Metal stabilization with

Samarium has a bright silver luster and is reasonably stable in air. Three crystal modifications of the metal exist, with transformations at 734 and 922oC. The metal ignites in air at about ISOoC. The sulfide has excellent high-temperature stability and good thermoelectric efficiencies up to llOOoC. 

BackTitrations. In the performance of aback titration, a known, but excess quantity of EDTA or other chelon is added, the pH is now properly adjusted, and the excess of the chelon is titrated with a suitable standard metal salt solution. Back titration procedures are especially useful when the metal ion to be determined cannot be kept in solution under the titration conditions or where the reaction of the metal ion with the chelon occurs too slowly to permit a direct titration, as in the titration of chromium(III) with EDTA. Back titration procedures sometimes permit a metal ion to be determined by the use of a metal indicator that is blocked by that ion in a direct titration. Eor example, nickel, cobalt, or aluminum form such stable complexes with Eriochrome Black T that the direct titration would fail. However, if an excess of EDTA is added before the indicator, no blocking occurs in the back titration with a magnesium or zinc salt solution. These metal ion titrants are chosen because they form EDTA complexes of relatively low stability, thereby avoiding the possible titration of EDTA bound by the sample metal ion. 

Ultimately, as the stabilization reactions continue, the metallic salts or soaps are depleted and the by-product metal chlorides result. These metal chlorides are potential Lewis acid catalysts and can greatiy accelerate the undesired dehydrochlorination of PVC. Both zinc chloride and cadmium chloride are particularly strong Lewis acids compared to the weakly acidic organotin chlorides and lead chlorides. This significant complication is effectively dealt with in commercial practice by the co-addition of alkaline-earth soaps or salts, such as calcium stearate or barium stearate, ie, by the use of mixed metal stabilizers. 

Displacement of activated chlorine atoms also proceeds with certain types of organic compounds, but only in the presence of Lewis acid catalysts. Particular examples include epoxides, polyhydric alcohols, trialkylphosphites (12), and P-aminocrotonates (13). These additives are commonly used in conjunction with metallic stabilizers to provide complete, high performance, commercial stabilizer packages. 

Cost bilizers. In most cases the alkyl tin stabilizets ate particularly efficient heat stabilizers for PVC without the addition of costabilizers. Many of the traditional coadditives, such as antioxidants, epoxy compounds, and phosphites, used with the mixed metal stabilizer systems, afford only minimal benefits when used with the alkyl tin mercaptides. Mercaptans are quite effective costabilizets for some of the alkyl tin mercaptides, particularly those based on mercaptoethyl ester technology (23). Combinations of mercaptan and alkyl tin mercaptide ate currendy the most efficient stabilizers for PVC extmsion processes. The level of tin metal in the stabilizer composition can be reduced by up to 50% while maintaining equivalent performance. Figure 2 shows the two-roU mill performance of some methyl tin stabilizers in a PVC pipe formulation as a function of the tin content and the mercaptide groups at 200°C. 

Typically, soHd stabilizers utilize natural saturated fatty acid ligands with chain lengths of Cg—C g. Ziac stearate [557-05-1/, ziac neodecanoate [27253-29-8] calcium stearate [1592-23-0] barium stearate [6865-35-6] and cadmium laurate [2605-44-9] are some examples. To complete the package, the soHd products also contain other soHd additives such as polyols, antioxidants, and lubricants. Liquid stabilizers can make use of metal soaps of oleic acid, tall oil acids, 2-ethyl-hexanoic acid, octylphenol, and nonylphenol. Barium bis(nonylphenate) [41157-58-8] ziac 2-ethyIhexanoate [136-53-8], cadmium 2-ethyIhexanoate [2420-98-6], and overbased barium tallate [68855-79-8] are normally used ia the Hquid formulations along with solubilizers such as plasticizers, phosphites, and/or epoxidized oils. The majority of the Hquid barium—cadmium formulations rely on barium nonylphenate as the source of that metal. There are even some mixed metal stabilizers suppHed as pastes. The U.S. FDA approved calcium—zinc stabilizers are good examples because they contain a mixture of calcium stearate and ziac stearate suspended ia epoxidized soya oil. Table 4 shows examples of typical mixed metal stabilizers. 

Cost bilizers. The variety of known costabiHzers for the mixed metal stabilizers is a very long listing. There are, however, a relatively small number of commercially used costabiHzers. Some of these additives can also be added by the PVC compounder or processor ia addition to the stabilizer package to further enhance the desired performance characteristics. The epoxy compounds and phenoHc antioxidants are among the most commonly used costabiHzers with the mixed metal stabilizers. 

A.ntioxidants. PhenoHc antioxidants, added at about 0.1—0.5 phr, are usually chosen from among butylated hydroxytoluene [128-37-0] (BHT), and Nnonylphenol [104-40-5] for Hquid stabilizer formulations and bisphenol A [80-05-7] (2,2-bis-(/)-hydroxyphenyl)propane) for the soHd systems. Low melting thioesters, dilauryl thiodipropionate [123-28-4] (DLTDP) or distearyl thiodipropionate [693-36-7] (DSTDP) are commonly added along with the phenoHcs to enhance their antioxidant performance. Usually a 3 1 ratio of thiodipropionate to phenoHc antioxidant provides the desired protection. Most mixed metal stabilizer products contain the antioxidant iagredient. 

Phosphites. Tertiary phosphites are also commonly used and are particularly effective ia most mixed metal stabilizers at a use level of 0.25—1.0 phr. They can take part ia a number of different reactions duting PVC processing they can react with HCl, displace activated chlorine atoms on the polymer, provide antioxidant functionaHty, and coordinate with the metals to alter the Lewis acidity of the chloride salts. Typical examples of phosphites are triphenyl phosphite [101 -02-0], diphenyl decyl phosphite [3287-06-7], tridecyl phosphite [2929-86-4], and polyphosphites made by reaction of PCl with polyols and capping alcohols. The phosphites are often included in commercial stabilizer packages. 

Economics. As with the alkyl tin stabilizers, the market pricing of the mixed metal stabilizers tend to be directed by the particular appHcation. The calcium—zinc and barium—cadmium packages are typically used at 2.0—4.0 parts per hundred of PVC resin (phr) in the formulation. These completely formulated products are sold for 2.50— 4.40/kg for the Hquid products and 3.20— 6.50/kg for the soHds and pastes. The higher efficiency products aimed at rigid appHcations tend toward the higher end of the cost range. 

The basic metal salts and soaps tend to be less cosdy than the alkyl tin stabilizers for example, in the United States, the market price in 1993 for calcium stearate was about 1.30— 1.60, zinc stearate was 1.70— 2.00, and barium stearate was 2.40— 2.80/kg. Not all of the coadditives are necessary in every PVC compound. Typically, commercial mixed metal stabilizers contain most of the necessary coadditives and usually an epoxy compound and a phosphite are the only additional products that may be added by the processor. The requited costabilizers, however, significantly add to the stabilization costs. Typical phosphites, used in most flexible PVC formulations, are sold for 4.00— 7.50/kg. Typical antioxidants are bisphenol A, selling at 2.00/kg Nnonylphenol at 1.25/kg and BHT at 3.50/kg, respectively. Pricing for ESO is about 2.00— 2.50/kg. Polyols, such as pentaerythritol, used with the barium—cadmium systems, sells at 2.00, whereas the derivative dipentaerythritol costs over three times as much. The P-diketones and specialized dihydropyridines, which are powerful costabilizers for calcium—zinc and barium—zinc systems, are very cosdy. These additives are 10.00 and 20.00/kg, respectively, contributing significantly to the overall stabilizer costs. Hydrotalcites are sold for about 5.00— 7.00/kg. 

The stability of the alkali metal ozonides increases from Li to Cs alkaline-earth ozonides exhibit a similar stability pattern. Reaction of metal ozonides with water proceeds through the intermediate formation of hydroxyl radicals. 

Very unstable modifications, like the reddish, chlorine-free a-copper phthalocyanine, can be stabilized with amides or salts of copper phthalocyanine sulfonic acids (59—63). Mixture with other metal phthalocyanines, eg, tin, vanadium, aluminum, or magnesium, also inhibits crystallization change and poor performance in binders and prints (flocculation) due to the hydrophobic character of unsubstituted phthalocyanines. 

Pyrrole is soluble in alcohol, benzene, and diethyl ether, but is only sparingly soluble in water and in aqueous alkaUes. It dissolves with decomposition in dilute acids. Pyrroles with substituents in the -position are usually less soluble in polar solvents than the corresponding a-substituted pyrroles. Pyrroles that have no substituent on nitrogen readily lose a proton to form the resonance-stabilized pyrrolyl anion, and alkaU metals react with it in hquid ammonia to form salts. However, pyrrole pK = ca 17.5) is a weaker acid than methanol (11). The acidity of the pyrrole hydrogen is gready increased by electron-withdrawing groups, eg, the pK of 2,5-dinitropyrrole [32602-96-3] is 3.6 (12,13). 

However, most recentiy, mixed metal stabilizers are being introduced into this area. Whereas some mixed metal stabilizers are used in rigid apphcations, it is difficult for these newer materials to compete with lead and tin based stabilizers on a cost/efficiency basis. These materials find their largest apphcations in flexible compounds, especially those requiring good stabihty to uv exposure. 

In acidic solution, the degradation results in the formation of furfural, furfuryl alcohol, 2-furoic acid, 3-hydroxyfurfural, furoin, 2-methyl-3,8-dihydroxychroman, ethylglyoxal, and several condensation products (36). Many metals, especially copper, cataly2e the oxidation of L-ascorbic acid. Oxalic acid and copper form a chelate complex which prevents the ascorbic acid-copper-complex formation and therefore oxalic acid inhibits effectively the oxidation of L-ascorbic acid. L-Ascorbic acid can also be stabilized with metaphosphoric acid, amino acids, 8-hydroxyquinoline, glycols, sugars, and trichloracetic acid (38). Another catalytic reaction which accounts for loss of L-ascorbic acid occurs with enzymes, eg, L-ascorbic acid oxidase, a copper protein-containing enzyme. 

Antimony may be added to copper-base alloys such as naval brass. Admiralty Metal, and leaded Muntz metal in amounts of 0.02—0.10% to prevent dezincification. Additions of antimony to ductile iron in an amount of 50 ppm, preferably with some cerium, can make the graphite fliUy nodular to the center of thick castings and when added to gray cast iron in the amount of 0.05%, antimony acts as a powerflil carbide stabilizer with an improvement in both the wear resistance and thermal cycling properties (26) (see Carbides). 

Many reactions catalyzed by the addition of simple metal ions involve chelation of the metal. The familiar autocatalysis of the oxidation of oxalate by permanganate results from the chelation of the oxalate and Mn (III) from the permanganate. Oxidation of ascorbic acid [50-81-7] C HgO, is catalyzed by copper (12). The stabilization of preparations containing ascorbic acid by the addition of a chelant appears to be negative catalysis of the oxidation but results from the sequestration of the copper. Many such inhibitions are the result of sequestration. Catalysis by chelation of metal ions with a reactant is usually accomphshed by polarization of the molecule, faciUtation of electron transfer by the metal, or orientation of reactants. 

The tips used for STM experiments should be sharp and stable. Chemical stability can be achieved by using a noble metal. Mechanical rigidity can be reached by short wires. Alloys of Pt and Ir are frequently used for fabrication of STM tips. They can be produced in a surprisingly simple way just by cutting a metal wire with conventional cutting tools. Because of their high chemical stability, such Pt/Ir tips are well... 

Chemical Reactivity - Reactivity with Water. Reacts slowly with water, but considerable heat is liberated when contacted with spray water Reactivity with Common Materials Corrodes iron, steel and other metals Stability During Transport Stable Neutralizing Agents for Acids and Caustics Dilute with water and use sodium bicarbonate solution to rinse Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

Chemical Reactivity - Reactivity with Water Dissolves and forms dilute solution of hydrofluoric acid Reactivity with Common Materials May corrode glass, cement and most metals Stability During... 

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