Unit orthorhombic

Fig. 4. Structure of orthorhombic polyethylene unit cell projected on the ab plane. The right-hand pictures define the setting angle .

The many commercially attractive properties of acetal resins are due in large part to the inherent high crystallinity of the base polymers. Values reported for percentage crystallinity (x ray, density) range from 60 to 77%. The lower values are typical of copolymer. Poly oxymethylene most commonly crystallizes in a hexagonal unit cell (9) with the polymer chains in a 9/5 helix (10,11). An orthorhombic unit cell has also been reported (9). The oxyethylene units in copolymers of trioxane and ethylene oxide can be incorporated in the crystal lattice (12). The nominal value of the melting point of homopolymer is 175°C, that of the copolymer is 165°C. Other thermal properties, which depend substantially on the crystallization or melting of the polymer, are Hsted in Table 1. See also reference 13. 

The equimolar copolymer of ethylene and tetrafluoroethylene is isomeric with poly(vinyhdene fluoride) but has a higher melting point (16,17) and a lower dielectric loss (18,19) (see Fluorine compounds, organic-poly(VINYLIDENE fluoride)). A copolymer with the degree of alternation of about 0.88 was used to study the stmcture (20). Its unit cell was determined by x-ray diffraction. Despite irregularities in the chain stmcture and low crystallinity, a unit cell and stmcture was derived that gave a calculated crystalline density of 1.9 g/cm. The unit cell is befleved to be orthorhombic or monoclinic (a = 0.96 nm, b = 0.925 nm, c = 0.50 nm 7 = 96%. 

Poly(vinyl fluoride) [24981-14-4] (PVF) is a semicrystaltiae polymer with a planar, zig-zag configuration (50). The degree of crystallinity can vary significantly from 20—60% (51) and is thought to be primarily a function of defect stmctures. Wide-line nmr and x-ray diffraction studies show the unit cell to contain two monomer units and have the dimensions of a = 0.857 nm, b = 0.495 nm, and c = 0.252 nm (52). Similarity to the phase I crystal form of poly (vinytidene fluoride) suggests an orthorhombic crystal (53). 

The crystal stmcture of PPT is pseudo-orthorhombic (essentially monoclinic) with a = 0.785/nm b = 0.515/nm c (fiber axis) = 1.28/nm and d = 90°. The molecules are arranged in parallel hydrogen-bonded sheets. There are two chains in a unit cell and the theoretical crystal density is 1.48 g/cm. The observed fiber density is 1.45 g/cm. An interesting property of the dry jet-wet spun fibers is the lateral crystalline order. Based on electron microscopy studies of peeled sections of Kevlar-49, the supramolecular stmcture consists of radially oriented crystaUites. The fiber contains a pleated stmcture along the fiber axis, with a periodicity of 500—600 nm. 

Physical Properties. The absorption of x-rays by iodine has been studied and the iodine crystal stmcture deterrnined (12,13). Iodine crystallizes in the orthorhombic system and has a unit cell of eight atoms arranged as a symmetrical bipyramid. The cell constants at 18°C (14) are given in Table 1, along with other physical properties. Prom the interatomic distances of many iodine compounds, the calculated effective radius of the covalently bound iodine atom is 184 pm (15). 

Physical Properties. LLDPE is a sernicrystaUine plastic whose chains contain long blocks of ethylene units that crystallize in the same fashion as paraffin waxes or HDPE. The degree of LLDPE crystallinity depends primarily on the a-olefin content in the copolymer (the branching degree of a resin) and is usually below 40—45%. The principal crystalline form of LLDPE is orthorhombic (the same as in HDPE) the cell parameters of nonbranched PE are a = 0.740 nm, b = 0.493 nm, and c (the direction of polymer chains) = 0.2534 nm. Introduction of branching into PE molecules expands the cell slightly thus a increases to 0.77 nm and b to around 0.50 nm. 

Syndiotactic polypropylene also forms hehcal molecules however, each chain unit consists of four monomer units having a spacing of 0.74 nm. The unit cell is orthorhombic and contains 48 monomer units having a crystaHographic density of 0.91 g/cm (27). 

Aminophenol. This is the most stable of the isomers under atmospheric conditions. It forms white prisms when crystallized from water or toluene. The orthorhombic crystals have a tetramolecular unit and a density of 1.195 g/cm (1.206 and 1.269 also quoted) (15,16) (see Tables 3—5). 

Aminophenol. This compound forms white plates when crystallized from water. The base is difficult to maintain in the free state and deteriorates rapidly under the influence of air to pink-purple oxidation products. The crystals exist in two forms. The a-form (from alcohol, water, or ethyl acetate) is the more stable and has an orthorhombic pyramidal stmcture containing four molecules per unit cell. It has a density of 1.290 g/cm (1.305 also quoted). The less stable P-form (from acetone) exists as acicular crystals that turn into the a-form on standing they are orthorhombic bipyramidal or pyramidal and have a hexamolecular unit (15,16,24) (see Tables 3—5). 

Strontium Carbonate. Strontium carbonate, SrCO, occurs naturally as strontianite in orthorhombic crystals and as isomorphs with aragonite, CaCO, and witherite, BaCO. There are deposits in the United States in Schoharie County, New York in WestphaUa, Germany and smaller deposits in many other areas. None is economically workable. Strontianite has a specific gravity of 3.7, a Mohs hardness of 3.5, and it is colorless, gray, or reddish in color. 

The known uranium(VI) carbonate soHds have empirical formulas, 1102(003), M2U02(C03)2, and M4U02(C03)3. The soHd of composition 1102(003) is a well-known mineral, mtherfordine, and its stmcture has been determined from crystals of both the natural mineral and synthetic samples. Rutherfordine is a layered soHd in which the local coordination environment of the uranyl ion consists of a hexagonal bipyramidal arrangement of oxygen atoms with the uranyl units perpendicular to the orthorhombic plane. Each uranium atom forms six equatorial bonds with the oxygen atoms of four carbonate ligands, two in a bidentate manner and two in a monodentate manner. 

Sohd uranium—phosphate complexes have been reported for the IV and VI oxidation states, as well as for compounds containing mixed oxidation states of U(IV) and U(VI). Only a few sohd state stmctures of U(IV) phosphates have been reported, including the metaphosphate U(P03)4, the pyrophosphate U(P202), and the orthophosphate, CaU(PO4)2. The crystal stmcture of orthorhombic CaU(POis similar to anhydrite (194). Compounds of the general formula MU2(PO4)3 have been reported for M = Li, Na, and K, but could not be obtained with the larger Rb and Cs ions (195). In the sohd state, uranium(IV) forms the triclinic metaphosphate, U(P03)4. Each uranium atom is eight-coordinate with square antiprismatic UOg units bridged by... 

The PVC crystaUites are smaU, average 0.7 nm (3 monomer units), in the PVC chain direction, and are packed lateraUy to a somewhat greater extent (4.1 nm) (21,33). A model of the crystaUite is shown in Figure 6. The crystalline stmcture of PVC is found to be an orthorhombic system, made of syndiotactic stmctures, having two monomer units per unit cell and 1.44—1.53 specific gravity (34—37). 

Antimony Trioxide. Antimony(III) oxide (antimony sesquioxide) [1309-64-4] Sb203, is dimorphic, existing in an orthorhombic modification valentinite [1317-98-2] is colorless (sp gr 5.67) and exists in a cubic form and senarmontite [12412-52-17, Sb O, is also colorless (sp gr 5.2). The cubic modification is stable at temperatures below 570°C and consists of discrete Sb O molecules. The molecule is similar to that of P40 and As O and consists of a bowed tetrahedron having antimony atoms at each corner united by oxygen atoms lying in front of the edges. This solid crystallizes in a diamond lattice with an Sb O molecule at each carbon position. 

Orthorhombic HBO2 consists of trimeric units B303(0H)3 which are linked into layers by H bonding (Fig. 6.26) all the B atoms are 3-coordinate. Monoclinic HBO2 is built of chains of composition [B304(0H)(H20)] in which some of the B atoms are now 4-coordinate, whereas cubic HBO2 has a framework structure of tetrahedral BO4 groups some of which are H bonded. The increase in CN of B is paralleled by an increase in density and mp. 

Figure 6.26 Layer structure of orthorhombic metaboric acid HBOafni), comprising units of formula BaOafOHla linked by O H O bonds.

In the vapour phase As is known to exist as tetrahedral Asa molecules with (As-As 243.5 pm) and when the element is sublimed, a yellow, cubic modification is obtained which probably also contains Asa units though the structure has not yet been determined because the crystals decompose in the X-ray beam. The mineral arsenolamprite is another polymorph, e-As it is possibly isostructural with metallic orthorhombic P. 

For instance, in the three crystalline forms (a, 3, y) of i-PP the chains are always in the conformation of threefold helix (s(3/l)l symmetry) but are packed in different ways in monoclinic [24], hexagonal [25], and orthorhombic [26] unit cells, respectively. The X-ray diffraction spectra of unoriented samples in the crystalline forms a, P, y are reported in Fig. 6. 

This is, for instance, the case of the a and 5 forms of PVDF (also called form II and form lip, that is form II polarized), both contain chains with a TG+TG" conformation and have an orthorhombic unit cell with substantially identical dimensions [30, 31]. Detailed X-ray diffraction analyses have shown that the two chains in the unit cells are with the dipole vectors pointing in opposite directions in the a form, while they are in the same direction in the 8 form [32],... 

Fig. 7 a, b. Possible models of packing, for trans-planar chains of s-PS, for the limiting ordered modifications a) hexagonal (a") the relative heights of the centers of the phenyl rings are indicated in c/6 units [28] b) orthorhombic (P") the relative heights of the centers of the phenyl rings are indicated in c/4 units [7, 29]... 

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