe's earlier discoveries. In spite of this their business progress was rapid and by 1897 their firm was mercerizing considerable quantities of cloth. Until the spring of 1897,the English andGerman progress attracted little attention in America. There is well-authenticated evidence that the J. R. Montgomery & Co.. Windsor Locks, Conn.; the Pennypack Yarn Finishing Co.; the William H. Lorimer's Sons Co., Phil., and the Aberfoyle Mfg. Co., Chester, Pa., were mercerizing skein yarns in a limited but satisfactory manner early as the summer of 1897, and that Jos. Bancroft & Sons Co., were experimenting with cloth mercerizing. It was not until after John Bancroft of the latter fum returned from Europe in the fall of 1897 that they commenced to make regular deliveries of mercerized dath on contract. The J. R. Montgomery & Co., still retain their 1897 records showing deliveries starting in June 1897 to several firms who later became competitors in the mercerizing business (13).
A complete "Bibliography of Mercerization" is given in the American Dyestuf Reporter for 1937. This
assembles in one list the references to most all the journal articles on mercerization and related snhjects which have appeared since the original patent in 1850 to the end of 1935. The articles are grouped according to the year of their publication and arranged alphabetically by their authors' names. The reference to each article is followed whenever possible by a reference to an abstract of the article in some standard abstract journal. All titles of foreign articles are given in English (15). INVENTIONS AND HONORS
The mercerization of cotton in 1844 was only one of a long'list of his discoveries. So numerous and varied are the topics that a classified list would be difficult to give. Among the more prominent ones may be included: an ingenious process for discharging indigo blue by means of alkali and red prussiate of soda (17); improvements in chrome colors (16); "scouring salts" used for cleaning woolen fabrics; bleached palm oil for a soapery in 1839 near Accrington; invention of a vegetable parchment; artificial manures; experiments on catalysis, and the chlorination of woolen and mixed fabrics of wool and cotton, whereby greater facility for retaining colors is given to wool. Had Mercer patented this last process of chlorination there would have accrued to him a large fortune but he gave it to the priuting trade with no reservations ( 1 ) . This inveterate experimenter was greatly interested in theoretical chemistry, and his theory of catalysis provided Playfair with ideas that led to the discovery of the nitroprussides (26). We read in a letter to Playfair that he anticipated Pasteur's germ theory (26). Although the discovery of the solubility of cellulose in cnprammonium hydrate is attributed to Schweizer (18),according to Parnell (3) the effectwas first noticed by Mercer. In 1855 he presented a paper before the British Association at Leeds, "On the relation of the atomic weights of the families of the elements " (19). During his leisure moments he had worked out some interesting relationships between atomic weights of several elementary substances. In an 1854 memorandum, he says: "I have at times thought about the arrangement of atoms, but my conjectures are not so plausible probably as those of Gmelin. Still there are to my mind, difficulties in his arrangements" (22). Seven patents were granted to him and collaborators (25): 1. Processes ta be used in the dyeing or colouring of cotton, woolen. silk, or other yarns. August 1. 1839, to John Mercer, John Dyneiey Prince, William Blythe. 2. Manufacture of articles used in printing and dyeing cotton, silk, woolen, and other fabrics, November 10, 1842, to John Mercer, John Barnes. . Manufacture of certain chemical agents used in dyeing and printing cottons, woolen, and other fabrics. July 8, 1845, to John Greenwood, John Mercer, John Barnes. 4. Dyeing Turkey-red and other colours. June 22, 1846, to John Mercer, John Greenwood. 5. Certain materials used in processes of dyeing and printing. Octoher 12. 1849. to John Mercer. William Blythe. 6. Preparation of cotton and other fabrics and fibrous materials. October 24, 1850, to John Mercer.
7. Preparing cotton and fabrics for dyeing. March 15, 1852, to John Mercer, John Greenwood.
Photography was one of his favorite hobbies, and he was the first to apply it to the production of patterns on calico. A brief entry in an old memorandum book says:
in keeping with the curiously slow evolution of the process which kept his memory green. Mercerization was of no commercial value during his life time" (10).
I spotted a piece of white cotton with solution of pernitrate of iron, and exposed it to the sun; on testing it afterwards with a solution of red prussiate of potash it gave a blue, but it gave no blue before exposure. This is.worthy of note. I have not seen it noticed by any chemical writer (22)."
Mercer worked at length on the photochemistry of iron salts and at the British Association a t Leeds in 1858 exhibited colored photographs on paper. Some of these were sent to the Journal of Photographers Society of Vienna. A picture of Mercer used for the February, 1941, frontispiece of THIS JOURNAL is a reproduction of a photograph made by himself on cloth by means of a light-sensitive mordant (23). He acted as judge for the Great Exhibition of London of 1851 and again in 1862. After much hesitation on his part, he accepted a Fellowship in the Royal Society of London at the annual meeting, June 3, 1852 (201, and was later elected to honorary membership in the Literary and Philosophical Society of Manchester and the Glasgow Philosophical Society. Mercer had two sons and three daughters. The son named for him followed closely in his footsteps. Gifted with a keen mind and aptitude for chemistry he was afforded all the advantages denied his father. After attending Edmonson's Academy a t Blackburn, and University College, Edinburgh, at the age of 21 he assumed management of his father's business, later establishing a cotton-spinning firm a t Great Harwood, under the title of Mercer, Brother & Co. Like his father, he held many township officesand was elected to the Chemical Society of London (24). Seeking no honors, the elder Mercer lived a simple and unselfish life, endearing himself to all who knew him by his kindness and generosity to the poor whose struggles and hardships he could well understand. Like many another great scientist he was fond of music, and when no longer able to attend public performances he contented himself with listening to the music of his children's voices. After a long and painful illness borne with exemplary resignation, he died on November 30, 1866, a t the advanced age of 75 years. In the "Obituary notice" of the Fellows of the Royal Society of London for 1868 (21) we see the name of John Mercer, Esq., listed, and yet even here, his name may often have been overlooked, for occurring in this same list is that of the great Michael Faraday, who died one year later than Mercer. His remains were interred in the family vault a t Great Harwood, but fully a generation passed by before his native town honored him with a monument in the form of a clock-tower. "This tardy recognition was
Cou~trrya/ Terlile World
JOHNMERCER AT Gne~rHARWOOD, ENG.(FROM "MERCERIZATION.") MONUMENT TO
The part of the invention that Mercer valued the most and others the least became successful about 30 years after his death. LITERATURE CITED
(1) "Obituary notice," I. Chem. Soc., 26, 395 (1867). (2) PENNINGTON, RockdaleLit. & Sci. Soc. Trans., 7 , 2 1 (1901). (3) MARSH,"Mercerising,'' Chapman & Hall, London, 1941. (4) SANSONE, Textile World, 65, 797 (1924). (5) British Patents, 13,296, 1850. (6) GLADSTONE,J. Chem. Soc., 5, 17 (1853). (7) CRUM,ibid., 16,404 (1863). "Outline , of Organic'Chemistry," Barnes & (8) D E G E ~ N G Noble, New York, 1941. (9) KARnEn, "Organic Chemistry," Nordemann Publishing Company. New York, 1938. (10) Monnrs, Magazine of Commerce, 3, 103-6 (1903). (11) P~aYaArn,British Association Reportr, 21, Part 2, 51 (1851). Am. Dyestuff Reporter, 13,612 (1924). (12) GOLDTHWAIT, (13) CLARK,Textile World, 65, 782 (1924). (14) British Patents, 4, 452 (1890). AND CADY.Am. Dyestuff Reporfcr, 26, 446-60 (15) EDELSTEIN (1937). MERCER, British Assodation Reports, 28, Part 2, 57 (1858). MERCER, J. pmk. Chem., 42.43-5 (lW7) Sc~waIzsn,ibid., 72, 109 (1857). MERCER,British A ~ s o ~ i a t i m RePorts, 28, Part 2, 57-8 ,,QCQ>
I'YYY,.
Proc. d R o y . Soc. (London). 6 (June3, 1852). Ibid., 16, 53 (1858). PARNELL, "Life and Labours of John Mercer, F.R.S., F.C.S.." Lonmans. Green & Comoanv. London. 1886. RHEINH~LDT. J-CHEM. EDUC., 18,8oi194i). "Obituary notice," I. Chem. Soc., 37, 260 (1880). "Index of Patents of Invention," Part 1, 1617 to 1852, London. 1854
