ALUMINIUM NITRIDE and RELATED MATERIALS a Thesis Presented
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University of Plymouth PEARL https://pearl.plymouth.ac.uk 04 University of Plymouth Research Theses 01 Research Theses Main Collection 1970 THE FORMATION AND REACTIVITY OF ALUMINUM NITRIDE AND RELATED MATERIALS COLES, N.G. http://hdl.handle.net/10026.1/1953 University of Plymouth All content in PEARL is protected by copyright law. Author manuscripts are made available in accordance with publisher policies. Please cite only the published version using the details provided on the item record or document. In the absence of an open licence (e.g. Creative Commons), permissions for further reuse of content should be sought from the publisher or author. ALUMINIUM NITRIDE AND RELATED MATERIALS A Thesis presented for the degree of DOCTOR OP PHILOSOPHY of the COUNCIL FOR NATIONAL ACADJMIC AWARDS London by No G„ COLES, MoSCo Depajrtment of Chemistry^ The Fblytechnic, Plymouth, August. 1970 " ^.500214 CLOSS T Fk^. l-U CoL No. Abstract The preparation and properties of aluminiuin nitride are reviewed v/ith special reference to the nev/er production methods and fabrication techniqueSo Information so far available on the sintering of materials is summarised. For nitrides the sintering is influenced by additives or impurities such as oxides formed by partial hydrolysis and oxidationo Resistance to oxidation is increased by sintering and hot-pressing the refractories. The kinetics and products of oxidation of nitrides so far studied depend mainly on the intrinsic reactivity of the material and available surface at whi.ch oxidation can occur. In the present research conditions are investigated for preparing aluminium nitride from ammonium hexafluoroaluminatCi, The x-ray characteristics and the thermal stability of a new compound, ^-AlP^ are established. Attempts to study the kinetics of the commercial methods of aluminium nitride formation are summarised. The reactivity of aluminium nitride is examined by correlating changes in phase composition, surface area, crystallite and aggregates sizes with hydrolysis and oxidation time and temperature. The kinetics and rates of reaction are influenced by the crystallite and aggregate sizes of the aluminium nitride, by differences in type of crystal structure, by the molecular volume of the oxide products, and by fluoride additives. Ageing and sintering of the aluminas are additional factors* The activation energy of the oxidation of aluminium nitride in air is determined as 53 k>cals/molec Acknowledgements I wish to thank Dr« A« Bo Meggy for the helpp comment and general supervision of this worko I also yrish to acknowledge the helpful discussions I have had with Dr* D© Ro Glasson, Thanks are also due to Miss lo Gratton^ the Polytechnic Ldbrariarip and her staff, for their patient and willing cooperationo The help of Mr, Tapper with the computation has been gratefully appreciated., I would also like to thank Mrso Eo Adams, JoAoCa^ A, Down^ Dro So A. A, Jayaweera and Mai^garet Sheppard for their assistance and cooperation. I am indebted to the Governors of the Polytechnic for the research award and the facilitieso Finallyp I would like to express my thanks to Anne for her understanding and encouragement throughout this work* ii Ta.bles 1. The effect of vajrlous media on aiijjniniujn nitride^ 9 2. The lattice parameters of alujiiira.\iin nitrideo 11 3« The heat of forniation of aliJininium nitride. 13 The decomposition temperature of aluminium nitride„ 15 5» A canparison of the mechanical p.roperties of al^jminium nitride with certain ceramcs, 17 6. The tiierraal expansri.on of certain materials- 19 7o A compari.son of the cr^'stal structures of certain materials. 20 8« Ammonium hexafluoroaluminate heated at 220°G in dry air. 63 9« Ammonium hexaflucroaluminate heated at 3hO^C in dry air, 64 lOo Comparison of the observed and calculated d-spacings for ^ -AlP^o 66 11. Comparison of d-spacings of ammonium hexaifluoroaluminate heated in moist air for various times with Y-AlPjj, some basic fluorides and aluminium hydroxide» • ^ 68 12- Ammonium hexafluorcalumi.nate heated at "lO'^C for 18 hours in dried air. 71 13*> AmmoQium hexaiT-uoroaluminate heated^in dried ammonia at 960"C for 1 hour and cooled to h-00 C in ammonia. 75 14. Compari.son of the observed x-ray intensities of ammonium he.xafluoicaliiminate heated at 960 C in variou;3 flow rates of ammonia. 79 15- X-ray data of basic fluorides and alumir^Lum fluoride hvurates. 83 16. Comparison of the d-spacings of tiie reported S -AlF, and I^ -AIP^. I du IJo Lattice parameters of some complex hexafluorides* 86 XIX 18. (a) Infra-red analysis of the thernial decomposition of ammonium hexaLfiuoroaluminatea 58 (b) Density of some aluminium compounds • 89 19. Intsratomic distances in (j^..-aluminium fluoride and related compounds. 93 20o Comparison of the crystal properties of AIN v/ith possible impur-ities in the Serpek pnDcesSe 99 21* X-ray analysis of hydrolysed aluminium nitride. 118 22. Infra-red analysis of hydrolysed aluminium nitride. 119 23o Activation energies of aluminium nitri.de and related compoiinds^ IZ4.3 24- A comparison of the rate constants of milled samples at various temperatures. 149 2^. Aluminium nitride heated at 900°C for 96 ho^jx-s« I56 26. Silicon nitride heated at 1000°G for 96 hoi:rs. 157 27o Variations in aggregate sizes during the conversion of AIN to iX -^-^2*^3 at 1000*^0 in air. l62 280 Free energy of formation of aluminium carbide from the reaction of alumi.n-a and car^bon. 130 1. The change in conductivity of AlP^ solution when adding NH^F solution, 192 2, (a) The Van-Arkel arrangement a (b) Determination of the knife edge angle of a 9 cm povrcLer camerao 3« The percentage v.-eight loss of aruj:onium h'.y r-Quoroaluminate h-?att^ "in dried air for various tefnoeratures and times. 39 I it 13 \J. t - .0 (b) Differejitial -uheraal ar-.^aiy:^!of V|'-..i^'\.. 6o The -ihtinnal decomposition of amironiv-^ hev'^fX>Jorcgallate, 7- .-,mi:".c (a)- (d) The fijTimoni'jir. rctrafluororoiumin^ire/-aluminium flucjri.oe o-.y'.t-ll-:^-j--:>iic - j..'^ ti'.:.. ^1, atcr.-dc arror:gan'cnt ino<^-/'l?^o 9b (b) The atomic arr.-»xif;cr-ent in .'Jl.o IG. (a) Electron diffraction pattern of the aluminium fiirr, lev (b) :ile:;tron dj.ffraction pattern of th-: ' r.7z*-]^. dr-c' aluninium .filrPo (a) Electrrjr^ mi'::r:. 1'h-: ci-r.r;- ^r. , -^.r.j '-'U- 3'^riace during trie nrdxiing of alun^^ r.iMi:; --iit :d d^c 115 (b) m±il-'.ng of aluminj'^m r.itrldec 13. (a)- (d) Comparison of the -specifa.c surfac-i. surface are; and average CiystaJlits si^'.r. \7i:;h perr:^r.-^ag^: h>'droIysi£. lit-. The percentage conversion of aluminium nitride to oC-alumir^ at various temper^tursso 132 15. The percentage conversion of alumini-am nitride heated at 930 C for 3 hours. I36 16• (a) A plot of fi.rst-order kinetics v/ith time for vajrious temperatureso 138 (b) A plot of log t (time) wi.th log x (x is % conversion)^ 17. A plot of y against timeg t, at 905*^C. 139 18. A plot of 2^ and y against timej, t, for periods up to 30 hours, 141 2 19o A plot of Z against timer t, for various teinperatures. 1A4 20» Arrhenius plot for the oxidation of alumini--^ nitride. 145 21. The effect of milling on the oxida.tion of aluminium nitride at 872 C. I5I 22. The effect of milling on the oxidation of aluminium nitride at 905 C. 152 25o The effect of aluminium fluoride on the oxidation of aluminium nitride. l^h- ?.L*~ Srrnie electron micrographs of alumijiium and silicon 158- 27, nitrides and oxidised samples. I6I 28* Comparison of the rate of oxidation of AlN at lOOO^^C with the change in (i) specific surface, (ii) the number of crystallites^ (^'/g) p (iii) the average cr^'stallite size. I63 29. Comparison of the oxidation of aluminium and silicon nitrides,. I66 30. The free energy of formation of some nitrides. 173 31. A comparison of the free energy of formation of AlN from its elonents. 175 32. Free energy of formation of AlN from various methods of preparation. 177 33. Plot of against oC (p^^ or V-^) * > 178 34. Comparison of the free energy of the formation of oC-alumina and silica from the nitrides. 184 vx OONTmTS Abstract mo oo o <> .o oo o <> oo oo oo o. i Aclaiowledgements •<> o* co oo r. .<> co «. •<> ii Tables oe ou oo o o o o .o OD oo o> oo oa oi Hi Figureso. o« o* «. , <, .o v CHAPTER 1 Literature survey of alijminium nitride and related rna-terials 1,1 Tj}^_formation and chemical properties of aluminium nitride »c .e «• en oo oo oe I^lei The formation of aluminium nitride .o o - * 1 I»lc:i(a) The formation of aluminium nitride from its elements 1 I,l.i(b) The formation of the nitride from the decomposition of alumina v/ith caxbon in the presence of ammonia or nj.tmgen lo .o o. o. «« »» 2 I.l.i(c) The thermal decomposition of ammonium hexafluorc- aluminate in ammonia oo .o c ^ oc c 4 I„loi(d) l.iiscellaneous methods of preparation <>• «o ». 3 1*1.ii. The chemical properlles of aluminium nitride .* 7 I^2 The cryatalloaraphy and the heat of formation and thermal, stabi3.ity_of^ aluminium nitride lB2oi The crystallography of aluminiiom nit ride«« 10 Ig2oii The heat of formation and thermal stability of aluminiiim nitride oo .» oo .o .o .o 12 I«3 The physical and mecb^anlcal proper-bies of aluminium nitri.de and related materj.als Io3oi The physical properties of aluminium nitride oo lit- 1*3*31 The mechanical properties of aluminium nitride and related materials .o ..