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USRE41646E1 - Cemented carbide body with increased wear resistance - Google Patents

Cemented carbide body with increased wear resistance Download PDF

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Publication number
USRE41646E1
USRE41646E1 US11/484,834 US48483497A USRE41646E US RE41646 E1 USRE41646 E1 US RE41646E1 US 48483497 A US48483497 A US 48483497A US RE41646 E USRE41646 E US RE41646E
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grain size
grains
ratio
group
cemented carbide
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US11/484,834
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Ake Ostlund
Mats Waldenstrom
Ove Alm
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Sandvik Intellectual Property AB
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Sandvik Intellectual Property AB
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Priority claimed from PCT/SE1997/001242 external-priority patent/WO1998003690A1/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01MTESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
    • G01M11/00Testing of optical apparatus; Testing structures by optical methods not otherwise provided for
    • G01M11/30Testing of optical devices, constituted by fibre optics or optical waveguides
    • G01M11/37Testing of optical devices, constituted by fibre optics or optical waveguides in which light is projected perpendicularly to the axis of the fibre or waveguide for monitoring a section thereof
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/24Coupling light guides
    • G02B6/255Splicing of light guides, e.g. by fusion or bonding
    • G02B6/2551Splicing of light guides, e.g. by fusion or bonding using thermal methods, e.g. fusion welding by arc discharge, laser beam, plasma torch

Definitions

  • the present invention relates to coated cemented carbide bodies particularly useful in tools for turning, milling and drilling of steels and stainless steels.
  • Cemented carbide bodies are manufactured according to powder metallurgical methods including milling, pressing and sintering.
  • the milling operation is an intensive mechanical milling in mills of different sizes and with the aid of milling bodies.
  • the milling time is of the order of several hours up to days. Such processing is believed to be necessary in order to obtain a uniform distribution of the binder phase in the milled mixture, but it results in a wide WC grain size distribution.
  • It is an aspect of this invention to provide a method of making a cemented carbide body comprising wet mixing without milling of at least two different WC-powders with deagglomerated powders of other carbides, binder metal and pressing agent such that the WC-powders are coated with the binder phase, said WC-grains being carefully deagglomerated before and after being coated with binder metal, the grains of the WC-powder being classified in at least two groups in which a group of smaller grains has a maximum grain size a max and a group of a larger grains has a minimum grain size b min , each group containing at least 10% of the total amount of WC grains wherein b min ⁇ a max >0.5 mm, the variation in grain size within each group being >1 ⁇ m, drying said mixture, pressing to a desired shape and sintering said pressed bodies.
  • the present invention relates generally to a cemented carbide body comprising WC with an average grain size of ⁇ 10 ⁇ m in a binder phase.
  • the WC grains are classified in at least two groups in which a group of smaller grains has a maximum grain size a max and a group of larger grains has a minimum grain size b min .
  • Each group contains at least 10% of the total amount of WC grains.
  • the cemented carbide body according to the invention is characterized in that b min ⁇ a max >0.5 ⁇ m and that the variation in grain size within each group is >1 ⁇ m.
  • the WC grains have a narrow bimodal grain size distribution with grain sizes in the ranges 0-1.5 ⁇ m and 2.5-6.0 ⁇ m respectively, and with a weight ratio of fine WC particles (0-1.5 ⁇ m) to coarse WC particles (2.5-6.0 ⁇ m) in the range of 0.25-4.0, preferably 0.5-2.0.
  • the amount of W dissolved in the binder phase is controlled by adjustment of the carbon content by small additions of carbon black or pure tungsten powder.
  • the CW-value in inserts according to the invention shall be 0.82-1.0, preferably 0.86-0.96.
  • a cemented carbide body comprising wet mixing without milling of at least two different WC-powders with deagglomerated powders of other carbides, generally TiC, TaC and/or NbC, binder metal and pressing agent, dried preferably by spray drying, pressed to inserts and sintered.
  • the grains of the WC-powder are classified in at least two groups in which a group of smaller grains has a maximum grain size a max and a group of larger grains has a minimum grain size b min each group containing at least 10% of the total amount of WC grains wherein b min ⁇ a max >0.5 ⁇ m and the variation in grain size within each group is >1 ⁇ m.
  • the WC grains are carefully deagglomerated before and after being coated with binder metal.
  • WC-powders with two narrow grain size distributions of 0-1.5 ⁇ m and 2.5-6.0 ⁇ m respectively and a weight ratio of fine WC particles (0-1.5 ⁇ m) to coarse WC particles (2.5-6.0 ⁇ m) in the range of 0.25-4.0, preferably 0.5-2.0 are wet mixed without milling with other carbides generally TiC, TaC and/or NbC, binder metal and pressing agent, dried preferably by spray drying, pressed to inserts and sintered.
  • Cemented carbide tool inserts of the type SEMN 1204 AZ, an insert for milling, with the composition in addition to WC of 8.4 wt % Co, 1.13 wt % TaC and 0.38 wt % NbC were produced according to the invention.
  • Cobalt coated WC, WC-6 wt-% Co, prepared in accordance with U.S. Pat. No. 5,505,902 was carefully deagglomerated in a laboratory jetmill equipment, mixed with additional amounts of Co and deagglomerated uncoated (Ta,Nb)C and TaC powders to obtain the desired material composition.
  • the coated WC-particles consisted of 50 wt % with an average grain size of 3.5 ⁇ m and 50 wt % with 1.2 ⁇ m average grain size, giving a bimodal grain size distribution.
  • the mixing was carried out in an ethanol and water solution (0.25 l fluid per kg cemented carbide powder) for 2 hours in a laboratory mixer and the batch size was 10 kg. Furthermore, 2 weight-% lubricant, was added to the slurry.
  • the carbon content was adjusted with carbon black to a binder phase alloyed with W corresponding to a CW-ratio of 0.89. After spray drying, the inserts were pressed and sintered according to standard practise and dense structures with no porosity were obtained.
  • the inserts were coated with a 0.5 ⁇ m equiaxed TiCN-layer (with a high nitrogen content corresponding to an estimated C/N-ratio of 0.05) followed by a 4 ⁇ m thick TiCN-layer with columnar grains by using the MTCVD-technique (temperature 885-850° C. and CH 3 CN as the carbon and nitrogen sources).
  • a 1.0 ⁇ m thick layer of Al 2 O 3 was deposited using a temperature 970° C. and a concentration of H 2 S dopant of 0.4% as disclosed in EP-A-523 021.
  • a thin (0.3 ⁇ m) layer of TiN was deposited on top according to known CVD-technique. XRD-measurement showed that the Al 2 O 3 -layer consisted of 100% ⁇ -phase.
  • the coated inserts were brushed by a nylon straw brush containing SiC grains. Examination of the brushed inserts in a light microscope showed that the thin TiN-layer had been brushed away only along the cutting edge leaving there a smooth Al 2 O 3 -layer surface.
  • Coating thickness measurements on cross sectioned brush samples showed no reduction of the coating along the edge line except for the outer TiN-layer that was removed.
  • Cemented carbide tool inserts of the type SEMN 1204 AZ, an insert for milling, with the composition 9.1 wt % Co, 1.23 wt % TaC and 0.30 wt % NbC and the rest WC with unimodal distribution and an average grain size of 1.2 ⁇ m were produced in the following way.
  • Cobalt coated WC, WC-6 weight-% Co, prepared in accordance with U.S. Pat. No. 5,505,902 was carefully deagglomerated in a laboratory jetmill equipment, mixed with additional amounts of Co and deagglomerated uncoated (Ta,Nb)C and TaC powders to obtain the desired material composition.
  • the mixing was carried out in an ethanol and water solution (0.25 l fluid per kg cemented carbide powder) for 2 hours in a laboratory mixer and the batch size was 10 kg. Furthermore, 2 weight-% lubricant, was added to the slurry. The carbon content was adjusted with carbon black to a binder phase highly alloyed with W corresponding to a CW-ratio of 0.89. After spray drying, the inserts were pressed and sintered according to standard practise and dense structures with no porosity were obtained.
  • the inserts were coated in the same coating batch as the inserts A above.
  • the coated inserts were brushed by a nylon straw brush containing SiC grains. Examination of the brushbed inserts in a light microscope showed that the thin TiN-layer had been brushed away only along the cutting edge leaving there a smooth Al 2 O 3 -layer surface.
  • Coating thickness measurements on cross sectioned brushed samples showed no reduction of the coating along the edge line except for the outer TiN-layer that was removed.
  • Two parallel bars each of a thickness of 35 mm were centrally positioned relative the cutter body (diameter 100 mm ), and the bars were placed with an air gap of 10 mm between them.
  • the cutting data were:

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Mechanical Coupling Of Light Guides (AREA)
  • Length Measuring Devices By Optical Means (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Powder Metallurgy (AREA)

Abstract

As there is disclosed a cemented carbide body comprising WC with an average grain size of <10 μm in a binder phase. In the cemented carbide body the WC grains can be classified in at least two groups in which a group of smaller grains has a maximum grain size amax and a group of larger grains has a minimum grain size bmin and each group contains at least 10 % of the total amount of WC grains. According to the invention bmin−amax>0.5 μm and the difference in grain size within each group is >1 μm.

Description

CROSS-REFERENCES TO RELATED APPLICATIONS
The present application is a reissue of U.S. Pat. No. 6,210,632 B1, which is a national stage application of PCT/SE97/01242 filed on Jul. 8, 1997, and which claims the benefit of priority to Swedish Application No. 9602812 - 1 filed Jul. 19, 1996.
BACKGROUND OF THE INVENTION
The present invention relates to coated cemented carbide bodies particularly useful in tools for turning, milling and drilling of steels and stainless steels.
Cemented carbide bodies are manufactured according to powder metallurgical methods including milling, pressing and sintering. The milling operation is an intensive mechanical milling in mills of different sizes and with the aid of milling bodies. The milling time is of the order of several hours up to days. Such processing is believed to be necessary in order to obtain a uniform distribution of the binder phase in the milled mixture, but it results in a wide WC grain size distribution.
In U.S. Pat. Nos. 5,505,902 and 5,529,804 methods of making cemented carbide are disclosed according to which the milling is essentially excluded. Instead, in order to obtain a uniform distribution of the binder phase in the powder mixture, the hard constituent grains are precoated with the binder phase, the mixture is further wet mixed with pressing agent dried, pressed and sintered. In the first mentioned patent the coating is made by a SOL-GEL method and in the second, a polyol is used.
EP-A-665 308 discloses a coated cutting insert with a bimodal distribution of WC grain size with WC grains in two groups 0.1-1 μm and 3-10 μm. The insert according to this application is produced with conventional milling technique resulting in a broadening of the WC grain size distribution.
OBJECT AND SUMMARY OF THE INVENTION
It is an aspect of this invention to provide a method of making a cemented carbide body comprising wet mixing without milling of at least two different WC-powders with deagglomerated powders of other carbides, binder metal and pressing agent such that the WC-powders are coated with the binder phase, said WC-grains being carefully deagglomerated before and after being coated with binder metal, the grains of the WC-powder being classified in at least two groups in which a group of smaller grains has a maximum grain size amax and a group of a larger grains has a minimum grain size bmin, each group containing at least 10% of the total amount of WC grains wherein bmin−amax>0.5 mm, the variation in grain size within each group being >1 μm, drying said mixture, pressing to a desired shape and sintering said pressed bodies.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT OF THE INVENTION
It has now surprisingly been found that a further improvement of the properties of a cemented carbide according to EP-A-665 308 can be obtained it such a material is made using the technique disclosed in the above mentioned U.S. Pat. No. 5,505,902 or 5,529,804.
The present invention relates generally to a cemented carbide body comprising WC with an average grain size of <10 μm in a binder phase. The WC grains are classified in at least two groups in which a group of smaller grains has a maximum grain size amax and a group of larger grains has a minimum grain size bmin. Each group contains at least 10% of the total amount of WC grains. The cemented carbide body according to the invention is characterized in that bmin−amax>0.5 μm and that the variation in grain size within each group is >1 μm.
More particularly, the invention relates to a coated cutting insert with a bimodal distribution of the WC grains particularly useful for machining of steels and stainless steels comprising WC and 4-20 wt-% Co, preferably 5-12.5 wt-% Co and 0-30 wt-% cubic carbide, preferably 0-15 wt-% cubic carbide, most preferably 0-10 wt-% cubic carbide such as TiC, TaC, NbC or mixtures thereof. The WC grains have a narrow bimodal grain size distribution with grain sizes in the ranges 0-1.5 μm and 2.5-6.0 μm respectively, and with a weight ratio of fine WC particles (0-1.5 μm) to coarse WC particles (2.5-6.0 μm) in the range of 0.25-4.0, preferably 0.5-2.0.
The amount of W dissolved in the binder phase is controlled by adjustment of the carbon content by small additions of carbon black or pure tungsten powder. The W-content in the binder phase can be expressed as the “CW-ratio” defined as
CW-ratio=Ms/(wt %Co*0.0161)
where Ms is the measured saturation magnetization of the sintered cemented carbide body in kA/m hAm2 /kg and wt % Co is the weight percentage of Co in the cemented carbide. The CW-value in inserts according to the invention shall be 0.82-1.0, preferably 0.86-0.96.
The sintered inserts according to the invention are used coated or uncoated, preferably coated by MTCVD, conventional CVD or PVD, with or without Al2O3. In particular, multilayer coatings comprising TiCxNvOz with columnar grains followed by a layer of α-Al2O3, κ-Al2O3 or a mixture of α- and κ-Al2O3, have shown good results. In another preferred embodiment, the coating described above is completed with a TiN-layer which can be brushed or used without brushing.
According to the method of the present invention, a cemented carbide body is made comprising wet mixing without milling of at least two different WC-powders with deagglomerated powders of other carbides, generally TiC, TaC and/or NbC, binder metal and pressing agent, dried preferably by spray drying, pressed to inserts and sintered. The grains of the WC-powder are classified in at least two groups in which a group of smaller grains has a maximum grain size amax and a group of larger grains has a minimum grain size bmin each group containing at least 10% of the total amount of WC grains wherein bmin−amax>0.5 μm and the variation in grain size within each group is >1 μm. Preferably, prior to mixing, the WC grains are carefully deagglomerated before and after being coated with binder metal.
Particularly according to the method of the present invention, WC-powders with two narrow grain size distributions of 0-1.5 μm and 2.5-6.0 μm respectively and a weight ratio of fine WC particles (0-1.5 μm) to coarse WC particles (2.5-6.0 μm) in the range of 0.25-4.0, preferably 0.5-2.0 are wet mixed without milling with other carbides generally TiC, TaC and/or NbC, binder metal and pressing agent, dried preferably by spray drying, pressed to inserts and sintered.
It is essential according to the invention that the mixing takes place without milling, i.e., there should be no change in grain size or grain size distribution as a result of the mixing.
In a preferred embodiment, the hard constituents, at least those with narrow grain size distributions, are after careful deagglomeration coated with binder metal using methods disclosed in U.S. Pat. No. 5,505,902 or 5,529,804. In such case, the cemented carbide powder according to the invention is preferably of Co-coated WC+Co-binder, with or without additions of the cubic carbides such as TiC, TaC, NbC, (Ti,W)C, (Ta,Nb)C, (Ti,Ta,Nb)C, (W,Ta,Nb)C, and (W,Ti,Ta,Nb)C coated or uncoated, preferably uncoated, possibly with further additions of Co-powder in order to obtain the desired final composition.
The invention is additionally illustrated in connection with the following Examples which are to be considered as illustrative of the present invention. It should be understood however, that the invention is not limited to the specific details of the Examples.
EXAMPLE 1
A. Cemented carbide tool inserts of the type SEMN 1204 AZ, an insert for milling, with the composition in addition to WC of 8.4 wt % Co, 1.13 wt % TaC and 0.38 wt % NbC were produced according to the invention. Cobalt coated WC, WC-6 wt-% Co, prepared in accordance with U.S. Pat. No. 5,505,902 was carefully deagglomerated in a laboratory jetmill equipment, mixed with additional amounts of Co and deagglomerated uncoated (Ta,Nb)C and TaC powders to obtain the desired material composition. The coated WC-particles consisted of 50 wt % with an average grain size of 3.5 μm and 50 wt % with 1.2 μm average grain size, giving a bimodal grain size distribution. The mixing was carried out in an ethanol and water solution (0.25 l fluid per kg cemented carbide powder) for 2 hours in a laboratory mixer and the batch size was 10 kg. Furthermore, 2 weight-% lubricant, was added to the slurry. The carbon content was adjusted with carbon black to a binder phase alloyed with W corresponding to a CW-ratio of 0.89. After spray drying, the inserts were pressed and sintered according to standard practise and dense structures with no porosity were obtained.
Before coating a negative chamfer with an angle of 20 degrees was ground around the whole insert.
The inserts were coated with a 0.5 μm equiaxed TiCN-layer (with a high nitrogen content corresponding to an estimated C/N-ratio of 0.05) followed by a 4 μm thick TiCN-layer with columnar grains by using the MTCVD-technique (temperature 885-850° C. and CH3CN as the carbon and nitrogen sources). In subsequent steps during the same coating cycle, a 1.0 μm thick layer of Al2O3 was deposited using a temperature 970° C. and a concentration of H2S dopant of 0.4% as disclosed in EP-A-523 021. A thin (0.3 μm) layer of TiN was deposited on top according to known CVD-technique. XRD-measurement showed that the Al2O3-layer consisted of 100% κ-phase.
The coated inserts were brushed by a nylon straw brush containing SiC grains. Examination of the brushed inserts in a light microscope showed that the thin TiN-layer had been brushed away only along the cutting edge leaving there a smooth Al2O3-layer surface.
Coating thickness measurements on cross sectioned brush samples showed no reduction of the coating along the edge line except for the outer TiN-layer that was removed.
B. Cemented carbide tool inserts of the type SEMN 1204 AZ, an insert for milling, with the composition 9.1 wt % Co, 1.23 wt % TaC and 0.30 wt % NbC and the rest WC with unimodal distribution and an average grain size of 1.2 μm were produced in the following way. Cobalt coated WC, WC-6 weight-% Co, prepared in accordance with U.S. Pat. No. 5,505,902 was carefully deagglomerated in a laboratory jetmill equipment, mixed with additional amounts of Co and deagglomerated uncoated (Ta,Nb)C and TaC powders to obtain the desired material composition. The mixing was carried out in an ethanol and water solution (0.25 l fluid per kg cemented carbide powder) for 2 hours in a laboratory mixer and the batch size was 10 kg. Furthermore, 2 weight-% lubricant, was added to the slurry. The carbon content was adjusted with carbon black to a binder phase highly alloyed with W corresponding to a CW-ratio of 0.89. After spray drying, the inserts were pressed and sintered according to standard practise and dense structures with no porosity were obtained.
Before coating a negative chamfer with an angle of 20 degrees was ground around the whole of each insert.
The inserts were coated in the same coating batch as the inserts A above.
The coated inserts were brushed by a nylon straw brush containing SiC grains. Examination of the brushbed inserts in a light microscope showed that the thin TiN-layer had been brushed away only along the cutting edge leaving there a smooth Al2O3-layer surface.
Coating thickness measurements on cross sectioned brushed samples showed no reduction of the coating along the edge line except for the outer TiN-layer that was removed.
C. Cemented carbide tool inserts of the type SEMN 1204 AZ with the same chemical composition, average grain size of WC, CW-ratio, chamfering, CVD-coating and brushing respectively as the insert B above but produced from powder manufactured with conventional ball milling techniques were used as reference for comparison with the test specimens according to above.
Inserts from A, B and C were compared in a wet milling test in a rather highly alloyed steel (HB=310). Two parallel bars each of a thickness of 35 mm were centrally positioned relative the cutter body (diameter 100 mm ), and the bars were placed with an air gap of 10 mm between them.
The cutting data were:
    • Speed=150 m/min
    • Feed=0.40 mm/rev
    • Cutting depth 2 mm, single tooth milling with coolant.
Evaluated tool life expressed as cutting length of variant A according to the invention was 8200 mm and for variant B 6900 mm and finally for the standard variant C only 6100 mm. In this test the insert according to the invention with a bimodal WC grain size distribution, variant A, obtained the best result.
EXAMPLE 2
A. Inserts from the same batch as insert A in Example 1 above and
B. Inserts from the same batch as insert B in Example 1 above and
C. Inserts from the same batch as insert C in Example 1 above
were compared in a wet milling test in a low alloyed steel (SS 1650, HB=180). Two parallel bars each of a thickness 30 mm were centrally positioned relative the cutter body (diameter 100 mm). The bars were placed with an air gap of 10 mm between them.
The cutting data were:
    • Speed=285 m/min
    • Feed=0.38 mm/rev
    • Cutting depth 2 mm, single tooth milling with coolant.
Evaluated tool life expressed as cutting length of variant A according to the invention was 4800 mm and for variant B, 4200 mm and finally for the standard variant C only 3600 mm. In this test the insert according to the invention with a bimodal WC grain size distribution, variant A, performed best.
The principles, preferred embodiments and modes of operation of the present invention have been described in the foregoing specification. The invention is intended to be protected herein, however, is not to be construed as limited to the particular forms disclosed, since these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by those skilled in the art without departing from the spirit of the invention.

Claims (14)

1. A method of making a cemented carbide body comprising wet mixing without milling of at least two different WC-powders with deagglomerated powders of other carbides and a binder metal such that the WC-powers WC-powders are coated with the binder phase, said WC-grains being deagglomerated before and after being coated with binder metal, the grains of the WC-powder being classified in at least two groups in which a group of smaller grains has a maximum grain size amax and a group of larger grains has a minimum grain size bmin, each group containing at least 10% of the total amount of WC grains wherein bmin−amax >0.5 mm μm, the variation in grain size within each group being >1 μm, drying said mixture, pressing to a desired shape and sintering said pressed bodies.
2. The method of claim 1 wherein said other carbides comprise one or more of TiC, TaC and NbC.
3. The method of claim 1 wherein said sintered bodies are coated with an Al2O3 layer.
4. The method of claim 1 wherein said two groups of WC-powder have grain size distributions of 0-1.5 μm and 2.5-6.0 μm, respectively.
5. The method of claim 4 wherein the weight ratio of particles with a grain size distribution of 0-1.5 μm to 2.5-6.0 μm is from 0.25 to 4.0.
6. The method of claim 5 wherein said weight ratio is from 0.5-2.0.
7. The method of claim 1 wherein said sintered bodies have a CW-ratio of 0.82-1.0.
8. The method of claim 7 wherein said CW-ratio is 0.86-0.96.
9. The method of claim 3 wherein said sintered bodies have a CW-ratio of 0.82-1.0.
10. The method of claim 9 wherein said CW-ratio is 0.86-0.96.
11. The method of claim 4 wherein said sintered bodies have a CW-ratio of 0.82-1.0.
12. The method of claim 11 wherein said CW-ratio is 0.86-0.96.
13. The method of claim 5 wherein said sintered bodies have a CW-ratio of 0.82-1.0.
14. The method of claim 13 wherein said CW-ratio is 0.86-0.96.
US11/484,834 1996-07-19 1997-07-08 Cemented carbide body with increased wear resistance Expired - Lifetime USRE41646E1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE9602821A SE511817C2 (en) 1996-07-19 1996-07-19 Method and apparatus for determining the angular position of at least one axial optical asymmetry, and use of the method and apparatus, respectively.
SE9602821 1996-07-19
PCT/SE1997/001242 WO1998003690A1 (en) 1996-07-19 1997-07-08 Cemented carbide body with increased wear resistance

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US08/895,573 Expired - Lifetime US5850283A (en) 1996-07-19 1997-07-16 Determination of angular position of weak axial asymmetries of optical fibers and alignment of and splicing fibers

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SE0200569L (en) 2002-02-26 2003-10-23 Ericsson Telefon Ab L M Alignment of PM fibers
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SE511817C2 (en) 1999-11-29
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JPH10307227A (en) 1998-11-17
DE69738121T2 (en) 2008-06-12

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