CN105603329A - High-carbon and high-strength-and-toughness tungsten-molybdenum composite secondary hardening stainless bearing steel and preparation method - Google Patents
High-carbon and high-strength-and-toughness tungsten-molybdenum composite secondary hardening stainless bearing steel and preparation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
- C21D1/28—Normalising
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/007—Heat treatment of ferrous alloys containing Co
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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Abstract
The invention relates to high-carbon and high-strength-and-toughness tungsten-molybdenum composite secondary hardening stainless bearing steel and a preparation method and belongs to the technical field of alloy steel. The steel is prepared from, by weight, 0.20-0.40% of C, 10.0-14.0% of Cr, 2.0-8.0% of Ni, 1.0-5.0% of Mo, 0-2.0% of W, 10-16% of Co, 0-0.6% of V, 0-0.2% of Nb, smaller than or equal to 0.5% of Si, smaller than or equal to 0.5% of Mn, smaller than or equal to 0.01% of S, smaller than or equal to 0.01% of P and the balance Fe and other inevitable impurity elements and rare earth elements. The high-carbon and high-strength-and-toughness tungsten-molybdenum composite secondary hardening stainless bearing steel and the preparation method have the advantages that compared with the prior art, the steel has good toughness and corrosion resistance while higher tensile strength and yield strength are archived; the stainless bearing steel is good in overall performance.
Description
Technical field
The invention belongs to field of alloy steel, particularly the compound post-curing stainless bearing steel of the high tough tungsten of a kind of high-carbonAnd preparation method thereof. This alloy has high strength, high tenacity, long-life, the excellent properties such as anticorrosive, and processing performance is goodGood, can adopt conventional two vacuum metallurgy technique and simple aging thermal treating process, compared with prior art, the property such as intensityEnergy and manufacturability have clear superiority.
Technical background
With the development of the industries such as Aero-Space, machinery, traffic, to the rotation of top load, long-life and environmental corrosion resistingParts steel increase in demand, as high-intensity bearing, gear, rolling member and securing member etc., needs steel both to have heightIntensity has high toughness and good corrosion resistance again, exists in recent years taking the U.S., Japan as the developed country of representativeThis field has been dropped into a large amount of manpower and materials and has been developed research, constantly has the appearance of new steel grade, to substitute traditional material,Improve the life-span under toughness and Service Environment.
The 9Cr18 pansclerosis Bearing gear steel that used is used is due to the existence of net carbide, and fatigue life neverReach the Expected Results of use, although and taking 9310, M50NiL improved as the carburizing bearing steel of representative has improved toughnessLife-span, but because Cr content in the bulk strength deficiency of steel and steel is lower, the performance in top load and corrosive environmentNot good.
On the basis of the even Chinese secondary hardened steel based on good combination of strength and toughness in recent years of the U.S., Japan, developHave high strength, high tenacity, corrosion resistant Novel transmission parts special steel, the common feature of this type of steel is to adopt secondary hardChange strengthening, rely on separate out in ag(e)ing process with the M2C type carbide of Mo, W and taking V as main MC type carbide strongTurn to main raising intensity, in steel, Cr content is brought up to more than 12% and to be improved decay resistance, rely on strict composition proportion andHeat treating regime design obtains good combination of strength and toughness:
The U.S. discloses the stainless gear-bearing steel of high-strength tenacity CSS-42L patent nineteen ninety-five, patent No. US5424028,Adopt Mo strengthening, Cr content reaches 14%, and this steel is after vacuum metling and forging molding, through 1050 solid solutions ,-73After deep cooling and 496 timeliness, can obtain the good obdurability of Rm >=1800MPa, A >=16%;
Japan discloses a kind of high-intensity high-tenacity stainless steel for 1994, and the patent No. is JP06264189, and its Ni contentLow, this steel, after vacuum metling and forging, through after 1050 solid solutions ,-73 deep coolings and 475 timeliness, can obtainRm≥1700MPa、A≥16％、KIC≥110MPam1/2Good obdurability.
The people such as Iron and Steel Research Geueral Inst Li Yong disclose a kind of containing the high strength and high toughness secondary hardened stainless steel of W for 2010, the patent No.CN102031459A, after 1050 solid solutions ,-73 deep coolings and 490-530 timeliness, can obtain Rm >=1800MPa,A≥16％、KIC≥90MPam1/2Good obdurability.
The Iron and Steel Research Geueral Inst poplar fourth of the twelve Earthly Branches is raw wait people disclose in 2011 a kind of high-strength high-ductility corrosion high temperature gear-bearing steel andManufacture method, patent No. CN102226254A, during through 1000-1150 solid solution ,-80～-100 deep coolings and 500-530After effect, can obtain Rm >=1800MPa, Rp0.2 >=1400MPa, core hardness >=50HRc, carburized surface hardness >=65HRc,KIC≥110MPam1/2Good obdurability.
Long your people such as grade of Baosteel Yao discloses a kind of tough ultra-strength stainless steel and manufacture method thereof, the patent No. for 2008CN101205595A, adopts W, Mo strengthening, and its C content, Ni content are lower, can obtain Rm >=1800MPa, Rp0.2≥1400MPa，KIC≥110MPam1/2Good obdurability.
The composition of above patent alloy contrasts in table 1, finds out thus, in transmissions such as advanced high-strength corrosion-resisting gear-bearingsParts, with in the exploitation of steel, have all adopted post-curing alloying thought both at home and abroad, reach good combination of strength and toughness with it.Table 2 is performance comparison of Patents, and the tensile strength of the general post-curing type corrosion resisting bearing steel of announcing at present exists1800MPa, yield strength reach 1400MPa.
The chemical composition of patent both at home and abroad such as table 1CSS-42L steel
Although the disclosed patent combination of strength and toughness such as the U.S. and Japan are better, tensile strength and yield strength are on the low side, limitMade its wider applying, with the development of high-speed overload transmission system, the bulk strength of material can not be expired at presentThe application demand of foot top load condition, therefore wishes that development one has the above intensity of 2000MPa and has good organization and toughProperty steel, there is high strength, high tenacity and good corrosion resistance.
The mechanical property of table 2 comparative example steel
Summary of the invention
The object of the present invention is to provide the above intensity of a kind of 2000MPa, there is excellent toughness, good Technology for Heating ProcessingThe corrosion resisting bearing steel of property and delicate tissues, has good combination property. Can significantly improve anti-overload ability, improveApplication under the high torque conditions of top load.
According to above-mentioned purpose, the technical scheme of entirety of the present invention is:
The present invention adopts the good post-curing type of combination of strength and toughness unimach for basis, utilizes high carbon martensite to improveMatrix strength, utilizes the M of Mo, W composition generation2The secondary that the MC type alloy carbide that C type and V produce producesSclerous reaction strengthening obtains superhigh intensity, and 12% left and right Cr content has ensured that steel has good corrosion resistance, higherNi content ensures to have good toughness, reasonably heat treating regime ensures that material obtains good tissue and mechanical property is joinedClose.
According to above-mentioned purpose and overall technical architecture, concrete technical scheme of the present invention is:
The concrete chemical composition (percetage by weight) of steel of the present invention is:: C0.20-0.40%, Cr10.0-14.0%,Ni2.0-8.0，Mo1.0-5.0％，W0-2.0％，Co10-16％，V0-0.6％，Nb0-0.2％，Si≤0.5％，Mn≤0.5%, S≤0.01%, P≤0.01%, all the other are Fe and other inevitable impurity element and rare earth element.
The design considerations of above-mentioned chemical composition is as follows:
C is one of most important alloying element in steel of the present invention, and the Properties and Microstructure of steel is decided by a great extentContent and the distribution form thereof of carbon in steel, particularly remarkable in post-curing type superhigh strength stainless steel. C is stable difficult to understandThe element of family name's body, and the degree of effect very large (be about Ni element 30 times). C can form M with Mo, W2C(Mo2C、W2C) type carbide, becomes MC type alloy carbide with V-arrangement, and the increase of C content, carbide quantityIncrease, carbonization material dot spacing reduces, and increases post-curing peak value, obtains high-yield strength, and C content is less than 0.20%Time can make undercapacity. Along with the increase of C content, the tensile strength of steel improves, but impact flexibility reduces. Too high CContent reduces Ms point, increases retained austenite and twin crystal martensite, and twin crystal martensite damage toughness; Simultaneously too highThe carbide that is also easy to form with Cr series of complex when C content exceedes 0.4%, organizes it wayward, significantly carriesHigh solid solubility temperature, thus the unstable properties of steel caused. And can cause the Cr content of solid solution in steel to reduce, thereby fallThe corrosion resistance of low steel; The present invention is according to the content of Cr and consider intensity, toughness and corrosion resistance and determine the control of C contentBetween 0.20-0.40%.
Cr is one of most important alloying element in steel of the present invention, and Cr plays a decisive role in stainless steel, and causes steelThe Cr content of corrosion resistance sudden change be about 12%, be less than 10% corrosion resistance that reduces steel. Cr makes steel passivation also at presentGive good corrosion resistance and rustless property and unique element that has industrial application to be worth. In addition, Cr can also carry heavy alloyed quenchingProperty thoroughly, produces solution strengthening; Can also replace Mo2Part Mo element in C forms (Mo, Cr)2The carbonization of C type alloyThing, promotes post-curing reaction, forms small and dispersed precipitation. In invention steel, Cr content can seriously reduce higher than 15% timeThe intensity of steel also increases the possibility that ferrite exists, but still the Cr that must contain sufficient amount is to improve corrosion resistance, thereforeControl its content at 10-14%.
Mo is intensified element main in steel of the present invention, and Mo and C can form Mo2C carbide, thus produceStrong post-curing reaction is the reason that forms post-curing peak. Along with the increase of Mo content, post-curing peak valueHardness improves, and yield strength improves. Mo increases quenching degree in addition, produce solution strengthening, improve steel resistance to tempering withAnd the effect of inhibition temper brittleness, in normal conditions post-curing stainless steel, the content of Mo is no less than 2%. In addition Mo,Also there is the effect of stable passive state skin covering of the surface, thereby improved the pitting corrosion resistance of steel. Consider from obdurability proportioning and corrosion resistance,Mo is controlled at 1.0-5.0%.
W: be main intensified element, W2The main forming element of C carbide, strong generation post-curing reaction,It is the reason that forms post-curing peak. Along with the increase of W content, post-curing peak hardness improves, and yield strength improves,Compare W and can significantly reduce the overaging sensitiveness of alloy carbide with Mo, improve alloy temper stability. For obtainingEnough age hardening effect, but should too high W content make solid solubility temperature too high cause organize thick, in steel of the present inventionW content should be higher than 2.0%. According to the particularly needs of toughness of intensity, in steel of the present invention, W content is controlled at 0-2.0%.
Ni is malleableize element main in the present invention, and Ni is the toughness that austenite stabilizer element can improve steel, simultaneouslyNi improves the quenching degree of steel, produces solution strengthening, keeps high dislocation lath martensite, improves the anti-cleavage of martensitic matrixFracture energy, reduces mould-brittle transition temperature, ensures that steel has enough toughness. Ni also can promote Fe3C back dissolving, fromAnd be M2The formation of C provides enough carbon contents. But adding of Ni will be noted coordinating of [Ni equivalent] and [Cr equivalent],Otherwise can, due to the too much infringement intensity of austenite content, exceed 8.0% and will can not get complete martensitic structure, therefore controlMake its content at 2.0-8.0%.
Co is austenite stabilizer element, improves toughness and promotes again post-curing reaction, can press down owing to adding CoSystem delays martensite dislocation substructure replys, and keeps the high dislocation density of martensite lath, thereby is precipitated phase subsequently M2Separating out of C provides more nucleation site. And Co improves the activation energy of C atom in ferrite, reduce C atomDiffusion coefficient in ferrite, increases M2The nucleation rate of C carbide, thereby, can promote that forming small and dispersed dividesThe M of cloth2C carbide, and reduce Precipitation carbide particle spacing; Co can reduce Mo consolidating in martensiteSolubility and Cr are at M3Solid solubility in C cementite, thus M promoted2The formation of C precipitated phase; Promote that austenite turns completelyBecome martensite, improve Ms point, reduce martensite transfor mation and turn austenitic tendency for reversing. In addition, Ni, Co are commonAdd and can mutually strengthen promoting Fe3C back dissolving and M2The promotion induration of the formation of C carbide and enhancing Co. LogicalIn normal secondary hardened steel, the content of Co is more than 8%, but owing to being equivalent to increase [Ni equivalent] adding of Co, thereforeThe content of Co is no more than 16%. Patent of the present invention is controlled at 10-16%.
V, Nb can solid solution in steel, cause the lattice distortion of lattice, thereby play the effect of solution strengthening. ButBecause the addition of these elements is less, thus rigidity can raising master if it were not for relying on the solution strengthening effect of alloying element,And be mainly because thereby V, Nb can cause grain refinement and separate out precipitation with C, N formation carbide and nitrideStrengthen, improve intensity and the toughness of steel simultaneously. The wherein precipitation strength effect maximum of V, under general hot forging temperature,The carbide of V or nitride are fully dissolved in austenite, along with follow-up cooling disperse educt, produce precipitation strength and crystal grainRefining effect. V, Nb add respectively 0-0.6% and 0-0.2%.
Other elements in alloy:
Can comprise the additional elements of not damaging performance. For example, Mn, Si can reach 0.5%, and Ti, Al can reach0.02%, these additional elements can be used for the deoxidier of alloy; In addition rare earth metal Ce and La from trace to0.006%, for controlling the form of sulfide and oxide.
Unimach of the present invention is easy to adopt the remelting of vacuum induction+vacuum consumable or vacuum induction+electric slag refusion and smelting workSkill is cast into ingot, steel ingot through high temperature homogenization process after forge become a useful person or cogging after be rolled into rod, wire rod.
Its concrete technology parameter is as follows:
Steel ingot carries out 1200-1250 DEG C of homogenising processing, and 8 hours≤diffusion time≤100 hour, 0 DEG C≤shove charge temperatureSpend≤600 DEG C;
Heating-up temperature: 1180-1220 DEG C, 1160 DEG C≤open forging temperature≤1200 DEG C, 900 DEG C≤final forging temperature≤1000 DEG C;
Finished product conditioning treatment system: normalizing: 1100～1180 DEG C, 1 hour≤insulation≤3 hours; Air coolingHigh tempering: 640～700 DEG C, 5 hours≤insulation≤40 hours.
Final heat treatment:
Quenching Treatment: be heated to 1050-1180 DEG C, be incubated 1-1.5 hour, oil quenching after heat penetration; Subzero treatment :-100 DEG C≤ insulation≤-73 DEG C 1 hour≤time≤10 hour, is then raised to room temperature in air;Ageing Treatment: be heated to 490～530 DEG C, be incubated 5-10 hour, air cooling after heat penetration;
Secondary ageing processing:
Subzero treatment :-100 DEG C≤insulation≤-73 DEG C, 1 hour≤time≤10 hour, then existIn air, be raised to room temperature;
Ageing Treatment: be heated to 500～540 DEG C, be incubated 5-10 hour, air cooling after heat penetration;
Compared with prior art, steel of the present invention has concurrently good anti-corrosion in having superhigh intensity, good plasticity and toughnessProperty.
Detailed description of the invention
The chemical composition scope of steel according to the present invention, adopts 25 kilograms of vaccum sensitive stoves to prepare the alloy pig 16 of 21 kilogramsStove, its specific chemical composition is in table 3, and heat (batch) number is 1#～16#.
16 stove steel smeltings are cast into after steel ingot, first carry out high temperature homogenization resolving system to be before forging: 1200 DEG C of insulationsAfter 10 hours, cooling is forged, and forging temperature is 1180 DEG C. Be forged into the bar that specification is φ 20mm.
After forging, first coupon carries out normalizing, annealing heat treatment: 1180 DEG C × 1h of normalized treatment, 680 DEG C of air cooling, annealing in process× 6h, air cooling.
Finally quench, deep cooling and tempering heat treatment: 1150 DEG C × 1h of Quenching Treatment, oil quenching, subsequently-100 DEG C are coldProcess 10h, in air, be raised to room temperature. 490 DEG C of air coolings of temper, secondary ageing processing subsequent-100 DEG C cold treatment 10h,In air, be raised to room temperature. 510 DEG C of air coolings of temper. Sample blank is processed into mechanical property sample finished product, records mechanicsPerformance is in table 4.
In order to contrast, list chemical composition and the mechanical property of comparative example CSS-42L steel etc. at table 3 and table 4.
As seen from Table 3, compared with these post-curing type bearing steels of comparative example such as CSS-42L steel, of the present invention mainTechnical side's feature is to ensure good toughness by raising C content raising matrix strength, higher Ni content, but due toSignificantly improve [Ni] equivalent, for obtaining martensitic structure, relied on strict composition proportion and calculating on basis inventionThe secondary ageing heat treating regime that steel adopts.
Found out by table 4, compared with steel of the present invention and comparative example CSS-42L steel etc., anti-corrosion and keep higher plasticity and toughnessTime, can there is higher tensile strength and yield strength.
Steel chemical composition (wt%) contrast tables such as table 3 embodiment of the present invention and comparative example CSS-42L
Table 4 embodiment of the present invention and comparative example S53, CSS-42L, AerMet100 steel mechanical property contrast table
Claims (2)
1. the high tough tungsten post-curing stainless bearing steel of high-carbon, is characterized in that, the chemical composition of this steel becomesPoint percetage by weight is: C0.20-0.40%, and Cr10.0-14.0%, Ni2.0-8.0, Mo1.0-5.0%, W0-2.0%,Co10-16％，V0-0.6％，Nb0-0.2％，Si≤0.5％，Mn≤0.5％，S≤0.01％，P≤0.01％，All the other are Fe and other inevitable impurity element and rare earth element.
2. a preparation method for the high tough tungsten post-curing stainless bearing steel of high-carbon claimed in claim 1,Adopt the remelting of vacuum induction+vacuum consumable or electroslag remelting, it is characterized in that, the technical parameter of controlling in technique is as follows:
Steel ingot carries out 1200-1250 DEG C of homogenising processing, 8 hours≤diffusion time≤100 hour, 0 DEG C≤shove chargeTemperature≤600 DEG C;
Heating-up temperature: 1180-1220 DEG C, 1160 DEG C≤open forging temperature≤1200 DEG C, 900 DEG C≤final forging temperature≤1000℃；
Finished product conditioning treatment system: normalizing: 1100～1180 DEG C, 1 hour≤insulation≤3 hours; Air coolingHigh tempering: 640～700 DEG C, 5 hours≤insulation≤40 hours;
Final heat treatment:
Quenching Treatment: be heated to 1050-1180 DEG C, be incubated 1-1.5 hour, oil quenching after heat penetration; Subzero treatment:-100 DEG C≤insulation≤-73 DEG C, 1 hour≤time≤10 hour, then in air, riseTo room temperature;
Ageing Treatment: be heated to 490～530 DEG C, be incubated 5-10 hour, air cooling after heat penetration;Secondary ageing processing:
Subzero treatment :-100 DEG C≤insulation≤-73 DEG C, 1 hour≤time≤10 hour, soAfter in air, be raised to room temperature;
Ageing Treatment: be heated to 500～540 DEG C, be incubated 5-10 hour, air cooling after heat penetration.
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| CN105838861A (en) * | 2016-05-26 | 2016-08-10 | 中国科学院金属研究所 | Heat treatment method for maraging stainless steel |
| CN106148668A (en) * | 2016-08-22 | 2016-11-23 | 武汉理工大学 | A kind of manufacture method of high accuracy retentivity precision machine tool bearing |
| CN106191705A (en) * | 2016-08-12 | 2016-12-07 | 刘少尊 | A kind of Mo, Al composite cementation N high-strength stainless bearing steel and preparation method |
| CN106555040A (en) * | 2016-12-02 | 2017-04-05 | 机械科学研究总院青岛分院 | A kind of Technology for Heating Processing for improving bearing steel toughness |
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| CN110527911A (en) * | 2019-09-16 | 2019-12-03 | 北京航空航天大学 | Anti-corrosion gear-bearing steel of a kind of low-density high-strength height and preparation method thereof |
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| CN113088799A (en) * | 2021-03-31 | 2021-07-09 | 安徽富凯特材有限公司 | Low-cost ultrapure high-strength-toughness low-carbon stainless bearing steel and preparation method thereof |
| CN114717485A (en) * | 2022-03-08 | 2022-07-08 | 四川大学 | Nano precipitation strengthening ultrahigh-strength high-alloy steel and preparation method thereof |
| CN117305679A (en) * | 2023-09-20 | 2023-12-29 | 中国科学院金属研究所 | M50NiL bearing steel bar and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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