EP0563203B1 - Method of producing a sintered carbonitride alloy for intermittent machining of materials difficult to machine - Google Patents

Abstract

According to the invention there now is provided a method of producing a sintered titanium based carbonitride alloy with 3-25 weight-% binder phase with extremely good properties at intermittent machining of materials difficult to machine. The method relates to the use of a raw material comprising a complex cubic carbonitride containing the main part of the metals from groups IV and V of the periodic system and carbon and nitrogen to be found in the finished alloy whereby said alloy has the composition 0.86 </= XIV </= 0.97, 0.44 </= XC </= 0.55, where XIV is the molar ratio of the group IV elements of the alloy and XC is the molar ratio of carbon.

Description

• The present invention relates to a method of producing a sintered carbonitride alloy with titanium as main constituent particularly suited for intermittent machining of materials difficult to machine.
• Sintered carbonitride alloys based on mainly titanium usually referred to as cermets have during the last years increased their use at the expense of more traditional cemented carbide i.e. tungsten carbide based alloys.
• US 3,971,656 discloses the production of an alloy with a duplex hard constituent where the core has a high content of Ti and N and the surrounding rim has a lower content of these two elements which is compensated for by a higher content of group VI metals i.e. in principle Mo and W and by higher carbon content. The higher content of Mo, W and C has inter alia the advantage that the wetting against the binderphase is improved i.e. the sintering is facilitated. As a raw material a carbonitride of titanium and a group VI metal is used.
• By changing the raw material it is possible to vary the core-rim-composition. In e.g. Swedish Patent Specification 459 862 it is shown how it is possible to use (Ti,Ta)C as a raw material to get a duplex structure with cores with a high content of titanium and tantalum but low content of nitrogen. The surrounding rims have higher contents of group VI-metals, i.e. molybdenum and tungsten and higher contents of nitrogen than the cores. This leads inter alia to an improved resistance against plastic deformation.
• Furthermore, it has in Swedish Patent Application 8902306-3 been shown how by mixing various types of core-rim structures in one and the same alloy advantages and drawbacks can be balanced out in such a way that optimized alloys are obtained.
• EP-A-259192 discloses a sintered alloy comprising a mixed carbonitride of titanium and at least one element from the group consisting of group IV, V and VI elements except titanium in a binder phase based on Co and/or Ni. The alloy is produced by mixing powders of the hard constituents, heating the mixture in a nitrogen atmosphere at a temperature of at least the sintering temperature to form a complex carbonitride solid solution comprising also the group VI element(s), milling said solid solution to obtain a carbonitride powder which is mixed with Co and/or Ni and sintered.
• It has now turned out that unique structures as well as unique properties are obtained in producing sintered titaniumbased carbonitride alloys if one uses complex cubic carbonitride raw material consisting of metals from groups IV and V of the periodic system and carbon and nitrogen as the main part of the powder mixture such that >95% of the amount of the metals in the finished alloy come from the said complex carbonitride. At least two, preferably at least three from the groups IV and V metals are present in the finished sintered carbonitride alloy. Preferably all of the nitrogen shall be present in the mentioned carbonitride raw material.
• The invention is defined in claim 1.
• In particular, as the above-mentioned metals titanium and tantalum shall be present in the raw material according to the invention. Preferably also vanadium, niobium and suitably also zirconium and hafnium are present in the complex carbonitride form if they are part of the finished sintered alloy. Metals from group VI, Cr, Mo and W, shall, if they are present, be added as multiple carbides, single carbides and/or as metal+carbon.
• The raw material acording to the invention is produced directly by carbonitriding of the oxides of the metals or the metals themselves. As a result a carbonitride powder with essentially equiaxial grains and a narrow grain size distribution is obtained with a mean grain size of 0.8 - 3 µm, preferably 1 - 2 µm.
• As mentioned interesting properties of a sintered carbonitride alloy are obtained if the special raw materials according to this invention are used. Thus, it has turned out that a carbonitride alloy with extremely positive properties at intermittent machining of materials difficult to machine which materials have a tendency to clad if a raw material with e.g. the composition (Ti_0.93,Ta_0.07) (C_0.48,N_0.52) is used. This effect is further increased if in addition vanadium is added whereby the corresponding formula will be (Ti_0.88,Ta_0.06,V_0.06)(C_0.51,N_0.49). Corresponding inserts made from simple raw materials and in exactly the same equipment give considerably decreased properties in toughness inter alia greater scatter at the same wear resistance. This means that the reliability of such inserts is considerably decreased which means that they are not as efficient when producing with limited manning a production form with increased importance due to increasing labour costs.
• One of the reasons for this positive behaviour has turned out to be that a considerably lower porosity level is obtained with this complex raw material compared to conventional raw materials without having to use any other means such as HIP and this with even lower compaction pressure than for conventional material. This is a great advantage from production point of view inter alia due to reduced tool wear and considerably lower risk for unfavourable pressing cracks.
• The invention thus relates to a method of producing a titanium based carbonitride alloy with 3-25 % by weight binderphase based on Co, Ni and/or Fe using the above mentioned complex raw material. This raw material is milled together with carbides from group VI, if any, and binderphase elements and carbon addition, if any, and minor additions of e.g. TiC, TiN, TaC, VC or combinations thereof due to small deviations in composition of the complex raw material whereafter compaction and sintering, preferably in an inert atmosphere, is performed according to known technique.
• Fig 1 shows the 'window' in the composition diagram for Group IV-Group V - C-N, expressed in molar ratio, of the complex raw material which shows the above mentioned advantages in high magnification, whereas fig 2 shows where in the total molar ratio diagram this small area is situated.
• Group IV metals are Ti, Zr and/or Hf and Group V metals are V, Nb and/or Ta.
• As is evident from figure 1 the window comprises the composition area: $${\text{0.84≤ X}}_{\text{IV}}\text{≤ 0.97}$$

  

  $${\text{0.44≤ X}}_{\text{C}}\text{≤ 0.55}$$

  

  and in particular: $${\text{0.86≤ X}}_{\text{IV}}\text{≤ 0.95}$$

  

  $${\text{0.46≤ X}}_{\text{C}}\text{≤ 0.53}$$

  
• The latter restricted window can be divided into two, one without other group V metals than Ta: $${\text{0.905≤ X}}_{\text{IV}}\text{≤ 0.95}$$

  

  $${\text{0.46≤ X}}_{\text{C}}\text{≤ 0.53}$$

  

  and another one with other group V elements than Ta i.e. V and Nb: $${\text{0.86≤ X}}_{\text{IV}}\text{≤ 0.905}$$

  

  $${\text{0.46≤ X}}_{\text{C}}\text{≤ 0.53}$$

  
• Particularly good properties are obtained for the compositions $${\text{0 .91≤ X}}_{\text{IV}}\text{≤ 0.95}$$

  

  $${\text{0.46≤ X}}_{\text{C}}\text{≤ 0.50}$$

  

  respectively $${\text{0.86≤ X}}_{\text{IV}}\text{≤ 0.90}$$

  

  $${\text{0.49≤ X}}_{\text{C}}\text{≤ 0.53}$$

  
• For titanium the following applies x_Ti>0.7 preferably x_Ti>0.75.
• In the above given molar ratios for carbon and nitrogen usual amounts of oxygen may be present i.e. substitute carbon and nitrogen even if it is desirable to keep such amounts of oxygen low <0.8 %, preferably <0.5 %. The invention comprises stoichiometric as well as usually substoichiometric carbonitrides.
Example
• Titanium-based carbonitride alloys with 17.5 % Ni+Co binder phase were produced with the use of a complex raw material according to the invention (Ti_0.88, Ta_0.06, Nb_0.06) (C_0.51, N_0.49) as well as with the use of simple raw material: TiN, TiC and VC. In both cases also WC and Mo₂C were added in addition to Co and Ni. The following compaction pressure and porosity after milling and sintering to the same grain size were obtained:

  Compaction	Porosity	pressure, N/mm2
  Alloy according to the invention	A00	154
  Simple raw materials	A06-A08	206
  	B04

Claims (1)

1. Method of making a sintered titanium based carbonitride alloy for fine machining with 3 - 25 weight % binder phase by milling, pressing and sintering of a powder mixture according to known powder metallurgical technique in which the main part of said powder mixture is a complex cubic carbonitride powder consisting of metals from groups IV and V of the periodic system and carbon and nitrogen, more than 95 % of the amount of said metals in the finished alloy coming from said complex carbonitride and said complex carbonitride having the composition $${\text{0.86 ≤ X}}_{\text{IV}}\text{≤ 0.97}$$

   

   $${\text{0.44 ≤ X}}_{\text{C}}\text{≤ 0.55}$$

   

   wherein X_IV is the molar ratio of the group IV elements and X_C is the molar ratio of carbon, the complex carbonitride comprising essentially equiaxial grains with a narrow grain size distribution with a mean grain size of 0.8 - 3 µm, said complex carbonitride being produced directly by carbonitriding of the oxides of the metals or of the metals themselves.

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