US20180002783A1 - Light weight cemented carbide for flow erosion components - Google Patents
Light weight cemented carbide for flow erosion components Download PDFInfo
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- US20180002783A1 US20180002783A1 US15/540,907 US201515540907A US2018002783A1 US 20180002783 A1 US20180002783 A1 US 20180002783A1 US 201515540907 A US201515540907 A US 201515540907A US 2018002783 A1 US2018002783 A1 US 2018002783A1
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- cemented carbide
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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
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- 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%
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- 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
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- 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
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- 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
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- 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 therefore relates to a cemented carbide for a flow control component for controlling the pressure and flow of well products comprising in wt % about 7 to about 9 Co; about 5 to about 7 Ni; about 19 to about 24 TiC; about 1.5 to about 2.5 Cr 3 C 2 ; and about 0.1 to about 0.3 Mo; and the balance WC.
- the cemented carbide composition as defined hereinabove or hereinafter has an average grain size of 0.80 ⁇ m measured by FSSS (Fisher Sub Sieve Sizer). In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter comprises from about 20 to about 22 wt % TiC, such as about 21 wt % TiC.
- the cemented carbide composition as defined hereinabove or hereinafter comprises from about 1.8 to about 2.2 wt % Cr 3 C 2 , such as about 2 wt % Cr 3 C 2 .
- the cemented carbide composition as defined hereinabove or hereinafter comprises from about 5.3 to about 6.0 wt % Ni, such as about 5.7 wt % Ni.
- the cemented carbide composition as defined hereinabove or hereinafter comprises from about 8.0 to about 8.6 wt % Co, such as about 8.3 wt % Co.
- the cemented carbide composition as defined hereinabove or hereinafter comprises from about 0.15 to about 0.25 wt % Mo, such as about 0.2 wt % Mo.
- the cemented carbide composition as defined hereinabove or hereinafter has a density of from about 9.6 to about 10.2 g/cm 3 , such as of from about 9.8 to about 10 g/cm 3 .
- the cemented carbide composition as defined hereinabove or hereinafter has a hardness of from about 1350 to about 1500 HV30.
- the cemented carbide composition as defined hereinabove or hereinafter has a toughness of about 8.5 to 9.5 MPa ⁇ m.
- the cemented carbide composition as defined hereinabove or hereinafter comprises a balance of WC, such as 50 wt % to about 69 wt %.
- the present disclosure also relates to a second cemented carbide for fluid handling components and seal ring comprising in wt %; about 15 to about 30 TiC; about 12 to about 20 Co+Ni; about 0.5 to about 2.5 Cr 3 C 2 ; and about 0.1 to about 0.3 Mo and the balance WC.
- the second cemented carbide composition as defined hereinabove or hereinafter comprises from about 19.8 to about 21.8 wt % TiC, such as about 20.8 wt % TiC.
- the second cemented carbide composition as defined hereinabove or hereinafter comprises from about 1.8 to about 2.2 wt % Cr 3 C 2 , such as about 2 wt % Cr 3 C 2 .
- the second cemented carbide composition defined hereinabove or hereinafter comprises from about 5.3 to about 5.9 wt % Ni, such as about 5.6 wt % Ni.
- the second cemented carbide composition as defined hereinabove or hereinafter comprises from about 7.9 to about 8.5 wt % Co, such as about 8.2 wt % Co. In an embodiment, the second cemented carbide composition as defined hereinabove or hereinafter comprises from about 0.15 to about 0.25 wt % Mo, such as about 0.2 wt % Mo.
- the second cemented carbide composition as defined hereinabove or hereinafter comprises of from about 62.2 to about 64.2 wt % WC, such as about 63.2 wt % WC.
- the second cemented carbide composition as defined hereinabove or hereinafter has a density of from about 9.6 to about 10.2 g/cm 3 , such as of from about 9.8 to about 10 g/cm 3 .
- the second cemented carbide composition as defined hereinabove or hereinafter has a hardness of from about 1350 to about 1500 HV30.
- the second cemented carbide composition as defined hereinabove or hereinafter has a toughness of about 8.5 to 9.5 MPa ⁇ m.
- the second cemented carbide composition has an average grain size of about 4 to about 8 ⁇ m.
- the present disclosure also relates to a third cemented carbide for fluid handling components and seal ring comprising in wt % about 15 to about 30 TiC; about 5 to about 20 Ni; about 0.5 to about 2.5 Cr 3 C 2 ; and about 0.5 to about 2.5 Mo; and the balance WC.
- the third cemented carbide composition as defined hereinabove or hereinafter comprises from about 20 to about 23 wt % TiC, such as about 20 to about 22 wt % TiC.
- the third cemented carbide composition as defined hereinabove or hereinafter comprises from about 0.8 to about 1.5 wt % Cr 3 C 2 , such as about 0.95 to about 1.3 wt % Cr 3 C 2 .
- the third cemented carbide composition as defined hereinabove or hereinafter comprises from about 9.5 to about 14.5 wt % Ni, such as about 10 to about 14 wt % Ni.
- the third cemented carbide composition as defined hereinabove or hereinafter comprises from about 0.7 to about 1.6 wt % Mo, such as about 0.95 to about 1.3 wt % Mo.
- the third cemented carbide composition as defined hereinabove or hereinafter comprises about 62 to about 66 wt % WC. In an embodiment, the third cemented carbide composition as defined hereinabove or hereinafter has a density of from about 9.8 to about 10.4 g/cm 3 , such as of from about 10.02 to about 10.2 g/cm 3 .
- the third cemented carbide composition as defined hereinabove or hereinafter has a hardness of from about 1390 to about 1550 HV30.
- the third cemented carbide composition as defined hereinabove or hereinafter has a toughness of from about 8.5 to about 9.3 MPa ⁇ m.
- the third cemented carbide composition as defined hereinabove or hereinafter has an average WC grain size of from about 9.9 ⁇ m to about 1.3 ⁇ m, such as of about 1.05 ⁇ m to about 1.15 ⁇ m measured by FSSS.
- FIG. 1 is an optical microscopy image of an embodiment of the present disclosure of cemented carbide for a flow control apparatus and a seal ring.
- FIG. 2 is a scanning electron microscope (SEM) image of the embodiment of FIG. 1 .
- FIG. 3 is an SEM image of another embodiment of FIG. 1 .
- FIG. 4 is an SEM image of a comparative example.
- FIG. 5 is an SEM image of an embodiment of cemented carbide for a seal ring.
- FIG. 6 is an SEM image of another embodiment of cemented carbide for a seal ring.
- FIG. 7 is an SEM image of another embodiment of cemented carbide for a seal ring.
- FIG. 8 is an SEM image of another embodiment of cemented carbide for a seal ring.
- 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 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 primary function of which is to control the pressure and flow of well products, such as pumps.
- choke valve components whose 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 components will also
- 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 embodiment of a light weight cemented carbide for use in flow components, 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 first 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 (KIc) being about 8.5 to about 9.5 MPa ⁇ m by indentation technique according to KIc (SEVNB)>8.5 MPa ⁇ m and the transverse rupture strength (TRS) according to IS03327 type C>1700 N/mm 2 .
- the WC in the first, second or third cemented carbide may have an average sintered grain size of about 0.8 ⁇ m and the (Ti,W)C (titanium tungsten carbide) in the first, second or third 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.
- 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.
- the embodiment of the first cemented carbide disclosure shows improved wear resistance to scratch testing in comparison to a comparative example of a fine grained oil and gas grade with 10.5 wt % 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 an embodiment 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 an embodiment 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 (KIc) being about 8.7 MPa ⁇ m using Palmqvisst toughness technique according to IS028079 or KIc (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 FIG. 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.
- LW+CR Light weight cemented carbide for seal rings according to the present disclosure
- (LW+CR) 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 0.5 to about 2.5 wt % Mo and the balance WC.
- the sintered structure is shown in FIG. 6 .
- 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 hardness of the cemented carbide component may be about 1550 HV30 (IS03878), the toughness (KIc) being about 8.5 MPa ⁇ m using Palmqvist toughness technique according to ISO28079 and a density of about 10.2 g/cm 3 .
- 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 (KIc) 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/cm3.
- 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 D1141 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.
- a cemented carbide for a flow component for controlling the pressure and flow of well products having a composition comprising in wt % of:
- cemented carbide for a flow component of item 1 wherein the composition comprises WC in an amount of from 50 wt % to 69 wt %.
- cemented carbide for a flow component of any of the preceding items, wherein the composition comprises 2 wt % Cr 3 C 2 .
- cemented carbide for a flow component of any of the preceding items, wherein the composition comprises 5.7 wt % Ni.
- cemented carbide for a flow component of any of the preceding items, wherein the composition comprises 8.3 wt % Co.
- cemented carbide for a flow component of any of the preceding items, wherein the composition comprises 0.2 wt % Mo.
- cemented carbide for a flow component of any of the preceding items, wherein the composition has a density of from 9.8 to 10 g/cm 3 , a hardness of from 1350 to 1550 HV30, a toughness of 9.5 MPa ⁇ m.
- cemented carbide for a flow component of any of the preceding items, wherein the composition has an average WC grain size of about 0.8 ⁇ m.
- a cemented carbide for a seal ring having a composition comprising in wt %:
- cemented carbide for fluid handling components and seal rings of item 10 wherein the composition comprises WC in an amount of 63.2 wt %.
- cemented carbide for fluid handling components and seal rings of any of items 10-15, wherein the composition comprises 0.2 wt % Mo.
- cemented carbide for fluid handling components and seal rings of any of items 10-16, wherein cemented carbide composition has an average WC grain size of about 0.8 ⁇ m.
- cemented carbide for fluid handling components and seal rings of any of items 10-17 wherein the composition has a density of from 9.8 to 10 g/cm 3 , a hardness of from 1350 to 1550 HV30, and a toughness of from about 8.7 MPa ⁇ m.
- cemented carbide for fluid handling components and seal rings of any of items 10-16, wherein cemented carbide composition has an average WC grain size of from about 4 ⁇ m to about 8 ⁇ m.
- a cemented carbide for fluid handling components and seal rings having a composition comprising in wt %:
- cemented carbide for fluid handling components and seal rings of item 20 wherein the composition comprises WC in an amount of from 62 to 66 wt %.
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Abstract
Description
- 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.
- One of the most important properties for seal rings is corrosion resistance. During operation of the pump, 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. There is need for a corrosion resistant cheaper tungsten carbide seal ring.
- Similarly, 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.
- Light-weight cemented carbide for improved service life of can punches is disclosed in EP2439294B1, assigned to the assignee of the present disclosure. 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.
- It is an aspect of the present disclosure to provide a cemented carbide for a flow control component with improved service life.
- It is another aspect of the present disclosure to provide a light weight cemented carbide for fluid handling components and seal ring having improved corrosion resistance.
- The present disclosure therefore relates to a cemented carbide for a flow control component for controlling the pressure and flow of well products comprising in wt % about 7 to about 9 Co; about 5 to about 7 Ni; about 19 to about 24 TiC; about 1.5 to about 2.5 Cr3C2; and about 0.1 to about 0.3 Mo; and the balance WC.
- In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter has an average grain size of 0.80 μm measured by FSSS (Fisher Sub Sieve Sizer). In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter comprises from about 20 to about 22 wt % TiC, such as about 21 wt % TiC.
- In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter comprises from about 1.8 to about 2.2 wt % Cr3C2, such as about 2 wt % Cr3C2.
- In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter comprises from about 5.3 to about 6.0 wt % Ni, such as about 5.7 wt % Ni.
- In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter comprises from about 8.0 to about 8.6 wt % Co, such as about 8.3 wt % Co.
- In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter comprises from about 0.15 to about 0.25 wt % Mo, such as about 0.2 wt % Mo.
- In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter has a density of from about 9.6 to about 10.2 g/cm3, such as of from about 9.8 to about 10 g/cm3.
- In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter has a hardness of from about 1350 to about 1500 HV30.
- In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter has a toughness of about 8.5 to 9.5 MPa·√m.
- In an embodiment, the cemented carbide composition as defined hereinabove or hereinafter comprises a balance of WC, such as 50 wt % to about 69 wt %.
- The present disclosure also relates to a second cemented carbide for fluid handling components and seal ring comprising in wt %; about 15 to about 30 TiC; about 12 to about 20 Co+Ni; about 0.5 to about 2.5 Cr3C2; and about 0.1 to about 0.3 Mo and the balance WC.
- In an embodiment, the second cemented carbide composition as defined hereinabove or hereinafter comprises from about 19.8 to about 21.8 wt % TiC, such as about 20.8 wt % TiC.
- In an embodiment, the second cemented carbide composition as defined hereinabove or hereinafter comprises from about 1.8 to about 2.2 wt % Cr3C2, such as about 2 wt % Cr3C2.
- In an embodiment, the second cemented carbide composition defined hereinabove or hereinafter comprises from about 5.3 to about 5.9 wt % Ni, such as about 5.6 wt % Ni.
- In an embodiment, the second cemented carbide composition as defined hereinabove or hereinafter comprises from about 7.9 to about 8.5 wt % Co, such as about 8.2 wt % Co. In an embodiment, the second cemented carbide composition as defined hereinabove or hereinafter comprises from about 0.15 to about 0.25 wt % Mo, such as about 0.2 wt % Mo.
- In an embodiment, the second cemented carbide composition as defined hereinabove or hereinafter comprises of from about 62.2 to about 64.2 wt % WC, such as about 63.2 wt % WC.
- In an embodiment, the second cemented carbide composition as defined hereinabove or hereinafter has a density of from about 9.6 to about 10.2 g/cm3, such as of from about 9.8 to about 10 g/cm3.
- In an embodiment, the second cemented carbide composition as defined hereinabove or hereinafter has a hardness of from about 1350 to about 1500 HV30.
- In an embodiment, the second cemented carbide composition as defined hereinabove or hereinafter has a toughness of about 8.5 to 9.5 MPa·√m.
- In an embodiment, the second cemented carbide composition has an average grain size of about 4 to about 8 μm.
- The present disclosure also relates to a third cemented carbide for fluid handling components and seal ring comprising in wt % about 15 to about 30 TiC; about 5 to about 20 Ni; about 0.5 to about 2.5 Cr3C2; and about 0.5 to about 2.5 Mo; and the balance WC.
- In an embodiment, the third cemented carbide composition as defined hereinabove or hereinafter comprises from about 20 to about 23 wt % TiC, such as about 20 to about 22 wt % TiC.
- In an embodiment, the third cemented carbide composition as defined hereinabove or hereinafter comprises from about 0.8 to about 1.5 wt % Cr3C2, such as about 0.95 to about 1.3 wt % Cr3C2.
- In an embodiment, the third cemented carbide composition as defined hereinabove or hereinafter comprises from about 9.5 to about 14.5 wt % Ni, such as about 10 to about 14 wt % Ni.
- In an embodiment, the third cemented carbide composition as defined hereinabove or hereinafter comprises from about 0.7 to about 1.6 wt % Mo, such as about 0.95 to about 1.3 wt % Mo.
- In an embodiment, the third cemented carbide composition as defined hereinabove or hereinafter comprises about 62 to about 66 wt % WC. In an embodiment, the third cemented carbide composition as defined hereinabove or hereinafter has a density of from about 9.8 to about 10.4 g/cm3, such as of from about 10.02 to about 10.2 g/cm3.
- In an embodiment, the third cemented carbide composition as defined hereinabove or hereinafter has a hardness of from about 1390 to about 1550 HV30.
- In an embodiment, the third cemented carbide composition as defined hereinabove or hereinafter has a toughness of from about 8.5 to about 9.3 MPa·√m.
- In an embodiment, the third cemented carbide composition as defined hereinabove or hereinafter has an average WC grain size of from about 9.9 μm to about 1.3 μm, such as of about 1.05 μm to about 1.15 μm measured by FSSS. The foregoing summary, as well as the following detailed description of the embodiments, will be better understood when read in conjunction with the appended drawings. It should be understood that the embodiments depicted are not limited to the precise arrangements and instrumentalities shown.
-
FIG. 1 is an optical microscopy image of an embodiment of the present disclosure of cemented carbide for a flow control apparatus and a seal ring. -
FIG. 2 is a scanning electron microscope (SEM) image of the embodiment ofFIG. 1 . -
FIG. 3 is an SEM image of another embodiment ofFIG. 1 . -
FIG. 4 is an SEM image of a comparative example. -
FIG. 5 is an SEM image of an embodiment of cemented carbide for a seal ring. -
FIG. 6 is an SEM image of another embodiment of cemented carbide for a seal ring. -
FIG. 7 is an SEM image of another embodiment of cemented carbide for a seal ring. -
FIG. 8 is an SEM image of another embodiment of cemented carbide for a seal ring. - As used herein, 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%.
- As will be described fully herein, 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 primary function of which is to control the pressure and flow of well products, such as pumps. Under severe conditions of multi flow media; 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 components will also suffer due to galvanic corrosion due to a electropotential difference between the binder and the housing for the flow control part.
- The light weight cemented material can also be used in, for example, seal rings, to reduce the weight of the seal ring. In order to improve the corrosion resistance the light weight cemented carbide of the present disclosure can have a Ni—Cr—Mo binder.
- An embodiment of a light weight cemented carbide for use in flow components, 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 μm. 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.
- Referring to
FIG. 1 , the first 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 % Cr3C2, 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 (KIc) being about 8.5 to about 9.5 MPa·√m by indentation technique according to KIc (SEVNB)>8.5 MPa·√m and the transverse rupture strength (TRS) according to IS03327 type C>1700 N/mm2.
- The WC in the first, second or third cemented carbide may have an average sintered grain size of about 0.8 μm and the (Ti,W)C (titanium tungsten carbide) in the first, second or third cemented carbide may have an average sintered grain size of about 1.5 μm 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 μT m3 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 Eb Eb Ereprass Product 10 μm/cm2 100 μm/cm2 10 μm/cm2 Comparative 24 46 −333 Example 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 μA/cm2 may be considered to give an indication of the ease of initiation of corrosion. The difference between this and the higher criterion of 100 μA/cm2 provides an indication of the propagation process.
- “Erepass” is the potential required to repassivate the specimen
- Conventional powder metallurgical methods such as milling, drying, pressing, shaping, sintering and sinter hipping, which are used for manufacture of conventional cemented carbides are used to manufacture the embodiments of the present disclosure.
- It should be appreciated that the following examples are illustrative, non-limiting example. The compositions and results of the embodiments are shown in Tables 2 and 3 below.
- In the examples below the powders were sourced from the following suppliers: (W,Ti)C from Zhuzhou or HC Starck, Co from Umicore or Freeport, Ni from Inco, Mo from HC Starck and Cr3C2 from Zhuzhou or HC Starck
- Cemented carbide grades with the composition in wt-% 21 TiC; 8.3 Co; 5.7; Ni; 0.2 Mo and 2 Cr3C2 with the balance of WC was produced using WC and (Ti,W)C powder with an average FSSS particle size (d50) of 0.8 μm and about 3 μm, 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 μm together with (Ti,W)C grains with an average grain size of 1.5 μm 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.
- As shown in
FIG. 3 , the embodiment of the first cemented carbide disclosure, LW shows improved wear resistance to scratch testing in comparison to a comparative example of a fine grained oil and gas grade with 10.5 wt % binder (FIG. 4 ) with similar or hardness values. Testing was carried out using a diamond stylus with a 20 μm radius tip at 200 mN. - Wear resistance damage from scratching is considerably improved for an embodiment of the disclosure, LW, as shown by reduced ‘grey’ amorphous damage in
FIG. 3 as compared to the comparative example inFIG. 4 . Further, corrosion resistance for an embodiment 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 (KIc) being about 8.7 MPa·√m using Palmqvisst toughness technique according to IS028079 or KIc (LW15, SEVNB)>8.5 MPa·√m and the transverse rupture strength (TRS) according to IS03327 type C>1700 N/mm2.
- A cemented carbide grades with the compositions in wt-% of about 63.2 WC; about 20.8 TiC; about 2 Cr3C2; 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 (d50) of 4-8 μm, respectively. The sintered structure is shown in
FIG. 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.
- Another embodiment of the light weight cemented carbide for seal rings according to the present disclosure, (LW+CR), 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 0.5 to about 2.5 wt % Mo and the balance WC.
- A cemented carbide grades with the compositions in wt-% of about 66.04 WC; about 21.95 TiC; about 0.95 Cr3C2; about 0.95 Mo; about 10.11 Ni using WC and (Ti,W)C powder with an average FSSS particle size (d50) of greater than about 1 μm, for example 1.1 and 1.15 μm, respectively. It should be appreciated that a particle size of up to about 8 μm can be used.
- The sintered structure is shown in
FIG. 6 . - 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 hardness of the cemented carbide component may be about 1550 HV30 (IS03878), the toughness (KIc) being about 8.5 MPa·√m using Palmqvist toughness technique according to ISO28079 and a density of about 10.2 g/cm3.
- A cemented carbide grades with the compositions in wt-% of about 62.79 WC; about 20.86 TiC; about 1.29 Cr3C2; about 1.29 Mo; about 13.78 Ni WC and (Ti,W)C powder with an average FSSS particle size (d50) of greater than about 1 μm, for example 1.1 and 1.15 μm, respectively. It should be appreciated that a particle size of up to about 8 μm can be used.
- 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 (KIc) 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/cm3.
- 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 D1141 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. The value measured for a standard seal ring grade was Epit=263 mV SCE. However, for the LW grade Epit=318 mV SCE showing improved corrosion resistance.
-
TABLE 2 Ref A B C D Sample LW flow LW seal LW + CR seal LW + CR control ring ring seal ring WC (wt %) balance 63.2 66.04 62.79 WC grain size 0.8 4.0-8.0 1.05-1.15 1.05-1.15 (μm) TiC (wt %) 21 20.8 21.95 20.86 Co (wt %) 8.3 8.2 0 0 Ni (wt %) 5.7 5.6 10.11 13.78 Mo (wt %) 0.2 0.2 0.95 1.29 Cr3C2 (wt %) 2 2 0.95 1.29 -
TABLE 3 Ref A C D Sample LW flow control LW + CR seal ring LW + CR seal ring Density 9.8-10 10.2 10.02-10.17 (gm/cm3) Hardness 1350-1500 1550 1390-1400 (Hv30) Toughness 9.5 8.5-9.5 8.6-9.3 (K1C) - 1. A cemented carbide for a flow component for controlling the pressure and flow of well products the cemented carbide having a composition comprising in wt % of:
- balance WC;
- 7 to 9 Co;
- 5 to 7 Ni;
- 19 to 24 TiC;
- 1.5 to 2.5 Cr3C2; and
- 0.1 to 0.3 Mo.
- 2. The cemented carbide for a flow component of
item 1, wherein the composition comprises WC in an amount of from 50 wt % to 69 wt %. - 3. The cemented carbide for a flow component of
1 or 2, wherein the composition comprises 21 wt % TiC.item - 4. The cemented carbide for a flow component of any of the preceding items, wherein the composition comprises 2 wt % Cr3C2.
- 5. The cemented carbide for a flow component of any of the preceding items, wherein the composition comprises 5.7 wt % Ni.
- 6. The cemented carbide for a flow component of any of the preceding items, wherein the composition comprises 8.3 wt % Co.
- 7. The cemented carbide for a flow component of any of the preceding items, wherein the composition comprises 0.2 wt % Mo.
- 8. The cemented carbide for a flow component of any of the preceding items, wherein the composition has a density of from 9.8 to 10 g/cm3, a hardness of from 1350 to 1550 HV30, a toughness of 9.5 MPa·√m.
- 9. The cemented carbide for a flow component of any of the preceding items, wherein the composition has an average WC grain size of about 0.8 μm.
- 10. A cemented carbide for a seal ring, the cemented carbide having a composition comprising in wt %:
-
- balance WC;
- 15 to 30 TiC;
- 2 to 20 Co+Ni;
- 0.5 to 2.5 Cr3C2; and
- 0.1 to 0.3 Mo.
- 11. The cemented carbide for fluid handling components and seal rings of item 10, wherein the composition comprises WC in an amount of 63.2 wt %.
- 12. The cemented carbide for fluid handling components and seal rings of item 10 or 11, wherein the composition comprises 20.8 wt % TiC.
- 13. The cemented carbide for fluid handling components and seal rings of any of items 10-12, wherein the composition comprises 2 wt % Cr3C2.
- 14. The cemented carbide for fluid handling components and seal rings of any of items 10-13, wherein the composition comprises 5.6 wt % Ni.
- 15. The cemented carbide for fluid handling components and seal rings of any of items 10-14, wherein the composition comprises 8.2 wt % Co.
- 16. The cemented carbide for fluid handling components and seal rings of any of items 10-15, wherein the composition comprises 0.2 wt % Mo.
- 17. The cemented carbide for fluid handling components and seal rings of any of items 10-16, wherein cemented carbide composition has an average WC grain size of about 0.8 μm.
- 18. The cemented carbide for fluid handling components and seal rings of any of items 10-17, wherein the composition has a density of from 9.8 to 10 g/cm3, a hardness of from 1350 to 1550 HV30, and a toughness of from about 8.7 MPa·√m.
- 19. The cemented carbide for fluid handling components and seal rings of any of items 10-16, wherein cemented carbide composition has an average WC grain size of from about 4 μm to about 8 μm.
- 20. A cemented carbide for fluid handling components and seal rings, the cemented carbide having a composition comprising in wt %:
- 15 to 30 TiC;
- 5 to 20 Ni;
- 0.5 to 2.5 Cr3C2;
- 0.5 to 2.5 Mo; and
- balance WC.
- 21. The cemented carbide for fluid handling components and seal rings of item 20, wherein the composition comprises WC in an amount of from 62 to 66 wt %.
- 22. The cemented carbide for fluid handling components and seal rings of
item 20 or 21, wherein the composition comprises of from 20 to 22 wt % TiC. - 23. The cemented carbide for fluid handling components and seal rings of any of items 20-22, wherein the composition comprises of from 0.95 to 1.3 wt % Cr3C2.
- 24. The cemented carbide for fluid handling components and seal rings of any of items 20-23, wherein the composition comprises of from 10 to 14 wt % Ni.
- 25. The cemented carbide for fluid handling components and seal rings of any of items 20-24, wherein the composition comprises of from 0.95 to 1.3 wt % Mo.
- 26. The cemented carbide for fluid handling components and seal rings of any of items 20-25, wherein the composition has a density of from 10.02 to 10.2 g/cm3, a hardness of from 1390 to 1550 HV30 and a toughness of from 8.5 to about 9.3 MPa·√m.
- Although the present embodiments have been described in relation to particular aspects thereof, many other variations and modifications and other uses will become apparent to those skilled in the art. It is preferred therefore, that the present embodiment(s) be limited not by the specific disclosure herein, but only by the appended claims.
Claims (24)
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| US15/540,907 US20180002783A1 (en) | 2014-12-30 | 2015-12-28 | Light weight cemented carbide for flow erosion components |
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| US201462098229P | 2014-12-30 | 2014-12-30 | |
| US15/540,907 US20180002783A1 (en) | 2014-12-30 | 2015-12-28 | Light weight cemented carbide for flow erosion components |
| PCT/EP2015/081284 WO2016107843A1 (en) | 2014-12-30 | 2015-12-28 | Light weight cemented carbide for flow erosion components |
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| US (1) | US20180002783A1 (en) |
| EP (1) | EP3240916B1 (en) |
| AU (1) | AU2015373452A1 (en) |
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| CN108913953A (en) * | 2018-07-31 | 2018-11-30 | 成都工业学院 | A kind of VC particle enhanced nickel base high temperature alloy and preparation method thereof |
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| US6375707B1 (en) * | 1997-12-22 | 2002-04-23 | Sandvik A.B. | Point ball for ball point pens |
| US6521353B1 (en) * | 1999-08-23 | 2003-02-18 | Kennametal Pc Inc. | Low thermal conductivity hard metal |
| US20130247641A1 (en) * | 2010-10-07 | 2013-09-26 | Sandvik Intellectual Property Ab | Cemented carbide punch |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2097258A5 (en) * | 1970-06-18 | 1972-03-03 | Ugine Carbone | |
| SE512668C2 (en) * | 1997-09-05 | 2000-04-17 | Sandvik Ab | Ways to manufacture a corrosion resistant cemented carbide |
| SE0602813L (en) * | 2006-12-27 | 2008-06-28 | Sandvik Intellectual Property | Corrosion resistant tool for cold working operations |
| DK2433727T3 (en) * | 2010-09-24 | 2015-05-26 | Sandvik Intellectual Property | A process for preparing a sintered composite member |
| EP2439300A1 (en) * | 2010-10-08 | 2012-04-11 | Sandvik Intellectual Property AB | Cemented carbide |
-
2015
- 2015-12-28 ES ES15822955T patent/ES2759730T3/en active Active
- 2015-12-28 EP EP15822955.9A patent/EP3240916B1/en active Active
- 2015-12-28 WO PCT/EP2015/081284 patent/WO2016107843A1/en not_active Ceased
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- 2015-12-28 CA CA2970584A patent/CA2970584A1/en not_active Abandoned
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- 2015-12-28 RU RU2017127054A patent/RU2675432C1/en active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6375707B1 (en) * | 1997-12-22 | 2002-04-23 | Sandvik A.B. | Point ball for ball point pens |
| US6521353B1 (en) * | 1999-08-23 | 2003-02-18 | Kennametal Pc Inc. | Low thermal conductivity hard metal |
| US20130247641A1 (en) * | 2010-10-07 | 2013-09-26 | Sandvik Intellectual Property Ab | Cemented carbide punch |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108913953A (en) * | 2018-07-31 | 2018-11-30 | 成都工业学院 | A kind of VC particle enhanced nickel base high temperature alloy and preparation method thereof |
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| WO2016107843A1 (en) | 2016-07-07 |
| EP3240916B1 (en) | 2019-09-18 |
| SG11201704721UA (en) | 2017-07-28 |
| MX2017008637A (en) | 2017-10-11 |
| ES2759730T3 (en) | 2020-05-12 |
| CA2970584A1 (en) | 2016-07-07 |
| RU2675432C1 (en) | 2018-12-19 |
| AU2015373452A1 (en) | 2017-06-29 |
| EP3240916A1 (en) | 2017-11-08 |
| MY179165A (en) | 2020-10-30 |
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