EP3240916B1 - Carbures cémentés légers pour composants soumis à l'érosion par fluides - Google Patents

Carbures cémentés légers pour composants soumis à l'érosion par fluides Download PDF

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Publication number
EP3240916B1
EP3240916B1 EP15822955.9A EP15822955A EP3240916B1 EP 3240916 B1 EP3240916 B1 EP 3240916B1 EP 15822955 A EP15822955 A EP 15822955A EP 3240916 B1 EP3240916 B1 EP 3240916B1
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EP
European Patent Office
Prior art keywords
cemented carbide
components
seal rings
light weight
seal ring
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EP15822955.9A
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German (de)
English (en)
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EP3240916A1 (fr
Inventor
Selassie DORVLO
Eugene Keown
Jane Smith
Henrik NORDENSTRÖM
Milena MECH
Michael Carpenter
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Hyperion Materials and Technologies Sweden AB
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Hyperion Materials and Technologies Sweden AB
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B22F3/156—Hot isostatic pressing by a pressure medium in liquid or powder form

Definitions

  • the present disclosure relates to cemented carbides for flow components, and more particularly to a flow control apparatus, fluid handling components and sealing rings with improved service life.
  • Seal rings are the key critical component in mechanical shaft seals for pumps. Cemented carbides show a good mechanical performance in this kind of application. However, energy consumption and corrosion resistance is an issue in pumps. If the weight of the cemented carbide seal ring can be reduced, so will the energy consumption. A reduction in weight will also reduce the cost of the seal rings and in turn the cost of the pump.
  • seal rings One of the most important properties for seal rings is corrosion resistance.
  • the seal surface will be exposed to the pumping media which can often be corrosive. Corrosion during life of a seal ring will lead to the binder being dissolved. This will lead to the increased wear of the seal ring. When this happens there will be a significant increase in the amount fluid leaking from the pump.
  • cemented carbide flow components the primary function of which is to control the pressure and flow of well products used in, for example, the oil and gas industry where components are subjected to high pressures of multi-media fluid where there is a corrosive environment.
  • the cemented carbide has a hard phase comprising WC and a binder phase, wherein the cemented carbide composition comprises, in wt-%, from 50 to less than 70 WC, from 15 to 30 TiC, and from 12 to 20 Co+Ni.
  • the present disclosure relates to a cemented carbide for fluid handling components and seal rings comprising in wt %; 15 to 30 TiC; 5 to 20 Ni; 0.5 to 2.5 Cr 3 C 2 ; 0.7 to 1.6 Mo and the remainder WC.
  • the cemented carbide composition as defined hereinabove or hereinafter comprises from 20 to 23wt % TiC.
  • the cemented carbide composition as defined hereinabove or hereinafter comprises from 0.8 to 1.5 wt % Cr 3 C 2 , such as about 0.95 to about 1.3 wt % Cr 3 C 2 .
  • the cemented carbide composition as defined hereinabove or hereinafter comprises from 9.5 to 14.5 wt% Ni, such as about 10 to about 14 wt% Ni.
  • the cemented carbide composition as defined hereinabove or hereinafter has an average WC grain size of from 0.9 ⁇ m to 1.3 ⁇ m, such as of about 1.05 ⁇ m to about 1.15 ⁇ m measured by FSSS.
  • the term "about” means plus or minus 10% of the numerical value of the number with which it is being used. Therefore, about 50% means in the range of 45%-55%.
  • embodiments of the present disclosure relate to cemented carbides for flow components (herein, the term "component” means parts or pieces), particularly for seal rings and for choke trim components used in the oil and gas industry, where the components are subjected to high pressures of multi-media fluid and where there is a corrosive environment, particularly for choke valve components whose 10 primary function of which is to control the pressure and flow of well products, such as pumps.
  • component means parts or pieces
  • seal rings and for choke trim components used in the oil and gas industry where the components are subjected to high pressures of multi-media fluid and where there is a corrosive environment, particularly for choke valve components whose 10 primary function of which is to control the pressure and flow of well products, such as pumps.
  • choke valve components whose 10 primary function of which is to control the pressure and flow of well products, such as pumps.
  • these components may suffer from extreme mass loss by exposure to solid particle erosion, acidic corrosion erosion-corrosion synergy and cavitation mechanisms even when fitted with cemented carbide trims.
  • the light weight cemented material can also be used in, for example, seal rings, to reduce the weight of the seal ring.
  • the light weight cemented carbide of the present disclosure can have a Ni-Cr-Mo binder.
  • An illustrative example of a light weight cemented carbide for use in flow components not forming part of the present invention, such as seal rings, has a composition in wt % of about 15 to about 30 TiC, about 12 to about 20 Co + Ni, about 0.5 to about 2.5 Cr; and about 0.1 to about 0.3 Mo and the balance WC.
  • the WC may have an average sintered grain size of about 0.5 ⁇ m.
  • the sintered structure is also shown in Figs. 1 and 2 .
  • Seal rings are the key critical component in mechanical shaft seals for pumps. Cemented carbide show a good mechanical performance in this kind of application.
  • the cemented carbide seal rings of the present disclosure have a reduced weight and therefore allow for less energy consumption. Furthermore, the cemented carbide seal rings have improved application relevant properties, such as improved corrosion resistance.
  • the cemented Carbide for a flow component, LW as defined hereinabove or hereinafter and used, for example, in a flow control apparatus, has the following composition ranges in weight %: about 7 to about 9 wt% Co, about 5 to about 7 wt% Ni, about 19 to about 24 wt% TiC, about 1.5 to about 2.5 wt% Cr 3 C 2 , about 0.1 to about 0.3 wt % Mo and the balance WC.
  • the hardness of the cemented carbide component as defined hereinabove or hereinafter may be of from about 1350 to about 1500 HV30 (IS03878), the toughness (Klc) being about 8.5 to about 9.5 MPa ⁇ m by indentation technique according to Klc (SEVNB) >8.5 MPa ⁇ m and the transverse rupture strength (TRS) according to IS03327 type C>1700 N/mm 2 .
  • the WC in the cemented carbide may have an average sintered grain size of about 0.8 ⁇ m and the (Ti,W)C (titanium tungsten carbide in the cemented carbide may have an average sintered grain size of about 1.5 ⁇ m according to IS04499-2-2010.
  • the carbon content within the sintered cemented carbide as defined hereinabove or hereinafter should be kept within a narrow range in order to retain a high resistance to corrosion and wear, as well as have a high toughness.
  • the carbon level of the sintered structure is held in the lower portion of the range between free carbon in the microstructure (top limit) and eta-phase initiation (bottom limit).
  • Magnetic saturation measurements for the magnetic binder phase of the sintered cemented carbide is expressed in terms of ⁇ T m 3 kg-1 and relate to the nature of the combined multi element binder. For the sintered material according to the disclosure, this should lie between 80 % and 90% of the 2-phase field of the binder. No eta-phase or graphite is permitted in the sintered structure. The sintered structure is shown in Fig. 1 .
  • the re-passivity of the embodiment, depicted as LW is improved due to the significant addition of TiWC hard phase added to the composition.
  • Corrosion resistance was determined using the ASTM G61.
  • ASTM G61 covers a procedure for conducting potentiodynamic polarization measurements. See Table 1 below showing the results of ASTM G61 comparing an embodiment with a comparative example.
  • Table 1 ASTM G61 Evaluated parameters from polarization curves Product Eb 10 ⁇ m/cm 2 Eb 100 ⁇ m/cm 2 Ereprass 10 ⁇ m/cm 2 Comparative Example 24 46 -333 LW 118 156 -76
  • Eb is the breakdown potential, at which localised corrosion occurs and is evaluated at two different criteria.
  • the lower criterion of 10 ⁇ A/cm 2 may be considered to give an indication of the ease of initiation of corrosion.
  • the difference between this and the higher criterion of 100 ⁇ A/cm 2 provides an indication of the propagation process.
  • Cemented carbide grades with the composition in wt-% 21 TiC; 8.3 Co; 5.7; Ni; 0.2 Mo and 2 Cr 3 C 2 with the balance of WC was produced using WC and (Ti,W)C powder with an average FSSS particle size (d 50 ) of 0.8 ⁇ m and about 3 ⁇ m, respectively.
  • the cemented carbide samples were prepared from powders forming the hard constituents and powders forming the binder. The powders were wet milled together with lubricant and anti -flocculating agent until a homogeneous mixture was obtained and granulated by drying. The dried powder was pressed on the Tox press to bodies and 'green machined' before sintering. Sintering was performed at 1360 -1410°C for about 1 hour in vacuum, followed by applying a high pressure, 50 bar Argon, at sintering temperature for about 30 minutes to obtain a dense structure before cooling.
  • the sintered cemented carbide structure comprises of some hexagonal WC with an average grain size of 0.8 ⁇ m together with (Ti,W)C grains with an average grain size of 1.5 ⁇ m as measured using the linear intercept method.
  • the material has a hardness of about 1350 to about 1500 HV30 depending on the selected composition and sinter temperature.
  • LW shows improved wear resistance to scratch testing in comparison to a comparative example of a fine grained oil and gas grade with 10.5wt% binder ( Fig. 4 ) with similar or hardness values. Testing was carried out using a diamond Stylus with a 20 ⁇ m radius tip at 200 mN.
  • Wear resistance damage from scratching is considerably improved for the example of the disclosure, LW, as shown by reduced 'grey' amorphous damage in Fig. 3 as compared to the comparative example in Fig. 4 . Further, corrosion resistance for the example of the disclosure, LW, in seawater is improved and with better repassivity (See Table 1).
  • the hardness of the cemented carbide component may be about 1350 to about 1500 HV30 (IS03878), the toughness (Klc) being about 8.7 MPa ⁇ m using Palmqvist toughness technique according to ISO28079 or Klc (LW15, SEVNB) > 8.5 MPa ⁇ m and the transverse rupture strength (TRS) according to IS03327 type C>1700 N/mm 2 .
  • a cemented carbide grades with the compositions in wt-% of about 63.2 WC; about 20.8 TiC; about 2 Cr 3 C 2 ; about 8.2 Co; about 5.6 Ni and about 0.2 Mo was produced using WC powder with an average FSSS particle grain size (d 50 ) of 4-8 ⁇ m, respectively.
  • the sintered structure is shown in Figs. 5 .
  • the cemented carbide samples were prepared from powders forming the hard constituents and powders forming the binder.
  • the powders were wet milled together with lubricant and anti -flocculating agent until a homogeneous mixture was obtained and granulated by drying.
  • the dried powder was pressed on the Tox press to bodies and 'green machined' before sintering. Sintering is performed at 1360 -1410°C for about 1 hour in vacuum, followed by applying a high pressure, 50 bar Argon, at sintering temperature for about 30 minutes to obtain a dense structure before cooling.
  • An embodiment of the light weight cemented carbide for seal rings according to the present disclosure has a composition of about 15 to about 30 wt% TiC, about 5 to about 20 wt% Ni, about 0.5 to about 2.5 wt% Cr, and about 0.7 to about 1.6 wt% Mo and the balance WC.
  • Example 3 according to an aspect of the present invention ('LW + CR seal ring' - reference C)
  • the sintered structure is shown in Fig. 6 .
  • the cemented carbide samples were prepared from powders forming the hard constituants and powders forming the binder.
  • the powders were wet milled together with lubricant and anti-flocculating agent until a homogeneous mixture was obtained and granulated by drying.
  • the dried powder was pressed on the Tox press to bodies and 'green machined' before sintering. Sintering is performed at 1360 -1410°C for about 1 hour in vacuum, followed by applying a high pressure, 50 bar Argon, at sintering temperature for about 30 minutes to obtain a dense structure before cooling.
  • the hardness of the cemented carbide component may be about 1550 HV30 (IS03878), the toughness (Klc) being about 8.5 MPa ⁇ m using Palmqvist toughness technique according to ISO28079 and a density of about 10.2 g/cm 3 .
  • Example 4 according to an aspect of the present invention ('LW + CR seal ring' - reference D)
  • the cemented carbide samples were prepared from powders forming the hard constituents and powders forming the binder.
  • the powders were wet milled together with lubricant and anti-flocculating agent until a homogeneous mixture was obtained and granulated by drying.
  • the dried powder was pressed on the Tox press to bodies and 'green machined' before sintering. Sintering is performed at 1360 -1410°C for about 1 hour in vacuum, followed by applying a high pressure, 50 bar Argon, at sintering temperature for about 30 minutes to obtain a dense structure before cooling.
  • the sintered structure is shown in Figs. 7 and 8 .
  • the hardness of the cemented carbide component may be about 1390 to about 1400 HV30 (IS03878), the toughness (Klc) being about 8.6 to about 9.3 MPa ⁇ m using Palmqvist toughness technique according to ISO28079 and a density of about 10.02 to about 10.17 g/cm 3 .
  • the grades disclosed herein demonstrate improved corrosion resistance in comparison to a standard seal ring grade. Corrosion resistance was determined using a modified test to ASTM G61. ASTM G61 covers a procedure for conducting potentiodynamic polarization measurements. The modification of this standard has been in the media used. Instead of using 3.5% NaCl solution in the tests, artificial seawater according to ASTM DI141 was used as the media. Furthermore, the flushed port cell used in ASTM G61 was replaced by sealing the specimen with epoxy to avoid crevice corrosion on the edge of the sample.
  • the pitting potential was used as a measure for comparison. The higher the value the better the corrosion resistance of the material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Ceramic Products (AREA)

Claims (5)

  1. Carbure cémenté pour composants de manipulation de fluide et bagues d'étanchéité, le carbure cémenté ayant une composition comprenant :
    15 à 30 % en poids de TiC ;
    5 à 20 % en poids de Ni ;
    0,5 à 2,5 % en poids de Cr3C2 ;
    0,7 à 1,6 % en poids de Mo ; et
    du WC pour le reste.
  2. Carbure cémenté pour composants de manipulation de fluide et bagues d'étanchéité selon la revendication 1, dans lequel la composition comprend 20 à 23 % en poids de TiC.
  3. Carbure cémenté pour composants de manipulation de fluide et bagues d'étanchéité selon la revendication 1 ou la revendication 2, dans lequel la composition comprend 0,8 à 1,5 % en poids de Cr3C2.
  4. Carbure cémenté pour composants de manipulation de fluide et bagues d'étanchéité selon l'une quelconque des revendications 1 à 3, dans lequel la composition comprend 9,5 à 14,5 % en poids de Ni.
  5. Carbure cémenté pour composants de manipulation de fluide et bagues d'étanchéité selon l'une quelconque des revendications 1 à 4, dans lequel la composition du carbure cémenté a une granulométrie moyenne du WC, telle que mesurée par FSSS, de 0,9 µm à 1,3 µm.
EP15822955.9A 2014-12-30 2015-12-28 Carbures cémentés légers pour composants soumis à l'érosion par fluides Active EP3240916B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201462098229P 2014-12-30 2014-12-30
PCT/EP2015/081284 WO2016107843A1 (fr) 2014-12-30 2015-12-28 Carbure cémenté léger pour éléments d'érosion d'écoulement

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Publication Number Publication Date
EP3240916A1 EP3240916A1 (fr) 2017-11-08
EP3240916B1 true EP3240916B1 (fr) 2019-09-18

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US (1) US20180002783A1 (fr)
EP (1) EP3240916B1 (fr)
AU (1) AU2015373452A1 (fr)
CA (1) CA2970584A1 (fr)
ES (1) ES2759730T3 (fr)
MX (1) MX2017008637A (fr)
MY (1) MY179165A (fr)
RU (1) RU2675432C1 (fr)
SG (1) SG11201704721UA (fr)
WO (1) WO2016107843A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN108913953B (zh) * 2018-07-31 2019-07-05 成都工业学院 一种vc颗粒增强镍基高温合金及其制备方法
CN111961939A (zh) * 2020-08-17 2020-11-20 苏州用朴精密科技有限公司 一种硬质合金材料制备方法

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Publication number Priority date Publication date Assignee Title
FR2097258A5 (fr) * 1970-06-18 1972-03-03 Ugine Carbone
SE512668C2 (sv) * 1997-09-05 2000-04-17 Sandvik Ab Sätt att tillverka en korrosionsresistent hårdmetall
SE511212C2 (sv) * 1997-12-22 1999-08-23 Sandvik Ab Kula för kulspetspennor och användning av denna för kulspetspennor med vattenbaserat bläck
US6521353B1 (en) * 1999-08-23 2003-02-18 Kennametal Pc Inc. Low thermal conductivity hard metal
SE0602813L (sv) * 2006-12-27 2008-06-28 Sandvik Intellectual Property Korrosionsresistent verktyg för kallbearbetningsoperationer
EP2433727B1 (fr) * 2010-09-24 2015-04-08 Sandvik Intellectual Property AB Procédé de production d'un corps composite fritté
EP2439294B1 (fr) * 2010-10-07 2014-03-05 Sandvik Intellectual Property AB Poinçonneuse au carbure cémenté
EP2439300A1 (fr) * 2010-10-08 2012-04-11 Sandvik Intellectual Property AB Carbure cémenté

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* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
RU2675432C1 (ru) 2018-12-19
MY179165A (en) 2020-10-30
US20180002783A1 (en) 2018-01-04
EP3240916A1 (fr) 2017-11-08
ES2759730T3 (es) 2020-05-12
AU2015373452A1 (en) 2017-06-29
CA2970584A1 (fr) 2016-07-07
SG11201704721UA (en) 2017-07-28
MX2017008637A (es) 2017-10-11
WO2016107843A1 (fr) 2016-07-07

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