CN1292862C - Method for adding carbon nanometer tube adjustable hard alloy carbon content - Google Patents
Method for adding carbon nanometer tube adjustable hard alloy carbon content Download PDFInfo
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- CN1292862C CN1292862C CNB2005100096185A CN200510009618A CN1292862C CN 1292862 C CN1292862 C CN 1292862C CN B2005100096185 A CNB2005100096185 A CN B2005100096185A CN 200510009618 A CN200510009618 A CN 200510009618A CN 1292862 C CN1292862 C CN 1292862C
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Abstract
The present invention relates to a method for adding a carbon nanometer tube so as to adjust hard alloy carbon contents, particularly to a method for adjusting hard alloy carbon contents, and the present invention belongs to the technical field of hard alloy materials. The method of the present invention comprises the following steps: calculating the quantity of the carbon nanometer tube which needs to be added according to a formula, pouring weighed carbon nanometer tube in a bunsen beaker with absolute alcohol solutions so as to carry out ultrasonic dispersion for a proper time, and then, pouring the solutions in hard alloy powder so as to carry out low-energy ball milling technology for a proper time; adding right quantity of surface active agents, and using inert gas or vacuum as protection; after finishing ball milling, carrying out vacuum drying so as to obtain uniform mixing powder of the hard alloy and the carbon nanometer tube. The method of the present invention solves the problem of the decarbonization of the hard alloy, and the carbon nanometer tube performs functions of strengthening and toughening the hard alloy and improving mechanical properties of hardness, strength, etc. of the hard alloy in an alloy structure. The present invention is suitable for decarbonization problems of hard alloy block bodies and coating layers.
Description
Technical field:
The present invention relates to a kind of method of adjusting the carbide alloy phosphorus content, belong to the Hardmetal materials field.
Background technology:
Carbide alloy is with refractory carbide (WC, TiC, Cr
2C
3Deng) be matrix, make a kind of heterogeneous composite material of binding agent with iron group metal (Co, Fe, Ni).Characteristics such as carbide alloy has the hardness height, wearability is good, mechanical strength is high, good corrosion resistance, as cutter, mould, wear-resisting, corrosion-resistant and exotic material etc., use very extensive in fields such as metal cutting processing, mine excavation, oil drilling, geological prospecting and defence and militaries.The carbide alloy of China is divided into five classes according to main component, and W-Co kind (symbol YG, composition WC, Co), tungsten titanium cobalt class (symbol YT, composition WC, TiC, Co), general-purpose alloy class (symbol YW, composition WC, TiC, TaC (NdC), Co), titanium carbide base class (symbol YN, composition TiC, Ni, Mo or Mo
2C) and steel knot class (symbol YE, composition WC or TiC, carbon steel or chrome-molybdenum steel or high-speed steel or nickel chromium stainless steel).
Carbide alloy mainly adopts the powder metallurgical technique preparation, and the performance of alloy sintered compact is very sensitive to the phosphorus content in the alloy bonding phase solid solution (being called the γ phase), and wherein yg-type carbide is the most responsive to phosphorus content, and other series hard alloy takes second place slightly.From phasor, γ phase regional smaller, the trace of carbon content changes the γ that all might cause sintered body and produces free carbon or hard crisp phase η phase in mutually in the sintering process.When carbon content was too high in the carbide alloy, can go out existing Seepage carbon phenomenon was free carbon, and generation black point-like or bunch shape graphite are mingled with in the alloy structure, cause hardness of alloy and intensity all to descend.Crossing when low when carbon content in the carbide alloy, can produce the decarburization phenomenon, produce hard crisp η phase in the alloy structure, often is the pitting of argenteous bright spot or recessed tadpole shape at the alloy section, causes the increase of alloy fragility.The present invention is primarily aimed at the problem of decarburization in the cemented carbide sintered body.
The cemented carbide sintered body phosphorus content is main relevant with two factors: the phosphorus content of original powder and oxygen content, the selection of sintering process.Cross when low when carbon content in the original carbide powder, can cause that the amount of liquid phase of powder press body under same sintering temperature reduces in the sintering process, thereby have influence on the mechanical property of alloy behind the sintering.Metal phase Co in the carbide alloy powder, Ni or Fe and WC, TiC, Cr
2C
3All may form oxide-film in carbide, powder thin more (as ultra-fine, nano hard alloy powder), the oxygen that exists with the oxide-film form is many more, can remove at initial stage of sintering with the oxygen that adsorbed gas exists, and the oxygen amount that is dissolved in the alloy powder seldom can be ignored.Carbon oxygen generation chemical reaction in sintering process generates carbon monoxide, and the alloy carbon content is reduced, and therefore more is easy to generate the decarburization phenomenon in the sintering of ultra-fine, nano hard alloy.In the production of carbide alloy, adopt vacuum-sintering at present, gas pressure sintering, sintering process such as high temperature insostatic pressing (HIP) are more general, adopt hot pressed sintering, and discharge plasma sinterings etc. at home and abroad also begin to grow up, and traditional hydrogen sintering is replaced.Owing to there has not been the deoxidation of hydrogen, can only rely on carbon to come deoxidation, cause that the carbon content of alloy reduces behind the sintering, thereby must improve the phosphorus content of carbide alloy.
Improve the carbide alloy carbon content following several approach is generally arranged: improve carbide (WC, TiC, Cr
2C
3) phosphorus content, adopt this method can only select the high carbide raw material of carbon content again for use, and avoid its oxidation in processing procedure as far as possible; Come carburetting by the kind (rubber, paraffin wax etc.) of selecting forming agent for use and the technology (hydrogen flowing quantity, temperature, time, programming rate etc.) that removes forming agent, but that this mode is controlled is inaccurate, can only be relied on experience; In the carbide alloy powder, add a small amount of hydrocarbon black powder, it is many that this mode is used in industrial production, and the mixed carbon raw material carbon black in the CEMENTED CARBIDE PRODUCTION is the imperfect combustion product of oil, is a kind of very thin powder, purity is very high, has the crystal structure of graphite to a certain extent.Though the method for above-mentioned several raising carbide alloy phosphorus content can improve the phosphorus content of alloy, they do not have the Strengthening and Toughening carbide alloy, increase substantially the effect of alloy mechanical property more greatly.
CNT (Carbon nanotubes) is the another kind of allotrope of carbon, is the typical case representative of nano material, is described as " king of nanometer ", and it is that Electronic Speculum expert by Japan found in 1991.CNT can be regarded as by hexagonal graphite cake and become 360 ° of tubular materials that curl and form, it has unique one dimension tubular structure, the internal diameter of pipe in several nanometers between tens nanometers, length can reach micron even centimeter scale, draw ratio is up to 1000 to 10000, and specific area is big, the heat endurance height, intensity, toughness height, percentage elongation, elastic modelling quantity are big.At present, the application of nanometer technology has been penetrated in some conventional industries, as: dyestuff, coating, food, chemical industry etc., but do not have more practical application in traditional Hardmetal materials field, major part is in conceptual phase.
Summary of the invention:
The object of the present invention is to provide a kind of phosphorus content that not only can improve in the carbide alloy, can also improve simultaneously the method for the interpolation carbon nanometer tube adjustable hard alloy carbon content of carbide alloy performance by a relatively large margin, a. in cemented carbide powder, add CNT, the addition of CNT calculates according to following formula, and total addition is less than the 1.0wt% of cemented carbide powder:
In the formula: the Cx-CNT is added weight; The weight of M-cemented carbide powder; The shared percentage by weight of total carbon that the Cn-carbide alloy requires; The shared percentage by weight of total carbon of Ca-carbide alloy reality; B. load weighted CNT is poured in the beaker that fills ethanol solution and reached suspended state, ultrasonic wave disperseed 0.5～5 hour, the ethanolic solution that will be mixed with CNT is then poured into and is carried out ball-milling treatment in the cemented carbide powder, the lauryl sodium sulfate of interpolation 0.1～1.0wt% and the odium stearate of 0.1～1.0wt% are as surfactant, inert gas or vacuum protection, adopt the low energy ball-milling technology, ratio of grinding media to material was at 5: 1～10: 1, ball milling speed is 100～250 rev/mins, 12～32 hours ball milling time; C. ball milling finishes, and the cemented carbide powder that is mixed with CNT is carried out vacuum drying treatment, promptly obtains being mixed with the cemented carbide powder product of CNT.The present invention has used nanometer technology and has transformed traditional carbide alloy industry, adopt CNT to adjust the phosphorus content of carbide alloy, not only can solve the decarburization problem of carbide alloy, and CNT also can play the Strengthening and Toughening carbide alloy, the effect of mechanical properties such as the hardness of raising carbide alloy, intensity in the carbide alloy tissue.The present invention is suitable for the decarburization problem of carbide alloy block and hard alloy coating.
Description of drawings:
Fig. 1 is the X-ray diffractogram of the WC-6Co carbide alloy of decarburization behind the sintering, Fig. 2 is the X-ray diffractogram that adds behind the WC-6Co sintering cemented carbide of CNT, Fig. 3 is the ESEM picture of the WC-6Co carbide alloy of decarburization behind the sintering, Fig. 4 is the surface sweeping Electronic Speculum picture that adds behind the WC-6Co sintering cemented carbide of CNT, Fig. 5 is the high resolution scanning Electronic Speculum picture that adds behind the WC-6Co sintering cemented carbide of CNT, and Fig. 6 is the WC-6Co carbide alloy of decarburization and the contrast schematic diagram of the mechanical property of the WC-6Co carbide alloy that adds CNT.
The specific embodiment:
The specific embodiment one: the interpolation process of present embodiment CNT is as follows: a. adds CNT in cemented carbide powder, and the addition of CNT calculates according to following formula, and total addition is less than the 1.0wt% of cemented carbide powder:
In the formula: the Cx-CNT is added weight; The weight of M-cemented carbide powder; The shared percentage by weight of total carbon that the Cn-carbide alloy requires; The shared percentage by weight of total carbon of Ca-carbide alloy reality; B. load weighted CNT is poured in the beaker that fills ethanol solution and reached suspended state, ultrasonic wave disperseed 0.5～5 hour, the ethanolic solution that will be mixed with CNT is then poured into and is carried out ball-milling treatment in the cemented carbide powder, the lauryl sodium sulfate of interpolation 0.1～1.0wt% and the odium stearate of 0.1～1.0wt% are as surfactant, inert gas or vacuum protection, the purity of inert gas is more than 99.99999%, adopt the low energy ball-milling technology, ratio of grinding media to material was at 5: 1～10: 1, ball milling speed is 100～250 rev/mins, 12～32 hours ball milling time; C. ball milling finishes, and the cemented carbide powder that is mixed with CNT is carried out vacuum drying treatment, promptly gets the purpose product.
The specific embodiment two: the interpolation process of present embodiment is as follows:
1) raw material adopts purity greater than 95% SWCN, and the diameter of CNT is between 1nm～10nm.
2) cemented carbide powder adopt various alloy powders all can, the granularity of powder is between 10 nanometers to 50 micron.
3) according to the weight that lacks carbon, calculate the addition of CNT according to following formula, general total addition should be less than 1.0% of cemented carbide powder weight:
In the formula: Cx-CNT additional amount (Kg); The weight of M-cemented carbide powder (Kg); The total carbon content (%) that the Cn-carbide alloy requires; The total carbon content (%) of Ca-carbide alloy reality.
4) adding method of CNT is the physics method: ultrasonic wave disperses and the low energy ball-milling technology, and chemical method: the method that the interpolation surfactant combines.Load weighted CNT is poured in the beaker that fills ethanol solution; ultrasonic wave disperseed one hour; the ethanolic solution that will be mixed with CNT is then poured into and is carried out ball-milling treatment in the cemented carbide powder; the lauryl sodium sulfate of interpolation 0.5wt% and the odium stearate of 0.5wt% are as surfactant; high purity inert gas or vacuum protection; the purity of inert gas will reach 99.99999%; adopt the low energy ball-milling technology; ratio of grinding media to material was at 5: 1～10: 1; ball milling speed is 100～250 rev/mins, 12～32 hours ball milling time.
5) ball milling finishes, and carries out vacuum drying treatment, promptly obtains being mixed with the cemented carbide powder of CNT; When utilizing gained powder preparation carbide alloy block, in powder, mix glue, compression moulding, sintering, the vacuum height of will trying one's best is lower than 6Pa when adopting vacuum-sintering, adopts inert gas such as Ar, N
2During the protection sintering, the purity of inert gas will reach 99.99999%; Perhaps utilize this powder to carry out coating process such as thermal spraying or plasma spraying, can obtain hard alloy coating.
The specific embodiment three: the interpolation process of present embodiment is as follows: the WC-6Co cemented carbide powder that 10Kg is arranged, the total carbon content that records alloy through sintering test and Co magnetic is 5.52wt%, with reference to Fig. 1, Fig. 3, Fig. 1 is the X-ray diffractogram of the WC-6Co carbide alloy of decarburization behind the sintering, wherein W
3C
3C is that η is the decarburization phase mutually, and the ESEM picture of the WC-6Co carbide alloy of decarburization behind Fig. 3 sintering detects to such an extent that carbon content is on the low side for 5.52wt%, and needed total phosphorus content is 5.81wt%, calculates according to formula:
Therefore need to add the CNT of 30.79 grams; the multi-walled carbon nano-tubes of load weighted diameter between 1nm～100nm poured in the beaker that fills ethanol solution in three batches; ultrasonic wave disperseed one hour; the ethanolic solution that will be mixed with CNT is then poured into and is carried out ball-milling treatment in the WC-6Co cemented carbide powder; the odium stearate of adding 50 lauryl sodium sulfate that restrain and 50 grams are as surfactant; adopt the protection of high-purity argon gas; ratio of grinding media to material is 8: 1; ball milling speed is 200 rev/mins, 24 hours ball milling time.
Ball milling finishes, and carries out vacuum drying and handles, and mixes forming agents such as paraffin wax, compression moulding, and gas pressure sintering, vacuum is 6Pa in the vacuum-sintering of last stage, gas that after-stage adds is that high-purity Ar gas purity will reach 99.99999%, obtains the carbide alloy block.Add tissue and performance such as Fig. 2 of the carbide alloy of CNT at last, 4,5, shown in 6, Fig. 2 is the X-ray diffractogram that adds behind the WC-6Co sintering cemented carbide of CNT, can be observed η disappears mutually, Fig. 4 adds the surface sweeping Electronic Speculum picture behind the WC-6Co sintering cemented carbide of CNT, organize densification more after adding CNT as can be seen, Fig. 5 is the high resolution scanning Electronic Speculum picture that adds behind the WC-6Co sintering cemented carbide of CNT, arrow is depicted as the CNT on the crystal boundary, Fig. 6 is the WC-6Co carbide alloy of decarburization and the contrast schematic diagram of the mechanical property of the WC-6Co carbide alloy that adds CNT, as seen hard and crisp (the hardness 93.5HRA of the alloy of decarburization, bending strength 1700MPa), hardness of alloy and intensity all have raising (hardness 94.2HRA, bending strength 2800MPa) by a relatively large margin after the interpolation CNT.
Claims (4)
1. method of adding carbon nanometer tube adjustable hard alloy carbon content, it is characterized in that the interpolation process is as follows: a. adds CNT in cemented carbide powder, the addition of CNT calculates according to following formula, and total addition is less than the 1.0wt% of cemented carbide powder:
In the formula: the Cx-CNT is added weight; The weight of M-cemented carbide powder; The shared percentage by weight of total carbon that the Cn-carbide alloy requires; The shared percentage by weight of total carbon of Ca-carbide alloy reality; B. load weighted CNT is poured in the beaker that fills ethanol solution and reached suspended state, ultrasonic wave disperseed 0.5～5 hour, the ethanolic solution that will be mixed with CNT is then poured into and is carried out ball-milling treatment in the cemented carbide powder, the lauryl sodium sulfate of interpolation 0.1～1.0wt% and the odium stearate of 0.1～1.0wt% are as surfactant, inert gas or vacuum protection, adopt the low energy ball-milling technology, ratio of grinding media to material was at 5: 1～10: 1, ball milling speed is 100～250 rev/mins, 12～32 hours ball milling time; C. ball milling finishes, and the cemented carbide powder that is mixed with CNT is carried out vacuum drying treatment, promptly gets the purpose product.
2. a kind of method of adding carbon nanometer tube adjustable hard alloy carbon content according to claim 1, the purity that it is characterized in that CNT is greater than 95%, and the diameter of CNT is between 1nm～100nm.
3. a kind of method of adding carbon nanometer tube adjustable hard alloy carbon content according to claim 1, the granularity that it is characterized in that described cemented carbide powder are between 10 nanometers to 50 micron.
4. according to claim 1,2 or 3 described a kind of methods of adding carbon nanometer tube adjustable hard alloy carbon content, the purity that it is characterized in that the inert gas that adopted is more than 99.99999%.
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| CN102719719B (en) * | 2012-07-17 | 2014-05-14 | 王永富 | Graphene-modified hard alloy and application thereof |
| CN102747243B (en) * | 2012-07-27 | 2014-06-04 | 王永富 | Process for preparing grapheme modified hard alloy |
| CN103014602A (en) * | 2012-12-14 | 2013-04-03 | 苏州新锐合金工具股份有限公司 | Processing method for eliminating carbon-lack defect of hard alloy products |
| CN115491536A (en) * | 2022-09-20 | 2022-12-20 | 重庆长安汽车股份有限公司 | Carbon nanotube reinforced hard alloy and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07242958A (en) * | 1994-03-07 | 1995-09-19 | Toshiba Tungaloy Co Ltd | Composition for powder metallurgy and its production |
| US5482670A (en) * | 1994-05-20 | 1996-01-09 | Hong; Joonpyo | Cemented carbide |
| CN1254628A (en) * | 1999-08-13 | 2000-05-31 | 武汉工业大学 | Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07242958A (en) * | 1994-03-07 | 1995-09-19 | Toshiba Tungaloy Co Ltd | Composition for powder metallurgy and its production |
| US5482670A (en) * | 1994-05-20 | 1996-01-09 | Hong; Joonpyo | Cemented carbide |
| CN1254628A (en) * | 1999-08-13 | 2000-05-31 | 武汉工业大学 | Industrilized process for preparing nm-class non-eta-phase compound powder of tungsten carbide and cobalt |
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