EP3204535A1 - Verbundstofflager mit selbstschmierung - Google Patents

Verbundstofflager mit selbstschmierung

Info

Publication number
EP3204535A1
EP3204535A1 EP15784289.9A EP15784289A EP3204535A1 EP 3204535 A1 EP3204535 A1 EP 3204535A1 EP 15784289 A EP15784289 A EP 15784289A EP 3204535 A1 EP3204535 A1 EP 3204535A1
Authority
EP
European Patent Office
Prior art keywords
coating
watch
graphene
graphene oxide
component according
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP15784289.9A
Other languages
English (en)
French (fr)
Other versions
EP3204535B1 (de
Inventor
Agnès Marlot Doerr
Stewes Bourban
Brice Drieux
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Swatch Group Research and Development SA
Original Assignee
Swatch Group Research and Development SA
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 Swatch Group Research and Development SA filed Critical Swatch Group Research and Development SA
Publication of EP3204535A1 publication Critical patent/EP3204535A1/de
Application granted granted Critical
Publication of EP3204535B1 publication Critical patent/EP3204535B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/04—Metals; Alloys
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/02—Carbon; Graphite
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/05—Metals; Alloys
    • C10M2201/053—Metals; Alloys used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/06—Instruments or other precision apparatus, e.g. damping fluids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B15/00—Escapements
    • G04B15/14—Component parts or constructional details, e.g. construction of the lever or the escape wheel
    • G—PHYSICS
    • G04—HOROLOGY
    • G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
    • G04B31/00—Bearings; Point suspensions or counter-point suspensions; Pivot bearings; Single parts therefor
    • G04B31/08—Lubrication
    • G—PHYSICS
    • G04—HOROLOGY
    • G04D—APPARATUS OR TOOLS SPECIALLY DESIGNED FOR MAKING OR MAINTAINING CLOCKS OR WATCHES
    • G04D3/00—Watchmakers' or watch-repairers' machines or tools for working materials
    • G04D3/0074—Watchmakers' or watch-repairers' machines or tools for working materials for treatment of the material, e.g. surface treatment
    • G04D3/0087—Watchmakers' or watch-repairers' machines or tools for working materials for treatment of the material, e.g. surface treatment for components of the escapement mechanism, e.g. lever escapement, escape wheel

Definitions

  • the invention relates to a self-lubricating composite solid coating, in particular for an application to clockwork mechanisms.
  • liquid lubricants oil lubricants
  • pastes fats
  • These lubricants are used sparingly on well-defined areas and in suitable quantities.
  • This type of lubricant must be able to slip between two parts to minimize friction or must be removed during assembly.
  • the ability to slip between two rooms can also escape from the space where it has been deposited. It is also very sensitive to the environmental conditions of temperature and relative humidity because its viscosity evolves according to these.
  • lubricants are constituted by a liquid or viscous support which may contain particles having tribological properties such as carbon.
  • WO2012 / 128714 describes for example a liquid containing graphene. Graphene was isolated by André Geim in 2004. It is a two-dimensional carbon crystal whose stacking leads to graphite. It appears to have interesting tribological properties.
  • dry coatings which reduce friction are known. These coatings are integral with the part to be protected and present less risk of loss or chemical degradation. In addition, these coatings are less sensitive to environmental conditions. For example, coatings based on carbon nanotubes dispersed in a nickel matrix are known. Such coatings are for example described in US-A-2008 1323475.
  • the coating metal is gold but this coating is derived from a bath which contains a percentage of Cadmium well above the percentage allowed by the European directives which is problematic.
  • Graphite is also used as an anti-wear agent in electro-deposited composite coatings.
  • the subject of the invention is a metal composite solid coating having self-lubricating properties, characterized in that it comprises particles of graphene and / or graphene oxide distributed in a metal matrix.
  • FIG. 1 Schematic section of the substrate coated with the graphene metal composite.
  • FIG 2 Variation of the relative amplitude of a clockwork mechanism with a coating according to the invention (a) and without coating (b) with respect to a clockwork mechanism lubricated with oil.
  • FIG. 3 cut of a coated support with an extra layer of gold.
  • This coating 2 comprises particles 3 of graphene and / or graphene oxide distributed in a metal matrix 4.
  • particles 3 of graphene or graphene oxide are used which are in the form of fibers or flakes (aggregates of fibers or particles).
  • the thickness of this coating is generally between 0.2 micron and 20 microns but preferably it is between 0.5 micron and 2 microns.
  • a layer of hook 5 is for example formed of nickel or chrome gold or gold.
  • the deposition of the coating is done by electroplating if the part to be coated is conductive. If it is a non-conductive part, a purely chemical deposit will be carried out for example by a process called "electroless" using an oxidizing agent (the metal cation or cations), a reducing agent and a catalyst.
  • a bath containing metal ions and particles of graphene and / or graphene oxide is used, in which the object to be coated is immersed, the latter forming the cathode in a conventional electrochemical deposition assembly. in a bath.
  • this bath may contain other types of particles 6 such as particles of alumina, boron nitride, tungsten carbide, diamond, bisulphide. molybdenum, PTFE and / or silicon in pure form, encapsulated carbide, nitride or oxide, or even oil droplets (eg fluorinated oil), including a mixture thereof.
  • the metal ions may optionally be bonded to complexing agents well known electrochemical processes such as cyanide in the case of a bath of gold.
  • the pH of the bath can be adapted with buffers at a fixed value depending on the bath chemistry, for example with boric acid in a bath of nickel buffered at acidic pH.
  • the bath may also contain additives well known in electrochemical processes such as, for example, leveling agents, brighteners and voltage reducers.
  • the latter may also contain surfactants which bind to the above-mentioned particles, surround them and prevent their agglomeration in solution.
  • the bath will be subjected to mechanical agitation and / or ultrasonic type in order to distribute the various components as well as possible.
  • the composite coating is formed according to the same principles: addition of particles 3 and 6 in the bath with surfactant and co-deposition of particles 3 and 6 with metal 4 on the object to be coated, with mechanical and / or ultrasonic agitation of the bath.
  • the deposited metal may be pure metal such as pure nickel or a metal alloy such as nickel with phosphorus or an alloy of copper, tin and zinc (bronze).
  • the choice of the metallic material depends on the desired side result. For example, phosphorus nickel will make it possible to obtain a coating having non-magnetic properties and bronze will make it possible to obtain a decorative coating.
  • Graphene or graphene oxide can also be deposited with gold and / or copper ions for coating with a base matrix of gold or gold-copper. Other metal ions for producing this base matrix can still be used, for example noble metal ions such as palladium or platinum ions.
  • graphene or graphene oxide particles can co-deposit with nickel and phosphorus in a bath containing nickel (II) ions and phosphorous acid.
  • nickel (II) ions and phosphorous acid Another example would be the co-deposition of graphene or graphene oxide in the presence of gold and copper ions. It should be noted that if graphene oxide is used in the bath, it can be co-reduced during the electrochemical deposition process and can be converted into reduced graphene oxide.
  • a deposit of gold with a thickness of 5 to 100 nm can be done by a galvanic process or other methods (vapor phase deposition or sputtering) over the coating deposited by electrochemistry or electroless deposit and after polishing (see FIG 3).
  • This thin layer of gold is subjected to frictional forces which cause a superficial penetration of gold into the metal matrix containing graphene and / or graphene oxide.
  • Such a solid coating is not possible with pure graphene especially because of the cost of the material and a too small thickness.
  • the chosen solution combines the effects of graphene with metal and other components. It is possible to choose a coating having the property of greatly reducing friction by increasing the level of graphene or obtaining a hard surface which therefore limits wear by adding to graphene hard particles selected from the group comprising alumina, diamond, boron nitride, tungsten carbide, including a mixture of these.
  • the interest is therefore to combine in a metal matrix of a particular metal or alloy particles or aggregates of graphene incidentally combined with other inorganic or organic particles to meet each specific need. It is not a matter of a chemical combination but of the presence of various particles distributed in the metal matrix.
  • the coating is integral with the timepiece which is a guarantee of longevity and better resistance to environmental conditions
  • the deposition of the coating can be limited to the zones that are subjected to friction, the rest of the part being able to be masked during the deposition.
  • composite coatings comprising a nickel metal matrix in which graphene or graphene oxide agglomerates are dispersed.
  • the coatings are produced from a bath comprising from 150 to 600 g / l of nickel sulphate, from 4 g / l to 40 g / l of nickel chloride, from 30 g / l to 50 g / l of boric acid and from 0.5 g / l to 5 g / l of graphene oxide in powder form.
  • the pH of the bath is between 3 and 4 and the bath temperature maintained between 50 and 70 ° C.
  • the coatings are deposited directly on watch parts by applying a current density of 1 to 20 A / dm2.
  • Another example is that of coatings obtained from a bath comprising from 60 to 150 g / l of nickel in the form of nickel sulphate, from 5 g / l to 30 g / l of phosphorous acid, from 30 g / l to 50 g. / L of boric acid and 0.1 g / L to 5 g / L of graphene oxide in powder form.
  • a pH of between 1 and 2 composite coatings based on nickel phosphorus and graphene oxide can be obtained by applying a current density between 0.5 and 10 A / dm2 and more particularly between 1 and 5 A / dm2. Coatings thus formed lead to performances such as those described in FIG. 2 (curve (a)) at thicknesses between 0.5 and 5 microns.
  • Curve (a) corresponds to the ratio in percentage between the amplitude of oscillation amplitude of the balance of a standard movement with an escape wheel provided with a coating according to the invention divided by the amplitude value of oscillation of the rocker of the same type of movement provided with an exhaust (teeth of the escape wheel and pallets of anchor) lubricated according to the prior art.
  • Curve (b) corresponds to the percentage ratio between the oscillation amplitude value of a rocker with an escape wheel and uncoated and unlubricated anchor pallets divided by the oscillation amplitude value exhaust (teeth of the escape wheel and pallets anchor) lubricated according to the prior art.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Lubricants (AREA)
  • Chemically Coating (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
EP15784289.9A 2014-10-08 2015-10-05 Verbundstofflager mit selbstschmierung Active EP3204535B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14188163.1A EP3006605A1 (de) 2014-10-08 2014-10-08 Selbstschmierende verbundbeschichtung
PCT/EP2015/072927 WO2016055409A1 (fr) 2014-10-08 2015-10-05 Revetement composite auto-lubrifiant

Publications (2)

Publication Number Publication Date
EP3204535A1 true EP3204535A1 (de) 2017-08-16
EP3204535B1 EP3204535B1 (de) 2021-07-21

Family

ID=51844491

Family Applications (2)

Application Number Title Priority Date Filing Date
EP14188163.1A Withdrawn EP3006605A1 (de) 2014-10-08 2014-10-08 Selbstschmierende verbundbeschichtung
EP15784289.9A Active EP3204535B1 (de) 2014-10-08 2015-10-05 Verbundstofflager mit selbstschmierung

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP14188163.1A Withdrawn EP3006605A1 (de) 2014-10-08 2014-10-08 Selbstschmierende verbundbeschichtung

Country Status (5)

Country Link
US (1) US10047450B2 (de)
EP (2) EP3006605A1 (de)
JP (1) JP6360973B2 (de)
CN (1) CN106795640B (de)
WO (1) WO2016055409A1 (de)

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EP3171230B1 (de) * 2015-11-19 2019-02-27 Nivarox-FAR S.A. Uhrwerkkomponente mit verbesserter tribologie
CN106084530B (zh) * 2016-06-07 2018-09-28 芜湖海泰科新材料有限公司 一种亲水自润滑微球及其制备方法与应用
CN106419209A (zh) * 2016-11-10 2017-02-22 无锡市明盛强力风机有限公司 一种自润滑滑轨
CN106381509A (zh) * 2016-11-10 2017-02-08 无锡市明盛强力风机有限公司 一种固体润滑的滚珠螺杆
CN106402309A (zh) * 2016-11-10 2017-02-15 无锡市明盛强力风机有限公司 一种固体润滑的滚珠螺杆
CN106544619A (zh) * 2016-11-10 2017-03-29 无锡市明盛强力风机有限公司 一种固体润滑的滚珠轴承及其制备方法
CN106567120A (zh) * 2016-11-10 2017-04-19 无锡市明盛强力风机有限公司 一种固体润滑的滚珠轴承及其制备方法
CN106367781A (zh) * 2016-11-10 2017-02-01 无锡市明盛强力风机有限公司 一种风机转子自润滑方法
CN106319605A (zh) * 2016-11-10 2017-01-11 无锡市明盛强力风机有限公司 一种汽车座椅滑轨
CN106567033A (zh) * 2016-11-10 2017-04-19 无锡市明盛强力风机有限公司 一种自润滑锁芯
CN106567121A (zh) * 2016-11-10 2017-04-19 无锡市明盛强力风机有限公司 一种汽车滑动门用滑轨
CN106481478A (zh) * 2016-11-10 2017-03-08 无锡市明盛强力风机有限公司 一种自润滑汽缸活塞
CN106523422A (zh) * 2016-11-10 2017-03-22 无锡市明盛强力风机有限公司 一种风机转子自润滑方法
CN106321640A (zh) * 2016-11-10 2017-01-11 无锡市明盛强力风机有限公司 一种固体润滑的滚珠轴承及其制备方法
CN106319582A (zh) * 2016-11-10 2017-01-11 无锡市明盛强力风机有限公司 一种自润滑锁芯
CN106438899A (zh) * 2016-11-10 2017-02-22 无锡市明盛强力风机有限公司 一种固体润滑的滚珠螺杆
CN106555146A (zh) * 2016-11-10 2017-04-05 无锡市明盛强力风机有限公司 一种自润滑锁芯
CN106567030A (zh) * 2016-11-10 2017-04-19 无锡市明盛强力风机有限公司 一种固体润滑的滚珠螺杆
CN106350857A (zh) * 2016-11-10 2017-01-25 无锡市明盛强力风机有限公司 一种摩擦力小的汽缸活塞及其制备方法
CN106321497A (zh) * 2016-11-10 2017-01-11 无锡市明盛强力风机有限公司 一种风机转子自润滑方法
CH713746A1 (fr) * 2017-04-28 2018-10-31 Montblanc Montre Sa Procédé de dépôt d'un revêtement d'or sur un article et article obtenu par ce procédé.
CN106929887A (zh) * 2017-05-03 2017-07-07 上海电力学院 一种镍‑氧化石墨烯复合电镀溶液及其制备方法和应用
EP3407143A1 (de) * 2017-05-24 2018-11-28 Rolex Sa Mechanische verbindungsvorrichtung
CN107311175B (zh) * 2017-06-28 2021-04-20 中国航发北京航空材料研究院 一种石墨烯改性碳化钨自润滑耐磨添加剂的制备方法
CN107630244B (zh) * 2017-08-24 2020-06-19 南京理工大学 一种镍-改性石墨烯耐磨复合镀层的制备方法
CN108531240B (zh) * 2018-04-20 2019-04-30 厦门六烯科技有限公司 一种石墨烯基硫化钼纳米抗磨剂及其制备方法
WO2021005564A1 (fr) * 2019-07-10 2021-01-14 Patek Philippe Sa Geneve Ensemble horloger d'au moins deux éléments en contact
CN110452589B (zh) * 2019-08-14 2021-08-20 大庆市盛日石油技术开发有限公司 一种石墨烯涂覆剂及其制备方法
CN110358377B (zh) * 2019-08-14 2021-08-20 大庆市盛日石油技术开发有限公司 一种石墨烯自润滑耐磨防腐阻垢蜡涂覆剂及其制备方法
EP3839649A1 (de) * 2019-12-20 2021-06-23 Nivarox-FAR S.A. Starre uhrwerkskomponente für oszillatormechanismus oder uhrhemmungsmechanismus, und uhrwerk, das eine solche komponente umfasst
CN111394156B (zh) * 2020-04-28 2022-06-03 北京稳力科技有限公司 一种合金-氟树脂双层自润滑耐磨复合材料、其制备方法及摩擦副
CN114775004A (zh) * 2022-05-20 2022-07-22 中国石油大学(华东) 一种镍-石墨烯超疏水镀层及其制备方法

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Also Published As

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EP3204535B1 (de) 2021-07-21
WO2016055409A1 (fr) 2016-04-14
JP2017531714A (ja) 2017-10-26
EP3006605A1 (de) 2016-04-13
CN106795640B (zh) 2019-03-08
US20170298528A1 (en) 2017-10-19
CN106795640A (zh) 2017-05-31
JP6360973B2 (ja) 2018-07-18
US10047450B2 (en) 2018-08-14

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