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SHELTON BAR IRON and STEELWORKS

Below is a handout produced by the Training Department (Human Resources' in the modern terminology) 

As early as 1341 Iron and Steel were made in Staffordshire, but it was not until 1837 that Lord Granville leased land from the Duchy of Lancaster to begin iron-making at Etruria. By 1839 Blast Furnaces were being built which were blown in on January 4th, 1841, and were the best in the district, at that time being situated on the north east side of the present day Cobridge Road.

About 1850 Forges and Mills were erected and in 1852 new Blast Furnaces were built on newly leased land on the Etruria Hall estate. In 1835 Lord Granville built a railway line to enable a much speedier carriage of products. The year 1858 saw the erection of Blast Furnaces on the present site used, and by 1860 there were eight in blast. The Company at this time was known as the Shelton Bar Iron Company, and mined their own coal and ironstone. It is important to note that Shelton was one of the pioneers in the use of coke in the Blast Furnace.

More Rolling Mills and Puddling Forges were built in 1864 and records show that by 1874 there were ninety Puddling Furnaces and eight Rolling Mills at Shelton. Records for the year 1880 show a drop in the number of Blast Furnaces to five.

In 1885 improvements were made to the Mills and Open Hearth Furnaces were erected which used producer gas as fuel. These changes having taken place the name of the Company was altered the following year to Shelton Iron and Steel Company, with Lord Granville as its first Chairman. A further name change took place in 1891 when it became the Shelton Iron, Steel and Coal Company.

Between the years 1905-1914 Coke Ovens were erected which led to Shelton having a surplus of Pig Iron. It was this Pig Iron which attracted the attention of J. Summers and Sons Ltd, of Shotton and led to Shelton's acquisition by them in 1919. (Pig Iron was sent to Shotton from Shelton until 1958). In 1920 production of wrought iron ceased and the following year the Works was made up of a Coke Oven Plant, 3 Blast Furnaces and one being built, five Open Hearth Furnaces, 32", 18'', 12" and 10" Mills and a small Sheet Mill.

The Collieries belonging to the Company were nationalised in 1947 and in 1951 the firm was nationalised but was de-nationalised two years later, An Ore Preparation Plant and Sinter Plant were built in 1957.

The very important decision to replace the Open Hearth Furnaces and the 32" Mill was made in 1959; the new plant to cost in excess of twenty million pounds. Work was commenced in 1961, and completed in 1964, Re-nationalisation took place in 1967, and in 1968 the now aged and out-dated Coking Plant ceased production.

In March, 1970, the Corporation regrouped its Works into six Product Divisions, the main Shelton Works becoming part of the General Steels Division, whilst the Shelton Construction Department went into the Construction Division.

The 18" Mill was closed in June, 1971, after a very important and useful lifetime.

Today the present plant consists of:

1. Ore preparation plant and Sinter machine.

2. Three Blast Furnaces, (The largest - No.1 has a 17ft Hearth).

3. Pneumatic steelmaking plant - 2 x 70 ton Kaldo converters.

4. Continuous Casting plant - 'Concast' - 4 machines with a total of 11 strands

which mainly produce 360mm x 200mm (14" x 8"), 410mm x 280mm (16¼ " x 9") and

460mm x 3200 (18" x 12½").

5. Universal and Structural Rolling Mill - interchangeable stands together with the necessary straightening stacking and loading devices

Main products:

Channels from - 178mm x 76mm (7" x 3") to 305mm x 102mm (12" x 4").

Universal Columns 203mm x 203mm (8" x 8") and 152mm x 152mm (6" x 6").

Universal Beams 203mm. x 133mm (18" x 54") to 406mm x 140mm (16" x 5½").

Other products are Joists, Angles, Guide Rails, Tees and certain Special Sections.

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Aerial View of Shelton Bar (Sentinel Photo)

Sentinel Report

SHELTON BAR  -  A FAMILY CONCERN IN MANY WAYS

UNTIL the news last year that there was grave concern over the future of Shelton Works, the steelworks perhaps meant little more than a local landmark to most people of North Staffordshire. It was the place that caused the warm red glow in the night sky over the Potteries. With the shock of recent announcements —closure of iron and steelmaking by 1975 - local interest in the future economy of the area has been uppermost in the minds of many people who rely on the works for their livelihoods.

Shelton Bar, as everyone best knows the works, have been part of our local scene since 1837, when Lord Granville first leased land from the Duchy of Lancaster to begin ironmaking at Etruria. Ironmaking is probably the oldest of North Staffordshire's industries, with records showing the existence of early primitive furnaces in the Cheadle and Madeley areas as far back as the 13th century, and iron ore being mined in 1378 in Silverdale, Burslem, Tunstall and Chesterton.

Shelton's first blast furnaces were "blown in" in January, 1841, on the North East side of Cobridge-road and H. G. Wells has probably made these early furnaces immortal by writing a gruesome story "The Cone" based upon a brief stay in the area and a visit to the ironworks.

Throughout the 19th century the Shelton Bar Iron Company, as they became known, developed as one of the major local employers. Josiah Wedgwood's village of Etruria, created as a community for his potters, became the home of the iron and steelmakers and, ironically, Wedgwood's own home, the impressive Etruria Hall, still stands loftily on the industrial skyline as the main offices of the present day steelworks.

By the start of this century the steelworks had become the Shelton Iron, Steel and Coal Company. The works began to produce their own coke for firing their furnaces and gave employment for hundreds of men at the Racecourse, Florence, Hanley Deep, Holditch and Silver dale Collieries, as well as the huge workforce employed on their by now giant Etruria site.

The Shelton collieries were, of course, nationalized in 1947, and by 1964 the works had taken a brave and major step to secure their own future in a competitive steelmaking world by commissioning a £20 million new plant and pioneering the use of the then revolutionary continuous casting process. In 1967 the works were nationalised and became part at the giant British Steel Corporation.

Apart from these signposts in the history of the works, their activities have been largely unobtrusive on the local industrial scene. Shelton Bar from early days had built their workforce upon a tradition of long serving employees from whole families of local people and, together with nearly a century-and-a-half of almost continuous full time employment, this has helped to create a working environment and climate in which there have been no spasms of industrial unrest to hold even local headlines and the works have an unrivalled record for trouble—free industrial relations.

The long serving tradition at Shelton continues to this day. The works last year held a series of presentations for employees with more than 30 years service and more than 600 of the 2,500 workforce, including over 100 with more than 40 years, were presented with awards; a remarkable record.

The family tradition still exists as well. Computer programmer Pamela Dunn of Ashford-street, Shelton, is the fifth generation of her family to work at Shelton. Wally Wesley, Havelock-place, Shelton, of the Transport Department, has four sons all now basing their careers at the steelworks and there are many more examples, too numerous to mention.

In a closely knit and rather insular community it would be hard to find a North Staffs. family who have not relied upon part of their ancestry building their livelihood from Shelton Bar. Men like Bill Figgins, of Mulgrave-street, Cobridge, now 92, who started work at Shelton at 12, in 1892. He became one of the works best known characters as a steam locomotive driver and still attends Shelton's club for retired employees, along with scores of his old colleagues.

Over 600 of the present workforce live near the works in the Cobridge, Etruria and Shelton areas and the continued prosperity of these localities is still largely dependent upon the steelworks and their future.

Although the steelworks are something of a local industrial giant, with their 265 acres of industrial activity yielding £300,000 per annum in rates, the plant employees little more than one per cent of the mammoth B.S.C. workforce.

Lord Melchett, who visited the works early in March, has announced some of the details of the corporation's £3,000 million 10-year investment programme.

It centres on major development of five main bulk steelmaking sites and of special steel plants in the Sheffield-Rotherham area, plus building a major new steel complex at Redcar.

The five sites are Port Talbot and Llanwern in Wales, Ravenscraig in Scotland, Lackenby on Teesside, and Scunthorpe, Lincolnshire.

The object of the strategy, which has been fully agreed between the Government and B.S.C., is to create an efficient profitable industry able to compete with the rest of the world and assure future employment.

It has been forecast that B.S.C. steelmaking capacity will be increased from its present level of about 27 million tons to between 33-36 million tons in 1982.

The Shelton steelmen now know that the present iron and steelmaking plant at the works will cease operations by 1975, although the rolling mill will continue indefinitely employing about 950 people. The works is currently highly profitable and successful.

___________________________________________________________________________________________________________

As the battle to keep Shelton open continued the Victoria Theatre put on a play about the fight.

Polly Warren wrote the words to a rousing song to the tune of 'The Beggarman'
This is it.

1. We've been making iron at Shelton Bar since 1839,
    And through the years of war and strife, we've stood the test of time,
    But now they want to turf us out and throw us with the scrap,
    They must be bloody barmy if they  think we'll stand for that!

Chorus

    We're Shelton Men, We're not afraid, we've got our dignity,
   We'll fight and win the battle, boys, against the BSC
    They may be strong and powerful but that won't get them far,
    For we are all united now to fight for Shelton Bar!

2. The Sinter and Blastfurnace men are with us every one,
    They've joined the fight, although for them thre's nothing to be won,
    Electric Arcs don't need them, but they're proud and spirited men,
    They'll give all they've got and more, and won't surrender even then!

Chorus

3. We know we make a profit, and we know our steel's the best.
    Men  with money, brains and business sense are ready to invest,
    We get our orders out on time, we never get complaints,
    We're too bloody good to be alive, they ought to make us Saints! 

Chorus

4. And now they want to close us with their ten year strategy,
    They don't care about the man who has to face his family,
    The Kaldo and Con Cast men will fight it tooth and nail,
    To save their jobs and keep their pride - we know they'll never fail!

Chorus

5. They want to keep our Demag Mill, the finest in the land,
    And put the rest in mothballs, just to keep it near at hand,
    But we have got another plan, I'm sure you will agree,
    Put the BSC in mothballs, and then Shelton will be free!

Chorus

I represented the technical staff on the Action Committee (I was the Secretary of the Company's ASTM group at the time).
As we now know our steel industry, such as it is, is foreign owned and declining. The Rolling Mill has gone, so Stoke's industrial heritage continues to wither.

My Time at Shelton Bar (1962 – 1978)

1962: 18 years old, 6 ‘O’ levels to show for 2 years full time study at Stoke Technical College (which grew to be a Polytechnic and now a University). Having registered with the employment exchange I received a letter from them telling me I had an interview at Shelton Iron and Steel Works on Friday with the Chief Chemist.

The interview was a rigorous grilling:

“You have ‘O’ levels in Maths, Physics and Chemistry?”

“Yes”

“You don’t mind shift work?

“No”

“Can you start Monday?

“Yes”

“Nine o’clock”

He now stared at me, probably to check that I was actually alive and breathing, I got the feeling I was supposed to leave. So I did.

Two weeks working 9 to 5 to learn how to be a Junior Shift Chemist (aka Pig Iron Man).

Raw materials come into the Works and basically they are turned into iron by Blast Furnaces, which are cast (via a casting machine) into small ingots called ‘pigs’. This iron has about 3.5% carbon and other impurities that have to be removed (by refining in Open Hearth Furnaces) to produce steel, which typically will have 0.2% carbon.

The pig iron man must analyse each sample of iron that comes in on his shift. As a Blast Furnace becomes ready (i.e. the iron is molten and in suitable condition) it is ‘tapped’. The molten metal is released from the base of the furnace and as it runs out a long handled ladle is used to take a sample.

Slag is also run off at this time and is also sampled. Slag is a by-product of the process of iron production and is made up of added limestone which fluxes with the unwanted products from the reduction of iron ore to a molten iron. After the iron has been cast another sample is taken (because additions are made to the molten iron to reduce some more of the impurities, particularly sulphur content.) The results were recorded in a hard backed notebook, one for each furnace, and these did get a bit tatty after a while. The results were transferred, by a day chemist, into a proper ledger that had every page printed to show the date, tapping time and a headed column for all the elements.

To carry out this analysis you need equipment and chemicals. Each chemist is allocated cupboard space and must maintain their own stuff. Making up mixtures of acids (q.v. appendix) is a time consuming business, (try adding concentrated sulphuric acid to water; it is known as an exothermic reaction – water gets hot fast, so must be cooled between each addition of acid. Get it wrong and the glass container will crack or the solution will boil over), so pinching someone else’s is a sin. If the guy finds you out and is bigger than you it will be apparent how big a sin it is!

The acids and alkalis we use are delivered in 2½ litre bottles that we call Winchesters. The made up solutions are stored in the empties.

Distilled water was made in a gas heated cast iron enclosed container. The steam was forced into a pipe that fed into a large wooden barrel. Oxygen was filtered through the barrel to prevent carbon dioxide pickup. Constant boiling water was made available by filling 2 litre glass flasks and leaving them to boil on hotplates. Most of the hotplates were made up of firebricks and gas rings topped off with a thick steel plate, although a few were electric.  These were mostly situated under extractor hoods; there was also a fume cupboard with a pull down shutter with glass window to seal obnoxious gases of from the laboratory and our lungs!

The next rung of the ladder is the Bath Sample Man; when the Open Hearth furnaces have fully melted, the iron scrap steel and the slag making elements added, the steel in the ‘bath’ is sampled and sent to the Lab for rapid analysis. On the basis of this result the metal will undergo further refining or be ‘tapped’ if ready.

If the former then another sample will be taken later and the process repeated until the furnace is ready.

The Carbon Man analyses the Bath sample for its carbon content (you deduced that already? So sue me). This involves a piece of apparatus called a carbon train (appendix).

He was also responsible for the analysis of the final sample after the furnace had been tapped. Various additions would be added to the molten metal to give the solidified steel the required properties. As with pig iron the results would be recorded in a hard backed notebook. The final analysis of the steel after tapping was recorded directly into a pre-printed ledger – the Carbon man was charged with this task, legibility being a paramount requisite.

The samples (of both iron and steel) were delivered to the Lab via pneumatic tubes. The canisters would swish across the works at breakneck speeds; the results would be returned the same way, although the Bath sample results would be reported by telephone as well. He was also in charge of the shift when the Foreman was absent (i.e. at weekends).

This is the result sheet that was filled in and sent:

Finally the Shift Foreman: he analysed Blast Furnace slag, Basic (steelmaking) slag and other bits and bobs that the Day chemists may have lumbered him with. Oh! And supervising (on the night shift this involved ‘getting his head down for a few hours, wake me if World War 3 starts’).

The Lab consisted of 3 long wooden central benches with cupboards down each side and large sinks at the ends and a bench adjacent to the wall. The building was set out something like below.

The building itself was detached and sat at the top of a grassy knoll a few hundred feet in from the main Etruria entrance. Next door was the Nurses Station used for first aid and examinations.

Anecdotes.

The elongated area between the benches made an ideal ‘pitch’. The plastic top from a winchester bottle made a great football (puck). The puck would travel at fantastic speeds if you kicked it just right and if you could get it airborn it really flew.  Great fun on noons and nights. However it did have drawbacks; missing and hitting a corner of the bench was excruciatingly painful (I have two misshapen big toenails to prove how bad I was at this game.) A flying puck could and did break things. On more than one occasion a large window pane would be broken on the night shift; a chemist would be at the local glaziers at 6.00 am to buy the appropriate size of glass and some putty. The pane would be replaced and the putty aged with some dirt. The only evidence that remained during the following day was the lingering smell of the putty.

The propensity of certain (all!) shift foremen to get their head down has been mentioned. One such had the habit of bringing a blanket and small pillow to facilitate the endeavour and to ensure the hussle and bussle of work did not interrupt his dreams he would break into the locked Chief Chemists office and there lay his head in peace and quiet. However one night he had to leave his bed slightly early due to the inconvenience of work and forgot to remove his ‘bed’ prior to going home. Whoops!   Needless to say he arrived at work the following night with some trepidation. No letter of admonition or indeed any sign of accusation was to be found, except the ‘bed’ had been taken up, neatly folded with the pillow perched on top and placed on a chair – in the locked office. The evidence was retrieved and no mention of it was ever made. I fancy our Chief Chemist was not the type of man who enjoyed confrontation.

The Day chemists, supported by members of the morning shift, would play Bridge during their dinner hour. This was a popular pastime at work; it was a pity we had no idea how to play. On the night shift the serious card games were played: Newmarket , Solo Whist, German Whist and the big favourite Brag. All the games were played for money of course, but brag was the one were you could win or lose a lot. Winning 10 shillings (50p) in those days was a big deal (my starting pay was £5.2s a week).

There are occasions when a solution needs to be agitated vigorously to bring about precipitation of a substance (e.g. phosphorus in iron and steel). This was done by ‘wobbling’. Take up the 600 ml beaker off the hot plate (wearing rubber finger protectors), add the precipitating agent and spin the liquid by wrist movement anticlockwise; once the solution is well in motion whip the beaker away from you vigorously clockwise so that the solution’s direction of motion is reversed. This produces a satisfying ‘whop’ sound. Repeat half a dozen times in rapid succession. Watching a master of the wobble is awesome. You need to practise with cold water first! Getting a faceful of hot acid is not recommended. If you were a wimp then stirring with a glass rod with a rubber end would do the job (like beating an egg) – but where is the fun in that? Nowadays they have electric stirrers…boring.

If you are unfortunate enough to drop a winchester of hydrochloric acid onto the laboratory floor, it is very rare that it bounces. Acrid fumes quickly fill the area and you need to take quick action. The situation is saved as follows: first, everybody opens all windows; second, all but the idiot vacates the premises at a speed that ensures breathing acid fumes is not an option; third, the idiot fetches a winchester of ammonium hydroxide and, while holding his breath, chucks it into the centre of the previous crash site. He then legs it at a pace.  A rather satisfying fog is produced which begins coating everywhere with a white dust; once all the dust is settled chemists return to clean up and wipe down.

The idiot is ostracised for the remainder of the shift.

Back to the serious stuff.

The Day Chemists, of which there were 3 (and supported by the shift foreman q.v. appendix, analysed the incoming iron ores, burnt lime, sinter, scales and all ‘unusual’ materials that came in from time to time.

Employees were expected to attend college one day a week, studying either chemistry or metallurgy.

I can’t for the life of me remember what we did when on nights and going to college; did we have the night before off, the night after?

When I started the Works was part of the John Summers Group, their main steelworks being based in Wales . Nationalisation followed, which broke that connection and left the company as an ‘independent body’. The conversion to a rapid refining method (Kaldo Furnaces) and a Continuous Casting Plant brought about changes. A new laboratory was built; a cheap insubstantial building that also incorporated offices and the Fuel Department (a group of felons who did engineering type things around the Works). Rapid steel making required even faster analysis than could be provided by wet chemistry. The solution was a Hilger and Watts Fluorite Vacuum Polychromator. Needless to say that mouthful was shortened to Polyvac. The Polyvac was housed in its own air-conditioned room and consisted of a power unit (about 5ft tall, 4ft wide and 2ft deep), The emission chamber and vacuum chamber leading to the Polychromators (5ft by 6ft by 3ft) and an electronic consul, which converted the electrical output to percentages (5ft by 2½ft by 2ft). The percentages were sent to a large electric typewriter that hammered out the results machinegun fashion. I would love to see the modern equivalent of this machine – it’s probably portable! The samples were solid circular tubes of steel that were cut through and polished prior to being analysed by the machine.

Pig Iron continued to be made as usual so the Pig Iron Man (Junior Chemist) was as before, but now we had a Junior Polyvac Operator and a Senior Polyvac Operator as well as the Shift Foreman who was redesignated as Senior Shift Chemist. As well as the Polyvac room we had a sample preparation area that was manned by blue-collar staff obtained from the Steelmaking area. These neer-do-wells were all ‘characters’, which was probably why they were inflicted on us – they were far too good at Brag, Nap, Cribbage and Dominoes. The wet lab was similar in layout to the old building.

Having moved through the ranks I was eventually promoted to Lab Supervisor and left the shift system in 1972. The card school in the dinner hour moved to bridge; I got really hooked and eventually went to play at a Bridge Club – a new stage in my life had begun.

Fred Brown using the Polyvac.
He is cleaning the silver electrode prior to putting the sample in the machine. Once enclosed the chamber is flushed out with argon to ensure the spectra is pure. The excited atoms are collected and converted to a percentage for each element and the result printed by the electronic typewriter. The result is rung through to the Kaldo foreman who then decides whether further refinement is necessary or the metal is ready to pour.

 This is the preparation area.
Jack (the sample prep man) is setting up the automatic saw to cut a part required by the Fuel Dept lad in the white safety helmet.
The white circular object in the foreground to the left is a knocking-up pot for preparing pig iron samples (to produce a powder sample).
In the background is a tall feature which is a drill for producing the traditional samples for wet analysis if the Polyvac were to malfunction.
The large machine (with the motor attachment) is the circular saw used for cutting the Kaldo samples. These come via pneumatic tube in the form of a cylinder of steel. These are cut in half and the cut surface is polished with a surface grinder to produce a flat surface suitable for use in the Polyvac.

Photograph showing the wet laboratory.
Here the ores, sinter and slags are analysed by chemical methods. 
The large 'umbrella' structure is a fume hood. There is a fume cupboard, a distilled water barrel and a muffle furnace (not in picture).
The end of a tube furnace can be seen on the right.
In rooms off the lab are a carbon/sulphur analyser and a chemical storeroom.
In the white coat is Derek Bissell (known as Fred) and the handsome chap in glasses is me.

 People I Knew 

When I started the Chief Chemist was Ralph Pritchard and Bill Allen was the Chief Day Chemist.

Later Don Williams became the Chief Chemist after Ralph and Bill retired.

Others were, in alphabetical order:
Jim Alcock; Mick Bell; Derek (Fred) Bissell; Fredrick Brown; Dave Barnes; Dave Bourne; Ray Cairns; John Dutton; Frank Hazlehurst; Roy Hawkins; Roy Hibbitt; Pete MacLocklin; John (Jack) Latimer; W. Lonsdale; Graham Lawrence; Pat Lavelle; Don Morgan; Geoff Morgan; Harold (H) Malpass; Vic Marsh; Mick (Sid) Millward; Alan Parker; Malcolm Palmer; Mike Peacock; Mick Ratchford; George Rouse; Pete Rushton; Fred Salt; Mike Steventon; Ray Shore; Lionel (Lefty) Wright; Ken Weaver; Ray Withington; George Wood; Dave Wooliscroft; Pete Warrilow; Dave Welsh; Dave Waltho; Pete Whalley.

Fred Bissell used to cut hair for 10p a time. Frank Hazlehurst was a wiz at crosswords and betting on horses - he was killed by a drunken driver when cycling home from work. Graham Lawrence was a special pal; good at sports and cards. Don Morgan was a day chemist who bought coffee beans to work and had them simmering on a hotplate until dinnertime - it was the best coffee I ever tasted. H was an entrepreneur; he could get you almost anything at a good price - saucy magazines a speciality!  Sid was given his new name by Fred Salt 'because he looks like a Sid'. He was a cheeky chappie; many's the time we fetched him out of bed for the morning shift because he was hung-over from the night before. He introduced me to Deep Purple and I bought a tape deck (7" reel to reel, it cost a small fortune) because his was great.

APPENDIX

1. Shift Pattern

            There are 4 crews.

            Each crew in turn works:

                        7 Mornings (7 til 2), Friday to Thursday (off Friday, Saturday, Sunday).

                        7 Noons (2 til 11), Monday to Sunday (off Monday and Tuesday until 11).

                        7 Nights (11 til 7), Tuesday to Monday (off Wednesday and Thursday).

            The shift Foreman worked: 

                        6 Mornings, (7 til 2), Monday to Saturday (off Sunday)

                        5 Noons, (2 til 11), Monday to Friday (off Saturday and Sunday)

                        5 Nights, (11 til 7), Monday to Friday (off Saturday and Sunday)

                        5 Day Shift (9 til 5), Monday to Friday (off Saturday and Sunday)

The noon shift was extended to allow the night shift to enjoy a little more of their evening.

 While it was possible to shut down the Open Hearth Furnaces over Christmas, it would have been very expensive to stop a Blast Furnace whose lining was still in good condition. Hence for some of the shift crew Christmas Day and Boxing Day were working days.

2. Solutions

                        Strength of Commercial Solutions

                        Solution                       Normality                    Specific Gravity

                        HCl                             10N                             1.16

            HNO₃                          16N                             1.42

            H₂SO₄                         36N                             1.84

            NH₄OH                       20N                             0.88

            H₃PO₄                         -                                   1.70

            Important Solutions

            Milton Gargle

            340g of NaCl; 4g of Na₂CO₃; 3g of Na₂SO₄; 240g NaOCl

            Add to 1600mls of water.

            Health Salts

            Five parts of citric acid and six parts of NaHCO₃

            Mix and add to water, drink while fizzing.

            Macleans Stomach Powder

            One part BiCO₃; two parts NaHCO₃; four parts CaCO₃; four parts MgCO₃

            Battery Acid 1.25 S.G.

            1800mls of water + 525mls of H₂SO₄ (carefully!)

            Cyanide Antidote

                        Solution (A): 79g of ferrous sulphate + 1.5g of citric acid + 419.5mls of water.

                        Solution (B): 6g of anhydrous sodium carbonate + 94mls of water.

Better is not to ingest in the first place!  The glass jar in which potassium cyanide is supplied is

weighed after each use and the information recorded in a poisons book. It is kept in a locked

storeroom.

            1. Acid Mixture for Silicon Determination

               1100 mls of distilled water + 300 mls of Nitric Acid  + 400mls of Sulphuric Acid

            2. Acid Mixture for Manganese Determination

               1050 mls of distilled water  + 500 mls of Nitric Acid  + 250 mls Phosphoric Acid + 200mls

   of Sulphuric Acid

3. Nitric Acid Solution for Pig Iron (Phosphorus)

    1480 mls of distilled water + 520 mls of Nitric Acid 

4. Cadmium Chloride Solution for the Determination of Sulphur

    Dissolve 12.5 g of CdCl₂ in 2 litres of distilled water, and then add 500 mls of ammonia

    (NH₄OH)

5. Ammonium Molybdate Stock Solution

    Dissolve 300 g Ammonium Molybdate in distilled water and make up to 1800 mls. Add 30

    mls of ammonia.

6. Nitro-Ammonium Molybdate

    24.5 mls of distilled water + 92 mls of Nitric Acid. Add, with constant agitation, 217.5 mls of 

    Ammonium Molybdate Stock Solution.

7. Potassium Nitrate Stock Solution for Phosphorous Determination

    Dissolve 200 g KNO₃ in distilled water and make up to 2 litres.

    Take 20 mls of the above and make up to a litre for washing solution.

8. Antimony Sulphate Solution for the Determination of Tin

    Dissolve 2.7 g  Sb₂ (SO₄)₃ in 720 mls of distilled water and add 180 mls of hydrochloric acid.

9. Mercuric Chloride Solution

    40g HgCl₂ dissolved in distilled water and  dilute to 1 litre.

         10.  Sulphuric/Phosphoric Acid Mixture

                1400 mls of distilled water + 300 mls H₃PO₄ + 300 mls H₂SO₄

         11.  Ammonium Citrate Solution for Gravimetric P₂O₅

                200g ammonium citrate dissolved in 1336 mls of distilled water. Add 664 mls Nitric acid.

         12.  Magnesia Mixture for Gravimetric P₂O₅

                    110g magnesium chloride + 140g ammonium chloride dissolved in 1300 mls of distilled

    water. Add 700 mls of 8% ammonia, which is 175 mls of 0.88 NH₄OH + 525 mls of distilled

    water.

        13.  Starch Solution for Sulphur Determination

               2.5g starch in 20 mls of cold distilled water, vigorously agitate (wobble), then add 250 mls of

   boiling distilled water and boil for about 3 minutes.

        14.  Preparation of N/10 F.A.S - Ferrous Ammonium Sulphate (FeSO₄ (NH)₄ SO₄ 6H₂O)

               9.804g with 20ml of 1:4 H₂SO₄, dilute to 250ml with water. 10ml of this solution in water

               with 20ml of 1:4 H₂SO₄  ≡  10ml N/10 KMnO₄ 

        15.  Standardisation of Potassium Permanganate.

              Weigh off 6.325g of  KMnO₄ crystals and wash into a standard one litre flask using a

  clean filter funnel [6.325 is .005g too heavy – this compensates for the small amount of

  undissolved MnO₂]. Add to the flask about 800mls of cold distilled water and leave for 24

  hours to dissolve. Dilute to 2 litres. Weigh off 0.335g of sodium oxalate into a 600ml beaker

 and add about 250mls of hot distilled water and 20 mls of 1:4 H₂SO₄ and boil. Titrate against

  the KMnO₄ from a burette.

            0.335g of sodium oxalate ≡ 50mls N/10 KMnO₄

        16.  Standardisation of Sodium Arsenite

                        Weigh off 16g As₂O₃ and 42g Na₂CO₃ crystals (this will make 8 litres) and place in a

             600ml beaker. Add about 400mls of hot distilled water and simmer gently until dissolved. Cool

            and dilute to 8 litres. First check: Run 37.5mls of solution into a conical flask, dilute with cold

            distilled water to about 150mls and titrate against standard N/32 iodine solution using starch

            indicator.

            37.5mls of sodium arsenite   48.2mls I₂ (± 0.2ml).

            Second check: Do an analysed steel standard in the usual manner.

        17.  Standardisation of Potassium Dichromate.

                        Weigh off 21.9534g of potassium dichromate and transfer to a one litre standard flask;

            leave overnight to dissolve and then dilute to 5 litres.

            Check: Weigh off 0.25g of iron granules and continue as for determination of iron in ores.

                        0.25g Fe  50mls K₂Cr₂O₇

       18.  Standardisation of N/32 Iodine Solution

                        This solution is deliberately made too strong and then adjusted to the correct strength.

            Weigh off 16.4g of I₂ crystals and 24g of potassium iodide and transfer to a one litre standard

            flask. Add about 200mls of water and allow to stand for 24 hours to dissolve. Dilute to 4 litres.

            Check: Dissolve 2 or 3g of sodium bicarbonate in 150 to 200mls of water in a conical flask.

            Add 37.5mls of 2N/5 sodium arsenite solution (q.v 16 above). Add a few mls of starch and

            titrate against the I₂. 37.5mls sodium arsenite ≡ 48.2mls I₂

            say the titre comes out as 47.5mls i.e. 0.7mls too strong. Therefore 1ml = 0.7/48.2 = 0.145

            So in 4 litres this is 58 mls to bring to correct strength. Add 56mls (erring on the right side).

            Shake vigorously and repeat from ‘Check’. Continue until within ±0.1ml.

      19. Zinc Fusion Mixture

                        70 parts ZnO plus 100 parts NaHCO₃. Mix thoroughly.

      20.  Standardisation of NaOH for Irons (3/5 N)

                        Weigh off 99g NaOH pellets and dissolve (carefully); make up to 4 litres. Take 25mls

            and titrate against standard HNO₃ (irons). Usually comes out too strong. Say x mls over 25mls.

            i.e. x in 25; 4x in 100; 160x in 4 litres. Therefore add 160x mls of water. Mix and take another

            25ml aliquot and titrate again. Continue until within ±0.1ml and then take 2g potassium

            hydrogen phthalate and dissolve in about 250mls of water. Titrate against the NaOH – it should

            take 16.72mls of NaOH.

     21.  Sodium Diphenylamine ρ – Sulphonate

                        Weigh 0.1g and dissolve in 100mls water.

     22.  Methyl Red Indicator

                        0.1g in 60mls of alcohol, then add 40mls water

     23.  6.5N Nitric Acid

                        Mix 500mls of water and 420mls HNO_3. Cool and dilute to one litre. Standardise

against anhydrous sodium carbonate. Dissolve 8.6125g of Na₂CO₃ in water. Titrate with the

nitric acid using methyl red indicator.

            8.6125g of Na₂CO₃  ≡ 25mls 6.5N HNO₃

     24.  Iron/Nitric Acid Solution

            5g of pure iron in 80mls of 6.5N HNO₃. Boil to dissolve and expel oxides of nitrogen.

Dilute to one litre with 6.5N HNO₃

     25.  Phenolphthalein Indicator

                        1g in 100mls of alcohol

    26.  Surface Active Agent

                        0.5% solution of sodium dodecyl benzene sulphonate

    27.  E.D.T.A. (M/80)

                        Otherwise known as ethylenediamine-tetra-acetic acid disodium salt or sequestric acid disodium salt. Weigh 4.653g of sequestric acid and dissolve in water. Dilute to one litre with water. Standardise against CaCO₃ solution. {1.25g of A.R. anhydrous CaCO₃ dissolved in water (a little HCl can be added to complete dissolution if necessary). Dilute to one litre with water}. Take 25mls and titrate against the E.D.T.A. adding erichrome black T indicator and 15mls of buffer solution (NH4Cl/ NH₄OH/MgSO₄/ E.D.T.A.)

            25mls Ca²⁺  ≡ 25mls E.D.T.A.

    28.  Buffer Solution (NH4Cl/ NH₄OH/MgSO₄/ E.D.T.A.)

                        (a) 67.5g NH4Cl + 570mls NH₄OH + 250mls water.

                                    (b) 0.931g E.D.T.A. + 100mls water

                                    (c) 0.616g MgSO₄.7H₂O + 25mls water

            Mix (b) with (c) and add to (a).

Methods of Analysis

Whenever water is mention as an additive it is distilled water that is meant.

A “Bobby” is a length of circular glass rod about 15 cm long to the end of which is attached a rubber ‘collar’ made from tubing. This would be about 3 or 4 cm long and the rubber end can be used to rub the sides of beakers to dislodge precipitants (known as “Bobbying”). It is also used for stirring where wobbling is inappropriate. Iron is brittle and the samples for analysis are provided as a powder. The steel samples are provided as drillings. For the routine and every day determinations charts are provided which convert weights or titres to percentages. Where filtering through paper pulp is mentioned it means that pulped filter paper is pressed into a pad on a filter cone that is in a funnel. This is connected to the top of a strong glass vacuum flask using a rubber bung. The flask is attached by rubber tubing to a vacuum pump which facilities efficient filtering. Where fumes are given off the test is perfumed under a hood and extractor fan or in a fume cupboard. Often a watch glass is placed on top of a beaker when boiling is taking place.

Analysis of Iron

Sulphur in Iron

Weigh 5g of powdered sample and place in a standard flask. Attach the flask to the apparatus. Attach the precipitation beaker (which contains about 350mls of distilled water and 35mls of cadmium chloride solution). Add, by means of the thistle funnel about 150mls of 1:1 HCl. Dissolve over a low Bunsen flame, taking care that HCl gas does not pass over into the beaker. When evolution has  completely finished remove the precipitation beaker and add a few mls of starch solution. Dissolve precipitate in 50mls of concentrated HCl and titrate immediately with standard iodide solution until a blue end-point is obtained.

The sulphur is present as mainly Manganese sulphide with some iron sulphide. These liberate hydrogen sulphide on treatment with HCl

CdCl₂ + H₂S     --------->      CdS + 2HCl

The CdS is a yellow precipitate. The acid is neutralised.

On liberation of H₂S by excess HCl

H₂S + I₂        ----------->       S + 2H⁺ + 2I^-

(In alkaline solution: S^2- +4I₂ + 8OH^-                SO₄^2-                + 8I^-  + 4H₂O)

Titration with N/32 Std I₂ solution on an original 5g sample gives  Direct reading/100 = %S.

i.e. 1cc of N/32 I₂ is equivalent to 0.01%S.

Notes

Indicator change: I^- + starch  = colourless; I₂ + starch = blue, i.e. first trace of excess I₂ turns

starch blue.

Sunlight on precipitate gives a low result.

HCl boiled over gives a high result.

Silicon in Iron

Weigh 1g of sample and transfer to a 250ml beaker. Add 30 mls of acid mixture cover with a watch glass and evaporate to a pasty mass. Allow to cool and then add about 10mls of concentrated HCl; wash sides of beaker and watch glass with hot water.

“Bobby” the beaker, wash, and boil up on a hot plate. Filter through paper pulp (using vacuum pump) bobbying out the beaker once more. Wash the pulp and residue alternately with warm 1:1 HCl and hot water (3 times with HCl; at least 8 times with water – all trace of acid must be removed). Place pulp and residue in a silica crucible, and transfer to the muffle. When burnt off to a white powder transfer to a dessicator and allow to cool. Weigh as silica.

Then, Weight of SiO₂  x  0.4672  = Weight of Si

            %Si  = Weight of Si x 100, or more simply:

            %Si  = Weight of SiO₂  x  46.72

Manganese in Iron

Weigh ½g of sample and transfer to a 500ml conical beaker. Add 30 mls of acid mixture and digest on a hotplate, boiling off the oxides of nitrogen. When dissolved add about 150mls of hot water (remove the beaker from the hotplate to do this) and add one silver nitrate pellet (or 10mls of AgNO₃ solution; 0.8%), and two ammonium persulphate pellets (10mls of ((NH₄)₂S₂O₈; 25g in 85mls water – this solution cannot be stored, it does not last much longer than two hours.) heat to boiling and boil briskly for one minute. Cool in a water bath to below 30^oC. Titrate the blue liquid with standard sodium arsenite solution to a yellow/green colour.

The manganese is present mainly as MnS (manganese sulphide)

MnS + H₂SO₄  → MnSO₄  + H₂O

The manganese ion is then oxidised to permanganic acid by

2 AgNO₃  + (NH₄)₂S₂O₈ → Ag₂ S₂O₈  + 2 NH₄ NO₃

The AgNO₃ acts as a catalyst.

2MnSO₄ + 5 Ag₂ S₂O₈  + 6H₂O →  2HMnO₄ + 5 Ag₂SO₄ + 7 H₂SO₄

The excess ammonium and/or silver persulphates are destroyed by boiling.

2 (NH₄)₂S₂O₈ + 2 H₂O →Heat→ 2(NH₄)₂ SO₄ + 2 H₂SO₄ + O₂

But prolonged heating (or high Mn content) will form MnO₂. When oxidation with persulphate is carried out in the presence of H₃PO₄ it is possible to oxidise as much as 100mg of Mn to HMnO₄ without separation of oxides of Mn. With such concentrations the end-point is difficult and the practical limit is 15mg. Chrome in concentrations >10mg/100ml may cause difficulty with end-point, but the arsenite does selectively reduce MnO₄^-  leaving  low concentration of Cr O₄^-   unaffected.

5As₂O₃ + 4 MnO₄^-   + 12H⁺ → 5As₂O₅ + 4Mn²⁺ + 6 H₂O

H₃PO₄ complexes the Fe³⁺ ions thus preventing the Fe³⁺/ Fe²⁺ oxidation-reduction reaction during the titration. Because of the difficulty of the end-point determination it is advisable to titrate rapidly, but consistent with accuracy.

1ml of titrant ≡ 0.134%Mn on 0.5g

Phosphorus in Iron 

1g for irons   < 0.3%

½g for irons   < 1.0%

¼g for irons   > 1.0%

Weigh off the sample and transfer to a 600ml beaker. Add 50mls of pig iron nitric acid solution and cover with a watchglass and simmer gently on a hotplate for five minutes; then add one sodium fluoride pellet and simmer for a further five minutes. Rinse the watchglass and sides of the beaker and make the bulk up to about 50mls if necessary. Bring to the boil and add two potassium permanganate pellets – simmer for two minutes. Add one ammonium chloride/ ammonium oxalate pellet and simmer until the solution is clear. Add, with constant shaking, a mixture of 15mls of cold water and 25mls of ammonium nitro-molybdate solution. Agitate (wobble) vigorously for one minute to bring down a yellow precipitate. Allow to settle for 15 minutes in a warm place. Filter through a thick filter paper pulp pad, washing beaker thoroughly with dilute Nitric acid (30mls of 1.25 S.G. nitric acid in about 750mls water). Wash the precipitate 8 or 9 times with the potassium nitrate solution (5mls of stock solution in 750mls of water). After washing the beaker out with water to remove any traces of acid, transfer to it the washed precipitate and pulp. From a burette add 10mls of standard sodium hydroxide. Add about 150mls of water and agitate (wobble) until precipitate dissolved. Add 10 drops of thymol blue/phenolphaleen indicator and back titrate with standard nitric acid solution.

Endpoint: Purple → Yellow

Subtract nitric acid reading from 10.       1ml ≡ 0.315%P on ¼g

The phosphides present in solution after dissolution of the sample in HNO₃ are oxidised to orthophosphates with KMnO₄ . Excess KMnO₄ is destroyed by the addition of ammonium oxalate, and ammonium chloride acts as a buffer. Phosphorus is then in solution as orthophosphate acid which is treated with ammonium nitro-molybdate.

P^-  + HNO₃ → phosphorus as anion [+KMnO₄ → P O₄^3-  ]

H₃PO₄ = {12H₂MoO₃ + 3NO₃} → {(NH₄)₃ PO₄ .12 MoO₃ H₂O} + HNO₃ + 11 H₂O

When dissolved in NaOH

(NH₄)₃ PO₄ .12 MoO₃ + 23 NaOH → 11Na₂ MoO₄ + (NH₄)₂ MoO₄ + NaNH₄ . HPO₄ + 11 H₂O

Total Carbon in Iron

Weigh ½g of sample and transfer to a ceramic boat (which has previously been refired in a muffle furnace) and cover with a piece of lead foil. Weigh a ‘run in’ Midvale bulb and place it into position in the ‘carbon train’(qv #) with its valve open. Transfer the ceramic boat and its contents to the tube furnace and close the train. Allow oxygen to pass through the train for 10 minutes then remove the bulb (close the valve) and reweigh.

Fe₃C + 4½O₂ → 3CO₂ + Fe₂O₃

C + O₂ → CO₂

Reaction in the bulb: 2NaOH + CO₂ → Na₂CO₃ + H₂O

Increase in weight of bulb X 54.54  =  % Carbon

# Train is made up of (L to R):

 1. Midvale bulb – containing NaOH impregnated asbestos (14/20 Mesh) and a small amount of

      magnesium perchlorate at the top.

 2. U-tube – containing magnesium perchlorate.

 3. Bubbler (small) – containing concentrated sulphuric acid.

 4. Empty bubbler – H₂SO₄ trap for 3.

 5. U-tube – containing cotton wool.

 5a. for very high sulphur irons only – two large bubblers containing a saturated solution of

      chrome oxide in concentrated H₂SO_4.

 6. Silica tube furnace.

 7. U-tube – containing 8/14 mesh NaOH impregnated asbestos

 8. Bubbler (large) - containing concentrated sulphuric acid.

 9. Empty bubbler – H₂SO₄ trap for 8.

10. Mercury trap – ensures steady flow of oxygen.

11. Oxygen tap.

All the above connected by rubber tubes and bungs.

Graphitic Carbon in Iron

Weigh 1.364g of sample and transfer to a 250ml beaker. Add 50mls of 1.2 S.G. HNO₃ and a few drops of hydrofluoric acid (HF). Allow to digest on a corner of a hot plate until action ceases (NB prolonged digestion will give a low result). Filter through a pad of burnt asbestos washing with 5% HCl and hot water. Transfer the asbestos pad to a combustion boat and dry in an oven at 110º C for one hour. Burn off for 10 minutes in the carbon train as for total carbon.

Increase in weight of bulb X 20 = % graphitic carbon.

Tin in Iron

Weigh 5g of sample and transfer to a 750ml flask. Add 150ml of HCl and 50ml of water and digest on a hotplate. When dissolved oxidise with 20ml of 5% KClO₃ and boil to expel Cl₂ for about two minutes [at this stage filtering through burnt asbestos is often required to give a reasonably clean solution]. The tin is now present as SnCl₄ – reduce to SnCl₂ by adding a few mls of antimony sulphate solution. Now add a couple of pieces of pure aluminium metal until there is a colour change. Add a further 10ml of antimony sulphate and connect the CO₂ apparatus [an attachment that connects the flask to a beaker containing a supersaturated solution of NaHCO₃, this keeps the atmosphere in the flask inert]. Boil the solution in the flask for about 20 minutes, then add another 10ml of antimony sulphate and boil for a further five minutes. Transfer the flask and attachment to a water bath and cool thoroughly. Make up the bulk with cold boiled water and add 5ml of starch solution. Titrate rapidly, but consistent with accuracy, against  standard N/32 iodine solution from a burette to a permanent blue end-point.

1ml of N/32 iodine solution ≡ 0.037% Sn

Chromium in Iron

Weigh 1g of sample and transfer to a 250ml beaker. Add 15ml of 1:6 H₂SO₄ and a few spots of HF. Take down to paste and then take up in water and 3ml of concentrated HNO_3.  Take down to paste once more. Take up in 100ml of water, and filter through a small pad – retaining the filtrate. Burn off the pad in a platinum crucible and fuse it with K₂ CO₃ /Na₂CO_3.  Extract from the crucible using water and add to the main solution. Add manganese acid mixture and carry on as for volumetric determination as for steels.

Analysis of Very High Silicon Irons

(1) Silicon Determination

Weigh 1g of sample and transfer to a 250ml beaker. In a fume cupboard, add 20mls of HCl and cover with a watchglass and stew for a few minutes; then add 10mls of perchloric acid and take down to strong fumes. Cool and then treat as normal.

(2) Manganese Determination

Weigh ½g of sample and transfer to a conical beaker. In a fume cupboard, add 20ml H₂SO₄ and a few mls of HF. Take down to strong sulphuric fumes. Cool, take up in water; when the salts have dissolved add the usual acid mixture and treat as normal.

(3) Phosphorus Determination

Weigh ¼g of sample and transfer to a 250ml beaker. In a fume cupboard, add 5ml of HNO₃ and 20ml of HCl and cover with a watchglass. Boil to dryness and roast. Cool and take up in 10ml HCl and water and boil until salts dissolved. Filter (through 31 or 54 paper) off SiO₂, etc into a 600ml beaker washing with HCl and water, keeping the bulk as low as possible (<200ml).  The filtrate is then made alkaline with NH₄OH and neutralised with HNO_3. [At this stage, if the P content is high, it is wise to oxidise further with potassium permanganate – forms a brown precipitate (oxalic)]. Now add 5ml excess of HNO₃ and bring to the boil. Shake or blow the solution to remove dissolved gas and then precipitate with 15ml of cold stock Ammonium Molybdate solution added slowly. Agitate (wobble) vigorously for one minute, allow to settle and treat as usual.

(4) Sulphur and Carbon Determinations

Are as normal

Analysis of Steel

Sulphur in Steel

Same as for iron but slightly more sophisticated apparatus (water trap added).

Sulphur in Freecutting Steel

Exactly as above, but after titration the contents of the water trap are added to the collection beaker until the endpoint is again reached. This last figure is taken as the titre.

Silicon in Steel

Weigh 4.67g of sample and transfer to a 600ml beaker. Add 80ml of acid mixture in 4 x 20ml portions (the reaction is very vigorous). The various combinations (Fe Si₂, Fe₃Si₂, MnSi, etc) are converted to orthosilicic acid. Evaporation converts to gelatinous silicic acid H₂SiO₃.

On dehydration → insoluble SiO₂

H₂SiO₃ → SiO₂ + 2H₂O

Once down to salts treat as for silicon in irons.

SiO₂ → Si    factor is 0.467

On a 4.67g sample:

Mass of Si = Weight of SiO₂ x 0.467/4.67

%Si = Weight of SiO₂ x 10

Manganese in Steel

As for iron but (i) 1g sample (ii) 40 ml of acid mixture.

For low Mn steels (vessel samples) use only one persulphate pellet.

%Mn = No of mls x 0.067

Phosphorus in Steel

Weigh 2g of sample and transfer to a 600ml beaker. Add 35ml of 1.2 S.G. HNO₃ and boil until dissolved; add one permanganate pellet and boil until solution chocolate brown in colour. Add one ammonium chloride/ ammonium oxalate pellet and simmer until the solution is clear. Add, with constant shaking, 15mls of ammonium nitro-molybdate solution. Agitate (wobble) vigorously for one minute to bring down a yellow precipitate. Continue as for Irons but use the special steel standard solutions of NaOH and HNO₃.

1ml ≡ 0.0095 %P

Carbon in Steel

Weigh 2.727g of sample and proceed as for Iron except leave on the ‘train’ for 7 minutes.

[For freecutting steel (high sulphur content): Put in stage 5(b) and leave for 10 minutes.

%C = Increase in weight of bulb x 0.2727 x 100/2.727

%C = Increase in weight of bulb x 10

%C = Increase in weight of bulb x 27.27 on 1g

Graphitic Carbon in High Carbon Semi-steel

Same as for Iron.

Tin in Steel

Same as for Iron

Manganese in High Chrome/Vanadium Steel

Dissolve 0.15 to 0.30g of sample in 5ml of 1:3 H₂SO₄ contained in a large test tube. When dissolved add 10ml of 1.2 S.G. HNO₃ and boil of nitrogen oxides. Cool, and add thick cream of ZnO until Cr and Fe hydrates are precipitated leaving a clear solution. Cool, dilute to about 75ml – shake, settle, filter and wash. Add about 50ml of acid mixture and proceed as for Mn in iron.

Chromium in Stainless Steel (18/8)

Weigh of 0.2g of sample and transfer to 600ml beaker. Add 20ml of 1:6 H₂SO₄ , dissolve and take down to paste on a hotplate. Take up in water and 5ml of HNO₃ and evaporate to paste again. Take up in 50ml of water and 5ml of HNO₃ and boil. Add half a AgNO₃ pellet and 2 (or more if necessary) persulphate pellets to bring out the permanganate colour. Add 5ml of 1:3 HCl (should go yellow) and cool. Add, from a burette, excess N/10 F.A.S. (run in until colour is pale green – then add as much again) Titrate the excess FAS against N/10 KMnO_4.

1ml of FAS ≡ 0.00173g of chromium ≡ 0.1733% Chromium on 1g

Analysis of Blast Furnace Slag

Preparation

Using a clean pestle and mortar grind about 5g of dry sample into a fine powder; pass a magnet over the sample to remove any metallic iron. For routine shift B/F slag weigh of 2g of this sample and place in an average sample packet (these are used for the weekly complete analysis).

Determination of Calcium Oxide

Weigh off 0.3g of sample and transfer to a 600ml beaker. Add, from a burette, 13mls of 1:2 HNO₃ and digest on a hot plate, washing down the sides of the beaker with hot water. When the oxides of nitrogen have been dispelled, add one sodium fluoride pellet to retain SiO₂ in solution. When the solution is clear, add about 250mls of hot water and two ammonium oxalate pellets. Allow to dissolve then boil for at least two minutes more. Filter through paper pulp, ensuring all the precipitate is removed from the beaker, wash the precipitate 5 or 6 times with hot water. Place both pad and precipitate into the original beaker, wash the residue from the filter funnel into the beaker. Add 250mls of hot water and 20 mls of 1:4 H₂SO₄ and bring the temperature up to above 85^o C. Titrate solution against standard potassium permanganate from a burette until the first persistent pale pink colour is evident.

N^o of mls of KMnO₄ x 2.8/3 = % CaO

Determination of Silica

Weigh off 0.5g of sample and transfer to a 250ml beaker. Add a few mls of hot water and place on the edge of a hot plate. When hot add at least 20mls of HCl and about 7mls of perchloric acid. Allow to evaporate until fumes of perchloric are given off – fume for one minute (but ensure that the residue does not begin to roast). Take from the source of heat and allow to cool. Wash and “bobby out” the beaker making the bulk up to about 50mls with water – add about 10mls of HCl and boil. Filter through a N^o 31 (or 54) paper and wash once with HCL and thoroughly with water (ensuring all traces of HCl and perchloric [HClO₃] are washed through). Save the filtrate for further analysis; transfer paper and residue to a silica crucible; char and burn off the paper in a muffle, remove, and allow to cool in a desiccator. Weigh as SiO₂ .

Weight of residue x 200 = % SiO₂

Alternative method for less soluble slag

Weigh off 0.5g of sample and transfer to a 250ml beaker. Dissolve sample in 20mls of aqua regia. Evaporate to dryness on a hot plate and roast at low temperature (110^o C). Take up in water and HCl and continue as usual.

The Blast Furnace management also liked the lime to silica ratio reported:

%CaO/% SiO₂  (usually between 1 and 1.5)

Determination of Alumina (+Fe₂O₃)

To the filtrate from the SiO₂ determination add about 2g of ammonium chloride and boil to dissolve. Add a slight excess (i.e. above the amount required to give a precipitate) of ammonium hydroxide (NH₄OH) and boil. Filter through 31’s or English paper and wash with hot water. Redissolve the precipitate into a separate clean 600ml beaker with HCl and washing the paper thoroughly with hot water. Boil the solution and re-precipitate using NH₄OH. Filter once more (into the beaker containing the first filtrate and save this for further analysis) and wash thoroughly with hot water. Transfer paper and residue to a silica crucible; char and burn off the paper in a muffle, remove, and allow to cool in a desiccator. Weigh as Al₂O₃ + Fe₂O₃

Weight of residue – weight of iron as Fe₂O₃ = weight of Al₂O₃

Weight of Al₂O₃ x 200 = % Al₂O₃

Determination of Fe, FeO and Fe₂O₃

Determined as in ores, Kaldo slag, etc but because of low concentrations larger sample weight is taken – usually 2.5g (therefore divide usual result by 5)

Determination of Magnesium (MgO)

First we must remove manganese and lime oxides.

(a) Removal of Manganese

            Acidify the filtrate from the Al₂O₃ determination with HCl (use methyl red indicator) and add with care, and under an extractor fan, about 5mls of bromine. Leave for 10 minutes by the side of a hot plate ensuring the solution just keeps warm and retains a slight excess of bromine. Add NH₄OH until the solution is ammoniacal and boil for 5 minutes. Filter of the MnOH through English or N^o 30’s paper and wash thoroughly with hot water – discard residue.

(b) Removal of Lime (CaO)

            Acidify the filtrate from the MnO removal stage with HCl using methyl red indicator. Add about 2g of ammonium oxalate. Boil to dissolve. Precipitate the lime with a slight excess of NH₄OH. Boil for 2 minutes, filter and wash through N^o 31’s paper. Dissolve the precipitate into a separate clean 600ml beaker with HCl and boil. Re-precipitate using NH₄OH and filter through N^o 42 or 44 paper into the previous filtrate and once more washing the paper thoroughly with hot water.

(c) Determination of (MgO)

            Transfer the above filtrate, which should be alkaline, to a water bath and cool thoroughly. Add 20mls of saturated solution of di-sodium hydrogen ortho-phosphate and agitate vigorously with a stirrer for 15 minutes to enable precipitation. Allow to stand for 8 hours. Filter through paper pulp washing thoroughly with slightly ammoniacal cold water. Transfer to a crucible, char and burn off in an oven. Cool in a desiccator and weigh.

Weight of Mg₂P₂O₇ x 0.3621 x 200 = % MgO   i.e. weight of ash x 72.42 = % MgO

Determination of Manganese (MnO)

Weigh off 0.5g of sample and transfer to a conical flask. Add a little water and place on a hot plate – add 5mls of HNO₃ and a few drops of HF (or a NaF pellet). Boil until nearly dry and remove from the plate. Add 35mls of acid mixture (same as for Mn determination in iron & steel) and boil until residue dissolves. Continue as for manganese in iron.

1ml ≡ 0.134 % Mn      %Mn x 1.2913 = % MnO

Determination of Sulphur

(a)  Evolution Method

Weigh off 0.5g of sample and transfer to a 750ml flask. To the flask and sample add about 2g of stannous chloride and 3 or 4 grams of aluminium metal. Connect the flask to a steel sulphur apparatus. The precipitation beaker contains about 350mls of water, 35mls of CdCl₂ and 10mls of NH₄OH. By means of the thistle funnel add about 150mls of cold HCl [a vigorous reaction takes place – the hydrogen gas generated by the dissolving aluminium acts as a ‘carrier’ for the H₂S liberated]. When the reaction has abated boil to finish dissolution. Titrate as for free-cutting steel.

Titre/10 = % S

(b) Gravimetric Method

Weigh off 1g of sample and transfer to a 250ml beaker. Add a little water and 5mls of bromine; stand in a warm place for 10 minutes. Add 10mls of HNO₃ and stand for 10 minutes followed by 10mls of HCl standing for 5 minutes. Evaporate to dryness on a hot plate and bake thoroughly. Cool, take up in HCl and water and boil. Filter residue off through N^o 31’s paper and wash thoroughly; discard the residue. Neutralise the filtrate with NH₄OH and then make slightly acidic using HCl (make use of the presence of hydroxides of Fe and Al). Boil and add 10mls of a 10% solution of barium chloride(BaCl₂). Boil for a further 10 minutes and settle for 3 or 4 hours. Filter through combined papers N^o 40/44 or use paper pulp. Wash thoroughly with first 5% HCl and then water. Transfer to a crucible, char, burn off, cool in a dessicator and then weigh as BaSO₄.

 BaSO₄ x 0.1373 x 100 = %S           Weight of ash x 13 73 = %S

Note: When calculating the ‘total’ remember that some S, present as CaS, will have already been included in the line figure. Therefore only add half of the S content to the total figure.

[weight of BaSO₄ x 34.3 = %SO₃]

Analysis of Ores

Preparation

            (a) Moisture

                        Most ores contain water and analysis is reported ‘as received’ and ‘dried’.

(sintered ores are an exception). For standard, reproducible results the analysis is carried out on

the dried sample and converted back to ‘as received’.

The sample is obtained from the incoming train wagons and a standard method is used to get a

representative amount of ore; from this a further more manageable sample is got by ‘coning and

quartering’. Weigh 50g of ‘as rec’d’ sample and transfer to a large watch glass. Place in an

oven, set at 110^o C, for one hour. Remove and reweigh.

            2 x (50 - dry sample weight) = % Moisture

            [100 - %Moisture] x dried results = as received results.

            (b) Grinding

                        The dry sample is ground to a fine powder using a clean pestle and mortar. The

sample is then placed back in the oven for 10 minutes to remove any moisture picked up from

the atmosphere. Place the sample in the small bottle provided (there is one for each different

ore). Ensure there is enough powdered sample to add to the large “average bottle”.

e.g.s. Rushton, Ferrersand      -           30g

         Pyrites    -           10g

Loss on Ignition

On some ores a L.O.I. is required and usually one gram of dried sample is taken, placed in a

silica crucible and transferred to a muffle furnace for at least one hour. For sinters a nickel

crucible is used. For sinters: LOI = [% Fe₂O₃ - % FeO] – [100 x gain on ignition]

% Fe₂O₃ = 10/7 x % FeO titre                        Fe₂O₃  =  (Fe – 7/9 FeO) x 10/7

Determination of Silica

            Weigh off 0.5g of sample and transfer to a platinum crucible (which contains about 4g

of zinc fusion mixture. Mix sample and mixture thoroughly and heat in a muffle furnace at

 about 950° C for 10 minutes (i.e. until the contents of the crucible have sintered to a ‘grey

button’). Remove to a dessicator and allow to cool. Transfer the button to a 600ml beaker and

wash the crucible with hot water and HCl into the beaker. Add a further 50ml of HCl and boil

until the fused material is dissolved. Add about 10ml of HNO₃ and two ml of perchloric acid (if

the silica content is high, >20%, then add correspondingly more HCLO₄). Evaporate the

solution to a thick gelatine, taking care not to bake. Allow the gel to cool, and then take up in

HCl and water and boil. Filter (save the filtrate for further analysis) and treat as for SiO₂

determination in Blast Furnace slag.

            residue x 200 = % SiO₂

Determination of Lime

            Weigh off 0.5g of sample and transfer to a 250ml beaker, Add a few mls of water

followed by 30mls of HCl and boil for about 10 minutes. Filter through N^o 54 or 31 paper,

collecting the filtrate in a 600ml beaker. Bobby out the 250 ml beaker and wash the residue

thoroughly with hot water. Transfer the paper and contents to a platinum crucible and burn off

to ash in a Davies furnace. Remove and add a few grams of fusion mixture (equimolecular

mixture of anhydrous K and Na carbonates) and replace in the furnace. Place a platinum lid on

the crucible and a conical ‘retort’ on the furnace. Fuse for about 10 minutes, remove and cool.

To the previous filtrate add the cool crucible and contents, allow to dissolve out (add extra HCl

if necessary) and remove the cleaned platinum ware washing well with water. Boil the filtrate to

fully dissolve the filtrate and then add 5mls HNO₃ and boil for a further 10 minutes. Add a few

grams of ammonium chloride and allow to dissolve. Add NH₄OH until Fe (and Al) are

precipitated and boil for a few minutes. Filter into a clean 600ml beaker using ‘English’ paper.

Wash the precipitate into the original beaker with HCl and water and reprecipitate with

NH₄OH- filter again into the first filtrate and wash thoroughly with hot water. Using methyl red

 indicator just acidify the filtrate with HCl. Add a few grams of ammonium oxalate and boil to

dissolve. Precipitate the CaO with NH₄OH (slight excess), boil for 5 minutes and then stand for

a few minutes, in a warm place, to settle. Filter through paper pulp, washing thoroughly with

hot water. Continue as for lime in Blast Furnace slag.

            N^o of mls of KMnO₄ x 0.56 = % CaO

            Lime in less soluble ores: Weigh off 0.5g of sample and transfer to a 250ml beaker. Add

20mls of aqua regia and evaporate to dryness and bake. Take up in HCl and water, filter and

continue as above.

Determination of Iron

            Weigh off 0.5g of sample and transfer to a 750ml flask. Add about 50ml of water and

boil; when boiling add 30mls of HCl and continue boiling until dissolved (if necessary a few

drops of HF may be added to aid dissolution – but boil for at least 10 minutes after this

addition). Make the bulk up to about 200mls, then reduce by adding stannous chloride dropwise

until the solution clears, then add two extra drops. Cool thoroughly. Add 12.5mls of mercuric

chloride and leave for 10 minutes. Add 25mls of H₂SO₄ / H₃PO₄  acid mixture and about 10

drops of sodium diphenylamine ρ – sulphonate indicator and titrate against standard potassium

dichromate solution.

            N° of mls of K₂Cr₂O₇ = % Fe

{Check on iron result: To the filtrate from the SiO₂ determination add a few grams of NH₄Cl

and boil to dissolve. Precipitate iron with NH₄OH and boil for a further 10 minutes. Filter

through English paper and wash thoroughly with hot water. Pierce  the filter paper and wash

precipitate into a 750ml flask with water and a little HCl. Add a further 20mls of HCl and boil.

Reduce with SnCl₂ etc and carry on as above.}

Determination of Ferrous Oxide

                Weigh off 0.5g of sample and transfer to a 750ml flask. Add about 50mls water and

boil. When boiling add 30mls of HCl and place an air trap in the neck of the flask (this prevents

oxidation). Boil until dissolved then cool. Add enough deoxygenated water to bring the bulk up

to about 250mls, followed by 25mls of H₂SO₄ / H₃PO₄ acid mixture and 10 drops of sodium

diphenylamine ρ – sulphonate indicator and titrate  rapidly against standard potassium

dichromate solution.

            N° of mls of K₂Cr₂O₇  x 9/7 = % FeO

Calculation of Ferric Oxide (Fe₂O₃)

            % Fe₂O₃  = 10/7[% Fe - % FeO x 7/9]

Determination of Phosphorus

                As for P in high silicon irons.

Determination of Sulphur

            As for the long method for S determination in Blast Furnace slag.

Determination of Copper

            Weigh off 0.5g of sample and transfer to a 250ml beaker. Add a few drops of water, a

little HCl and 6mls of H₂SO_4. Take down to fumes. Cool and take up in 30mls of water and

6mls of H₃PO₄ and boil. When dissolved add about 5mls of 1.2 SG HNO₃ and boil off oxides of

nitrogen. Cool, dilute as appropriate and use a Spekker instrument to determine the %Cu.

Determination of Alumina (in high iron ores)

            To the filtrate from the silica determination add a few grams of NH₄ Cl and boil to

dissolve. Precipitate Al and Fe as hydroxides with a slight excess of NH₄OH and boil for a few

minutes. Filter through N^o 31 paper and wash thoroughly (save the filtrate for MgO

determination). Wash the precipitate into a 600ml beaker with HCl and water and add 15mls of

tartaric acid solution (7.5g in 15mls of water) and boil. Make ammoniacal with NH₄OH

(solution turns slightly darker and when ammoniacal light again). Add 10mls of excess NH₄OH,

 then 12 mls of sodium sulphite solution (3g in 12 mls of water) very slowly. Remove from the

hot plate and add dropwise, and with continuous stirring, 35mls of potassium cyanide solution

(9g in 35mls of water). When the solution is colourless, heat to 70° C and add reagent 8-

hydroxyquinoline (0.5g in 3mls of concentrated acetic acid and 5mls of water). The weight of

the reagent must be approximately 10 times the weight of Al₂O₃ present.

Digest for 15 minutes on a warm plate and stir constantly to coagulate the yellow precipitate.

Filter and wash with 2% NH₄OH through a N^o 31 paper. Transfer to a crucible and burn off.

            Weight of residue x 200 = % Al₂O₃

Determination of MgO

            Using the filtrate from the determination of alumina, the lime is removed and analysis

proceeds as for Blast Furnace slag

Determination of Carbon

The sample weight will be determined by the amount of carbon thought to be present. The

determination is via the carbon train. Convert the CO₂ given off to the equivalent weight of that

would be given off by a 1g sample. Multiply that by 100 to give

            % CO₂  x  3/11 = %C

Determination of Strength of Sinter

            Weigh off 5 lots of 300g each of the as received sample. Using the drop test apparatus

treat each of the 5 lots in turn  - 10lb weight dropped from a height of 4 feet two times. Sieve

each lot, first through a ¼ inch sieve then through a ⅛ inch sieve. Save (a) that which remains

on the ¼ inch sieve (+¼) (b) that which passes through the inch sieve (-⅛). For each lot weigh

(a) and (b) and take the average of all the samples.

If (a) weights are x₁, x₂, x₃, x₄, x₅  and (b) weights are  y_1, y₂, y₃, y₄, y₅

then Average (+¼) = (x_{1 +} x_{2 +} x_{3 +} x_{4 +} x₅)/5 and Average   (-⅛) = (y_{1 +} y_{2 +} y_{3 +} y_{4 +} y₅)/5

Strength Index = Average (+¼)/3

Dust Index = Average   (-⅛)/3

Ratio = Strength Index

               Dust Index

Analysis of Scales

            Preparation

            (a) Moisture

                        Samples sometimes are received in a wet condition and for reproducibility of

results the samples are dried in an oven for one hour at 110° C. Usually 50g of sample is taken

and the moisture figure reported.

            (b) Grinding

                        The dry sample must be ground as fine as possible for scales are not noted for

their solubility.

Determination of Iron

(a) When soluble then treat as for iron in ores.

(b) When not so soluble use a sample weight of 2.5g and transfer to a 600ml beaker. Add 30mls

of HCl and boil. Add a few drops of HF to aid dissolution and boil for at least 30 minutes. Filter

through a N^o 31 paper and wash thoroughly. Make the filtrate up to 250mls with water in a

standard flask and shake well. Take 50ml of this solution (≡0.5g) and transfer to a 750ml flask.

Continue as for iron in ores.

Determination of Nickel and Chromium

            Weigh off 5g of sample and transfer to a 250ml beaker. Add 20mls HCl and boil to

dissolve as much as possible of the sample. Add 30mls of H₂SO₄ and boil for a further 10

minutes. Oxidise with 5mls of HNO₃ and take down to strong fumes. Cool and take up in water,

boiling to dissolve the salts if necessary. Dilute to 250mls with water using a standard flask.

(a) Nickel Determination

            Take 50mls (≡ 1g) of the above solution, add 6mls of H₃PO₄ and boil. Add 5mls of 1.2SG

            HNO₃ and boil for 5 minutes. Cool, dilute to 200mls and use a Spekker instrument to determine

            the %Ni. [Photo Electric Absorbiometer: A known sample is placed on one side of the lamp,

            and the specimen on the other. Filters are added, and the refraction of light is used to measure

            the unknown sample against the known one, using a galvanometer.]

            (b) Chromium Determination

                        Take 100mls (≡ 2g) of the above solution and dilute to 250mls in a conical flask.

Add 35mls of Mn acid mixture, half a silver nitrate pellet and 2 ammonium persulphate pellets.

Boil until the “Mn colour” persists. Add 5mls of 1:3 HCl and boil until clear (5 minutes). Cool

and add, from a burette, N/10 ferrous ammonium sulphate until the solution goes dark – note

the titre. back titrate with standard N/10 KMnO₄ solution until a persistent pink end-point is

obtained. Adjust the titre.

             N^o of mls of FAS x 0.1733/2  =  % Cr

Analysis of Basic Slag

            Basic slag is mainly used as fertilizer.

            Open Hearth Furnace Slag.

            Determination of Fineness

                        Weigh of 20g of sample and transfer to a standard sieve (100 mesh). Shake until no

            more sample is passing through the sieve, then weigh the sample remaining on the sieve.

            100 – [5 x weight on mesh] = Fineness  (specification: 70±4)

            Determination of P₂O₅

            (a) Volumetric

                        Weigh off 0.25g of sample and transfer to a 600ml beaker. Add 15mls of hot

water followed by 15mls of 1:2 SG HNO₃. Boil to dissolve and continue as for P in pig iron

but: (i) precipitate with a mixture of 35mls of ammonium nitro-molybdate and 35mls of water

(ii) dissolve the precipitate in 20mls of standard NaOH (the P content is usually high).

            1ml ≡ 0.315 % P                     % P x 2.29 ≡ % P₂O₅

            1ml ≡ 0.72 % P₂O₅                  P₂O₅ x 2.184 = (CaO)₃ P₂O₅

            (b) Gravimetric

                        Weigh off 1g of sample and transfer to a 600ml beaker. Add 25mls of aqua regia

(20mls HCl + 5mls HNO₃) – evaporate and bake. Take up in 20mls of HCl and water. Filter of

SiO₂ using N^o 31 paper and wash with HCl and water. To the filtrate add 100mls of ammonium

citrate solution (solution should darken – if not add a little ammonia). Cool to room temperature

or below and then add 25mls of magnesia mixture; agitate for 15 minutes. Settle for not less

than 3 hours, preferably 8.  Filter through paper pulp, washing precipitate thoroughly with 2%

NH₄OH (at least 6 times). Transfer to a silica crucible; char, ignite and weigh as Mg₂P₂O₇.

            Mg₂P₂O₇  x 100 x 0.6379 = % P₂O₅

            (c) Official

                        Weigh off 2.5g of sample and transfer to a 600ml beaker. Add 20 to 30mls of

water and agitate to wet the sample thoroughly. Add a further 70mls of water with continuous

stirring. Warm and add, dropwise with stirring, 10mls of HCl followed by 5mls HNO_3. Gently

simmer for 10 minutes; cool and dilute to 250mls in a standard flask. Filter solution through N^o

30 paper into a dry beaker, rejecting the first 20 to 30mls of filtrate. Pipette 25mls of solution (≡

0.25g) into a graduated 600ml beaker. Dilute to 100mls and heat to near boiling; add 5N NaOH

dropwise until a faint permanent turbidity or precipitate is formed. Add a few drops of HCl to

clear the solution (which is still on a hot plate). Dilute to 150mls; add 1g of citric acid followed

by 50mls of citric-molybdate solution. Boil gently for 3 minutes. Add, from a burette, 25mls of

quinoline solution with constant swirling (add the first few mls dropwise, the rest in a slow

stream). Again heat to boiling and boil gently for 1 or 2 minutes. Immerse the beaker in boiling

water for 5 minutes; then cool in running water until the contents of the beaker are about 15° C.

Filter through a thin triple layered paper pulp pad and wash beaker and precipitate with

successive small washes of cold water until they are free from acid. transfer the pad to the same

beaker, washing the funnel into the beaker (wipe with damp filter paper if necessary). Add no

more than 100mls of water and wobble vigorously until the pulp and precipitate are completely

dispersed. Add, from a burette, sufficient  standard NaOH (irons) to dissolve precipitate plus a

few mls of excess. Wobble vigorously to dissolve the precipitate (to facilitate this add a few

drops of the surface active agent). Add 0.5 to 1mls of thymol blue/phenolpthalein indicator and

back titrate excess NaOH with standard HNO₃ solution (iron). Endpoint: violet to green-blue

then very sharply yellow.

If m = N^o of mls of NaOH and n = normality of NaOH then,

            % P₂O₅  = m x n x 0.2732

Determination of Soluble P₂O₅  

            Weigh off 5g of sample and transfer to a one litre flask. Add 500mls of 2% citric acid

and agitate (manually or automatically) for 30 minutes. Filter into a dry clean beaker through N^o

 30 paper. Pipette 25mls of filtrate into a 600ml beaker and add 50mls of molybdic acid; heat

until the solution ‘blips’ then wobble for two minutes. Allow to settle for 15 minutes in a warm

place. Filter through a thick filter paper pulp pad, washing beaker thoroughly with dilute Nitric

acid (30mls of 1.25 S.G. nitric acid in about 750mls water). Wash the precipitate 8 or 9 times

with the potassium nitrate solution (5mls of stock solution in 750mls of water). After washing

the beaker out with water to remove any traces of acid, transfer to it the washed precipitate and

pulp. From a burette add 10mls of standard sodium hydroxide. Add about 150mls of water and

agitate (wobble) until precipitate dissolved. Add 10 drops of thymol blue/phenolphalein

indicator and back titrate with standard nitric acid solution.

Endpoint: Purple → Yellow

Calculation of Solubility

            Solubility = [(Soluble P₂O₅)/(Total P₂O₅) ] x 100

                             = [(Soluble phosphate)/(Total phosphate)] x 100

Report to two significant figures.

Basic Slag (Kaldo)

Preparation: Dry at 110°C in an oven. “Knock up” the larger pieces. Grind to a powder using a

pestle mortar or, more usually, sieve.

Determination of CaO

            As in Blast Furnace slag.

Determination of Fe, FeO and Fe₂O₃

            As in ores

Determination of P₂O₅

            As in basic slag

Determination of MnO

            As in Blast Furnace slag, but take a sample weight of 0.2g since the Mn content is

higher.

Determination of Silica

            As in Blast Furnace slag.

Determination of Alumina

            As in high iron ores.

Determination of MgO

            Gravimetric: As in Blast Furnace slag.

            Volumetric

            Weigh off 0.5g of sample into a dry 250ml beaker and add 5mls of water and boil. Add

15mls of HCl/HClO₄ acid mixture and evaporate to fumes – fume for about 5 minutes. Cool,

and wash watchglass and sides of beaker. Add 10-15 drops of phenolphalein; add 20% NaOH

dropwise until the first constant red colouration appears (not brown ferric hydroxide) {Note: at

this stage the NaOH has neutralised the excess acid, precipitated the iron, traces of aluminium

and left the other elements in solution.} Add 10mls HNO₃ – Fe solution {Note: this dissolves

hydrated ferric oxide, adds iron to solutions that are deficient and adjusts pH to about 4. A

reasonable precipitate of iron hydroxide is required at the end of the determination to facilitate

in filtration.} Cover the beaker and heat to boiling – remove from the source of heat and add

0.5g of potassium bromate  (KBrO₃) and boil gently for no longer than 5 minutes. {Note: the

KBrO₃ destroys the phenolphaleen and boiling for longer will cause hydrolysis of the iron

salts.} make the bulk up to 100mls with water {Note: this makes the volume of liquid right for

addition of the buffer solution.} heat to boiling and add buffer solution, which is firstly 10mls

of 20% NaAc followed by 20mls of 2.54N NaOH from a burette (whilst the solution is still

boiling on the plate). Boil for a further two minutes. {Note: the buffer solution adjusts the pH to

the range 8 – 9 and precipitates hydrated ferric hydroxide, traces of alumina, manganese

hydroxide; the silica remaining insoluble throughout.} Cool and filter through English paper (or

N^o 54) into a standard 250ml flask. Do not wash the paper and beaker more than twice with 5ml

portions of water. {Note: this ensures that peptisation does not occur.}

            Determination of CaO

                        Pipette 50mls of filtrate into a 500ml conical flask and add 50mls of water. Add

about 1g of urea {Note: this tends to hydrolise in preference to any Mn which is present.}, swirl

until dissolved and stand for one minute. Add 5mls H.S.N. murexide indicator followed by

5mls of 2.54N NaOH (to precipitate Mg(OH)₂) and titrate with standard E.D.T.A. 0.0125

(M/80) to the first pure blue colour.

            N^o of mls of E.D.T.A.  x  1.4  = %CaO

            Determination of MgO and CaO

                        Pipette 50mls of filtrate into a 500ml conical flask and add 50mls of water. Add

10-20mls of buffer solution {Note: raises pH to 11 which is the minimum value for operation of

the indicator, since its chelating action is very near its maximum and also the colour change is

right across the spectrum.} and heat to 65°C {Note: enhances the colour change}. Add 2mls of

erichrome black T indicator (this should be freshly made; alternately add a few mls of

triethanolamine + a speck of erichrome black T). Titrate with E.D.T.A., colour changes from

red to pure blue which is the end point.

            Titre for MgO + CaO – titre for CaO  = % MgO

Insoluble Slag

            Weigh off 0.25g of sample and transfer to a platinum crucible. Add 5mls of hydrofluoric

acid and 5mls of HNO_3. Evaporate down to about 4mls, then add 5mls of HClO₄ and evaporate

to fumes. Cool, wash the sides of the crucible with water a d again evaporate to fumes. Fume

for 5 minutes. Transfer to 250ml beaker with a small amount of water. Add 10-15 drops of

phenolphaleen and proceed from that point as described above.

Analysis of Burnt Lime

Reactivity (ASTM Method)

            Sieve the ‘as received’ sample through a N^o 6 screen mesh. Weigh off 76g of the fines

and transfer to a suitable container (such as a thermos flask which will retain the heat generated

by the reaction). Add 380mls of water (which is at a temperature of 24° C). Close the lid of the

container and agitate at between 250 and 350 revolutions per minute (shake like hell!). Take

thermometer readings every 30 seconds (between agitations) until three consecutive readings

are the same. Report the total temperature rise and the time to reach the first maximum reading.

Classify as follows:

            Time                                        Condition

            10 minutes or less                    Soft burnt

            10 to 20 minutes                     Medium burnt

            Over 20 minutes                      Hard burnt

Take the sieved material and dry in an oven at 110°C for 15 minutes and use this for the rest of

the determinations.

Sulphur Determination

            Grind a few grams to a fine powder using a pestle and mortar. Use the gravimetric

method as for sulphur in Blast Furnace slag but use a 2g sample.

Silica Determination

            Usual method.

Calcium Carbonate Determination

            Weigh of 1g of sample and transfer to a silica boat. Burn off in the carbon train,

following the method used for carbon in iron and steel.

            Difference in weight of bulb x 100 = % CO₂

            CO₂ x 2.274 = % CaCO₃

Combined Water Determination

            Weigh off 1g of sample into a crucible and place in a hot muffle for 30 minutes.

Reweigh and calculate the loss on ignition.

            % CO₂  -  L.O.I. = % combined water

Lime Determination

            100 – [%S + % SiO₂ + % CaCO₃] = %CaO

wash thoroughly with hot water

Job Descriptions.

All management at some time get the urge to play with new toys. The BSC were no exception and they chose to torture their subordinates with ‘Appraisals’. To this end each job had to be defined and benchmarked to enable the ‘worth’ of the job to be calculated and incorporated within a salary structure. (This would be about 1975).

The following were our rather sad efforts to realise these descriptions.

Junior Shift Chemist

Responsible to:            Senior Shift Chemist (or Senior Polyvac Operator if SSC absent)

Duties Involved:         1. “Wet” analysis of pig iron.

                                    2. Assist Junior Polyvac Operator in preparation of solutions.

                                    3. Assist Junior Polyvac Operator in maintaining laboratory equipment in

    a clean and tidy manner.

Responsibilities:          1. To provide accurate and rapid analysis of pig iron.

                                    2. To report all results obtained to the person involved with the approval

    of the SSC.

3. To record all results as a permanent laboratory record.

4. To assist SSC or SPO in tasks designated by them.

Personal Qualities: Quick and alert. Keen to learn. Intelligent and tidy worker.

Junior Polyvac Operator

Responsible to:            Senior Shift Chemist (or Senior Polyvac Operator if SSC absent)

Duties Involved:         1. To assist the SPO in the analysis of steel by Polyvac and “Wet”

    methods.

                                    2. Maintenance of the Carbon Train.

3. Maintenance of the sulphur apparatus.

4. Preparation of stock solutions.

            Technical Qualifications: Second year (T2) of Technicians Certificate in Chemistry or

     Metallurgy.

            Practical Experience:  Ideally one year as a JSC, during which time sufficient knowledge and

experience of the Polyvac to be capable of routine operation.

Responsibilities:          1. Assist SSC and SPO in tasks designated by them..

                                    2. To report all results obtained to the person involved with the approval

    of the SSC.

3. To record all results as a permanent laboratory record.

4. To maintain apparatus, reagent bottles etc, in clean condition.

Personal Qualities: Quick and alert. A willingness to receive instruction. Ability to work with a

        minimum of supervision.

Senior Polyvac Operator

Responsible to:            Senior Shift Chemist (or in his absent, Laboratory Manager)

Duties Involved:         1. Analysis of all steel samples by Polyvac and “Wet” methods.

                                    2. Routine Maintenance and standardisation of the Polyvac

3. Maintenance of the temperature stability of the Polyvac room and

   instrument.

4. To have sufficient knowledge of the Polyvac and temperature control

    system to give intelligent aid in the diagnosis of faults.

Technical Qualifications:  Technicians Certificate in Chemistry or Metallurgy.

Practical Experience:  Progression through junior positions.

Responsibilities:                      1. Provide accurate and rapid analysis using the Polyvac.

                                    2. Maintain instrument in correct state of calibration and

    standardisation at all times.

3. Ensure that laboratory equipment and solutions are available for

    “wet” analysis in the event of Polyvac breakdown. To prepare and

    maintain a Midvale bulb.

4. Rapidly report steel results to relevant departments.

5. To efficiently report other results to person directly involved.

6. Record all results obtained as a permanent laboratory record.

7. Instruct junior staff on request.

8. Assist the SSC on request.

9. Record and report all failures and abnormal occurrences concerning

    the Polyvac and any action taken.

10. In the absence of the SSC to assume his responsibilities (except

      appraisal).

Personal Qualities:  Quick and alert. Attentive to detail. A willingness to instruct others and to receive instruction. Ability to liase with personnel at foreman level. Ability to work with a minimum of supervision.

Further Details

1. Some theoretical knowledge of the Polyvac together with considerable practical experience of

    spectrographic and “wet” methods of analysis as a Junior Operator. Knowledge of other instruments

    used in the steel industry.

2. Awareness of the importance of speed and accuracy of reporting results and its effect on production.

3. Knowledge of other peoples functions within the department and in the production departments.

4. Conversant with department procedures. 

            Senior Shift Chemist

Responsible to:            Laboratory Manager

Duties Involved:         1. To supervise all analysis on his shift, including slags, steelworks

                            products, iron and raw materials.

                        2. To complete reports on all analyses, confirming or investigating

                            variances.

3. To carry out non-routine analysis when required.

Technical Qualifications:  Minimum of Advanced Technicians Certificate in Chemistry or Metallurgy.

Practical Experience:  Must know all the Departments on the Works and be aware of their products in order to gain sound knowledge of feasible analyses for each product. Must have experience and knowledge concerning available equipment. Must be aware of the accuracy required in each phase of the work.

Responsibilities:

1.      To designate and supervise the work programme on his shift and deal with

      questions of discipline within department policy.

2.      Assist in appraisal of staff.

3.      To cooperate with the training supervisor in training of junior staff; apportioning work so as to promote sound development of junior staff.

4.      To supervise and maintain safety requirements and ensure elimination of hazards.

5.      To ensure prompt treatment of injuries and to complete accident report forms.

6.      Assist in operation of department stock control system.

7.      To participate in management discussion on planning methods, staffing and equipment.

8.      Handling and providing reports, returns and statistics.

9.      To check suitability of samples prepared by staff other than those under his control.

10.  To report any abnormal happenings, and action taken regarding them.

11.  To ensure “good housekeeping”.

Laboratory Supervisor

Key Task: To supervise the day-to-day running of the laboratory with particular reference to the work carried out on shifts. To deputise for the Chief Chemist in his absence.

Directly Responsible to: Chief Chemist

Directly Supervises: Five Senior Shift Chemists; Four sample preparation operatives; Two labourers; One ore sampler.

Others with whom there are regular working relationships:

Internal Oral.

Chief Chemist to coordinate day shift work and to aid development of junior staff.

Managers and foremen of production and engineering departments to discuss variances occurring in analyses, continuous shift projects, technical problems and other relevant technical matters.

Other functions within the Technical Services Dept; to ensure cooperation and to coordinate efforts.

Foremen of service depts to inform of maintenance requirements.

Internal Written.

Technical reports to production and engineering dept managers for their information and use.

External Oral.

Material and equipment suppliers representatives to assist Chief  Chemist in determining the best materials and suppliers to fulfil the laboratories requirements.

External Written.

Suppliers and maintenance engineers concerning technical problems.

Use, and Effect on Use, of Resources.

(a)    5 SSC

4 SPO

4 JPO

4 JC and trainees

4 Sample Preparation Operatives

2 Labourers

1 Ore Sampler

       (b) Analytical laboratory fixtures and equipment including a direct reading spectrograph and

             sample preparation equipment.

Major Responsibilities for Results.

1. To assist the Chief  Chemist in ensuring that an efficient analytical service is provided by;

(a)    Allocating and coordinating specific work to laboratory staff.

(b)   Ensuring the availability and maintenance of the necessary equipment and materials.

(c)    Liaison with production depts to discuss their needs.

2. To monitor shift work performance and results and instigate investigations into variances when

       necessary. To instigate random checks to ensure reliability and consistency of operators and

       instruments.

3. To ensure observance of all safety regulations including elimination of hazards and replacement

      of safety equipment.

4. To assist in the control of costs by evaluating new products and ensuring efficient utilisation of

       materials.

5. To participate in management discussion on planning, manning, discipline and general dept

      policy.

6. To handle and provide reports, returns and statistics, and to maintain and monitor a data storage

      system.

7. To ensure liaison between Day Chemist (training) and the SSC’s concerning training and

      development of junior staff.

Limits of Responsibility.

            Absolute discretion on the allocation of specific jobs to shift working staff.

            Advises on the application of laboratory techniques and recommends changes in standard

            procedures.

Has the authority to requisition laboratory consumables within normal and reasonable stock

levels.

Can spend up to £20 on new equipment and can recommend purchase of equipment or materials

above this limit.

Has the authority to check and accept incoming laboratory supplies and to pass invoices for

payment.

Makes recommendations regarding appointment of staff within ‘graded staff’ range.

Qualifications and Experience.

Higher National Certificate or equivalent.

Extensive (not less than 5 years) experience in both chemical and spectrographic methods of

analysis on an integrated steelworks.

Sound knowledge of production plant layout, operations and materials.

Ability to communicate at all levels.

Ability to control and motivate working groups.

Attendance on supervisory or management courses desirable.

Previous supervisory experience required.

Normal working hours, but subject to occasional callouts.