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SE527199C2 - Användning av ett material i oxiderande miljö vid hög temperatur - Google Patents

Användning av ett material i oxiderande miljö vid hög temperatur

Info

Publication number
SE527199C2
SE527199C2 SE0300318A SE0300318A SE527199C2 SE 527199 C2 SE527199 C2 SE 527199C2 SE 0300318 A SE0300318 A SE 0300318A SE 0300318 A SE0300318 A SE 0300318A SE 527199 C2 SE527199 C2 SE 527199C2
Authority
SE
Sweden
Prior art keywords
range
alloy
carbon
titanium
nitrogen
Prior art date
Application number
SE0300318A
Other languages
English (en)
Other versions
SE0300318L (sv
SE0300318D0 (sv
Inventor
Mats Sundberg
Kjell Lindgren
Tamer El-Raghy
Gustav Malmqvist
Original Assignee
Sandvik Intellectual Property
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sandvik Intellectual Property filed Critical Sandvik Intellectual Property
Priority to SE0300318A priority Critical patent/SE527199C2/sv
Publication of SE0300318D0 publication Critical patent/SE0300318D0/sv
Priority to US10/544,467 priority patent/US7407903B2/en
Priority to EP04705566A priority patent/EP1599417A1/en
Priority to JP2006502779A priority patent/JP2006518810A/ja
Priority to PCT/SE2004/000104 priority patent/WO2004069745A1/en
Priority to KR1020057014421A priority patent/KR20050110625A/ko
Priority to CNB2004800037956A priority patent/CN100333997C/zh
Publication of SE0300318L publication Critical patent/SE0300318L/sv
Publication of SE527199C2 publication Critical patent/SE527199C2/sv

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Description

25 30 Föreliggande uppfinning hänför sig således till användning av ett material bestående av en legering mellan en metall, alu- minium (Al) och kol (C), alternativt kväve (N), vilken lege- ring har en sammansättning MgU¶Xw,där M utgöres av titan (ti), krom (Cr) och/eller niob (Nb) och där X utgöres av kol (C), alternativt där X utgöres av kväve (N) och/ eller kol (C) när M utgöres av titan (Ti), där z ligger i intervallet 1.8 till 2.2, y i intervallet 0.8-1.2 och w i intervallet 0.8-1.2 och utmärkes av, att materialet används vid tempera-“ turer överstigande 1200°C och i oxiderande miljö, varvid ett skyddande oxidskikt av Al2O3 utbildas efter uppvärmning till nämnda temperatur.
Det svenska patentet nr. 0102214-4 beskriver ett förfarande för framställning av en enfassammansättning MWQAQQ, där n ligger inom ett intervall 0.8 - 3.2 och där z ligger inom ett intervall 0.8 - 1.2, där M kan vara Ti där X kan vara C (kol) (titan), eller kväve (N) och där A kan vara Al(alumini- um). Förfarandet innefattar att bilda en pulverformig bland- ning av nämnda metall, icke metall och sistnämnda grundämne eller förening av nämnda ämnen samt antända nämnda pulverfor- miga blandning under inert atmosfär så att dissociation inte främjas, varvid ingående komponenter reagerar, och utmärkes av, att reaktionstemperaturen bringas att hållas vid eller över den vid vilken ingående komponenter bringas att reagera men under den temperatur vid vilken enfassammansättningen dissocierar.
Föreliggande uppfinning bygger på att det överraskande visat sig att i ett ternärt fasdiagram Ti - Al - C uppvisar ett material Ti2AlC och material med en sammansättning runt sam- mansättningen Ti2AlC överraskande goda egenskaper, vilka inte hñdocwoxinslutfóxcläggandcxioc , 2005-08-24 03002485 10 75 20 25 30 uppvisas utanför de i patentkravet 1 angivna snävare inter- vallen. Detsamma gäller Ti2AlN.
Detta gäller även då metallen Ti helt eller delvis substitue- ras med krom (Cr) och eller niob (Nb).
Föreliggande uppfinning innefattar även att X utgöres av kvä- ve (N) och/eller kol (C) förutsatt att M då är titan (Ti).
Fördelen med föreliggande uppfinning är att denna möjliggör tillämpningar vid hög temperatur i oxiderande miljöer där me- tallegeringar inte överlever acceptabla driftstider vid tem- peraturer överstigande 1200 °C och där de mekaniska egenska- perna hos intermetaller såsom molybdenaluminosilicider utgör en begräsning t.ex. medför begränsat motstånd mot termochock- ef.
Vidare kan nämnda metall (M) enligt en föredragen utförings- form till del ersätts med något av ämnena tantal (Ta) och vanadin (V) som legeringsämnen i nämnda legering.
Speciellt fördelaktig är dock en legering som har en samman- sättning TizAlyCw där z ligger i intervallet 1.8 till 2.2, y i intervallet 0.8-1.2 och w i intervallet 0.8-1.2 och av att z, y och w är så valda att materialet bildar ett skyddande oxid- skikt av Al2O3 vid uppvärmning.
En föredragen modifiering av nyssnämnda legering är sådan att z = 2.0, y ligger i intervallet 1.0 - 1.2 och w = 1.0.
Den ternära karbiden, Ti3SiC2, uppvisar liknande mekaniska egenskaper som materialet enligt uppfinningen, dock med den avgörande nackdelen att titankiselkarbid bildar en snabbt hfidocwütidslutfïireläggandudoc , 2005-08-24 03002ASE 70 75 20 25 30 527 199 växande ej passiverande blandoxid av TiO2 och SiO2 vilket i praktiken omöjliggör användning av materialet i oxiderande miljö under långa tider över 1100 °C utan att materialet degraderas.
Det bör även betonas att när materialet enligt uppfinningen används under förhållanden med tillräckligt lågt partialtryck av syre för att förhindra en aluminiumoxidbildning på materi- alets yta så kommer materialet att förbli intakt enligt for- meln Ti,AlyXw.
Den ternära fasen Ti3AlC2 med närliggande sammansättningar bildar också under vissa omständigheter aluminumoxid på ytan och kan således användas som sekundärfas i materialet.
Materialet enligt uppfinningen kan även innehålla Al2O3, TiC och/eller titanaluminider.
Titankarbid och titanaluminider kan förekomma i materialet utan att det inverkar negativt på oxidationsegenskaperna hos kompositer av materialet enligt uppfinningen.
Som en förstärkande fas i en komposit av materialet kan även ÅlgOg, tillSättâs .
Nedan ges ett tillverkningsexempel. l. 4000 g Ti, 1240 g Al and 501 g C (motsvarande samman- sättningen Ti2AlL1C ) i pulverform blandades i en kul- kvarn under 4 h. 2. Det blandade pulvret placerades i en rörugn av alumini- umoxid innehållande vätgas. 3. Pulvret värmebehandlades enligt följande cykler: nxmmwmkwmflmflmmmäm, 2005-08-24 030024SE 10 15 20 25 30 O O 10. ll. 12. 13. 14. hfidocworldsluttöxelâggandedoc, 2005-08-24 527 199 3 °C/min till 400 °C Hàllande vid 400 °C under 4h 2 °C/min till 800 °C Hållande vid 800 °C under 4h 2 °C/min till 1400 °C Hàllande vid 1400 °C under 4h Naturlig kylning Det reagerade pulvret krossades och maldes ned till 325 mesh.
En XRD analys av pulvret visade att huvudfasen var Ti2AlC med närvaro av något Ti3A1C2 och Al3Ti.
En blandning av Ti, Al, C (enligt förhållandena i steg 1) och 20 vikts% av det reagerade pulvret (steg 5) packades och placerades i en vattenkyld stàlbehållare.
Behållaren evakuerades och fylldes med renad Argon gas.
Pulvret antändes medelst elektrisk värmning. Processen är känd som SHS (Self propagating High temperature Synthesis).
Det reagerade materialet kyldes ned naturligt.
Det reagerade materialet maldes ned till 325 mesh.
En XRD analys av pulvret visade att huvudfasen var Ti2AlC med närvaro av något Ti3AlC2, TiC and Al3Ti (mindre än 10%).
Pulvret kyldes och kallpressades samt sintrades med kvävgas vid 1500 °C i 1 timme.
Optisk mikroscopi och en SEM (Svep Elektron Mikroskop) analys av det sintrade materialet visade att provet var tätt med mindre än 2% porositet. Några korn av Ti3AlC2 observerades med mindre än 5% TiAl3 vid korngränserna.
Kornstorleken var i storleksordningen 30 mikrometer, med några korn i storleksordningen 200 mikrometer.
Provet placerades i en utrustning för att studera dess oxidationsegenskaper. Provet hölls vid 1100 °C i 8 h, 030024SE 10 75 20 25 30 199 527 1200 °C i 8 h och 1300 °C i 8hrs. Oxidationsförloppet befanns vara nära paraboliskt. Oxidationsytan var blekt vit, vilket indikerar ett tunt oxidlager. 15.En SEM analys visade att oxidtjockleken var 5 microns och bestod av tät och vidhäftande Al2O3. 16.En del av en sintrad stång polerades ned till 1000 grit. l7.Detta prov placerades i en utrustning för att studera dess cykliska uppträdande. Provet hölls vid 1200 °C i 4 h och kyldes ned naturligt. Cykeln upprepades 10 gång- er. l8.0xidationsytan var blekt vit, vilket indikerar ett tunt oxidlager. 19.En SEM analys visade att oxidtjockleken var 3 mikrome- ter och bestod av tät och vidhäftande Al2O3. 20.En sintrad stång polerades ned till 1000 grit. 21.Provet placerades i en lådugn med luft vid 1200 °C i 980 h. 22.0xidationsytan var blekt vit, vilket indikerar ett tunt oxidlager. 23.Viktökningen hos provet var 10 mg med ett vitt lager av Al2O3 på ytan.
En extra föredragen tillämpning av det uppfunna materialet är av gas alt. av flyktiga bränslen värmda infraröda värmestrå- lare där materialet fungerar som en strålningsemitterande yta. IR-strålare av denna typ används bland annat inom pap- persindustrin för torkning, fuktprofilering och ytbeläggning av papper och närliggande material. Dylika strålningsemitte- rande ytor är med fördel designade som plattor. Plattorna kan vara konstruerade som plattor med genomgående hål, t.ex. med en hålbild i form av en bikakestruktur alternativt kan ytan t.ex. byggas upp av ett antal parallella tunnväggiga plattor. hàdocworkßlutíörelâggandadoc , 2005-08-24 030024SE 70 15 20 25 30 E27 199 Det uppfunna materialet bidrar till en robust värmestrålande platta tack vare dess unika kombination av goda egenskaper: långsam oxidationshastighet upp till 1400 °C, god värmeled- ningsförmåga, förenklad bearbetbarhet jämfört med andra kera- mer vilket leder till lägre tillverkningskostnader, den ut- märkta förmågan att motstå termochock vilket inte sätter restriktioner med avseende på design med skarpa kanter och varierande tjocklek hos godset.
Materialet enligt uppfinningen är elektriskt ledande med en resistivitet av cza 0.5 Qmm2/m vid rumstemperatur och cza 2.5 Qmm2/m vid 1200 °C. I kombination med materialets goda meka- niska egenskaper och övriga högtemperaturegenskaper är det fördelaktigt att använda det som elektriskt motståndselement i både oxiderande och reducerande atmosfärer samt under vacu- um. Andra tillämpningar där fördelarna kan utnyttjas är såsom gaständare, flamdetektor, glödstift och dylika användningar.
Användningsområdet i ugnar är inte begränsat av ovanstående exempel; utöver dessa kan materialet utgöra delar eller hel- heten av följande detaljer: brickor, substrathållare, inred- ning, stödrullar med mera.
Materialet enligt uppfinningen kan med stor fördel även an- vändas i pulverform i syfte att belägga ytor t.ex. medelst termiska sprutmetoder såsom HVOF, plasmasprutning o d. Ytbe- läggning med deponering från ångfas med s.k. PVD (Physical Vapour Deposition) och CVD (Chemical Vapour Deposotion) utgör också möjligheter att tillverka skikt beständiga mot högtem- peraturkorrosion. Dylika ytskikt kan också i form av ett kretsmönster designat för lämpligt elektriskt motstånd också fungera som platta värmeelement för värmebehandling av kisel- skivor. h:\docwork\slutförelåggande.doc , 2005-08-24 030024SE 10 527 199 Användningsområden utöver ovanstående för föreliggande mate- rial innefattar även rör till etenproduktion, värmeväxlare, brännarmunstycken, gasturbindelar m.m.
Ovan har olika tillämpningar av föreliggande uppfinning be- skrivits. Det är emellertid uppenbart att fackmannen kan välja att använda föreliggande material vid tillämpningar där dess egenskaper är fördelaktiga.
Föreliggande uppfinning skall därför inte anses begränsad till ovan angivna utföringsexempel, utan kan varieras inom dess av bifogade patentkrav angivna ram. hfldocwoxidslutförelåggandadoc , 2005-08-24 030024SE

Claims (2)

10 15 20 25 30 Patentkrav l. Användning av ett material bestående av en legering mellan (Al) och kol (C), vilken legering har en sammansättning M,AlyXw, där M utgöres (ti), krom (Cr) och/eller niob (Nb) och där X utgö- en metall, aluminium alternativt kväve (N), av titan res av kol (C), alternativt där X utgöres av kväve (N) och/ eller kol intervallet 1.8 till 2.2, y i intervallet 0.8-1.2 och w i (C) när M utgöres av titan (Ti), där z ligger i intervallet 0.8-1.2, k ä n n e t e c k n a d a v, att mate- rialet används vid temperaturer överstigande l200°C och i oxiderande miljö, varvid ett skyddande oxidskikt av A120; utbildas efter uppvärmning till nämnda temperatur. 2. Användning av ett material enligt krav l, k ä n n e - t e c k n a d a v, att nämnda ämne M till del utgörs av något av ämnena tantal (Ta) och vanadin (V) som legeringsäm- nen i nämnda legering. 3. Användning av ett material enligt krav 1 eller 2, k ä n - n e t e c k n a d a v, att legeringen har en sammansättning TizAlyXw där z ligger i intervallet 1.8 till 2.2, y i inter- vallet 0.8-1.2 och w i intervallet 0.8-l§2 och av att z, y och w är så valda att materialet bildar ett skyddande oxid- skikt av A120; vid uppvärmning. 4. Användning av ett material enligt krav 3, k ä n n e - t e c k n a d a v,
1.2 och w = 1.0. att z =
2.0, y ligger i intervallet 1.0 - hàdocworlflslutiömläggandedoc , 20054l8-24 030024515
SE0300318A 2003-02-07 2003-02-07 Användning av ett material i oxiderande miljö vid hög temperatur SE527199C2 (sv)

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US8192850B2 (en) * 2008-08-20 2012-06-05 Siemens Energy, Inc. Combustion turbine component having bond coating and associated methods
US8971476B2 (en) 2012-11-07 2015-03-03 Westinghouse Electric Company Llc Deposition of integrated protective material into zirconium cladding for nuclear reactors by high-velocity thermal application
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US10815896B2 (en) 2017-12-05 2020-10-27 General Electric Company Igniter with protective alumina coating for turbine engines
KR102079800B1 (ko) 2018-01-10 2020-02-20 영남대학교 산학협력단 접합재용 Ti3AlC2 테이프 제조방법 및 접합재용 Ti3AlC2 테이프를 이용한 탄화규소의 접합방법
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