CN106378455A - Molybdenum alloy rotary metal pipe material and preparation method thereof - Google Patents
Molybdenum alloy rotary metal pipe material and preparation method thereof Download PDFInfo
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- CN106378455A CN106378455A CN201510460613.8A CN201510460613A CN106378455A CN 106378455 A CN106378455 A CN 106378455A CN 201510460613 A CN201510460613 A CN 201510460613A CN 106378455 A CN106378455 A CN 106378455A
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Abstract
The invention relates to a molybdenum alloy rotary metal pipe material and a preparation method thereof. The preparation method of the molybdenum alloy rotary metal pipe material comprises the steps of powder mixing conducted through a wet method, mist spraying and drying, pressure sintering, hydrogen annealing and machining. By means of powder mixing conducted through the wet method, a doping source can be distributed uniformly in a base body; and meanwhile, by means of the preparation method, the effects that the technological process is simplified, the material utilization rate is increased, and production cost is lowered can be achieved.
Description
Technical field
The invention belongs to metal material field is and in particular to a kind of method of molybdenum alloy rotating metallic tubing and its preparation, this molybdenum alloy rotating metallic tubing can be used for photovoltaic module, the manufacture of plane display module.
Background technology
When the non-renewable energy resources such as electric power, coal, oil signal for help repeatedly, when energy problem is increasingly becoming the bottleneck of restriction international community economic development, countries in the world find new energy solution one after another.Solar energy is the inexhaustible regenerative resource of the mankind, is also clean energy resource, does not produce any environmental pollution.Therefore, solar energy power generating can occupy the important seat of world energy sources consumption in the near future, not only will substitute part conventional energy resource, and will become the main body of world energy supplies.Tubulose molybdenio target can be used for the back electrode preparation of CIGS thin film solaode.The MoNa pipe target mixing Na element is greatly improved the open-circuit voltage of thin-film solar cells, improves conversion efficiency, therefore demand is increasing in whole solar energy industry chain.
In plane display industry, molybdenum alloy doped chemical can include Nb, W, T, Cr, Zr, V etc..Raising with people's living standard and expanding economy, the requirement more and more higher to flat faced display for more and more people, it is mainly manifested in maximization aspect and the quality aspect of flat faced display.And the maximization of flat faced display then requires the maximization of sputtered film, thus it requires the maximization of target, higher and higher requirement is proposed to the length of target.For meeting the requirement of length, the traditional technique being welded by several sections of short targets, weld seam has more fine structures and pore, causes the uneven of etching, and leads to the uneven consequence of coating layer thickness.And molybdenum target material is in welding region and its fragility, has and compare major rupture risk.High-quality flat pannel display, then require sputtered film to have the high density uniformity of comparison, uniform texture, the relatively low resistivity of ratio, thus be accomplished by high-quality rotary target material to ensure, and high-quality target then needs advanced production technology to ensure.
Patent of invention in publication number CN104087903A《Molybdenum sodium cast target and its manufacture method and molybdenum sodium target》In, employ mechanical batch mixing and sodium element is scattered in Mo substrate, uniformity cannot ensure, the stable homogeneous of performance after being prepared into thin film, cannot be ensured.Patent of invention in publication number CN103045925A《A kind of preparation technology of the tubular target of molybdenum sodium alloy rotatable sputtering》In, employ the molding densification process of sintering forging after isostatic cool pressing, technological process is longer, reduces stock utilization, improves cost.Patent of invention in publication number CN103302295A《The method of producing molybdenum alloy sputtering target for flat-panel display by using hot isostatic press》In, carry out the molding densification process of high temperature insostatic pressing (HIP) after employing isostatic cool pressing, technological process longer it is impossible to make revolving part.
Content of the invention
Based on above-mentioned deficiency of the prior art, the technical problem to be solved is to provide and a kind of enables to the molybdenum alloy rotating metallic tubing that doped source is evenly distributed in matrix, problem to be solved by this invention be provide one kind can simplification of flowsheet, improve stock utilization and reduce production cost molybdenum alloy rotating metallic tubing preparation method.
The present invention includes a kind of preparation method of molybdenum alloy rotating metallic tubing, and it comprises the steps：Step A, molybdenum powder and the adulterated flour containing doped source is mixed to form mixed powder, is subsequently added organic solvent and continues to be mixed to form serosity；Step B, serosity is placed in ball milling in tumbling ball mill；Step C, carries out secondary mist projection granulating using spray dryer to described ball milling disposed slurry, thus obtaining the molybdenum alloy powder of uniform doping；Step D, above-mentioned gained molybdenum alloy powder is directly loadable into pipe and adopts mould jacket, be sintered densification under isotropism pressure condition；Step E, the pipe that sintering is obtained is annealed under hydrogen environment, the further homogenization of crystallite dimension, and oxygen content reduces further；Step F, is machined out obtaining molybdenum alloy rotating metallic tubing to the pipe after annealing.
Wherein, described adulterated flour contains titanium, niobium or sodium.
Wherein, the Ball-milling Time of described slurry was at 10～48 hours.
Wherein, 150～250 DEG C of described powder by spraying inlet temperature, 70～150 DEG C of outlet temperature.
Wherein, the pressure value of described pressure sintering is 20MPa～300MPa, and sintering temperature is not less than the 60% of alloy melting point.
Wherein, described annealing temperature is not less than the 60% of pressure sintering temperature, and the time is 1～10 hour.
Brief description
Fig. 1 is the molybdenum alloy rotating metallic tubing process chart of the present invention.
Specific embodiment
Below in conjunction with accompanying drawing, embodiment of the present invention is further elaborated.
Embodiment 1：
1. purity is more than the molybdenum powder of 3N5 and the doped source containing niobium element is mixed to form mixed powder, the wherein mass percent of niobium element is 10%wt.It is subsequently added ethanol to continue to be mixed to form serosity.
2. serosity is placed in ball milling 12 hours in tumbling ball mill.
3. using closed cycle spray drying machine, described slurry is carried out with secondary mist projection granulating, the inlet temperature of spray dryer is 160 DEG C, and outlet temperature is 140 DEG C, thus obtaining niobium element doping uniform molybdenum alloy powder.
4. above-mentioned gained molybdenum alloy powder is directly loadable into pipe and adopts mould jacket, be sintered densification under isotropism pressure condition, sintering pressure is set as 280Mpa, 1500 DEG C of sintering temperature.
5. the pipe obtaining sintering is annealed under hydrogen environment, the further homogenization of crystallite dimension, and oxygen content reduces further, 1200 DEG C of annealing temperature, and annealing time keeps 8 hours.
6. using water base processing, molybdenum alloy metal tube is machined out, suitably sized to obtain.
Through measuring, its density is 9.9g cm to gained metal tube-3, content of niobium 9.8wt%, oxygen content 600ppm, hydrogen content ＜ 10ppm.
Embodiment 2：
1. purity is more than the molybdenum powder of 3N5 and the doped source containing titanium elements is mixed to form mixed powder, the wherein mass percent of titanium elements is 5%wt.It is subsequently added ethanol to continue to be mixed to form serosity.
2. serosity is placed in ball milling 40 hours in tumbling ball mill.
3. using closed cycle spray drying machine, described slurry is carried out with secondary mist projection granulating, the inlet temperature of spray dryer is 200 DEG C, and outlet temperature is 120 DEG C, thus obtaining niobium element doping uniform molybdenum alloy powder.
4. above-mentioned gained molybdenum alloy powder is directly loadable into pipe and adopts mould jacket, be sintered densification under isotropism pressure condition, sintering pressure is set as 200Mpa, 1300 DEG C of sintering temperature.
5. the pipe obtaining sintering is annealed under hydrogen environment, the further homogenization of crystallite dimension, and oxygen content reduces further, 1000 DEG C of annealing temperature, and annealing time keeps 6 hours.
6. using water base processing, molybdenum alloy metal tube is machined out, suitably sized to obtain.
Through measuring, its density is 9.5g cm to gained metal tube-3, Ti content 4.8wt%, oxygen content 450ppm, hydrogen content ＜ 10ppm.
Embodiment 3：
1. purity is more than the molybdenum powder of 3N5 and the doped source containing sodium element is mixed to form mixed powder, the wherein mass percent of sodium element is 2%wt.It is subsequently added ethanol to continue to be mixed to form serosity.
2. serosity is placed in ball milling 24 hours in tumbling ball mill.
3. using closed cycle spray drying machine, described slurry is carried out with secondary mist projection granulating, the inlet temperature of spray dryer is 230 DEG C, and outlet temperature is 80 DEG C, thus obtaining niobium element doping uniform molybdenum alloy powder.
4. above-mentioned gained molybdenum alloy powder is directly loadable into pipe and adopts mould jacket, be sintered densification under isotropism pressure condition, sintering pressure is set as 40Mpa, 1000 DEG C of sintering temperature.
5. the pipe obtaining sintering is annealed under hydrogen environment, the further homogenization of crystallite dimension, and oxygen content reduces further, 700 DEG C of annealing temperature, and annealing time keeps 4 hours.
6. using anhydrous processing, molybdenum alloy metal tube is machined out, suitably sized to obtain.
Through measuring, its density is 7.9g cm-3 to gained metal tube, sodium content 1.8wt%, oxygen content 6.0%, hydrogen content ＜ 10ppm.
Above example is only used for the present invention is specifically described, and it does not play any restriction effect to protection scope of the present invention, and protection scope of the present invention is determined by claim.According to techniques known and technical scheme disclosed in this invention, can derive or association goes out many flexible programs, all these flexible programs, also being regarded as is protection scope of the present invention.
Claims (6)
1. a kind of preparation method of molybdenum alloy rotating metallic tubing is it is characterised in that comprise the steps：
Step A, molybdenum powder and the adulterated flour containing doped source is mixed to form mixed powder, is subsequently added organic solvent and continues to be mixed to form serosity；
Step B, serosity is placed in ball milling in tumbling ball mill；
Step C, carries out secondary mist projection granulating using spray dryer to described ball milling disposed slurry, thus obtaining the molybdenum alloy powder of uniform doping；
Step D, above-mentioned gained molybdenum alloy powder is directly loadable into pipe and adopts mould jacket, be sintered densification under isotropism pressure condition；
Step E, the pipe that sintering is obtained is annealed under hydrogen environment, the further homogenization of crystallite dimension, and oxygen content reduces further；
Step F, is machined out obtaining molybdenum alloy rotating metallic tubing to the pipe after annealing.
2. molybdenum alloy rotating metallic tubing according to claim 1 preparation method it is characterised in that：Described adulterated flour contains titanium, niobium or sodium.
3. molybdenum alloy rotating metallic tubing according to claim 1 preparation method it is characterised in that：The Ball-milling Time of slurry was at 10～48 hours.
4. molybdenum alloy rotating metallic tubing according to claim 1 preparation method it is characterised in that：150～250 DEG C of powder by spraying inlet temperature, 70～150 DEG C of outlet temperature.
5. molybdenum alloy rotating metallic tubing according to claim 1 preparation method it is characterised in that：The pressure value of pressure sintering is 20MPa～300MPa, and sintering temperature is not less than the 60% of alloy melting point.
6. molybdenum alloy rotating metallic tubing according to claim 1 preparation method it is characterised in that：Annealing temperature is not less than the 60% of pressure sintering temperature, and the time is 1～10 hour.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181826A (en) * | 2011-03-28 | 2011-09-14 | 扬州大学 | Gallium-molybdenum-codoped indium tin oxide ceramic target, gallium-molybdenum-codoped indium tin oxide transparent conductive film and preparation method |
| CN102597301A (en) * | 2009-10-26 | 2012-07-18 | 株式会社爱发科 | Method of manufacturing titanium-containing sputtering target |
| CN102806353A (en) * | 2012-08-17 | 2012-12-05 | 苏州晶纯新材料有限公司 | Production method of molybdenum alloy tube target |
| CN103014638A (en) * | 2011-09-26 | 2013-04-03 | 日立金属株式会社 | MoTi target material and method for manufacturing for the same |
| CN103045925A (en) * | 2013-01-29 | 2013-04-17 | 洛阳高新四丰电子材料有限公司 | Preparation process of sputtered rotary molybdenum-sodium-alloy tubular target |
| JP2013083000A (en) * | 2011-09-28 | 2013-05-09 | Hitachi Metals Ltd | METHOD OF MANUFACTURING SINTERED Mo ALLOY SPUTTERING TARGET MATERIAL |
| CN103740979A (en) * | 2013-12-30 | 2014-04-23 | 安泰科技股份有限公司 | Preparation method of molybdenum titanium alloy material with high density, large size and high homogeneity |
| WO2014171161A1 (en) * | 2013-04-15 | 2014-10-23 | Jx日鉱日石金属株式会社 | Sputtering target |
| WO2015012437A1 (en) * | 2013-07-23 | 2015-01-29 | 희성금속 주식회사 | Tantalum target for sputtering having micro crystalline particles and manufacturing method therefor |
| TW201504450A (en) * | 2013-07-26 | 2015-02-01 | shu-hua Xu | Method of making molybdenum alloy target |
| CN104611673A (en) * | 2013-11-04 | 2015-05-13 | 许舒华 | Manufacture method of molybdenum alloy target material |
-
2015
- 2015-07-31 CN CN201510460613.8A patent/CN106378455A/en active Pending
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102597301A (en) * | 2009-10-26 | 2012-07-18 | 株式会社爱发科 | Method of manufacturing titanium-containing sputtering target |
| CN102181826A (en) * | 2011-03-28 | 2011-09-14 | 扬州大学 | Gallium-molybdenum-codoped indium tin oxide ceramic target, gallium-molybdenum-codoped indium tin oxide transparent conductive film and preparation method |
| CN103014638A (en) * | 2011-09-26 | 2013-04-03 | 日立金属株式会社 | MoTi target material and method for manufacturing for the same |
| JP2013083000A (en) * | 2011-09-28 | 2013-05-09 | Hitachi Metals Ltd | METHOD OF MANUFACTURING SINTERED Mo ALLOY SPUTTERING TARGET MATERIAL |
| CN102806353A (en) * | 2012-08-17 | 2012-12-05 | 苏州晶纯新材料有限公司 | Production method of molybdenum alloy tube target |
| CN103045925A (en) * | 2013-01-29 | 2013-04-17 | 洛阳高新四丰电子材料有限公司 | Preparation process of sputtered rotary molybdenum-sodium-alloy tubular target |
| WO2014171161A1 (en) * | 2013-04-15 | 2014-10-23 | Jx日鉱日石金属株式会社 | Sputtering target |
| WO2015012437A1 (en) * | 2013-07-23 | 2015-01-29 | 희성금속 주식회사 | Tantalum target for sputtering having micro crystalline particles and manufacturing method therefor |
| TW201504450A (en) * | 2013-07-26 | 2015-02-01 | shu-hua Xu | Method of making molybdenum alloy target |
| CN104611673A (en) * | 2013-11-04 | 2015-05-13 | 许舒华 | Manufacture method of molybdenum alloy target material |
| CN103740979A (en) * | 2013-12-30 | 2014-04-23 | 安泰科技股份有限公司 | Preparation method of molybdenum titanium alloy material with high density, large size and high homogeneity |
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Effective date of registration: 20170829 Address after: 100101, No. 14, building 1, 7, 101, 0801, 3, building 8, building No. 2, West Beichen Road, Chaoyang District, Beijing Applicant after: Chinese LIAN mobile energy investment Limited Address before: 100101 Beijing, Beichen West Road, No. 8, Beichen Century Center, block B, floor 10, Applicant before: Hanergy New materials Technology Co., Ltd. |
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Application publication date: 20170208 |