Electrical properties of some single crystal dodecaborides /|nby Jyoti Burte. -- 260 St. Catharines [Ont. : s. n.],

PreVi011.3 ':i or~ : indicat e('. tk~t ho t~)rE's sed ~-Al B 12 1i~2, ~' a semiconductor. r:Toreove r , the s i mpl.(~ electronic t heory also indi cates that ~ -AIB1 2 should be a semico nductor, since thf're is one nonbonding e 'Le ctrofl per AlB12- uni t. JPor these reasons, we decided to measure t he electrical n ropert i ~ s of ~ -AlB1 2 single crystal s . Singl e crystal s of¥- AIB 12 ab ou t 1 x 1 r1n1 . size were grown from a copper mel t at 12500 C. The melt technique coupled. 1,vi th slow cooling vilas used because of i ts advantages such as : siTYInle set- up of the expe rimon t ; only e ;l.sil y available c hemi cals are required and it i s a c omparatively strair::bt forvvard y,le t hod still yielding crystal s big enouGh for OtU' purpose . Copper rms used as a solvent , i nst8ad of previOl.wly used aluminum , because it allows c.l.'ystal growth at hig he r t emneratures. HovlGver, the cry s tals of ] -AlB12 shm'red very hi gh res i s t ance a t r oom temperature . From our neasureJ'lents we conclude that the r esistivity of j3- Al B12 is, at least, given as ~ = 4. x 107 oblD .em •• Those results are inc ons i s t ent wi 'uh the ones .. reported by IIiss Khin fo r bot- pressed j3-AlB12 g i ven a s = 7600 ohm . em . or I e s s . ' Since tbe hot pressing was done at about 800 - ' 9000C i n ~ rap hi te moul ds 1,7i th 97% AlB12- p oVJder, vie thi nk there is pas s ib i 1 i ty th a.t lower borides or borot] carbide are , being formed, ':.Jhich are k11 own to be good semiconductors . v7e tried to ro-pe r-AlB12 by addi'J,'?: agents s uch as l:Ig , IG.-InO 4. ' HgS04 , KI12PO 4·' etc. to t he melt .. However , all these re age 11 t eel either reduced the yield and size of t lJe crystals or r;ave crystals of high r esis'can ce again. We think tba t molten copper keeps t he i mpurities off . There is also a pos s i bil i ty t hc:!,t these doping agents get oxidi~::;ed at '1 250°C • Hence, we co ~ clud e that J -AIB12 has v~ ry high r es i stance at r oom temperature . This was a l s o C011 - fi rmed by checki ng the siYlgle and. polycrystals of .~-AIB12 from Norton Co., Ontario and Cooper Nletallurgical Association. Boron carbide has been reported to be a semiconductor with ~ - 0.3 to 0.8 ohm . cm. for hotpres sed s araples. Boron carbide b e inq: struct urally related to ¥-AIB12 , we de cided to study the electrical prone rties of it~ Single crystals. These crystals were cut from a Single melt grovvn crystal a t Norton Co., Ontario. The resistivity of th," se crystal s was measured by the Van der Pam-v' s ~ nethod, which \vas very c onvenient fo r our crystal sha-pp.s. Some of the crystals showed resistivity ~ == 0.50 ob,Tn.cr] . i n agreement with the previously reported results . However , a few crystals showed lower resistivity e.g . 0 .13 and 0.20 ohm.cra • • The Hall mobility could .not be measured and th8reiore i s lower than 0 .16 em 2 v - 1 sec -1 • This is in agreement \vith t he re1)orted Hall mobility for pyrolytic boron . _ 2 -1 -1 carbide as 0.13 cm v sec • We also studied the orientation of the boron carbide crystals by the Jjaue-method. The inclination of c-axis with res pect to x-ray be81Il was det ermined . This was found to be 100 t o 20° f or normal resistivity sarnples (0.5 ohm . cm.) and 27 - 30° for t he lower r esistivity samples (0.1 ~5 to 0.20 ohm.cm .). This indica tes the possibility that th.e r es if.1tivity of B13C3 i s orientation dependent.

Petrography, Petrochemistry and petrogenesis of Huronian volcanic rocks of the Elliot Lake region, Ontario

In the Elliot lake region of northern Ontario, Yolcanlc lava piles represent the lowermost units of the Huronian SUpergroup. These rocks general1y trend east-west and belong to the Elliot lake Group. They are s1tuated on the north and south limbs or the QuIrke lake Syncline. The volcanIc rocks of this study contain a secondary minerai assemblage consisting of actinolite, biotite, chlorIte, eptdote/cllnozoislte tttanomagnettte and calcite characteristic of greenschist metamorphism. Compilation of data suggests that metamorphism of the volcanic rocks proceeded between 325- and 425-C and between 2.4 and 4.7 kb. Geochemtcally these lavas represent tholeiitic and calc-alkaline assemblages. The tholeiites are character1sttcally enriched tn Fe and Tt and consist mainly of basalts, basaltic andesites and andesites. These rocks are believed to have formed by the partIal melting of a peridottte source at low P-T. In contrast, the calc-alkaline rocks are depleted in Fe and TI, but show a signIficant enrichment In 51 and Zr; andesIte Is the major rock type for thIs assemblage. I·t Is postUlated that the calc-alkalIne sU1te of rocks was the result of eIther the partIal meltIng of abasaltic·magma at shallow depth, or the melttng of s1al1c crustal materIal due to the added we1ght of tholeiitIc material on an unstable crust and to downwarplng processes Inttlated by convection cells.

Strategies for economic development in the Commonwealth Caribbean: a comparative study of the foreign economic policy strategies adopted by the Manley government in Jamaica and the Williams government in Trinidad and Tobago

This thesis compares the foreign economic poUcy dimension of the development strategies adopted by the governments of two Commonwealth caribbean countries: The Hardey government In Jamaica, and the· Williams government in Trlnidad and T ooago, The foreign economic policIes adopted by these governments appeared, on the surface~ to be markedly dissimilar. The Jamakan strategv on the one hand, emphasised self-reliance and national autonomy; and featured the espousal of radical oonaHgnment together with attempts to re-deftne the terms of the Islands externaa economIc relaUoos. The Trinidadian strategy 00 the other hand, featured Uberal externaUy-oriented growth poUctes, and close relatjoos with Western governments and financial institutions. Th1s study attempts to identify the explanatory factors that account for the apparent dlssimUarUy 1n the foreign economic policies of these two govemnents. The study is based on a comparison of how the structural bases of an underdeveloped ecooomYg and the foreign penetration and vulnerabUUy to external pressures asSOCiated wUh dependence, shape and influence foreign economic poUcy strategy. The framework views fore1gn ecooom1c strategy as an adaptive response on the part of the decision makers of a state to the coostralnts and opportunities provided by a particular situation. The · situat i 00' in this case being the events, conditions, structures and processes, associated wUh dependente and underdevelopment. The results indicate that the similarities and dissimHarities in the foreign economic policies of the governments of Jamaica and Trinidad were a reflecUon of the simHarities and dissimilarities in their respective situations. The conclusion derived suggests that If the foreign pol1cy field as an arena of choice, Is indeed one of opportunities and constraints for each and every state, then poHcy makers of smaU, weak, hlghW penetrated and vulnerable states enter thlS arena with constraints outweighing opportunities. This places effective limits 00 their decisional latitude and the range of policy options avaUable. Policy makers thus have to decide critical issues with few estabUshed precedents, in the face of domestic social and political cleavages, as wen as serious foreign pressures. This is a reflection not only of the trappings of dependence, but also of the Umned capabilities arising from the sman size of the state, and the Impact of the resource-gap In an underdeveloped economy. The Trinidadian strategy 1s UlustraUve of a development strategy made viable through a combination of a fortuitous circumstance, a confluence of the interests of influential groups» and accurate perception on the part of poUcy makers. These factors enabled policy makers to minimise some of the constraints of dependence. The faUure of Manlets strategy on the other hand, 15 iHustraUve of the problems involved tn the adoption of poUcles that work against the interest of internal and external political and economic forces. It is also tUustraUve of the consequences of the faUure 00 the part of policy makers to clarify goals, and to reconcile the values of rapid economic growth with increased self-reliance and national autonomy. These values tend to be mutuany Incompatible given the existing patterns of relations in the jnternational economy.

The kinetics and mechanism of the thermal decomposition of sec-Butyl peroxide in liquid phase /|nby Sandor Szilagyi. -- 260 St. Catharines, Ont. : [s. n.],

Re~tes artd pJ~oducts of tllerma]. d,ecom.position of sec-butyl peroxide at 110 - 150°C i.n four solvents h,ave been determined. The d,ecompos i tion vJas sb.o\'\Tn to be tlnlmolecl.llar wi tho energies of activation in toluene, benzene, and cyclohexane of 36 .7-+ 1.0, 33.2 +- 1..0, 33.t~) +.. 1.0 I'(:cal/mol respectively. The activation energy of thermal decomposition for the d,et.1terated peroxide was found to be 37.2 4:- 1.0 KC8:1/1TIol in toluene. A.bo1J.t 70 - 80/~ ol~ tJJ.e' pl~od.1..1CtS could, be explained by kn01rJ11 reactions of free allcoxy raclicals J and very littJ...e, i.f allY, disPl"Opox~tiol'lation of tll10 sec-butoxy radica.ls in t116 solvent cage could be detected. The oth,er 20 - 30% of the peroxide yielded H2 and metb.:'ll etb..yl 1{etol1e. Tl1.e yield. o:f H2 "'lIas unafJ:'ected by the nature or the viscosity of the solvent, but H2 was not formed when s-t1U202 lrJaS phctolyzed. in tolttene at 35°C nor 'tl!Jrl.en the peroxide 1;'JaS tl1.ermally o..ecoJnposed. in the gas p11ase. ~pC-Dideutero-~-butYlperoxide was prepared and decomposed in toluene at 110 - 150°C. The yield of D2 was about ·•e1ne same 248 the yield. of I{2 from s-Bu202, bU.t th.e rate of decomposition (at 135°C) 1iJas only 1/1.55 as fast. Ivlecl1.anisms fOl') J:1ydrogen produ.ction are discussed, but none satisfactorily explains all the evidence.

Crystallinity, Magnetic and Electrical Properties of Bi doped LaVO3

We report the results of crystal structure, magnetization and resistivity measurements of Bi doped LaVO3. X-ray diffraction (XRD) shows that if doping Bi in the La site is less than ten percent, the crystal structure of La1-xBixVO3 remains unchanged and its symmetry is orthorhombic. However, for higher Bi doping (>10%) composite compounds are found where the XRD patterns are characterized by two phases: LaVO3+V2O3. Energy-dispersive analysis of the x-ray spectroscopy (EDAX) results are used to find a proper atomic percentage of all samples. The temperature dependence of the mass magnetization of pure and single phase doped samples have transition temperatures from paramagnetic to antiferromagnetic region at TN=140 K. This measurement for bi-phasic samples indicates two transition temperatures, at TN=140 K (LaVO3) and TN=170 K (V2O3). The temperature dependence of resistivity reveals semiconducting behavior for all samples. Activation energy values for pure and doped samples are extracted by fitting resistivity versus temperature data in the framework of thermal activation process.

Investigation of Frustrated Quasi-One-Dimensional Quantum Spin-Chain Materials

Copper arsenite CuAs2O4 and Copper antimonite CuSb2O4 are S=1/2 (Cu2+ 3d9 electronic configuration) quasi-one-dimensional quantum spin-chain compounds. Both compounds crystallize with tetragonal structures containing edge sharing CuO6 octahedra chains which experience Jahn-Teller distortions. The basal planes of the octahedra link together to form CuO2 ribbon-chains which harbor Cu2+ spin-chains. These compounds are magnetically frustrated with competing nearest-neighbour and next-nearest-neighbour intrachain spin-exchange interactions. Despite the similarities between CuAs2O4 and CuSb2O4, they exhibit very different magnetic properties. In this thesis work, the physical properties of CuAs2O4 and CuSb2O4 are investigated using a variety of experimental techniques which include x-ray diffraction, magnetic susceptibility measurements, heat capacity measurements, Raman spectroscopy, electron paramagnetic resonance, neutron diffraction, and dielectric capacitance measurements. CuAs2O4 exhibits dominant ferromagnetic nearest-neighbour and weaker antiferromagnetic next-nearest-neighbour intrachain spin-exchange interactions. The ratio of the intrachain interactions amounts to Jnn/Jnnn = -4.1. CuAs2O4 was found to order with a ferromagnetic groundstate below TC = 7.4 K. An extensive physical characterization of the magnetic and structural properties of CuAs2O4 was carried out. Under the effect of hydrostatic pressure, CuAs2O4 was found to undergo a structural phase transition at 9 GPa to a new spin-chain structure. The structural phase transition is accompanied by a severe alteration of the magnetic properties. The high-pressure phase exhibits dominant ferromagnetic next-nearest-neighbour spin-exchange interactions and weaker ferromagnetic nearest-neighbour interactions. The ratio of the intrachain interactions in the high-pressure phase was found to be Jnn/Jnnn = 0.3. Structural and magnetic characterizations under hydrostatic pressure are reported and a relationship between the structural and magnetic properties was established. CuSb2O4 orders antiferromagnetically below TN = 1.8 K with an incommensurate helicoidal magnetic structure. CuSb2O4 is characterized by ferromagnetic nearest-neighbour and antiferromagnetic next-nearest-neighbour spin-exchange interactions with Jnn/Jnnn = -1.8. A (H, T) magnetic phase diagram was constructed using low-temperature magnetization and heat capacity measurements. The resulting phase diagram contains multiple phases as a consequence of the strong intrachain magnetic frustration. Indications of ferroelectricity were observed in the incommensurate antiferromagnetic phase.