PREPARATION OF SHEET STEEL FOR PORCELAIN ENAMELING

Introduction 1
Normally, sheet steel as supplied is such that it cannot be porcelain enameled without further treatment. ASTM Types 1, 2 and 3 are usually shipped with a protective coating of mineral oil to prevent rusting. Ideally this mill oil should be removed prior to applying drawing compounds to the steel surface. The purpose of the metal cleaning stage is two fold: 1) to remove mill oils or rust preventives, And 2) to remove soaps and oils which might have been applied to the steel by the fabricator in the forming process.

Introduction 2
In some cases, the surface of the steel must be etched or roughened to form a suitable base for porcelain enamel application and to assure adherence. This etching is achieved by pickling the formed part in either sulfuric acid or ferric ions or both.

Introduction 3
Since alkaline materials are used to clean the metal and acid materials are used for the pickle, a final stage neutralizer must be used to neutralize the acid salts on the surface of the steel and prevent rusting prior to enamel application.

Cleaning
Cleaning sheet steel prior to porcelain enameling is the most important step in the operation. Competent cleaning is imperative to insure good porcelain enamel adherence with a minimum of defects. Five major factors must be carefully considered to insure efficient metal preparation in the cleaning phase: 1. Soils to be removed 2. Metal cleaning compounds 3. Equipment systems for cleaning 4. Pre-cleaning 5. Proper operation of cleaning phase

Soils to be Removed 1
These can be generally classified as follows: 1. Mill Oils - Mixtures of mineral oils, fats, petroleum sulfonates and heavy metal soaps. 2. Drawing Compounds (dry type) - Sodium and/or potassium soaps, borax, saturated or unsaturated fatty acids, and heavy metal soaps. 3. Drawing Compounds (oil soluble) - Mineral oils, fats, waxes, saturated or unsaturated fatty acids, polyhydric alcohols, and sulfurized or chlorinated fats or hydrocarbons. 4. Drawing Compounds (water emulsifiable) - Mixtures of free fats (both animal and vegetable), emulsified mineral oils, waxes, sulfurized or chlorinated fats or hydrocarbons and calcium carbonate pigments. 5. Synthetic Drawing Compound - Polymers, corrosion inhibitors, and lubricity additives. 6. Rust Preventives - Waxes, petrolatum, mineral oils, fats, and additives (such as heavy metal soaps and oxygenated hydrocarbons). 7. Shop Soils - Consisting primarily of dust and metal particles which may be organic or inorganic.

Metal Cleaning Compounds

There are three principal types of metal cleaners: 1) alkaline, 2) organic solvents, and 3) emulsion, emulsifiable or di-phase emulsion ALKALINE CLEANERS: These cleaners contain mixtures of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, sodium orthosilicate, trisodium phosphate, tetrasodium pyrophosphate, borates, wetting agents and chelating agents. Alkaline cleaners are used in two different ways: 1) immersion cleaning operated at a concentration of from 6 to 12 ounces per gallon of water and at temperaturesof 180(F to boiling, or 2) power spray cleaning operated at a concentration of to 2 ounces per gallon of water at temperatures of 120(F to 180(F. ORGANIC SOLVENTS : These metal cleaners include petroleum distillates, coal tar solvents, chlorinated hydrocarbons, and special solvents such as methyl ethyl ketone. When using organic solvent as a cleaner, adequate ventilation should be provided because these materials are either or both highly toxic and inflammable.

EMULSION, EMULSIFIABLE OR DI-PHASE EMULSION : These types of cleaners are mixtures of solvents, as mentioned above, and emulsifiers. They are operated at room temperature to 180(F, depending on the type of solvent which is emulsified, and at a concentration of 2-10% in water. These materials are usually operated as an immersion cleaner; however, some power spray units are employed. Alkaline cleaners are almost always used as the primary cleaning material. Selecting the proper cleaning material is very important.

Equipment Systems for Cleaning

Each of the three equipment systems mentioned previously can be used for the cleaning operation. 1. Batch System 2. Automatic Machines a. Immersion Cleaning System b. Spray Cleaning System c. Combination Immersion and Spray Cleaning System

Pre-Cleaning
Prolonged aging of even readily saponifiable or emulsifiable fabricating lubricants may result in a chemical reaction forming insoluble metal soaps on parts. These materials should be removed immediately after fabrication. If fabricating lubricants and other contaminants are allowed to dry and age on parts in storage, it may be necessary to use either emulsion or solvent type pre-cleaners prior to normal alkaline cleaning and pickling. There are four types of special pre-cleaners: 1. Di-phase emulsion 2. Full emulsion 3. Solvent emulsifiable 4. Vapor degreasing

Pickling
Pickling For Ground Coat Enameling The purpose of acid pickling is to remove oxides such as rust or welding oxides and to etch the steel surface. This is necessary to prepare the surface for the subsequent nickel flashing step, and also for the enameling operation. If left on the surface, iron oxide would be a detriment to both operations and would result in poor enamel-metal bond. Chemically, the reactions with sulfuric acid are as follows: a. Fe2O3 (rust) +3H2SO4 Fe2 (SO4)3+3H2 b. FeO (welding oxide) +H2 SO4 FeSO4 +H2 O c. Fe +H2 SO4 FeSO4 +H 2 Acid Tanks Acid tanks are usually constructed of acid bricks, ss316L, wood, or are lined with lead, plastic or rubber. All of these materials have advantages and disadvantages, as shown in Table II.

Typical Data

Pickling For Direct-On Enameling

Nickel Deposition Chemical Reactions: When freshly etched iron comes in contact with a solution of nickel sulfate of proper concentration at suitable temperature and pH, an electrochemical reaction takes place.

This results in the deposition of metallic nickel on the surface of the steel and the solution of an equivalent amount of iron. Chemically, the reaction is as follows: Ni + FeSO4 (solution). (6) Fe + NiSO4 (solution)

Neutralizing The function of the neutralizer in a porcelain enamel pickling operation is to: A. Neutralize acid residuals. B. Provide rust protection C. Control the residual surface chemicals to minimize their effect during the enamel application and adherence formation.

Test and Control

Titration Alkali Cleaner and Neutralizer: A. Pipette a 10 ml sample of the cleaner solution into a 250 ml beaker. B. Add 50 ml of distilled water and 2-3 drops of indicator solution. C. Titrate the: 1. Yellow colored solution if methyl orange indicator is used. 2. Red or Pink colored solution if phenolphthelain indicator is used with 1.0 normal sulfuric acid until one drop of the acid changes solution to: a. Red when methyl orange indicator has been used, or b. Clear or Colorless when phenolphthalein indicator has been used. D. Read the burette and multiply the number of ml of 1.0 normal acid used in the titration by the titration factor furnished by the cleaner supplier. The value resulting from the multiplication represents the concentration of the cleaner in terms of ounces per gallon or percent of concentration. Abrasive Blast Cleaning This section addresses the mechanical preparation process of abrasive blast cleaning, which is effective for cleaning heavy gauge steel parts and cast iron.

Cast iron, suitable for enameling

Cast iron with lamellar graphite complying to DIN 1691 (gray cast iron) The follwing limiting values of the main elements should be kept: a) Carbon, total C 3.20 - 3.40 b) Carbon, combined C max. 0.20 c) Silicon Si 2.50 - 3.00

d) Manganese Mn max.0.50 e) Phosphorus P 0.50 - 1.00 f) Sulphur S max.0.12 Trace elements: g) Chromium Cr max. 0.05 h) Copper Cu max. 0.10 i) Molybdenum Mo max. 0.05 j) Nickel Ni max. 0.05 k) Titanium Ti max. 0.10 l) Vanadium V max. 0.05 Saturation value: Sc = min. 1.04 max. 1.08 Cast iron with spherical graphite complying to DIN 1693 (spheriodical graphite iron) Chemical analysis The following limiting values of the main elements should be kept: Cast Iron with spherical graphite Structure after thermal treatment ferritic ferritic/pearlitic a) Carbon, total C 3.500 - 4.000 3.500 - 4.000 b) Carbon, combined C max. 0.100 max. 0.500 c) Silicon Si 2.800 - 4.000 2.200 - 3.000 d) Manganese Mn max. 0.200 max. 0.200 e) Phosphorus P max. 0.050 max. 0.050 f) Sulphur S max. 0.005 max. 0.005 g) Magnesium Mg max. 0.030 max. 0.030 h) Aluminium Al max. 0.005 max. 0.005 Trace elements : i) Chromium Cr max. 0.005 j) Copper Cu max. 0.100 k) Molybdenum Mo max. 0.050 l) Nickel Ni max. 0.050 m) Titanium Ti max. 0.100 n) Vanadium V max. 0.050

Enameling
For the enameling process the surface of the cast iron has to be clean and free of burned-in sand. Its medium roughness should not exceed 300 microns.
CLEANING

For cleaning the cast iron prior to enamelling only angular shot blasting material on the basis of cast-steel or chilled cast iron has been proved. Both grades are having the essential hardness and edge stability ( Vickers-Hardness HV above 650 ). Fractionated

Control of the sheet steel pre-treatment

Testing of degreasing baths Explanation Customary emulsifying degreasing is based on the emulsification of oily or greasy residues in blends of hydrocarbons under the addition of surfactants or wetting agents. These are mostly long catenary organic compounds posessing a lipophilic ( on-grease accumulating ) and a hydrophilic ( on-water accumulating ) part of a molecule. There are anionic or cationic active or non ionogeni surfactants.

Due to skilful combinations optimal degreasing results for each, oil, grease and emulsions are achieved by the manufacturers of degreasing agents. The multiplicity of combinations in degreasing agents does not permit to name a simple and in general valid analysis for enameling works. For controlling the degreasing baths manufacturers of degreasing agents issue obligatory processing guidelines. Because of the complicated control of degreasing baths it is recommendable to register on a daily basis the m2 - surface throughput and its degree of fouling. A good genera view about the efficiency of degreasing baths results from the quantity of degreasing agents used, the surface throughput and the degree of fouling. Quick-test of degreasing baths . In order to check the effectiveness quickly, the following small-scale test should be carried through several times per day. A degreased component out of production is to be immersed for about 30 sec. into the pickling bath ( e.g. hot, 9 % sulphuric acid ) and consequently rinsed with cold water. The water film on the surface must remain closed and should not pull apart.

Determination of acid concentration, sulphuric acid pickling.

ANALYSIS INSTRUCTIONS: 1. Take a cooled (20 C) sample of the pickling bath solution into a 100 ml measuring flask and top up to the mark with distilled water. 2. 10 ml of this solution ( = 1 ml original ) are to be pipetted in an Erlenmeyer flask. 3. After an addition of about 100 ml distilled water, about 5g ammonium sulphate and 5 drops bromocresol green, titrate with 0.1 n NaOH until the colour changes from orange to blue. ml consumption 0.1 n NaOH x 4.9 = g H2SO4 / l pickling solution REQUIRED REAGENTS: 1. Ammonium sulphate 2. Bromocresol green 3. 0.1 g bromocresol green dissolved in 100 ml ethanol 4. 0.1 n caustic soda solution

Determination of bivalent iron, sulphuric acid pickling

PURPOSE AND SCOPE Too high a content of iron (II) - sulphate can lead to a crystallizing pickling bath while cooling down. The concentration of iron in pickling baths has to be checked regularly. Analysis instructions 5 ml of a cooled (20 0C) sample of the pickling bath solution is to be mixed with about 100 ml distilled water and 10 ml Reinhardt - Zimmermann - solution in an Erlenmeyer flask and titrated under strong agitation with 0.1 n KMnO4 - solution. The titration is brought to an end when after the last addition of potassium permanganate the solution still shows after one minute a light pink. ml consumption 0.1 n KMnO4 x 1.1 = g Fe2+ / l pickling solution REQUIRED REAGENTS: 1. Reinhardt-Zimmermann-solution: 2. 67 g MnSO4 x 4 H2O, 138 ml H3PO4 (density 1.70 ) and 3. 130 ml H2SO4 ( density 1.82 ) are to be filled up with 1000 ml distilled water. 4. 0.1 n potassium permanganate solution