SIONDICA venture audit on 20.6.07 V. Shklover About coatings for ADC General comments helpful for our venture Re

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SIONDICA venture audit on 20.6.07 V. Shklover About coatings for ADC General comments (valuable for our task) Memory of ICMCTF2007 Papers on Si-O-N framework Patent list items Conclusions. Prerequisites to ADC materials B. Andresen, 2005

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Slide 1

SIONDICA extend audit on 20.6.07 V. Shklover About coatings for ADC General comments (helpful for our venture) Reminiscence of ICMCTF2007 Papers on Si-O-N framework Patent list items Conclusions

Slide 2

Requirements to ADC materials B. Andresen, 2005 Fracture sturdiness (rehashed withdrawal and development, prompting to warm checking) Die lifetime can be enhanced by ~ half by decreasing angle between T max and T min (part of TC!) Gross breaking resistance Soldering resistance. Al amalgams throwing by Fe of kick the bucket material at high-temperature. Intermetallics FeAl x have bring down TC, Al soften cools at lower rate and isolates from whatever is left of throwing. Fastening happens at problem areas on the kick the bucket surface

Slide 3

Tribology investigation of coatings for ADC O. Salas et al. 2003 Functions of ADC covering framework: Adhesion to substrate Accommodation of stress Good tribological properties Corrosion resistance Non-wettability with liquid Al as focal issue Best coatings (out of 15 contemplated) are TiAlN, TiN/TiCN/CrN

Slide 4

Coatings for ADC A. Lakare et al. 1999 Main disappointment modes in ADC: Soldering ( consumption , development of Fe-Al-Si intermetallics because of response H13 steel + Al thus of H13 dissolving in Al) Washout ( disintegration wear by high-speed of cast metal of 30-100 m/sec, injective weight 50-80 MPa) Thermal weariness (warm checks, because of option temperature change, 670-710 o C) CrN was best covering

Slide 5

PVD coatings for ADC E. Bernacchi et al., 1996 TiAlN is more appropriate for Al bite the dust throwing then CrN and CrC (imperviousness to wear and Al fastening were checked)

Slide 6

Soldering counteractive action by oxide surface treatment M. Z. Jahedi et al. 2001 Production of conservative oxide layer by oxidation in CO 2/H 2 gas blend: Steel H13, 550 o C reduced Fe 3 O 4 layer Incoloy MA956 (4.5wt% Al), 1100 o C minimized  - Al 2 O 3 layer Prevention of development of intermetallic Al/steel stages amid Al weight pass on throwing (fastening)

Slide 7

Design of covering frameworks for ADC S. Carrera et al. 2001 No one individual covering gives blend of properties: Be non-wetting with fluid Al Wear safe Oxidation safe at throwing conditions Accommodate leftover warm worries amid shot cycling Working layer (non-wetting, wear-and oxidation resistance) Multilayer or evaluated layer (FGM) to limit stresses Adhesion layer (~50 nm) with H13

Slide 8

Design of covering frameworks for ADC S. Carrera et al. 2001 Composition of "working layer" relies on upon Al combination - Candidates for "working layer" (poor wettability with Al): CrC, CrN, TiAlN, MoZrN, TiBCN, NoAl, TiCN - Coatings show diverse wettability with various Al amalgams - No best hopeful was distinguished, however all were less wetting than H13

Slide 9

Corrosion of H13 steel in liquid Al compounds R. Aharonov et al. 2001 CrN gives great security against liquid Al Smoother surface complete and thicker coatings result in better erosion resistance Optimum covering thickness is 4-5 µm Substrate (H13) erodes because of nearness of pinholes and different imperfections Thermal worries around ill tempers likewise prompt to consumption Coatings with higher compressive anxiety flop speedier then low-stretch coatings

Slide 10

General: conceivable connection grid parameters - hardness Sirdeshmukh et al. 2006 - Chemical holding is imperative for assurance of the precious stone hardness, accepting meaning of hardness as imperviousness to separations development - For NaCl structures, cross section steady can be utilized as parameter, describing hardness: the weaker is the security, the bigger is security length and the lower is hardness ln(H v x100) Gilman-Chin parameter (H v/C 44 ) H v , kg/mm 2 ln(C 44 x100) a, Å

Slide 11

Nanoindentation at hoisted temperature - Micro Materials (UK), test estimations in LOT-Oriel GmbH - Standard NanoTest hot stage (warmed indenter) to 500 o C - Hot stage works to 750 o C - Two examples, estimations at RT, 500, 600, 700 and 750 o C Samples: - CrSiON #1771 (best CrSiON test) on WCo substrate - CrN on WCo substrate (reference) Results expected: - End of June/starting July

Slide 12

General: surface arrangement in CrSiON movies Typical for CrN movies (200)- surface changes to (111) at increment of Si substance in Cr 1-x Si x N (Martinez et al. 2004) Switch of surface and stage change (Lee et al. 2005) Solubility farthest point of Si in CrN (~11at.%, Kim et al. 2006)

Slide 13

Understanding surface development in CrSiON movies F. H. Baumann et al. Monte Carlo demonstrating of thin-film development is arranged Al film Competition of (001) and (111) development three distinctive temperatures

Slide 14

General: Lab of Crystallography of ETH is purchasing instrument for TC estimations until 2000 o C

Slide 15

Ultrathin SiON movies K. Muraoka et al. 2003 Growth by SiH 4/N 2/O 2 plasma-upgraded CVD handle at Si(111) substrate temperature of 500 o C Compositions on hold SiO 2 … Si 3 N 4 considered N and O content contemplated by edge settled XPS (N1s and O1s groups) Compositions of (Si 3 N 4 ) x (SiO 2 ) 1-x movies stored at 500 o C and toughened at 850 o C

Slide 16

Thermodynamics of Si-O-N framework M. L. Green et al. 2001 Thermodynamic (mass) stage chart for Si-O-N framework Why N particles join into SiO 2 ? N can be caught dynamically N can be thermodynamically steady at the interfaces (There are likewise different clarifications) M. Hillert et al. 1992 Calculated SiO 2 - Si 3 N 4 stage outline

Slide 17

Nitridation of SiO 2 D. Fischer et al, 2004 Hydrogen passivation as an approach to adjustment of SiON in SiO x N y-z (NH) z structure MD reproduction of impact of nitridation on SiO 2 Up to nitrogen substance of ~25%, fundamental structure of oxide is saved Beyond basic N content, basic moves are normal Upper cutoff of N substance might be distinctive for mass and movies

Slide 18

Properties of superhard Si-O-N framework L. Torrison et al. 2003 Si 2 N 2 O has unrivaled oxidation resistance and warm stun resistance contrasted with Si 3 N 4 . However, no reasonable union procedure at relative low temperatures for Si 2 N 2 O is accessible - Si 2 N 2 O has structure of high-weight B 2 O 3 Characterization: RBS (with recreation), SIMS, HRTEM, FTIR Structure of non-stoichiometric SiN x O y : dominatingly Si 3 N 4 connect with some cross section destinations involved by O - Tuning of creation by development parameters

Slide 19

ICMCTF 2007: commitments identified with our venture

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ICMCTF 2007 (A1-2-11) DSC/TGA investigation of oxidation of CrN and CrAlN coatings on conciliatory backings J. Lin et al. 2007 Reactive sputtering onto stainless steel and glass secured with formvar (statement temperature 150-250 o C) - Different stage moves related with XRD - DSC, TGA and Kissinger plots for Cr 0.78 Al 0.22 N Reactions are more articulated with expanding warming rates Reactions are moved to higher temperatures with Cr content

Slide 21

Patent inquiry Software: Derwent Innovation Index (ISI Web of Knowledge) Patent Downloader (US, Japan, PCT) Search for: "ZrSiON" "ZrAlON" "TiAlON" "AlCrON" "Aluminium kick the bucket throwing coatings" "Oxynitride" "Coatings AND "pass on" "Chromium" AND "Silicon" AND "Oxynitride" "Chromium" AND "Silicon" AND "Nitride"

Slide 22

ZrSiON 1) Guardian, 2) Sumimoto, 3) Mitsubishi, 4) Toshiba, 5) Nippon Tungsten, 6) NGK Insulators, 7) Asahi Glass. No confirmations for Al pass on throwing, dispersion boundaries, TC

Slide 23

ZrAlON 1) Mitsubishi, 2) Shinko Kobelko, 3) Isuzu Motors, 4) Minnesota Mining, 5) Toshiba, 6) Nippon Tungsten. No confirmations for to Al bite the dust throwing, dissemination boundaries, one TC

Slide 24

TiAlON 1) Mitsubishi, 2) Sumimoto, 3) Juergen Bach, 4) Shanghai Tool, 5) Shinko Kobelko. One truly TiAlON, no proofs for Al bite the dust throwing, dissemination hindrances, TC

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AlCrON 1) Shinko Kobelko, No confirmations for to Al bite the dust throwing, dispersion boundaries, one TC

Slide 26

Coatings for Al bite the dust throwing (1) 1) Colorado school mines, 2) Unaxis, 3) Authors, 4) Ionbond, 5) Brush Wellman, 6) Daido Tokushuko, 7) Ube Ind, 8) Matsumoto, 9) Nippon steel.

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Coatings for Al pass on throwing (2) 1) Nippon Steel, 2) Aisin Seiki, 3) Volvo AB, 4) Hitachi Metals, 5) Toyota, 6) Swiss Aluminum, 7) Mallory & Co.

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Oxynitrides 1) Kigam, 2) Mitsubishi (numerous comparative licenses), 3) Toshiba, 4) Kennametal (numerous), 5) Winkhlover, 6) ELEMENT SIX (high R coordination number), 7) DIAMORPH CERAMIC, 8) Hitachi, 9) Sumimoto, 10) Unaxis, 11) KYOCERA No proofs for Al pass on throwing, dissemination boundaries, TC

Slide 29

Oxynitrides-2 1) Shanghai Tool, 2) Sumimoto, 3) Uni Donghua, 4) Mitsubishi, 5) Seramtec, 6) Shinko Kobelko, 7) Shinko Kobelko+Mitsubishi. No proofs for Al kick the bucket throwing, dissemination obstructions, TC

Slide 30

"Coatings" AND "bite the dust"- 1) Kobe Seiko Sho. 2) TDY Ind. 3) Unaxis. 4) Sumimoto Electric. 5) Toshiba Tung. 6) Syndia. 7) Sumimoto Metal. 8) Zaporo Ind. 9) Nippon Steel.

Slide 31

"Coatings" AND "bite the dust"- 2 1) GTE Lab Inc. 2) Aluminum Co. America. 3) Idemitsu Petrochem. 4) British Petr. 5) Swiss Aluminum. 6) Mallory & Co. 7) Surface innovation. 8) Fulmer Res. Inst. 9) Seiko Instr.

Slide 32

Different 1) Shinko Kobelko, 2) Unaxis.

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Chromium AND silicon AND oxynitride (48, 8 applicable) 1) Toshiba Tungaloy, 2) Subimoto Denko, 3) Sumimoto Electric, 4) Mitsubishi, 5) NGK SPARK PLUG Co.,

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