Inhibitors polyphosphates-silicates

Oxygen, carbon dioxide and various chemicals used to reduce scaling can cause corrosion. Corrosion control is provided largely by the use of inhibitors such as chromates, polyphosphates, silicates and alkalies. 

Cathodic inhibitors in near-neutral solutions interfere with the oxygen reduction reaction by restricting the diffusion of dissolved oxygen to the electrode surface. These substances usually form thick surface layers with poor electronic conductivity (the latter is an important prerequisite to avoid oxygen reduction on the film surface). Examples are phosphates, polyphosphates, silicates, borates, and inorganic inhibitors, such as Zn +, which precipitate as Zn hydroxide, and Ca ", which forms calcium carbonate films in the presence of CO3 [3]. These inhibitors... 

As an example of these types of inhibitors, polyphosphates, phosphates, silicates, and benzotriazole can be mentioned. The action of these inhibitors is highly dependent on the environmental factors such as pH and redox potential. Therefore, they are anodic under certain conditions and cathodic otherwise. 

It is very rare that a single inhibitor is used in systems such as cooling water systems. More often, a combination of inhibitors (anodic and cathodic) is used to obtain better corrosion protection properties. The blends which are produced by mbdng of multi-inhibitors are called synergistic blends. Examples include chromate-phosphates, polyphosphate-silicate, zinc-tannins, zinc-phosphates. Phosphonates have been used to cathodically protect ferrous materials. Following are the major applications of synergistic blends of inhibitors. 

Scale formation Controlled scale deposition by the Langelier approach or by the proper use of polyphosphates or silicates is a useful method of corrosion control, but uncontrolled scale deposition is a disadvantage as it will screen the metal surfaces from contact with the inhibitor, lead to loss of inhibitor by its incorporation into the scale and also reduce heat transfer in cooling systems. Apart from scale formation arising from constituents naturally present in waters, scaling can also occur by reaction of inhibitors with these constituents. Notable examples are the deposition of excess amounts of phosphates and silicates by reaction with calcium ions. The problem can be largely overcome by suitable pH control and also by the additional use of scale-controlling chemicals. 

Elsewhere, in a series of Japanese patents, mixtures of resorcinol + sodium nitrate, glycerine + sodium nitrate, lithium hydroxide + tungstate, etc., have been claimed to be effective. An example of the use of inhibited cooling mixtures of low toxicity is provided by a patent which describes a mixture of silicate-I- polyphosphate -I- a saccharide, e.g. sucrose or fructose, as the inhibitor formulation in a propylene glycol -I- potassium-hydrogen-carbonate mixture used in aluminium cooler boxes for ice-cream. 

The first two components are the active surfactants, whereas the other components are added for a variety of reasons. The polyphosphate chelate Ca ions which are present (with Mg ions also) in so-called hard waters and prevents them from coagulating the anionic surfactants. Zeolite powders are often used to replace phosphate because of their nutrient properties in river systems. Sodium silicate is added as a corrosion inhibitor for washing machines and also increases the pH. The pH is maintained at about 10 by the sodium carbonate. At lower pH values the acid form of the surfactants are produced and in most cases these are either insoluble or much less soluble than the sodium salt. Sodium sulphate is added to prevent caking and ensures free-flowing powder. The cellulose acts as a protective hydrophilic sheath around dispersed dirt particles and prevents re-deposition on the fabric. Foam stabilizers (non-ionic surfactants) are sometimes added to give a... 

Most usually, a preoperational cleaning (POC) process/passivation program uses a chemical cleaner formulation based on a polyphosphate such as SHMP or STTP, together with various dispersants and surfactants. Where polyphosphate is not permitted to be discharged to sewer, silicates can often be used. Formulations may also include NaEDTA and sometimes specific corrosion inhibitors such as tolyltriazole (TTA). 

Corrosion inhibitors such as chromates, silicates, polyphosphates, nitrites, nitrates, borates and mercaptobenzothiazole have been used in corrosion inhibition of aluminum and its alloys.45... 

As described in the discussion of heat exchanger fouling elsewhere in this encyclopedia, anodic and cathodic reactions occur. Chemicals may be added to prevent these reactions they are termed anodic and cathodic inhibitors. Cathodic inhibitors form a barrier at the cathode reducing or eliminating H" " or O2 transport to the cathode. They include nitrites, silicates, tannins, and orthophosphates. Anodic inhibitors prevent or restrict electron transfer and include polyphosphates, polyphosphonates, and molybdates. Some of these chemicals represent nutrients for aquatic life and may encourage the growth of microorganisms. 

Chemical Treatment. A wide variety of chemicals and water treatments are used for corrosion control. Corrosion inhibitors usually act by forming some type of impervious layer on the metallic surface of either the anode or cathode that impedes the reaction at the electrode and thereby slows or inhibits the corrosion reaction. For example, various alkali metal hydroxides, carbonates, silicates, borates, phosphates, chromates, and nitrites promote the formation of a stable surface oxide on metals. The presence of these chemicals in the electrolyte allows any faults in the metal surface or its oxide film to be repaired. If they are used in too small a quantity as anodic inhibitors, they may promote intense local attack because they can leave a small unprotected area on the anode where the current density will be very high. This is particularly true of chromates and polyphosphates. 

Formulations usually contain a combination of different anodic and cathodic inhibitors. Commonly used are ortho- and polyphosphates, phosphonates, tannins, lignins, benzoates, silicates, chromates, molybdates, nitrites, nitrates, zinc salts, aromatic azoles, carboxylic acids, amides, amines, soluble oils, and oxygen scavengers, such as hydrazine and sulfites [3, 46]. Some of these substances (e.g. silicates) are employed predominantly in synergy with other inhibitors, whereas in other cases the combination of inhibitors may have adverse effects (e.g. nitrites and organic amines or amides may form carcinogenic nitrosamines at elevated temperatures). 

The inhibition of metal corrosion in industrial water systems was first achieved by the use of inorganic salts or their blends, including chromates (Evans, 1936 Mayne and Pryor, 1949), nitrites (Hatch, 1952), phosphates (Patterson and Jones, 1952), borates (Mercer, 1990), silicates (Lehrman and Shuldenen, 1952), zinc salts (Hatch, 1965 a) and other cations (Hinton, 1989). Additionally, chromates and nitrites were mainly applied, and from the end of the 1950s the use of polyphosphates increased (May et al., 1981 Hwa, 1971). Treatments with anodic inhibitors such as nitrites or chromates require a high initial dose and a relatively high continuous dose in order to achieve an effective passive layer on the metal surface. The concentration of chromate and nitrite can be decreased in the presence of polyphosphates and zinc ions. 

Calcium sequesterers that give soluble calcium species are also growth inhibitors of insoluble salts. Sodium silicates in their polyanionic form, as well as the highly condensed polyphosphates, play this role as well. The shorter polyphosphates such as pyrophosphates and tripolyphosphate, and a fortiori the orthophosphates, fail to function as inhibitors, because in substoichiometric proportion to calcium, they forni insoluble salts that precipitate out. 

Corrosion Inhibitors. A water-soluble corrosion inhibitor reduces galvanic action by making the metal passive or by providing an insulating film on the anode, the cathode, or both. A very small amount of chromate, polyphosphate, or silicate added to water creates a water-soluble inhibitor. A slightly soluble inhibitor incorporated into the prime coat of paint may also have a considerable protective influence. Inhibitive pigments in paint primers are successful inhibitors except when they dissolve sufficiently to leave holes in the paint film. Most paint primers contain a partially soluble inhibitive pigment such as zinc chromate, which reacts with the steel... 

Inhibitors can be used to control corrosion of aluminum alloys. Chromates, silicates, polyphosphates, soluble oils, and others, are in common use. Inhibitors, however, must be used with care in order to achieve the desired result. Chromates ate effective inhibitors if used in sufficiently high concentrations. However, if concentration is insufficient, corrosive attack may be intensiffed. In addition, chromates impart conductivity to the electrolyte, thereby enhancing galvanic effects and altering the solution potential relationships between cladding and core in alclad alloys. 

---