Chromium basic

Chrome Tanning. The original chrome tanning was a two-bath process. The unhaired hides, delimed and bated, were treated with a solution of sodium bichromate [10588-01-9]. The amount of bichromate used was about 3—5% based on the weight of the hides. The bichromate was absorbed or adsorbed into the hide, the solution drained, and the hides refloated. Sodium bisulfite was added and two important reactions resulted in the formation of a basic chromium and coUoidal sulfur in the hide. This gave a chrome taimage and also helped to fiH the hide with the soHd sulfur. This cmde system, which continued in the industry in some types of leather for over 50 years, is obsolete. 

Modem chrome-tanning methods are weU controUed and employ an extensive knowledge of the chemistry of the system. The most common chromium-tanning material used is basic chromium sulfate [12336-95-7] Cr(0H)S04, made by the reduction of sodium bichromate with sulfur dioxide or by sulfuric acid and a sugar. 

Ionisation of the basic chromium salt results in the formation of complex ions such as L A The... 

After penetration of the hide by the chromium the pH is raised to about 3.5—4.0. At this higher pH a change occurs in the chromium complexes as the basicity of the chromium increases and binding to the protein becomes possible. Chromium binds firmly to the protein forming a cross-link species, and as the pH increases the hydrogen is removed from the complex forming a stable stmcture. 

The chromium can be stabilized in a limited way to prevent surface fixation by addition of formate ions. The formate displaces the sulfate from the complex and masks the hydroxyl ions from forming the larger higher basicity complexes. This stabilization can then be reversed in the neutralization to a pH of about 4.0 and taimage becomes complete. This simple formate addition has decreased the time of chrome tanning by about 50% and has greatly increased the consistent quaHty of the leather produced. 

Coatings, Paints, and Pigments. Various slightly soluble molybdates, such as those of zinc, calcium, and strontium, provide long-term corrosion control as undercoatings on ferrous metals (90—92). The mechanism of action presumably involves the slow release of molybdate ion, which forms an insoluble ferric molybdate protective layer. This layer is insoluble in neutral or basic solution. A primary impetus for the use of molybdenum, generally in place of chromium, is the lower toxicity of the molybdenum compound. 

Leather Taiming. Oxahc acid is used as a pH modifier in leather tanning by tannin and basic chromium sulfate. It also functions as a bleaching agent for leather (qv). 

Chemical Properties. The valence states of chromium are +2, +3, and +6, the latter two being the most common. The +2 and +3 states are basic, whereas the +6 is acidic, forming ions of the type CrO (chromates) and (Cr203 [ (dichromates). The blue—white metal is refractory and very hard. 

Hard plating is noted for its excellent hardness, wear resistance, and low coefficient of friction. Decorative plating retains its brilliance because air exposure immediately forms a thin, invisible protective oxide film. The chromium is not appHed directiy to the surface of the base metal but rather over a nickel (see Nickel and nickel alloys) plate, which in turn is laid over a copper (qv) plate. Because the chromium plate is not free of cracks, pores, and similar imperfections, the intermediate nickel layer must provide the basic protection. Indeed, optimum performance is obtained when a controlled but high density (40—80 microcrack intersections per linear millimeter) of microcracks is achieved in the chromium lea ding to reduced local galvanic current density at the imperfections and increased cathode polarization. A duplex nickel layer containing small amounts of sulfur is generally used. In addition to... 

Table 18. Basic Numbering System for Chromium-Bearing Low Alloy Steels...

Ghromium(III) Compounds. Chromium (ITT) is the most stable and most important oxidation state of the element. The E° values (Table 2) show that both the oxidation of Cr(II) to Cr(III) and the reduction of Cr(VI) to Cr(III) are favored in acidic aqueous solutions. The preparation of trivalent chromium compounds from either state presents few difficulties and does not require special conditions. In basic solutions, the oxidation of Cr(II) to Cr(III) is still favored. However, the oxidation of Cr(III) to Cr(VI) by oxidants such as peroxides and hypohaUtes occurs with ease. The preparation of Cr(III) from Cr(VI) ia basic solutions requires the use of powerful reducing agents such as hydra2ine, hydrosulfite, and borohydrides, but Fe(II), thiosulfate, and sugars can be employed in acid solution. Cr(III) compounds having identical counterions but very different chemical and physical properties can be produced by controlling the conditions of synthesis. 

The final consideration for the manufacture of Cr(III) compounds is the mole ratio of acid to Cr. This ratio determines the basicity value of the product. Basicity can also be stated as the amount of positive charge on chromium (ITT) neutralized by hydroxide. For example, is 0% basic,... 

Ceitain acid dyes can have thek fastness piopeities impioved by combining the dye with a metal atom (chelation). The most common metal is chromium, although cobalt is sometimes used, and this can be introduced in a number of ways. The basic mechanism is donation of electron pans by groups in the dye (ligands) to a metal ion. For example, has a coordination number of 6, and therefore will accept six lone pans of electrons. Typical ligand groups... 

Neutralizing removes the large amount of hexavalent chromium from the surface of the part. Hexavalent chromium shortens the life of the catalyst, and trace amounts completely inhibit electroless nickel deposition. The neutralizer is usually a mildly acidic or basic reducing agent, but other types of neutralizers are available, especially for substrates that are difficult to plate. The neutralizer may also contain surfactants (qv) or other compounds that increase catalyst absorption absorption promoters are often needed for non-ABS plastics. 

The reactions are generally run at room temperature or below. With steroids the product is usually isolated by addition of the reaction mixture to water followed by filtration or extraction. The inorganic product of the reaction, chromium III, is soluble in neutral or aqueous acid solutions and can be removed by washing. When steroidal amines are oxidized, the work-up is usually modified such that the steroid may be extracted from the insoluble basic chromium III salts. °... 

The basic corrosion behaviour of stainless steels is dependent upon the type and quantity of alloying. Chromium is the universally present element but nickel, molybdenum, copper, nitrogen, vanadium, tungsten, titanium and niobium are also used for a variety of reasons. However, all elements can affect metallurgy, and thus mechanical and physical properties, so sometimes desirable corrosion resisting aspects may involve acceptance of less than ideal mechanical properties and vice versa. 

The grades with the 410 or 420 numerals are the basic 13% chromium type with varied carbon content. The additions of sulphur or selenium (possibly with phosphorus) to some grades (416 group) is to improve machinability. 431S29 has increased chromium content to improve corrosion resistance, but reference to Fig. 3.11 shows that such addition alone would lead to a mixed martensite-5-ferrite structure with certain disadvantages to mechanical properties. The nickel addition is to limit ferrite content. 

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