CN114934207A - 一种制备高强高塑弥散强化钨合金的方法 - Google Patents
一种制备高强高塑弥散强化钨合金的方法 Download PDFInfo
- Publication number
- CN114934207A CN114934207A CN202210551592.0A CN202210551592A CN114934207A CN 114934207 A CN114934207 A CN 114934207A CN 202210551592 A CN202210551592 A CN 202210551592A CN 114934207 A CN114934207 A CN 114934207A
- Authority
- CN
- China
- Prior art keywords
- sintering
- powder
- tungsten
- plasticity
- tungsten alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 229910001080 W alloy Inorganic materials 0.000 title claims abstract description 40
- 238000005245 sintering Methods 0.000 claims abstract description 57
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 8
- 238000007731 hot pressing Methods 0.000 claims abstract description 8
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 230000006835 compression Effects 0.000 claims abstract description 5
- 238000007906 compression Methods 0.000 claims abstract description 5
- 230000009467 reduction Effects 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910052721 tungsten Inorganic materials 0.000 claims description 21
- 239000010937 tungsten Substances 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 150000003657 tungsten Chemical class 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 238000002490 spark plasma sintering Methods 0.000 claims description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005275 alloying Methods 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- -1 lanthanum (La) Chemical class 0.000 claims 1
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 238000000498 ball milling Methods 0.000 description 9
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 6
- 229910026551 ZrC Inorganic materials 0.000 description 6
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 5
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 206010010214 Compression fracture Diseases 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0031—Matrix based on refractory metals, W, Mo, Nb, Hf, Ta, Zr, Ti, V or alloys thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Powder Metallurgy (AREA)
Abstract
本发明提供了一种制备高强高塑弥散强化钨合金的方法，属于粉末冶金领域。具体制备方法为：以机械合金化法或湿化学法结合氢气还原制备纳米第二相粒子掺杂金属钨粉末；采用热等静压、热压烧结或多步放电等离子烧结技术制备高强高塑弥散强化钨合金。本方法制备的高强高塑弥散强化钨合金相对密度优选大于98.0％，晶粒尺寸优选小于2.0μm，室温压缩塑性甚至超过30.0％，室温压缩强度甚至超过5.0GPa，兼具强度和塑性。本方法的原料简单易得，工艺简单快捷，适合进行大规模生产。
Description
技术领域
本发明属于粉末冶金技术领域，涉及一种制备高强高塑弥散强化钨合金的方法。
背景技术
金属钨(W)是熔点(3390℃～3423℃)和沸点(5700±200℃)最高、蒸汽压最低的金属，此外，还具有高的密度(19.3g/cm3)、高的弹性模量和强度以及低的热膨胀系数等一系列优异特性，在现代国防、原子能、电真空等工程应用领域占有重要地位，在一些特殊高温应用领域具有不可取代的作用。但金属钨室温脆性大，且韧脆转变温度(DBTT)高，限制了金属钨的应用及其性能的充分发挥。提高金属钨的塑性对改善其加工性能及拓展其应用具有重要意义。
目前，弥散强化钨合金前驱粉体制备途径主要分为三种：固固掺杂法(S-S)、固液掺杂法(S-L)、液液掺杂法(L-L)。通常认为，L-L混合和S-L混合具有相对较好的混合效果，但是只能应用于氧化物弥散强化钨合金前驱体粉体的制备；S-S混合如机械合金化虽然会有杂质的引入，但它可以应用于各种第二相粒子弥散强化钨合金前驱体粉体的制备过程。
经过大量的实验探究，本发明中提供了一个高含量第二相粒子弥散强化钨合金的成分分布区间，在此成分分布区间通过所述方法制备的弥散强化钨合金会具有均衡的力学性能，兼具高强度和高塑性，其室温压缩断裂应变大于20.0％，室温压缩强度超过3.0GPa。并且在2000℃处理10h后，平均晶粒尺寸不超过5.0μm，甚至小于3.0μm，呈现出优异的热稳定性。
发明内容
本发明提供了制备高强高塑弥散强化钨合金的方法。具体工艺步骤如下：
(1)原料：湿化学法以可溶性的钨盐和第二相粒子源的可溶性金属盐为原料；机械合金化法以钨粉和第二相粒子粉末为原料。二者配比按照第二相粒子在金属钨中体积分数在3.0～40.0％之间计算。
(2)粉体制备：利用湿化学法将可溶性的钨盐和第二相粒子源的可溶性金属盐原位复合，制备出氧化钨与第二相粒子氧化物的复合前驱体粉体，将前驱体在氢气中600～1200℃范围内还原，制备出第二相粒子掺杂金属钨粉；利用高能球磨机将钨粉和第二相粒子粉末进行机械合金化，制备出第二相粒子掺杂金属钨粉。
(3)成形与烧结：步骤2得到的粉体在1200～2000℃范围内烧结，烧结技术采用热等静压烧结、热压烧结或多步放电等离子烧结技术，得到高强高塑弥散强化钨合金。
根据权利要求1所述高强高塑钨合金的制备方法，其特征在于步骤(1)所描述湿化学法原料中的第二相粒子源的可溶性金属盐为镧(La)、钇(Y)、铝(Al)、镥(Lu)、铈(Ce)、锆(Zr)、铪(Hf)、钍(Th)等金属盐中的至少一种；机械合金化法原料中的第二相粒子为氧化物(La2O3、Y2O3、Lu2O3、Ce2O3、Al2O3、ZrO2、ThO2、HfO2等)、碳化物(TiC、ZrC、TaC等)、氮化物(AlN、TiN、BN等)和硼化物(B4C、TiB2、ZrB2、HfB2等)中的至少一种。
根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(1)所描述可溶性钨盐和第二相粒子源的可溶性金属盐或钨粉和第二相粒子粉末的配比按照第二相粒子在金属钨中体积分数在3.0～40.0％之间计算，优选范围为6.0～20.0％。
根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(2)所描述的湿化学法制备的前驱体的优选还原温度区间为700～900℃，所得到还原粉末的平均粒径优选小于100nm；机械合金化所制备的第二相粒子掺杂金属钨粉的平均粒径优选小于100nm。
根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(3)所描述的热等静压烧结优选烧结条件为：在180～200MPa的压力下，1200～1500℃的温度下烧结，保温1～3h。
根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(3)所描述的热压烧结优选烧结条件为：在30～60MPa的压力下，1250～1600℃的温度下烧结，保温1～3h，烧结气氛为高真空。
根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(3)所描述的多步放电等离子烧结优选烧结条件为：首先升温至600～700℃，保温3～5min；随后升温至900～1100℃，保温3～5min；再升温至1200～1500℃，保温0.5～5min进行第三步烧结；升温速率为100℃/min；烧结过程中所加压力为40～60MPa，烧结气氛为高真空。
根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(1)～(3)所制备的钨合金：相对密度大于96.0％，相对密度优选大于98.0％；晶粒尺寸小于3.0μm，晶粒尺寸优选小于2.0μm；室温压缩塑性不低于20.0％，甚至超过30.0％；室温压缩强度不低于3.0GPa，甚至超过5.0GPa。
本方法采用高硬度的第二相粒子和金属钨基体复合设计，硬而细小弥散的第二相粒子在晶粒的长大过程中可以有效地阻碍晶界的迁移，从而细化晶粒；根据Orowan强化机制，在施加外力载荷时，弥散分布的第二相粒子可阻碍位错扩展，宏观上表现为材料硬度强度的提高。在这样的成分基础上，制粉工艺中的湿化学法可以满足氧化物第二相粒子弥散强化金属钨粉的制备，机械合金化法可以同时满足氧化物、碳化物、氮化物和硼化物等第二相粒子弥散强化金属钨粉的制备，弥补了湿化学方法的不足；烧结工艺采用了热等静压烧结、热压烧结或多步放电等离子烧结技术，快速高效的升温过程、较低的烧结温度及较短的保温时间，晶粒尺寸可得到有效的控制；加热和加压同时进行可以有效减少晶粒内部孔隙，提高致密度。
该方法的优点：1，采用的制粉工艺简单快捷，可以满足各种第二相粒子掺杂金属钨粉末的制备，粉末粒度细小，可同时进行大批量制粉，大幅减少了制粉所需的时间。2，采用的烧结技术均是加热和加压同时进行，粉末处于热塑性状态，形变阻力小，有助于颗粒的接触扩散、流动传质过程的进行，能有效降低烧结温度，缩短烧结时间，从而阻碍晶粒长大，得到晶粒细小、致密度高和机械性能良好的合金材料。3，与常用的制备方法得到的高塑性低强度或低塑性高强度钨合金相比，本发明所提供的钨合金具有优异的加工硬化能力和高强高塑特征，室温压缩断裂应变大于20.0％，室温压缩强度超过3.0GPa。4，本发明所提供的钨合金在2000℃处理10h后，平均晶粒尺寸不超过5.0μm，甚至小于3.0μm，呈现出优异的热稳定性。
具体实施方式
实施例1
以偏钨酸铵、硝酸镧、硝酸铵和甘氨酸为原料，偏钨酸铵和硝酸镧配比按照氧化镧在金属钨中体积分数在10.0％计算，硝酸铵和甘氨酸配比按照摩尔比1：2.5计算；将各种原料溶于水中配制成溶液，将溶液在200℃下加热，溶液发生挥发、浓缩、燃烧反应后得到前驱体粉末；将前驱体粉末在氢气中进行还原处理，还原温度为700℃，得到纳米氧化镧掺杂金属钨粉；在1500℃进行热压烧结，压力为40MPa，烧结气氛为高真空，保温2h，即可制备出氧化镧弥散强化钨合金。相对密度为98.3％，平均晶粒尺寸为1.3μm，材料的室温压缩强度为3.9GPa，压缩断裂应变25.1％。
实施例2
以偏钨酸铵、硝酸钇、硝酸铵和甘氨酸为原料，偏钨酸铵和硝酸钇配比按照氧化钇在金属钨中体积分数在10.0％计算，硝酸铵和甘氨酸配比按照摩尔比1：2.5计算；将各种原料溶于水中配制成溶液，将溶液在200℃下加热，溶液发生挥发、浓缩、燃烧反应后得到前驱体粉末；将前驱体粉末在氢气中进行还原处理，还原温度为700℃，得到纳米氧化钇掺杂金属钨粉；进行多步放电等离子烧结，首先升温至600℃，保温3min，随后升温至1000℃，保温3min，再升温至1450℃，保温5min进行第三步烧结，升温速率为100℃/min，烧结过程中所加压力为40MPa，烧结气氛为高真空，即可制备出氧化钇弥散强化钨合金。相对密度为99.1％，平均晶粒尺寸为0.8μm，材料的室温压缩强度为5.1GPa，压缩断裂应变33.7％。
实施例3
以偏钨酸铵、硝酸铝、硝酸铵和甘氨酸为原料，偏钨酸铵和硝酸铝配比按照氧化铝在金属钨中体积分数在10.0％计算，硝酸铵和甘氨酸配比按照摩尔比1：2.5计算；将各种原料溶于水中配制成溶液，将溶液在200℃下加热，溶液发生挥发、浓缩、燃烧反应后得到前驱体粉末；将前驱体粉末在氢气中进行还原处理，还原温度为700℃，得到纳米氧化铝掺杂金属钨粉；在1500℃进行热等静压烧结，压力为200MPa，保温2h，即可制备出氧化铝弥散强化钨合金。相对密度为98.8％，平均晶粒尺寸为1.1μm，材料的室温压缩强度为4.2GPa，压缩断裂应变29.9％。
实施例4
以钨粉和碳化钛粉为原料，钨和碳化钛配比按照碳化钛在金属钨中体积分数在10.0％计算；球料比为5：1，球磨介质无水乙醇，球磨转速为300rpm，球磨时间为24h，得到纳米碳化钛掺杂金属钨粉；在1500℃进行热压烧结，压力为40MPa，烧结气氛为高真空，保温2h，即可制备出碳化钛弥散强化钨合金。相对密度为97.8％，平均晶粒尺寸为1.4μm，材料的室温压缩强度为3.7GPa，压缩断裂应变23.6％。
实施例5
以钨粉和碳化锆粉为原料，钨和碳化锆配比按照碳化锆在金属钨中体积分数在10.0％计算；球料比为5：1，球磨介质无水乙醇，球磨转速为300rpm，球磨时间为24h，得到纳米碳化锆掺杂金属钨粉；进行多步放电等离子烧结，首先升温至600℃，保温3min，随后升温至1000℃，保温3min，再升温至1450℃，保温5min进行第三步烧结，升温速率为100℃/min，烧结过程中所加压力为40MPa，烧结气氛为高真空，即可制备出碳化锆弥散强化钨合金。相对密度为98.5％，平均晶粒尺寸为1.0μm，材料的室温压缩强度为4.1GPa，压缩断裂应变30.2％。
实施例6
以钨粉和氮化钛粉为原料，钨和氮化钛配比按照氮化钛在金属钨中体积分数在10.0％计算；球料比为5：1，球磨介质无水乙醇，球磨转速为300rpm，球磨时间为24h，得到纳米氮化钛掺杂金属钨粉；在1500℃进行热等静压烧结，压力为200MPa，保温2h，即可制备出氮化钛弥散强化钨合金。相对密度为98.0％，平均晶粒尺寸为1.1μm，材料的室温压缩强度为3.9GPa，压缩断裂应变27.5％。
Claims (7)
1.一种制备高强高塑弥散强化钨合金的方法，具体工艺步骤如下：
(1)原料：湿化学法以可溶性钨盐和第二相粒子源的可溶性金属盐为原料，第二相粒子源的可溶性金属盐为镧(La)、钇(Y)、铝(Al)、镥(Lu)、铈(Ce)、锆(Zr)、铪(Hf)、钍(Th)等金属盐中的至少一种，二者配比按照第二相粒子在金属钨中体积分数在3.0～40.0％之间计算；机械合金化法以钨粉和第二相粒子粉末为原料，第二相粒子为氧化物(La2O3、Y2O3、Lu2O3、Ce2O3、Al2O3、ZrO2、ThO2、HfO2等)、碳化物(TiC、ZrC、TaC等)、氮化物(AlN、TiN、BN等)和硼化物(B4C、TiB2、ZrB2、HfB2等)中的至少一种，二者配比按照第二相粒子在金属钨中体积分数在3.0～40.0％之间计算；
(2)粉体制备：利用湿化学法将步骤1的原料原位复合，制备出氧化钨与第二相粒子氧化物的复合前驱体粉体，将前驱体在氢气中600～1200℃范围内还原，制备出第二相粒子掺杂金属钨粉；利用高能球磨机将钨粉和第二相粒子粉末进行机械合金化，制备出第二相粒子掺杂金属钨粉；
(3)成形与烧结：步骤2得到的粉体在1200～2000℃范围内烧结，烧结技术采用热等静压烧结、热压烧结或多步放电等离子烧结技术，得到高强高塑弥散强化钨合金。
2.根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(1)所描述可溶性钨盐和第二相粒子源的可溶性金属盐或钨粉和第二相粒子粉末的配比按照第二相粒子在金属钨中体积分数在3.0～40.0％之间计算，优选范围为6.0～20.0％。
3.根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(2)所描述的湿化学法制备的前驱体的优选还原温度区间为700～900℃，所得到还原粉末的平均粒径优选小于100nm；机械合金化所制备的第二相粒子掺杂金属钨粉的平均粒径优选小于100nm。
4.根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(3)所描述的热等静压烧结优选烧结条件为：在180～200MPa的压力下，1200～1500℃的温度下烧结，保温1～3h。
5.根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(3)所描述的热压烧结优选烧结条件为：在30～60MPa的压力下，1250～1600℃的温度下烧结，保温1～3h，烧结气氛为高真空。
6.根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(3)所描述的多步放电等离子烧结优选烧结条件为：首先升温至600～700℃，保温3～5min；随后升温至900～1100℃，保温3～5min；再升温至1200～1500℃，保温0.5～5min进行第三步烧结；升温速率为100℃/min；烧结过程中所加压力为40～60MPa，烧结气氛为高真空。
7.根据权利要求1所述高强高塑弥散强化钨合金的制备方法，其特征在于步骤(1)～(3)所制备的钨合金：相对密度大于96.0％，相对密度优选大于98.0％；晶粒尺寸小于3.0μm，晶粒尺寸优选小于2.0μm；室温压缩塑性不低于20.0％，甚至超过30.0％；室温压缩强度不低于3.0GPa，甚至超过5.0GPa。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210551592.0A CN114934207A (zh) | 2022-05-20 | 2022-05-20 | 一种制备高强高塑弥散强化钨合金的方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210551592.0A CN114934207A (zh) | 2022-05-20 | 2022-05-20 | 一种制备高强高塑弥散强化钨合金的方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114934207A true CN114934207A (zh) | 2022-08-23 |
Family
ID=82865429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210551592.0A Pending CN114934207A (zh) | 2022-05-20 | 2022-05-20 | 一种制备高强高塑弥散强化钨合金的方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114934207A (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288968A (zh) * | 1999-09-17 | 2001-03-28 | 哈尔滨工业大学 | 碳化锆颗粒增强钨复合材料的制备方法 |
| CN1445377A (zh) * | 2002-03-20 | 2003-10-01 | 哈尔滨工业大学 | 一种复合碳化物颗粒增强钨基复合材料 |
| CN110273093A (zh) * | 2019-06-12 | 2019-09-24 | 北京大学 | 一种纳米晶钨合金及其制备方法 |
| CN110560700A (zh) * | 2019-09-30 | 2019-12-13 | 北京科技大学 | 一种制备高致密度超细晶稀土氧化物掺杂钨合金的方法 |
-
2022
- 2022-05-20 CN CN202210551592.0A patent/CN114934207A/zh active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288968A (zh) * | 1999-09-17 | 2001-03-28 | 哈尔滨工业大学 | 碳化锆颗粒增强钨复合材料的制备方法 |
| CN1445377A (zh) * | 2002-03-20 | 2003-10-01 | 哈尔滨工业大学 | 一种复合碳化物颗粒增强钨基复合材料 |
| CN110273093A (zh) * | 2019-06-12 | 2019-09-24 | 北京大学 | 一种纳米晶钨合金及其制备方法 |
| CN110560700A (zh) * | 2019-09-30 | 2019-12-13 | 北京科技大学 | 一种制备高致密度超细晶稀土氧化物掺杂钨合金的方法 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109879669B (zh) | 一种具有高强度的高熵陶瓷复合材料及其制备方法和应用 | |
| CN110002879B (zh) | 一种致密超硬的高熵硼化物陶瓷及其制备方法和应用 | |
| CN109987941B (zh) | 一种具有抗氧化性的高熵陶瓷复合材料及其制备方法和应用 | |
| CN109180189B (zh) | 一种高熵碳化物超高温陶瓷粉体及其制备方法 | |
| CN109678523B (zh) | 一种具有高温强度和硬度的高熵陶瓷及其制备方法和应用 | |
| CN110257684B (zh) | 一种FeCrCoMnNi高熵合金基复合材料的制备工艺 | |
| CN110627508A (zh) | 一种高熵硼化物基陶瓷及其制备方法和应用 | |
| CN114315359B (zh) | 一种利用固溶耦合法制备高强韧复相高熵陶瓷的方法和应用 | |
| CN110735076A (zh) | 一种高熵金属陶瓷及其制备方法和应用 | |
| CN112679213B (zh) | 一种超多元高熵陶瓷及其制备方法和应用 | |
| CN110606748A (zh) | 一种氧化铝增强高熵硼化物陶瓷及其制备方法和应用 | |
| CN112830790B (zh) | 一种铪铌基三元固溶体硼化物的导电陶瓷及其制备方法和应用 | |
| CN111732437A (zh) | 超高温复相陶瓷粉体的制备方法及其致密化工艺 | |
| CN111848170A (zh) | 一种碳化硼基复合陶瓷材料及其制备方法 | |
| CN115536403A (zh) | 一种高韧氮化硅陶瓷材料及其制备方法 | |
| CN109665848B (zh) | 一种超高温SiC-HfB2复合陶瓷及其制备方法和应用 | |
| CN112250442A (zh) | 一种高强韧无粘结相纳米晶硬质合金的制备方法 | |
| CN111875385B (zh) | 一种高强度、高硬度且低模量硼化钛纳米复相陶瓷的制备方法 | |
| CN115007871A (zh) | 一种制备高强高塑钼合金的方法 | |
| CN113416077A (zh) | 一种双复合结构的高温陶瓷刀具材料及其制备方法与应用 | |
| CN113149676A (zh) | 一种利用两步法烧结原位增韧碳化硼基复相陶瓷的方法 | |
| CN114934207A (zh) | 一种制备高强高塑弥散强化钨合金的方法 | |
| CN111378870A (zh) | 一种sps烧结钛基复合材料及其制备方法 | |
| CN115044792B (zh) | 一种颗粒增强钛基复合材料及其制备方法 | |
| EP4056540B1 (en) | Method for obtaining a high refractory composite from boron carbide and intermetallic compound of the ti-si system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |