Background technology
Himet, with titanium carbide (TiC) be main component, nickel molybdenum is the Wimet that Binder Phase is made.Be also called sintering metal Wimet.It has the feature such as high rigidity, high-wearing feature, is mainly used in the machining of various steel, also can be used as wear-resisting, anti-corrosion part; And facing exhaustion, as the substitute of wolfram varbide along with Wimet main raw material-tungsten resource---the application of titanium carbide is more and more by the concern of people.The processing method of current titanium carbide (TicC) CEMENTED CARBIDE PRODUCTION is by TiC, Ni and Mo (or Mo
2c) carry out wet-milling together, pressed compact carries out liquid phase sintering usually in vacuum at 1300 ~ 1500 DEG C; Also infiltration method and self-propagating high-temperature synthesis method can be adopted to produce.
Infiltration method is adopted to produce TiC-Mo2C%26mdash; During Ni alloy, produce titanium carbide (TiC) porous sintered body (skeleton) in advance, then use Ni%26mdash; Mo melt infiltration skeleton, thus form dense sintering body; Self-propagating high-temperature synthesis method is adopted to produce TiC-Mo2C%26mdash; During Ni alloy, titanium valve, carbon black, molybdenum powder and nickel powder are carried out batching ball milling, drying and pressure group, then in graphite mo(u)ld, carry out self-propagating high-temperature building-up reactions, and combustion wave by revolve afterwards add 0.05MN load under keep 6 ~ 10s.TiCN Wimet is in fact the mutation of Tic Wimet, its reparation technology is substantially the same, comprise the preparation of compound, shaping, sintering or hot pressing, time prepared by compound, Tic and TiN both can the form of TiC and TiN mixture add, can also the form of Ti (C, N) sosoloid add.
But existing TiC base alloy not only intensity is high and wear no resistance, by researching and analysing discovery, this is mainly because titanium carbide can not be moistening by cobalt (Co) nickel (Ni) very well, so titanium carbide is difficult to fully and nickel (Ni) forms sosoloid in sintering process.Therefore, how to improve TiC base alloy bending strength and just become with wear resistance the gordian technique needing to capture.In addition, because the production of TiC is by TiO
2+ C produces in High Temperature Furnaces Heating Apparatus.The C added is TiO
2the reductive agent of middle oxygen, reacts with Ti again simultaneously and generates TiC.Because technique limit, the TiC produced not only oxygen is high, and uncombined carbon also quite high (being generally 0.4%-0.6%).And uncombined carbon height also alloy produce unfavorable, alloy can be caused to occur graphite-phase and have a strong impact on the wear resistance of alloy.But reduce TiC Free Carbon and have suitable difficulty; be difficult to continue to react with TiC under normal alloy sintering temperature produce the high TiC of combined carbon; but the carbonization again of other metals can not be added separately; because one is that cost can increase; two is produce that the line is busy can extend, and three is that TiC crystal grain can be grown up and affect the wear resistance of alloy.Therefore be necessary to be studied further.
Find some document materials about TiC base alloy by pertinent literature retrieval, mainly contain relevant to the technology of the present invention is following:
1, the patent No. is CN201110256852.3, denomination of invention is the Chinese invention patent of " a kind of with cobalt nickel titanium carbide-titanium carbide tungsten basal body light hard alloy that is Binder Phase and preparation method thereof ", which disclose a kind of with cobalt nickel titanium carbide-titanium carbide tungsten basal body light hard alloy that is Binder Phase and preparation method thereof, be intended to solve that existing use wolfram varbide substitute exists that Wimet property indices declines, alloy substrate oxidation-resistance and corrosion stability is poor, production cost high-technology problem.What adopted is a kind of titanium carbide-titanium carbide tungsten basal body light hard alloy being Binder Phase with cobalt nickel, the composition containing, for example lower weight ratio: Ti17.24%-43.65%; Ni2.23%-9.68%; Co5.23%-10.51%; W27.37%-57.62%; C10.27%-13.87%.
2, the patent No. is CN201010524049.9, denomination of invention is the Chinese invention patent of " a kind of take nickel-molybdenum alloy as titanium carbide base hard alloy of binding agent and preparation method thereof ", which disclosing a kind of take nickel-molybdenum alloy as titanium carbide base hard alloy of binding agent and preparation method thereof, wherein titanium carbide base hard alloy is made up of following raw material by mass percentage: nickel powder is 13-20%, molybdenum powder is 7-10%, and surplus is carbonized titanium powder; Its preparation method nickel powder, molybdenum powder and carbonized titanium powder is added filtration after wet-milling, drying in ball mill, then paraffin is added, dry also compression molding after stirring, shaping being placed in hydrogen atmosphere is incubated 2-3 hour in 300-500 DEG C, with being placed on vacuum tightness 1 × 10-2-5 × 10-2Pa, sintering 1-1.5 hour under the condition of temperature 1400-1450 DEG C and obtaining finished product.Alloy material hardness prepared by the present invention is high, wear resistance, good corrosion resistance, and strategic resource consumes low, and porosity is low and cost performance is high, can be used for (partly) precision work of soft steel continuous cutting, also can be used as the body material of diamond-coated tools.
3, the patent No. is CN201010102226.4, the Chinese invention patent that denomination of invention is " a kind of method reducing titanium carbide and titanium nitride powder oxygen level ", which disclose a kind of method reducing titanium carbide and titanium nitride powder oxygen level, solid titanium carbide and solid titanium nitride powder are placed in trichloromethane liquid respectively, two pressed powders and trichloromethane liquid volume are than between 1: 1 ~ 10, titanium carbide treatment temp is 35 ~ 61.7 DEG C, titanium nitride temperature is 40 ~ 60 DEG C, after bubble-free produces, treating processes terminates.The present invention's trichloromethane chemical process removes the titanium dioxide TiO2 oxide film of titanium carbide and titanium nitride powder particle surface, the oxygen level of powder is reduced, solves because powder is in the problem that base titanium carbonitride porosity is high and mechanical property is low storing and occur in transportation to be oxidized the preparation caused.
Although above-mentioned patent all relates to titanium carbide base hard alloy and preparation method thereof, but be all adopt conventional titanium carbide powder to prepare alloy, although patent 1 and 2 refer to add nickelalloy to change alloy property, but all add in making processes, still effectively solving titanium carbide can not very well by problem that cobalt (Co) nickel (Ni) is moistening, so the titanium carbide base hard alloy made according to these patents still exists the not high and deficiency worn no resistance of intensity, be necessary to be studied further this.
Summary of the invention
Technical problem to be solved by this invention is can not very well by deficiency that cobalt (Co) nickel (Ni) is moistening for the titanium carbide of existing making titanium carbide base hard alloy, a kind of new titanium carbide base hard alloy making method is provided, adopt the method can effectively change titanium carbide base hard alloy make titanium carbide can not very well by problem that cobalt (Co) nickel (Ni) is moistening.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of titanium carbide base hard alloy making method, employing vaccum sintering process makes, and carbonized titanium powder, nickel powder are carried out wet-milling together with molybdenum powder, and pressed compact carries out liquid phase sintering usually in vacuum at 1300 ~ 1500 DEG C; Its feature is, in present raw-material preparation, part of nickel (Ni) is added in titanium carbide (TiC) powder, described titanium carbide (TiC) powder is made to be containing the mixing raw material of titanium carbide (TiC) with nickel (Ni) sosoloid, containing the titanium carbide (TiC) of volume percent 0.4%-6.7% and the sosoloid of nickel (Ni) in described titanium carbide raw material.
Further, described molybdenum powder is the mixture of molybdenum (Mo) and molybdenum carbide (Mo2C); Molybdenum (Mo) and molybdenum carbide (Mo
2c) both blending ratios are 1:1-10; Namely partly or entirely make the Mo2C of alloying ingredient into Mo powder according to the number of TiC Free Carbon, reaction equation is: 2Mo+C=Mo
2c, and the temperature of Mo powder carbonization is just in time the temperature of alloy production.So just well solve the impact of uncombined carbon height alloy, thus substantially increase the use properties of TiC base alloy.
Further, described titanium carbide base hard alloy making method at least comprises the following steps:
1, make in routine in the technique of titanium carbide, add the nickel (Ni) of volume percent 0.1%-2.6%, produce the compound carbonizing titanium valve body of the sosoloid of titanium carbide containing the 0.4%-6.7% accounting for total powder and nickel.
2, compound carbonizing titanium valve body is mixed with nickel and molybdenum the mixed powder being placed in ball mill wet-milling and becoming to mix;
3, the mixed powder of milled is placed in settler to precipitate, elimination moisture, then is placed in oven dry in loft drier;
4, the powder after oven dry is broken into pieces, form alloy compound;
5, alloy compound is placed in wiping screen(ing) machine and joins glue mixing, formed containing glue compound;
6, will be placed under press according to desired shape compression moulding containing glue compound;
7, be placed in sintering oven by the blank of compression moulding again, vacuum sintering is shaping;
8, the blank sintered is made finished product by precision work.
Further, the Ball-milling Time of described step 1 is 35-38 hour, grind come diameter of particle at 200-300 order; Described ball mill is tilting-type ball mill.
Further, the wet-milling of described step 1 refers to carries out ball milling in spirituous solution.
Further, it is suppress under press more than 16 tons that the press of described step 3 is pressed into blank, compacting.
Further, during the vacuum sintering of described step 4, fill multiple shielding gas to sintering oven, whole sintering is carried out under the protection of many atmosphere.
In made titanium carbide alloy, the proportioning of each composition is as follows:
Titanium carbide 86-89%
Nickel (Ni) 6-8%
Molybdenum (Mo) and molybdenum carbide (Mo
2c) mixture 4-6%
All the other are impurity
Wherein: molybdenum (Mo) and molybdenum carbide (Mo
2c) blending ratio is 1:1-10.
The present invention is by adopting the titanium carbide powder of the sosoloid containing titanium carbide and nickel, and molybdenum (Mo) and molybdenum carbide (Mo
2c) mixing molybdenum powder; and be filled with many atmosphere protections when sintering; substantially increase the solid solubility of titanium carbide and nickel in Himet; and the oxygen level of the Himet made is very low; efficiently solve titanium carbide base hard alloy making titanium carbide and very well by the problem that cobalt (Co) nickel (Ni) is moistening, intensity and the hardness of titanium carbide base hard alloy can not be improve.
Embodiment
Below will the present invention will be further described by the drawings and specific embodiments, the object, technical solutions and advantages of the present invention can be well understood to further.But they are not limitation of the invention.
Fig. 1 illustrates a process flow diagram of the present invention, can be found out by accompanying drawing, the present invention relates to a kind of titanium carbide base hard alloy making method, employing vaccum sintering process makes, carbonized titanium powder, nickel powder are carried out wet-milling together with molybdenum powder, and pressed compact carries out liquid phase sintering usually in vacuum at 1400 ~ 1500 DEG C; Its feature is, in present raw-material preparation, part of nickel (Ni) is added in titanium carbide (TiC) powder, described titanium carbide (TiC) powder is made to be containing the mixing raw material of titanium carbide (TiC) with nickel (Ni) sosoloid, containing the titanium carbide (TiC) of volume percent 0.4%-6.7% and the sosoloid of nickel (Ni) in described titanium carbide raw material.
Further, described molybdenum powder is molybdenum (Mo) and molybdenum carbide (Mo
2c) mixture; Molybdenum (Mo) and molybdenum carbide (Mo
2c) both blending ratios are 1:1-10; Namely according to the number of TiC Free Carbon by the Mo of alloying ingredient
2c partly or entirely makes Mo powder into, and reaction equation is: 2Mo+C=Mo
2c, and the temperature of Mo powder carbonization is just in time the temperature of alloy production.So just well solve the impact of uncombined carbon height alloy, thus substantially increase the use properties of TiC base alloy.
Further, described titanium carbide base hard alloy making method at least comprises the following steps:
1, make in routine in the technique of titanium carbide, add the nickel (Ni) of volume percent 0.1%-2.6%, produce the compound carbonizing titanium valve body of the sosoloid of titanium carbide containing the 0.4%-6.7% accounting for total powder and nickel.
2, compound carbonizing titanium valve body is mixed with nickel and molybdenum the mixed powder being placed in ball mill wet-milling and becoming to mix;
3, the mixed powder of milled is placed in settler to precipitate, elimination moisture, then is placed in oven dry in loft drier;
4, the powder after oven dry is broken into pieces, form alloy compound;
5, alloy compound is placed in wiping screen(ing) machine and joins glue mixing, formed containing glue compound;
6, will be placed under press according to desired shape compression moulding containing glue compound;
7, be placed in sintering oven by the blank of compression moulding again, vacuum sintering is shaping;
8, the blank sintered is made finished product by precision work.
Further, the Ball-milling Time of described step 1 is 35-38 hour, grind come diameter of particle at 200-300 order; Described ball mill is tilting-type ball mill.
Further, the wet-milling of described step 1 refers to carries out ball milling in spirituous solution.
Further, it is suppress under press more than 16 tons that the press of described step 3 is pressed into blank, compacting.
Further, during the vacuum sintering of described step 4, fill multiple shielding gas to sintering oven, whole sintering is carried out under the protection of many atmosphere.
In made titanium carbide alloy, the proportioning of each composition is as follows:
Titanium carbide 86-89%
Nickel (Ni) 6-8%
Molybdenum (Mo) and molybdenum carbide (Mo
2c) mixture 4-6%
All the other are impurity
Wherein: molybdenum (Mo) and molybdenum carbide (Mo
2c) blending ratio is 1:1-10.
The present inventor is by carefully studying discovery, TiC Wimet is the same with WC-Co hard alloy, the weave construction of alloy and performance depend on the formation of %26delta (Tic)+%26gamma (Ni) two-phase region to a great extent, carbon content is too high or too low all can generate the 3rd phase %26theta phase (uncombined carbon) or %26epsilon phase (TiNi3), and material property is obviously reduced.This situation is also adapted to add molybdenum (or Mo
2c) TiC%26mdash; Ni Wimet, along with Mo
2the raising of C content, two-phase region is moved to low-carbon (LC) side, and the width of two-phase region also increases.The performance of TiC%26mdashMo%26mdashNi Wimet, even if be also subject to nickel content, Mo within the scope of two-phase region
2the impact of C content, carbide amount and %26gamma phase composition (alloy carbon content), Carbide size, textural defect and size thereof.The density of TiC Wimet is a very responsive performance, and density reduces slightly, and alloy property can be made obviously to decline.In TiC%26mdashMo%26mdashNi alloy, when molybdenum content one timing, increase the rising of alloy bending strength, hardness decline with nickel content; When nickel content one timing, alloy bending strength and hardness increase with molybdenum content and improve, and after molybdenum content is increased to certain limit, the intensity of alloy and hardness then increase with molybdenum content and reduces.When the carbon content of alloy is 94% ~ 96% of theoretical content, alloy has the highest intensity and hardness value.
Therefore making TiC Wimet to give one's full attention to following some:
The first, the oxygen of TiC is low.TiC is in the production technique of carbon tube furnace, and its reactive chemistry equation is: TiO
2+ 3C=TiC+2CO ↑.Because the CO gas produced can not timely and effectively discharge, therefore, to a certain extent, above-mentioned reaction is reversible.Thus, the TiC oxygen level produced is general all about 0.5%.The alloy strength produced with the TiC that oxygen level is high is low, density is low and wear no resistance.
The second, because the wettability of cobalt nickel to TiC is poor, under normal alloy sintering temperature and time, the solid solubility of TiC and cobalt nickel (TiC base alloy mainly uses nickel) is not high.Therefore, the solid solubility improving TiC and nickel (Ni) improves a very important index of alloy strength and wear resistance.
In order to solve the problem, this invention takes following measures:
1, before production TiC Wimet, adopting the method that part Ni powder first adds, namely just with the addition of part Ni powder when producing TiC.Because the production of TiC is by TiO
2+ C has sintered in the carbon tube furnace of about 2300 degree.Like this except tiny segment Ni can volatilize, good sosoloid can be generated with TiC greatly.Thus the solid solubility of TiC and Ni is substantially increased.And in the production process of TiC, also suitably can reduce sintering temperature and reduce production cost.
2. in technique, according to the number of TiC Free Carbon by the Mo of alloying ingredient
2c, partly or entirely makes Mo powder into, and reaction equation is: 2Mo+C=Mo2C, and the temperature of Mo powder carbonization is just in time the temperature of alloy production.So just well solve the impact of uncombined carbon height alloy, not only greatly increase the bending strength of alloy, meanwhile, also substantially increase the wear resistance of alloy, thus substantially increase the use properties of TiC base alloy.Owing to making alloy bending strength and wear resistance greatly improve, thus greatly extend the use range of TiC base alloy.Traditional TiC base alloy is only applied to the workpiece of soft, low-loss.And by the present invention follow-on TiC base alloy owing to not using any wolfram varbide and tantalum carbide niobium, not only cost reduces (general is tradition 50%) greatly, and use range can expand 7 to 10 times.The almost trade mark alloy of YT30., YT15 and YT14 of complete alternative W-Co-Ti carbide alloy.
Embodiment one
A kind of titanium carbide base hard alloy making method, with compound carbonizing titanium valve body for main component, and adds appropriate nickel and molybdenum, makes titanium carbide base hard alloy by adopting vaccum sintering process; Carbonized titanium powder, nickel powder are carried out wet-milling together with molybdenum powder, and pressed compact carries out liquid phase sintering usually in vacuum at 1400 ~ 1500 DEG C; Its feature is, described titanium carbide (TiC) is containing the mixing raw material of titanium carbide (TiC) with nickel (Ni) sosoloid, containing the titanium carbide (TiC) of volume percent 0.4%% and the sosoloid of nickel (Ni) in described titanium carbide raw material.
In made titanium carbide base hard alloy, the proportioning of each composition is as follows:
Titanium carbide 89%
Nickel (Ni) 6%
The mixture 4% of molybdenum (Mo) and molybdenum carbide (Mo2C)
All the other are impurity
Wherein: molybdenum (Mo) and molybdenum carbide (Mo
2c) blending ratio is 1:1;
Make the titanium carbide production method of above-mentioned titanium carbide base hard alloy, at least comprise the following steps:
1, make in routine in the technique of titanium carbide, add the nickel (Ni) of volume percent 0.1%-2.6%, produce the compound carbonizing titanium valve body of the sosoloid of titanium carbide containing the 0.4%-6.7% accounting for total powder and nickel;
2, titanium carbide powder and nickel and molybdenum are mixed to be placed in alcohol be the mixed powder that the ball mill wet-milling of medium becomes to mix;
3, the mixed powder of milled is placed in settler to precipitate, elimination alcohol, then is placed in oven dry in loft drier;
4, the powder after oven dry is broken into pieces, form alloy compound;
5, alloy compound is placed in wiping screen(ing) machine and joins glue mixing, formed containing glue compound;
6, will be placed under press according to desired shape compression moulding containing glue compound;
7, be placed in sintering oven by the blank of compression moulding again, vacuum sintering is shaping;
8, the blank sintered is made finished product by precision work.
Further, the Ball-milling Time of described step 1 is 35-38 hour, grind come diameter of particle at 200-300 order; Described ball mill is tilting-type ball mill.
Further, the wet-milling of described step 1 refers to carries out ball milling in spirituous solution.
Further, it is suppress under press more than 16 tons that the press of described step 3 is pressed into blank, compacting.
Further, during the vacuum sintering of described step 4, nitrogen (N is filled to sintering oven
2), make whole sintering at nitrogen (N
2) protection under carry out.
Embodiment two
A kind of titanium carbide base hard alloy making method, with compound carbonizing titanium valve body for main component, and adds appropriate nickel and molybdenum, makes titanium carbide base hard alloy by adopting vaccum sintering process; Carbonized titanium powder, nickel powder are carried out wet-milling together with molybdenum powder, and pressed compact carries out liquid phase sintering usually in vacuum at 1400 ~ 1500 DEG C; Its feature is, described titanium carbide (TiC) is containing the mixing raw material of titanium carbide (TiC) with nickel (Ni) sosoloid, containing the titanium carbide (TiC) of volume percent 1.6% and the sosoloid of nickel (Ni) in described titanium carbide raw material.
In made titanium carbide base hard alloy, the proportioning of each composition is as follows:
Titanium carbide 86%
Nickel (Ni) 8%
Molybdenum (Mo) and molybdenum carbide (Mo
2c) mixture 5%
All the other are impurity
Wherein: molybdenum (Mo) and molybdenum carbide (Mo
2c) blending ratio is 1:5;
The titanium carbide production method making above-mentioned titanium carbide base hard alloy is the same with enforcement one.
Embodiment three
A kind of titanium carbide base hard alloy making method, is main component with titanium carbide, and adds appropriate nickel and molybdenum, makes titanium carbide base hard alloy by adopting vaccum sintering process; Carbonized titanium powder, nickel powder are carried out wet-milling together with molybdenum powder, and pressed compact carries out liquid phase sintering usually in vacuum at 1400 ~ 1500 DEG C; Its feature is, described titanium carbide (TiC) is containing the mixing raw material of titanium carbide (TiC) with nickel (Ni) sosoloid, containing the titanium carbide (TiC) of volume percent 1.2% and the sosoloid of nickel (Ni) in described titanium carbide raw material.
In made titanium carbide base hard alloy, the proportioning of each composition is as follows:
Titanium carbide 88%
Nickel (Ni) 7%
Molybdenum (Mo) and molybdenum carbide (Mo
2c) mixture 4%
All the other are impurity
Wherein: molybdenum (Mo) and molybdenum carbide (Mo
2c) blending ratio is 1:10;
The titanium carbide production method making above-mentioned titanium carbide base hard alloy is the same with enforcement one.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.