Zinc oxide salts

Henkel Rearrangement of Benzoic Acid and Phthalic Anhydride. Henkel technology is based on the conversion of benzenecarboxyhc acids to their potassium salts. The salts are rearranged in the presence of carbon dioxide and a catalyst such as cadmium or zinc oxide to form dipotassium terephthalate, which is converted to terephthahc acid (59—61). Henkel technology is obsolete and is no longer practiced, but it was once commercialized by Teijin Hercules Chemical Co. and Kawasaki Kasei Chemicals Ltd. Both processes foUowed a route starting with oxidation of napthalene to phthahc anhydride. In the Teijin process, the phthaHc anhydride was converted sequentially to monopotassium and then dipotassium o-phthalate by aqueous recycle of monopotassium and dipotassium terephthalate (62). The dipotassium o-phthalate was recovered and isomerized in carbon dioxide at a pressure of 1000—5000 kPa ( 10 50 atm) and at 350—450°C. The product dipotassium terephthalate was dissolved in water and recycled as noted above. Production of monopotassium o-phthalate released terephthahc acid, which was filtered, dried, and stored (63,64). 

Zinc oxide is a common activator in mbber formulations. It reacts during vulcanization with most accelerators to form the highly active zinc salt. A preceding reaction with stearic acid forms the hydrocarbon-soluble zinc stearate and Hberates water before the onset of cross-linking (6). In cures at atmospheric pressure, such as continuous extmsions, the prereacted zinc stearate can be used to avoid the evolution of water that would otherwise lead to undesirable porosity. In these appHcations, calcium oxide is also added as a desiccant to remove water from all sources. 

Magnesium oxide is a typical acid scavenger for chlorinated mbbers. Compounds containing zinc oxide or magnesium oxide may tend to swell upon immersion in water. These inorganic salts have some water solubiHty and osmotic pressure causes the vulcanizates to imbibe water to equalize pressure (8,9). As such, vulcanizates tend to sweU more in fresh (distilled) water than in salt water. To minimize water sweU, insoluble salts such as lead oxides can be substituted. Because of the health concerns associated with lead, there is much mbber industry interest in other acid acceptors, such as synthetic... 

Activators. Activators are chemicals that increase the rate of vulcanization by reacting first with the accelerators to form mbber soluble complexes. These complexes then react with the sulfur to achieve vulcanization. The most common activators are combinations of zinc oxide and stearic acid. Other metal oxides have been used for specific purposes, ie, lead, cadmium, etc, and other fatty acids used include lauric, oleic, and propionic acids. Soluble zinc salts of fatty acid such as zinc 2-ethyIhexanoate are also used, and these mbber-soluble activators are effective in natural mbber to produce low set, low creep compounds used in load-bearing appHcations. Weak amines and amino alcohols have also been used as activators in combination with the metal oxides. 

Anhydrous zinc chloride can be made from the reaction of the metal with chlorine or hydrogen chloride. It is usually made commercially by the reaction of aqueous hydrochloric acid with scrap zinc materials or roasted ore, ie, cmde zinc oxide. The solution is purified in various ways depending upon the impurities present. For example, iron and manganese precipitate after partial neutralization with zinc oxide or other alkah and oxidation with chlorine or sodium hypochlorite. Heavy metals are removed with zinc powder. The solution is concentrated by boiling, and hydrochloric acid is added to prevent the formation of basic chlorides. Zinc chloride is usually sold as a 47.4 wt % (sp gr 1.53) solution, but is also produced in soHd form by further evaporation until, upon cooling, an almost anhydrous salt crystallizes. The soHd is sometimes sold in fused form. 

The principal mbbers, eg, natural, SBR, or polybutadiene, being unsaturated hydrocarbons, are subjected to sulfur vulcanization, and this process requires certain ingredients in the mbber compound, besides the sulfur, eg, accelerator, zinc oxide, and stearic acid. Accelerators are catalysts that accelerate the cross-linking reaction so that reaction time drops from many hours to perhaps 20—30 min at about 130°C. There are a large number of such accelerators, mainly organic compounds, but the most popular are of the thiol or disulfide type. Zinc oxide is required to activate the accelerator by forming zinc salts. Stearic acid, or another fatty acid, helps to solubilize the zinc compounds. 

Azocarbonamide (I) Carbonamide N2, CO, CO2 190-230 220 Most widely used blowing agent in PVC and polyolefins. High decomposition temperature reduced by a variety of metal salts and oxides such as lead carbonate, lead phosphite and zinc oxide. High gas yield. Reaction products show little odour or discoloration. ... 

Accelerated sulphur systems also require the use of an activator comprising a metal oxide, usually zinc oxide, and a fatty acid, commonly stearic acid. For some purposes, for example where a high degree of transparency is required, the activator may be a fatty acid salt such as zinc stearate. Thus a basic curing system has four components sulphur vulcanising agent, accelerator (sometimes combinations of accelerators), metal oxide and fatty acid. In addition, in order to improve the resistance to scorching, a prevulcanisation inhibitor such as A -cyclohexylthiophthalimide may be incorporated without adverse effects on either cure rate or physical properties. 

Both zinc and zinc alloys have excellent resistance to corrosion in the atmosphere and in most natural waters. The property which gives zinc this valuable corrosion resistance is its ability to form a protective layer consisting of zinc oxide and hydroxide, or of various basic salts, depending on the nature of the environment. When the protective layers have formed and completely cover the surface of the metal, the corrosion proceeds at a greatly reduced rate. 

In dry air, a film of zinc oxide is initially formed by the influence of the atmospheric oxygen, but this is soon converted to zinc hydroxide, basic zinc carbonate and other basic salts by water, carbon dioxide and chemical impurities present in the atmosphere. 

Salt solutions When a zinc sheet is immersed in a solution of a salt, such as potassium chloride or potassium sulphate, corrosion usually starts at a number of points on the surface of the metal, probably where there are defects or impurities present. From these it spreads downwards in streams, if the plate is vertical. Corrosion will start at a scratch or abrasion made on the surface but it is observed that it does not necessarily occur at all such places. In the case of potassium chloride (or sodium chloride) the corrosion spreads downwards and outwards to cover a parabolic area. Evans explains this in terms of the dissolution of the protective layer of zinc oxide by zinc chloride to form a basic zinc chloride which remains in solution. 

Feitknecht has examined the corrosion products of zinc in sodium chloride solutions in detail. The compound on the inactive areas was found to be mainly zinc oxide. When the concentration of sodium chloride was greater than 0-1 M, basic zinc chlorides were found on the corroded parts. At lower concentrations a loose powdery form of a crystalline zinc hydroxide appeared. A close examination of the corroded areas revealed craters which appeared to contain alternate layers and concentric rings of basic chlorides and hydroxides. Two basic zinc chlorides were identified, namely 6Zn(OH)2 -ZnClj and 4Zn(OH)2 ZnCl. These basic salts, and the crystalline zinc hydroxides, were found to have layer structures similar in general to the layer structure attributed to the basic zinc carbonate which forms dense adherent films and appears to play such an important role in the corrosion resistance of zinc against the atmosphere. The presence of different reaction products in the actual corroded areas leads to the view that, in addition to action between the major anodic and cathodic areas as a whole, there is also a local interaction between smaller anodic and cathodic elements. 

The cement sets as the result of an acid-base reaction between a zinc oxide dental powder and a poly(alkenoic acid). The pH increases and an insoluble amorphous salt is formed which acts as the cement matrix. A general account of the gelation processes is given in Section 5.4. 

There is bound to be one problem with resin glass polyalkenoate cement. Because the matrix is a mixture of hydrogel salt and polymer, lightscattering is bound to be greater than in the conventional material. Moreover, the zinc oxide-containing glass of class II materials is bound to be opaque. This makes it difficult to formulate a translucent material and is the reason why their use is restricted to that of a liner or base. However, the class II material cited will be radio-opaque because it uses strontium and zinc, rather than calcium, in the glass. 

A more successful approach was that of Higashi et al. (1969a,b 1972). They blended solid add phosphate salts with zinc oxide powder. One add salt used was a predpitated hydrate of ZnH2P04. The cement was formed by mixing this powder blend with water. Work progressed to the point where three commercial brands of these so-called hydrophosphate cements appeared on the market. None met the spedfication requirements... 

The zinc oxide used in ZOE cements differs entirely from that used in zinc phosphate cements. Whereas the latter has to be ignited to a very high temperature to deactivate it, the opposite is true of the zinc oxides used in the ZOE cement, which are of an activated variety. They are normally prepared by the thermal decomposition of zinc salts at 350 °C to 450 °C such oxides are yellow. Zinc oxides prepared by oxidizing zinc in oxygen may also be used these are white. 

Zinc oxide is made either by the oxidation of the metal in oxygen (the indirect, IP, or French process), by the direct decomposition of zinc ores in air (the direct or American process) or by the thermal decomposition of zinc salts (TD zinc oxide). IP zinc oxides differ from TD zinc oxides in that their surfaces do not contain absorbed water. Also, whereas TD zinc oxide reacts with plain eugenol, IP zinc oxide hardly reacts unless activated by an acetic add or zinc acetate accelerator (Table 9.2). 

The liquids used were 1 1 mixtures of EBA-HV and liquid methacrylate which also contained dihydroxyethyl-p-toluidine as the accelerator. Both mono- and di-methacrylates were used. The benzoyl peroxide initiator was included in the EBA zinc oxide/silanized (1 1) glass powder. These polymer cements set 5 to 10 minutes after mixing. Since there is a substantial amount of monomer in the liquid (50%) the contribution of the polymer to the strength of the cement must be considerable. Brauer Stansbury (1984b) suggested that the two matrices, the polymer matrix and the salt matrix, may be interpenetrating but separation of the two phases is likely. 

Cowan Teeter (1944) reported a new class of resinous substances based on the zinc salts of dimerized unsaturated fatty acids such as linoleic and oleic acid. The latter is referred to as dimer acid. Later, Pellico (1974) described a dental composition based on the reaction between zinc oxide and either dimer or trimer acid. In an attempt to formulate calcium hydroxide cements which would be hydrolytically stable, Wilson et al. (1981) examined cement formation between calciimi hydroxide and dimer acid. They found it necessary to incorporate an accelerator, alimiiniiun acetate hydrate, Al2(OH)2(CHgCOO)4.3H2O, into the cement powder. 

Zinc hydroxy double salts are layered materials similar to layered double hydroxides which show intercrystalline reactivity and incorporate organic compounds between layers.337 Hydroxy double salts of high crystallinity can be obtained by reacting ZnO with organic metal salts in water. Zinc oxide crystals could then be prepared by thermal treatment of hydroxy zinc acetate.338... 

In a review of the course and mechanism of the catalytic decomposition of ammonium perchlorate, the considerable effects of metal oxides in reducing the explosion temperature of the salt are described [1], Solymosi s previous work had shown reductions from 440° to about 270° by dichromium trioxide, to 260° by 10 mol% of cadmium oxide and to 200°C by 0.2% of zinc oxide. The effect of various concentrations of copper chromite , copper oxide, iron oxide and potassium permanganate on the catalysed combustion of the propellant salt was studied [2], Similar studies on the effects of compounds of 11 metals and potassium dichromate in particular, have been reported [3], Presence of calcium carbonate or calcium oxide has a stabilising effect on the salt, either alone or in admixture with polystyrene [4],... 

The shift in the C=C frequency, vi, for adsorbed ethylene relative to that in the gas phase is 23 cm-1. This is much greater than the 2 cm-1 shift that is observed on liquefaction (42) but is less than that found for complexes of silver salts (44) (about 40 cm-1) or platinum complexes (48) (105 cm-1). Often there is a correlation of the enthalpy of formation of complexes of ethylene to this frequency shift (44, 45). If we use the curve showing this correlation for heat of adsorption of ethylene on various molecular sieves (45), we find that a shift of 23 cm-1 should correspond to a heat of adsorption of 13.8 kcal. This value is in excellent agreement with the value of 14 kcal obtained for isosteric heats at low coverage. Thus, this comparison reinforces the conclusion that ethylene adsorbed on zinc oxide is best characterized as an olefin w-bonded to the surface, i.e., a surface w-complex. 

Solution-grown zinc oxide nanowires by Greene etal. (2006). Strategies for growing ZnO nanowires from zinc salts in aqueous and organic solvents are reviewed. 

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