DOCSLIB.ORG

United States Patent (19) - (11) 4,178,317 A

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
United States Patent (19) - (11) 4,178,317 A United States Patent (19) - (11) 4,178,317 A. Horn et al. 45 Dec. 11, 1979 54 MANUFACTURE OF OLEFINICALLY (56) References Cited UNSATURATED ALPHATIC OR CYCLOALIPHATIC HYDROCARBONS U.S. PATENT DDOCUME MENT S 4,024,171 5/1977 McArthur ....................... 260/666A 75) Inventors: Peter Horn, Hirschberg; Otto-Alfred FOREIGN PATENT DOCUMENTS Grosskinsky; Hugo Fuchs, both of Ludwigshafen, all of Fed. Rep. of 943745 12/1963 United Kingdom. Germany Primary Examiner-Veronica O'Keefe w Attorney, Agent, or Firm-Keil & Witherspoon 73) Assignee: BSAngelschall, Fed. Rep. 57 ABSTRACT Olefinically unsaturated aliphatic or cycloaliphatic hy 21) Appl. No.: 907,678 drocarbons are manufactured by bringing alkanecar boxylic acids of 3 to 20 carbon atoms, alkanedicarboxy ilar. lic acids of 4 to 20 carbon atoms or 5-membered or (22) Filed: May 19, 1978 6-membered cycloalkanecarboxylic acids or their alkyl, O 9 cycloalkyl, aralkyl or phenyl esters, in the gas phase, at 30. Foreign Application Priority Data from 250 to 800 C., into contact with catalysts in Jun. 10, 1977 (DE) Fed. Rep. of Germany. 2726106 which the active composition consists of boron trioxide, boric acid and/or boron nitride, together with one or 51) Int. C.’................................................ C07C3/00 more of the oxides of aluminum, silicon, tin, lead, tita 52 U.S. C. .................................... 585/357; 585/638; nium and zirconium. 585/640 (58) Field of Search .................................... 260/666 A 9 Claims, No Drawings 4,178,317 1. 2 ahydrobenzoate, cyclohexyl hexahydrobenzoate, MANUFACTURE OF OLEFINICALLY phenyl hexahydrobenzoate and benzyl hexahydroben UNSATURATED ALPHATIC OR ZOate. : .. 8 CYCLOALPHATIC HYDROCARBONS Of course the decarbonylation of monocarboxylic acids or their esters gives monoolefinically unsaturated The present invention relates to a process for the compounds with one carbon atom fewer, whilst the manufacture of olefinically unsaturated aliphatic or decarbonylation of dicarboxylic acids gives diolefins cycloaliphatic hydrocarbons by heating alkanecarboxy with 2 carbon atoms fewer. lic acids of 3 to 20 carbon atoms, alkanedicarboxylic The reaction is carried out in the gas phase. Advanta acids of 4 to 20 carbon atoms or 5-membered or 6-men 10 geously, the carboxylic acids, or their esters, used as bered cycloalkanecarboxylic acids or the alkyl, cycloal starting materials, are vaporized, but inert gases, such as kyl, aralkyl or phenyl esters of these at from 250 to nitrogen, noble gases, carbon dioxide, carbon monox 800 C. in the gas phase in the presence of a catalyst. ide, steam or flue gases may additionally be employed in There is a frequent requirement to convert carboxylic order to facilitate using the starting materials in the gas acids, obtained, for example, by oxidation processes, or 15 phase. The amount of such inert gas used is not critical, to convert carboxylic acids or their esters, obtained as since the gas merely serves as a carrier gas. by-products of carbonylation processes, into the corre The reaction is advantageously carried out under sponding olefins by decarbonylation. The decarbonyla atmospheric pressure, slightly superatmospheric pres tion of carboxylic acids of their esters is of particular sure, or reduced pressure, for example down to 20 mm interest if it permits olefins which are not readily acces 20 Hg. A pressure range from atmospheric pressure to 100 sible to be obtained from the more easily accessible mm Hg has proved particularly suitable. carboxylic acids or their esters. The reaction takes place at from 250 to 800. C., It is true that German Published Application DAS advantageously from 250 to 700° C. No. 1,158,050 has disclosed that carboxylic acids can be The reaction is carried out in the presence of cata converted into acid anhydrides and/or ketones by heat 25 lysts, of which the active composition consists of boron ing at from 250 to 800° C. in the gas phase in the pres trioxide, boric acid and/or boron nitride, together with ence of a catalyst comprising oxides, hydroxides and one or more of the oxides of aluminum, silicon, lead, phosphates of main groups 2 to 4 and sub-groups 3 to 8 titanium or zirconium. Preferred active compositions of the periodic table. However, the corresponding ole contain from 10 to 60, especially from 20 to 55, 7% by fins cannot be obtained by this method. 30 weight of boron trioxide, boric acid and/or boron ni It is an object of the present invention to provide a tride. The remainder of the active composition then process by means of which carboxylic acids or their consists of one of the above oxides. Active compositions esters can be converted by decarbonylation into the which contain boron trioxide or boric acid, especially corresponding olefins. the former, have proved particularly suitable. We have found that this object is achieved by a pro 35 The preferredoxides also present in the active com cess for the manufacture of olefinically unsaturated positions include alumina, e.g. in the form of hydrargil aliphatic or cycloaliphatic hydrocarbons by heating lite, boehmite or bayerite and their dehydration prod alkanecarboxylic acids of 3 to 20 carbon atoms, al ucts, e.g. y-, e- or 8-alumina, as well as tin dioxide, kanedicarboxylic acids of 4 to 20 carbon atoms or 5 titanium dioxide and silica gel. The use of alumina, or of membered or 6-membered cycloalkanecarboxylic acids 40 titanium dioxide in the anatase modification, is pre or their alkyl, cycloalkyl, aralkyl or phenyl esters at ferred. a-Alumina is industrially of particular impor from 250 to 800° C. in the gas phase in the presence of tance since it reduces the isomerization of the olefini a catalyst whereof the active composition consists of cally unsaturated hydrocarbons formed. baron trioxide, boric acid and/or boron nitride together Further catalysts according to the invention are those with one or more of the oxides of aluminum, silicon, tin, 45 resulting from mixed phase formation between one of lead, titanium or zirconium. the boron compounds used and the oxides mentioned The new process has the advantage that carboxylic above, e.g. boron trioxide and alumina, giving com acids or their esters can be converted in a simple manner pounds of the empirical formula 9 Al2O3. 2 B2O3 or 2 into olefins. It has the further advantage that it is easily Al2O3. B2O3. In such mixed phases, alumina is no scaled up to industrial operation and runs with good 50 longer detectable by X-ray crystallography. yields and good conversions. Advantageously, the active compositions addition It is preferred to start from an alkanecarboxylic acid ally contain one or more of the elements of group VIII of 3 to 16 carbon atoms, an alkanedicarboxylic acid of 4 of the periodic table, manganese, chromium, copper, to 12 carbon atoms or cyclohexanecarboxylic acid. zinc, cadmium, silver and/or gold. The said elements. Their alkyl, cycloalkyl, aralkyl and phenyl esters, espe 55 are preferably present in the active composition in an cially their alkyl esters, where alkyl is of 1 to 8 carbon amount of from 0.1 to 10% by weight (calculated as atoms, their cyclohexyl esters, their benzyl esters and metal), based on the active composition. their phenyl esters, are also suitable. The use of the free Suitable catalysts are prepared by, for example, mix carboxylic acids or of the corresponding methyl esters ing alumina and boron oxide or boric acid, or com as starting materials is preferred. The new process is of 60 pounds which form these on heating, e.g. ammonium particular industrial importance for the manufacture of borate, with or without the addition of compounds of cyclohexene from hexahydrobenzoic acid or its esters. the above heavy metals, e.g. manganese nitrate, manga Specific examples of suitable starting materials are pro nese acetate, cobalt nitrate, cobalt acetate, nickel ni pionic acid, methyl propionate, isobutyric acid, butyl trate, rhodium chloride, tris-(triphenylphosphine)- isobutyrate, caproic acid, methyl caproate, decanecar 65 rhodium chloride, iridium chloride, palladium nitrate, boxylic acid, palmitic acid, methyl palmitate, dimethyl platinum chloride, zinc nitrate, cadmium nitrate, copper adipate, dimethyl methylglutarate, methyl cyclopen nitrate, silver nitrate or gold chloride, if appropriate tanecarboxylate, hexahydrobenzoic acid, methylhex working the mixture into a paste with water and knead 4, 178,317 3 4. ing the paste, and molding the material into shapes, e.g. pills, tablets or extrudates. Advantageously, the mate EXAMPLE 1. rial is then dried and heated at up to 400 C. If the active 200 g of hexahydrobenzoic acid per hour were passed composition is to be used as a fluidized bed catalyst, it is from a vaporizer into a fluidized bed reactor at 550 C., advisable to comminute the moldings to the desired 5 the reactor being charged with 630g of a catalyst which size, e.g. to an average particle size of from 0.01 to 2 consisted of 52.3 percent by weight of y-Al2O3 and 45.5 mm, especially from 0.2 to 1 mm. The catalyst composi percent by weight of B2O3, and had a particle size of tion is then heated at from 600 to 1,500 C., preferably from 0.1 to 0.3 mm and a bulk density of 0.63 kg per from 700 to 1,300° C. and especially from 1,000 to liter. The catalyst was fluidized by means of the hexahy 1,200 C. for a period of from 15 minutes to 20 hours, O drobenzoic acid vapor and a slight stream of nitrogen, especially from 30 minutes to 5 hours. as well as by maintaining a reduced pressure of 360 mm In another advantageous embodiment, the active Hg. The resulting reaction vapors were condensed. The compositions according to the invention are obtained following products were isolated after 3 hours' opera by impregnating, for example, alumina or one of the tion: 86 g of water and 384 g of an organic phase.
Load more

Recommended publications
  • United States Patent (19) 11 3,929,495 Broemer Et Al
    United States Patent (19) 11 3,929,495 Broemer et al. (45) Dec. 30, 1975 54) OPTICAL BORATE GLASS OF HIGH 3,149,984 9/1964 Faulstich........................... 106/47 R CHEMICAL RESISTANCE AND PROCESS 3,307,929 3/1967 Trap.................................. 106/47 R 3,480,453 it 1/1969 Reid et al.......................... 106/47 R OF MAKING SAME 3,486,915 12/1969 Broemer et al................... 106/47 R (75) Inventors: Heinz Broemer, Hermannstein; 3,510,325 5/1970 Broemer et al................... 106/47 R Norbert Meinert, Wetzlar, both of FOREIGN PATENTS OR APPLICATIONS Germany 863,352 3/1961 United Kingdom............... 106/47 Q 73 Assignee: Ernst Leitz G.m.b.H., Wetzlar, 4,424,420 10/1969 Japan................................ 106/47 Q Germany Filed: May 15, 1973 Primary Examiner-Winston A. Douglas 22) Assistant Examiner-Mark Bell 21 Appl. No.: 360,418 Attorney, Agent, or Firm-Erich M. H. Radde 30 Foreign Application Priority Data 57 ABSTRACT May 15, 1972 Germany............................ 2223564 An optical borate glass of high chemical resistance, with negative anomalous partial dispersion, refraction 52) U.S. Cl. ............................. 106/47 Q; 106/47 R index n between 1,65 and 1,79, and Abbe number ve 51 Int. CI..... C03C 3/14: CO3C 3/00; C03C 3/30 between 40 and 30 is composed of boron trioxide, 58) Field of Search......................... 106/47 O, 47 R lead oxide, and aluminum oxide. It may additionally contain lithium, sodium, and/or potassium oxides, zinc (56) References Cited oxide, zirconium dioxide, tantalum pentoxide, and, if UNITED STATES PATENTS desired, antimony trioxide and/or bismuthum trioxide.
    [Show full text]
  • United States Patent (19) (11) 4,154,806 Szabó Et Al
    United States Patent (19) (11) 4,154,806 Szabó et al. 45) May 15, 1979 54 PROCESS FOR THE PRODUCTION OF (56) References Cited NITROUS OXDE U.S. PATENT DOCUMENTS 75) Inventors: Zoltán Szabó; Jenö Trompler; 1,098,305 5/1914 Torley et al. ........................ 423/400 Erzsébet Hollós, née Rakosinyi, all of 2,111,277 3/1938 Castner et al. ....................... 423/400 Budapest, Hungary 2,425,582 8/1947 Vingee ................................. 423/400 3,411,883 11/1968 Smit ................................. 423/400X 73) Assignee: Eötvös Lóránd Tudományegyetem, FOREIGN PATENT DOCUMENTS Budapest, Hungary 276069 5/1913 Fed. Rep. of Germany ........... 423/400 (21) Appl. No.: 865,119 Primary Examiner-G. O. Peters 57 ABSTRACT (22 Filed: Dec. 28, 1977 Ammonium nitrate is mixed, in a weight ratio of higher than 1:5, with a melt containing ammonium hydrogen 30 Foreign Application Priority Data sulfate and ammonium sulfate respectively present in Dec. 30, 1976 HU) Hungary ............................. TO 1047 the melt in a ratio of at least 4:1. The resultant mixture is subjected to thermal decomposition at 200-240 de 51) Int. C.’.............................................. C01B 21/22 grees C to produce nitrous oxide. 52) U.S. C. .................................................... 423/400 58) Field of Search ......................................... 423/400 10 Claims, No Drawings 4,154,806 2 temperature, i.e. over 250 C., the nitrous oxide formed PROCESS FOR THE PRODUCTION OF NITROUS decomposes to higher nitrogen oxides and nitrogen. A OXDE further disadvantage of the increased temperature con sists in that ammonium nitrate sublimates and thus The invention concerns a process for the production causes material loss and operational problems.
    [Show full text]
  • Effects of B2O3 (Boron Trioxide) on Colon Cancer Cells: Our First-Step Experience and in Vitro Results
    Turkish Journal of Biology Turk J Biol (2019) 43: 209-223 http://journals.tubitak.gov.tr/biology/ © TÜBİTAK Research Article doi:10.3906/biy-1901-34 Effects of B2O3 (boron trioxide) on colon cancer cells: our first-step experience and in vitro results 1, 2 3 4 5 3 Özgür ALBUZ *, Dilek DÜLGER , Beste Çağdaş TUNALI , Feray AYDIN , Selim YALÇIN , Mustafa TÜRK 1 Department of General Surgery, Keçiören Training and Research Hospital, Ankara, Turkey 2 Department of Medical Microbiology of Basic Medical Sciences, Faculty of Medicine, Karabük University, Karabük, Turkey 3 Department of Bioengineering, Faculty of Engineering, Kırıkkale University, Kırıkkale, Turkey 4 Department of General Surgery, 29 Mayıs State Hospital, Ankara, Turkey 5 Department of Oncology, Faculty of Medicine, Kırıkkale University, Kırıkkale, Turkey Received: 15.01.2019 Accepted/Published Online: 11.06.2019 Final Version: 13.06.2019 Abstract: Boron oxide (B2O3) is derived from dehydration of boric acid and is a colorless, semitransparent, crystalline compound that is moderately soluble in water. On the other hand, boron oxide is chemically hygroscopic. This gives the molecule the ability to soak up water and adhere to tissues. Boron oxide can be used locally after tumor debulking in inoperable tumors and especially when the tumor-free margin distance cannot be provided. For all these reasons we aimed to evaluate the in vitro test results of B2O3 in terms of cytotoxicity, genotoxicity, apoptosis, and necrotic effects on L929 fibroblast cells and DLD-1 colorectal adenocarcinoma cells. Our studies demonstrated that boron oxide compounds appear to be highly cytotoxic for both cell lines according to WST cell viability assay (44.22% and 18.36% on DLD-1 and L929, respectively).
    [Show full text]
  • Improving Boron for Combustion Applications
    New Jersey Institute of Technology Digital Commons @ NJIT Dissertations Electronic Theses and Dissertations Summer 8-31-2019 Improving boron for combustion applications Kerri-lee Annique Chintersingh New Jersey Institute of Technology Follow this and additional works at: https://digitalcommons.njit.edu/dissertations Part of the Aerospace Engineering Commons, Chemical Engineering Commons, and the Materials Science and Engineering Commons Recommended Citation Chintersingh, Kerri-lee Annique, "Improving boron for combustion applications" (2019). Dissertations. 1420. https://digitalcommons.njit.edu/dissertations/1420 This Dissertation is brought to you for free and open access by the Electronic Theses and Dissertations at Digital Commons @ NJIT. It has been accepted for inclusion in Dissertations by an authorized administrator of Digital Commons @ NJIT. For more information, please contact [email protected]. Copyright Warning & Restrictions The copyright law of the United States (Title 17, United States Code) governs the making of photocopies or other reproductions of copyrighted material. Under certain conditions specified in the law, libraries and archives are authorized to furnish a photocopy or other reproduction. One of these specified conditions is that the photocopy or reproduction is not to be “used for any purpose other than private study, scholarship, or research.” If a, user makes a request for, or later uses, a photocopy or reproduction for purposes in excess of “fair use” that user may be liable for copyright infringement,
    [Show full text]
  • Position Paper of the European Glass Industry on the Proposed Inclusion of Boron Trioxide on the Candidate List for Authorization
    Position Paper of the European Glass Industry on the Proposed Inclusion of Boron Trioxide on the candidate list for authorization April 2012 Glass manufacturers support the REACH Regulation and believe that a reduction of the risk associated with worker exposure and the environmental impact of dangerous substances is welcome in the EU Market. Glass Alliance Europe welcomes the opportunity to provide its contribution to the public consultation on the inclusion of boron trioxide in the candidate list for authorization of the REACH Regulation. CONTRIBUTION TO THE CONSULTATION PROCESS Germany submitted to ECHA an Annex XV dossiers for the identification of boron trioxide as a Substance of Very High Concern to be included in the candidate list for authorization. The rationale for this identification is the classification of boron trioxide as toxic for reproduction category 1B in Regulation (EC) No 1272/2008, as amended and adapted to technical and scientific progress by Regulation (EC) No 790/2009.. Notwithstanding the rationale being perfectly in line with the REACH Regulation, the glass industries believe that the introduction of boron trioxide on the candidate list for authorization could lead to future misunderstanding. The glass industries do not want to engage in any discussion on the right classification of boron trioxide, which is outside of our competence. However, it is very well known that there are still a lot of discussions going on at EU and International level on the correct classification of boron trioxide. For example Poland has indicated its intention to submit borate reclassification dossiers under CLP. This is based on their review of the data arising from new studies on worker exposure (in China and Turkey) and concluded that a reclassification of these substances is warranted.
    [Show full text]
  • United States Patent 15 3,650,778 Dumesnil Et Al
    United States Patent 15 3,650,778 Dumesnil et al. (45) Mar. 21, 1972 (54) LOW-EXPANSION, LOW-MELTING 3,520,831 7/1970 Trap et al............................. 106/47 X ZINCPHOSPHOVANADATE GLASS 3,393,060 7/1968 Blair et al................................ 106/47 COMPOSITIONS 3,534,209 10, 1970 Anderson et al......................... 106/47 (72) Inventors: Maurice E. Dumesnil, Palo Alto; Robert R. OTHER PUBLICATIONS Hewitt, San Jose; Joseph L. Bozarth, Grossman et al., J. AM Cer. Soc. Vol. 47, (Sept., 1964) “Zinc Mountain View, all of Calif. Borophosphate Glass' page 471 (73) Assignee: Fairchild Camera and Instrument Cor Primary Examiner-Daniel E. Wyman poration, Syosset, Long Island, N.Y. Assistant Examiner-W. R. Satterfield 22) Fied: Oct. 29, 1969 Attorney-Roger S. Borovoy and Alan H. Macpherson (21) Appl. No.: 870,620 57) ABSTRACT Low-melting, low-expansion, lead-free glass compositions are 52) U.S.C. ............................... 106/47 R, 106/46, 117/125 provided for sealing ceramics parts and encapsulating ceramic 51 Int. Cl............................................................ C03c.3/00 substrates. In addition to having a thermal expansion matching 58 Field of Search................ 106/47, 48, 46; 1611196, 192; that of alumina, the glass compositions provide for the forma 252/519; 65/43; 117/125 tion of a glass-to-alumina seal in the 380 to 450° C. tempera ture range. 56) References Cited 1 Claims, 3 Drawing Figures UNITED STATES PATENTS 3,446,695 5/1969 Janakirama-Rao......................106/47 7 8 4 22 >- "l-D 5 6 2 IO Patented March 21, 1972 3,650,778 4 O F. G.2 NVENTORS O MAURCE EDUMESN ROBERT R HEWITT 0 00 200300 400 500 JOSEPH L BOZARTH TEMPERATURE OC BY %a 4 ATTORNEY 3,650,778 1.
    [Show full text]
  • Rohs/REACH Compliance
    Page 1 of 2 RoHS/REACH Compliance International Manufacturing Services, Inc. (IMS) recognizes and supports the worldwide effort for environmental protection and conservation. REACH Regulation REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) is a European Union Commission (EUC) Regulation on chemicals and their safe use (EC 1907/2006) entered into force on 01 June, 2007 and will be phased in until 2018. • REACH applies to all imports to the EU • There are three levels of interest defined by REACH: o Substances: Chemical elements and their compounds in the natural state, identifiable by CAS or EINIC number (Ex: metal) o Preparations: A combination or mixture of two or more substances (Ex.: ink, adhesive) o Article: An object whose special shape, surface or design determines its function to a greater degree than does its chemical composition; assembled products (Ex: cars, electronic components) • The REACH regulation focuses on the control of Substances of Very High Concern (SVHCs) published in accordance with Article 59 of the REACH regulation • SVHCs are relevant to Substances and Preparations, not Articles • Registration of SVHCs is required for Substances and Preparations, not Articles • Notification and communication is required for Articles under the following conditions: o The Article has an “intended release” of SVHC o SVHC content > 0.1% of Total Article Weight Products manufactured and supplied by IMS are “articles” as defined by the REACH regulation and do not release substances under their normal use. The diboron trioxide and lead oxide present in certain products supplied by IMS are an element of the glass material. The glass is a UVCB substance (substance of unknown or variable composition, Complex reaction products or biological materials) under the REACH regulation.
    [Show full text]
  • DENTSPLY International PROSTHETICS
    DENTSPLY International PROSTHETICS Safety Data Sheet Safety Data Sheet (conforms to with Regulation (EC) Date Issued: 31 August 2016 1907/2006, Regulation (EC) 1272/2008 and Regulation Document Number: 605 (EC) 2015/830), US 29CFR1910.1200, Canada Hazardous Date Revised: 29 August 2018 Products Regulation Revision Number: 3 1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE AND OF THE COMPANY/UNDERTAKING 1.1 Product Identifier: Trade Name (as labeled): Celtra® Ceram Powder Porcelains: Dentin, Opaceous Dentin, Natural Enamel, Opal Enamel, Power Dentin, Dentin Gingiva, Dentin Effect, Enamel Effect, Add-on Correction, Add-on Gingiva. Part/Item Number: 615130-615149, 615150 – 615156, 650130-650149, 615700-615725, 650700-650725; 615201-615206, 650201-650206, 615211-615216, 650211-650216; 615181-615186, 650181-650186; 615171-615175, 650171-650175; 615161-615169, 650161-650168; 615221-615226; 650221-650226; 615401-615404, 650401-650404; 615411-615415, 650411-650415. 1.2 Relevant Identified Uses of the Substance or Mixture and Uses Advised Against: Recommended Use: Used in the fabrication of dental crowns and bridges. Restrictions on Use: For Professional Use Only 1.3 Details of the Supplier of the Safety Data Sheet: Manufacturer/Supplier Name: Dentsply Sirona Prosthetics Manufacturer/Supplier Address: 570 West College Ave. York, PA 17401 Manufacturer/Supplier Telephone Number: 717-845-7511 (Product Information) Email address: [email protected] 1.4 Emergency Telephone Number: Emergency Contact Telephone Number: 800-243-1942 2. HAZARDS IDENTIFICATION 2.1 Classification of the Substance or Mixture: GHS Classification: Health Environmental Physical Not Hazardous Not Hazardous Not Hazardous 2.2 Label Elements: Not Required Celtra® Ceram Powder Porcelains Page 1 of 10 Signal Word: None Hazard Phrases Precautionary Phrases None Required None Required 2.3 Other Hazards: None known.
    [Show full text]
  • Diffusion 2.Key
    More on Diffusion • Diffusion systems • Multiple diffusion steps • Diffusion as nuisance • Lateral diffusion • dopant segregation • masks for dopants • The diffusion coefficient EE 432/532 diffusion II - 1 Diffusion systems In general, diffusion systems are similar to oxidation furnaces. The dopant can be provided in the form of gas, liquid, or solid. The basic approach is to deposit a glassy layer containing the dopant on the surface of the silicon. A reaction between the glass and the silicon transfers dopant into the silicon. boron: + + → phosphorus: + + → A potential problem with boron is that excess boron trioxide can cause “boron skin” on the silicon surface. This is difficult to remove by etching. A low-temperature oxidation step can help to break up the boron skin for easier removal. (See the lab information from the manufacturers of the boron source wafers to get more detail.) EE 432/532 diffusion II - 2 Gas sources silicon wafers in quartz boat quartz tube dopant gas + other carrier end cap and reactant gases (N2, O2, H2) boron doping: React diborane + + → with oxygen or carbon dioxide. + + → phosphorus doping: React + + phosphine with oxygen → In either case, the glassy oxide layer is formed on the silicon surface. The gases used are extremely toxic and special provisions must be used for handling and to clean the gas streams of any unreacted material. EE 432/532 diffusion II - 3 Liquid sources N2,O2 liquid dopant source temperature controlled vessel or bubbler boron doping: react boron + + tribromide with oxygen → phosphorus doping: react + + phosphorus oxychloride → with oxygen EE 432/532 diffusion II - 4 Solid sources (what we use) source wafers N2 or reactant gases (O2, H2) boron: Source wafers are made of nitride (BN).
    [Show full text]
  • ( 12 ) United States Patent
    US010529585B2 (12 ) United States Patent ( 10 ) Patent No.: US 10,529,585 B2 Manna et al. (45 ) Date of Patent : Jan. 7 , 2020 (54 ) DRY STRIPPING OF BORON CARBIDE (58 ) Field of Classification Search HARDMASK None See application file for complete search history . ( 71) Applicant: Applied Materials , Inc. , Santa Clara , CA (US ) (56 ) References Cited ( 72 ) Inventors : Pramit Manna, Sunnyvale , CA (US ) ; U.S. PATENT DOCUMENTS Shishi Jiang , Santa Clara , CA (US ) ; 4,524,587 A 6/1985 Kantor Abhijit Basu Mallick , Fremont, CA 5,050,540 A 9/1991 Lindberg (US ) ; Kurtis Leschkies, San Jose , CA (US ) ( Continued ) FOREIGN PATENT DOCUMENTS ( 73 ) Assignee : APPLIED MATERIALS , INC . , Santa Clara , CA (US ) CN 101871043 A 10/2010 CN 104047676 A 9/2014 ( * ) Notice : Subject to any disclaimer, the term of this ( Continued ) patent is extended or adjusted under 35 U.S.C. 154 ( b ) by 0 days. OTHER PUBLICATIONS (21 ) Appl . No.: 15 /995,698 International Search Report and Written Opinion for PCT/ US2018 / 021715 dated Jun . 22 , 2018 . (22 ) Filed : Jun . 1 , 2018 (Continued ) (65 ) Prior Publication Data Primary Examiner — Jiong - Ping Lu US 2018/0350621 A1 (74 ) Attorney, Agent, or Firm Patterson + Sheridan Dec. 6 , 2018 LLP Related U.S. Application Data (57 ) ABSTRACT (60 ) Provisional application No. 62 /648,073 , filed on Mar. Embodiments of the disclosure generally relate to a method 26 , 2018 , provisional application No. 62/ 514,554 , for dry stripping a boron carbide layer deposited on a filed on Jun . 2 , 2017 . semiconductor substrate. In one embodiment, the method includes loading the substrate with the boron carbide layer (51 ) Int.
    [Show full text]
  • TAXXI.-Y'he Compound H,R,O, and Its Salts
    View Article Online / Journal Homepage / Table of Contents for this issue BAY: THE COMPOUND E~R,O~AND ITS SALTS. 803 Published on 01 January 1918. Downloaded by Brown University 26/10/2014 14:32:25. TAXXI.-Y'he Compound H,R,O, and its Salts. By RAMESCHANDRA RAY. TN a previous coinmunication (T., 1914, 105, 2162), it was shown that the so-called amorphous berm, prepared by the reduction of boron trioxicle by means of riiagiiesium, probably consisted of a sollid solution cof a lower oxide of boron, sometimes in combination with a little magnesium oxide; in elenient,ary bo'ron. If thin were View Article Online 804 RAY : THE COMPOUND H,B,O, AND ITS SALTS. really the case, it appelared probable thab the soluble part! of the fusion would contain solme o€ the lower oxide, together with excess of boron trioxide, and the, present investigation was undertaken with a view to detect and isolate the lower oxide. The fusion obtained by heating a mixture oF boron trioxide with magnesium powder generally contains magnesium boride, amorphous boron (so-called), magnesium o'xide, partly in combina- tion with boron trioxide, and, as will be shown later, the lower oxide or oxides of boron. If the operation is carried out under conditions which will now be described, the quantity of magnesium boride in the mixture is very small, although it cannot' be altogether eliminated. A mixture of 1 part, of magnesium powder and 3.5 parts of anhydrous boron trioxide, finely powdered and passed through a 120-mesh sieve, was heated in a covered magnesia-lined crubible, through which a current of hydrogen was passed, to a bright red heat for about three hours.
    [Show full text]
  • Effects of Radiation Damage on the Optical Properties of Glass
    Effects of Radiation Damage on the Optical Properties of Glass Federica Simonettoa, Matteo Marmontib, Marco AC Potenzaa,c aUniversity of Milan, Physics Department, via Celoria 16, Milan, Italy, 20133 bOptec S.p.A., via Mantegna 34, Parabiago, Italy, 20015 cCIMAINA, University of Milan, via Celoria, 16 I-20133 Milan, Italy Abstract. We study the optical properties of glass exposed to ionizing radiation, as it occurs in the space environment. 24 glass types have been considered, both space qualified and not space qualified. 72 samples (3 for each glass type) have been irradiated to simulate a total dose of 10krad and 30krad, imposed by a proton beam at KVI- Centre of Advanced Radiation Technology (Groeningen). Combining the information about stopping power and proton fluence, the time required to reproduce any given total dose in the real environment can be easily obtained. The optical properties, such as spectral transmission and light scattering have been measured before and after irradiation for each sample. Transmission has been characterized within the wavelength range 200 nm – 1100 nm. Indications that systematical issues depend on the dopant or compiosition are found and described. This work aims at extending the existing list of space–compliant glasses in terms of radiation damage. Keywords: optics, radiation, space missions, transmission, scattering. *Federica Simonetto, [email protected] *Matteo Marmonti, [email protected] *Marco Potenza, [email protected] 1 Introduction Space–born optical components require a well–characterized stability upon radiation damage in the space environment overall the expected lifetime of the instrument. Ionizing space radiation appreciably reduces optical transmission in many optical materials.
    [Show full text]