CN1155729C - Novel corrosion resistant titanium alloy - Google Patents
Novel corrosion resistant titanium alloy Download PDFInfo
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- CN1155729C CN1155729C CNB971088985A CN97108898A CN1155729C CN 1155729 C CN1155729 C CN 1155729C CN B971088985 A CNB971088985 A CN B971088985A CN 97108898 A CN97108898 A CN 97108898A CN 1155729 C CN1155729 C CN 1155729C
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Abstract
The present invention relates to novel corrosion resistant titanium alloy which comprises the following components (parts by weight): 0.3 to 3 wt% of Ni, 0.3 to 3 wt% of Cr, 0.3 to 3 wt% of Mo, 0.3 to 3 wt% of Cu and equilibrium amount of Ti; in addition, the alloy can be manufactured by a casting pressure processing method or a powder metallurgical method. Because a small amount complex alloying method is adopted by the present invention, and the elements of Ni, Cr, Mo and Cu with proper quantity are added into the alloy, the mechanical strength of the alloy is greatly improved, the corrosion resistance of the alloy in various media is greatly improved, and the range of applicable media is enlarged. In addition, the alloy has the advantages of good processing performance, no existence of rare noble metals, low manufacture cost, good market competitiveness and good popularization and use value.
Description
The present invention relates to a kind of corrosion resistant Ti alloy.
Titanium metal is in oxidisability, neutrality or week reduction medium; because the surface forms the protectiveness passive film; has very strong solidity to corrosion; but in reductive acid solution or strong oxidizing property medium; because the surface is difficult to form complete protectiveness passive film; solidity to corrosion is just not ideal enough, also can produce crevice corrosion in high-temp chlorination thing solution.In order further to improve the solidity to corrosion of titanium metal, can pass through alloyage process, for example, adding can directly promote the element of passivation or promote the so-called negative electrode of passivation to contain the aurification element indirectly.The mid-1970s U.S. develops the Ti-0.3Mo-0.8Ni alloy, has obtained widespread use." Rare Metals Materials and engineering " the 21st volume 1 phase " development of anti-corrosion Ti-0.3Mo-0.8Ni alloy " literary composition describes this alloy in detail, it has solidity to corrosion preferably in reductive acids such as the hydrochloric acid of low concentration, sulfuric acid, high-temp chlorination thing solution had stronger anti-crevice corrosion ability, and good processability, but this alloy is because alloy element concentration is low, the medium scope that is suitable for is narrow, and physical strength is not compared with pure titanium and significantly improved.
The purpose of this invention is to provide a kind of middle high strength that has, the far-ranging corrosion resistant Ti alloy of Applicable media.
Technical solution of the present invention is: the composition of this corrosion resistant Ti alloy (by % weight) is Ni=0.3-3, Cr=0.3-3, Mo=0.3-3, the Ti of Cu=0.3-3 and equal amount.
The present invention makes alloy have middle high strength and has good solidity to corrosion in wider medium scope, its main points are to adopt a small amount of multi-element alloyed method, in alloy, add multiple a small amount of strengthening element, make alloy obtain higher physical strength by solution strengthening and precipitation strength, Ni, Cr, Mo, Cu is beta stable element, alloy is the alpha+beta tissue at normal temperatures, wherein Mo is an isomorphism beta stable element, all solid solution is in β-Ti, Ni, Cr, Cu is an eutectoid type beta stable element, can produce eutectoid transformation, and Ni wherein, Cu eutectoid transformation speed is fast, can play the precipitation strength effect to the Ti matrix by thermal treatment.Ni, Cr, Mo, Cu have the promotion passivation simultaneously, corrosion proof raising is made contributions to alloy by different way, wherein Cr makes and causes that blunt current potential (Ecp) is negative to be moved on the alloy anode polarization curve, promptly impel Ti to do sth. in advance passivation, Cr and Mo make the blunt current potential of dimension (Ep) bear and move, make the Ti alloy realize stablizing passive state easily, and reduce passive state corrosion current (ip), thereby improve the solidity to corrosion of alloy.Though Cu not as Pd, Pt, rare precious metals such as Ru, Re, also has the effect of indirect promotion anode passivation as the cathode alloy element interaction.The solid solubility of Ni in α-Ti minimum (under eutectoid temperature＜0.2%) separated out Ti by appropriate heat treatment
2The Ni phase, Ti
2Ni has low overpotential of hydrogen evolution, as effectively activated cathode existence, quickens the evolving hydrogen reaction of negative electrode in microbattery, and corrosion potential is brought up to α-Ti passivation region, promotes anode passivation.
The present invention has taken all factors into consideration raising physical strength and corrosion proof requirement, and the composition of choosing alloy is lower than lower limit as alloy concentrations in OK range, strengthen and improve corrosion proof effect deficiency, concentration is higher than the upper limit, and the plasticity of alloy, toughness reduce processing difficulties; For solidity to corrosion, concentration need not be too high, and because transpassivation, the current potential that breaks reduces, and ties up blunt scope and narrows down, and is unfavorable to solidity to corrosion.Consider its over-all properties, the preferred values of in general above-mentioned alloying constituent (by % weight) is Ni=1-2, Cr=0.5-2, Mo=0.5-2, the Ti of Cu=0.5-2.5 and equal amount.The total amount of 4 kinds of elements is good in the 2.5-5.5% weight range.
Above-mentioned titanium alloy can be made with the founding pressure processing method.
The also available powder metallurgy process manufacturing of above-mentioned titanium alloy.
The present invention is owing to adopt a small amount of multi-element alloyed method, in alloy, add an amount of Ni, Cr, Mo, Cu element, improve the physical strength and the solidity to corrosion in various media of alloy greatly and enlarged the medium scope that is suitable for, strengthened the ability of anti-crevice corrosion simultaneously greatly.The alloy processing characteristics does not well contain rare precious metal in addition, and low cost of manufacture has the stronger market competitiveness and popularizing value.
Following preparation and the The performance test results that describes alloy of the present invention according to embodiment in detail:
Embodiment 1: this example adopts the casting method alloying, specifically weigh in the Ti-1Ni-0.5Cr-0.5Mo-0.5Cu ratio with titanium sponge, electrolytic nickel sheet, chromium grain, red copper car bits and 50Ti-50Mo master alloy, mix and be pressed into electrode, through the secondary vacuum consumable arc-melting, obtain Φ 90mm ingot, peeling goes rising head to get 85mm circle base, is swaged into the 50mm square billet through 1050 ℃～1100 ℃ heating again, is swaged into Φ 20-30mm pole through 1000 ℃ of heating again.Its performance of sampling and testing obtains following result: density 4.58g/cm
3, hardness Hv195, tensile strength sigma b666Mpa, unit elongation δ 16%, relative reduction in area
37%, under the normal temperature in 15% hydrochloric acid and 20% sulfuric acid annual corrosion rate be respectively 0.025 and 0.042mm/.
Embodiment 2: this example adopts the casting method alloying, specifically weigh in the Ti-2Ni-1Cr-0.8Mo-0.5Cu ratio with titanium sponge, electrolytic nickel sheet, chromium grain, red copper car bits and 50Ti-50Mo master alloy, mix and be pressed into electrode, make bar with embodiment 1 the same method, its performance of sampling and testing obtains following result: density 4.62g/cm
3, hardness Hv260, tensile strength sigma b852Mpa, unit elongation δ 10%, relative reduction in area
17%, under the normal temperature in 15% hydrochloric acid and 20% sulfuric acid institute's corrosion rate be respectively 0.0071 and 0.011mm/.Four kinds of constituent contents are optimum formula in this routine alloy, and the contrast of its solidity to corrosion in the medium of various conditions and industrially pure titanium and Ti-0.8Ni-0.3Mo alloy as shown in Table 1.
Embodiment 3: this example adopts the powder metallurgy process alloying, specifically weigh in the Ti-0.3Ni-3Cr-2Mo-0.3Cu ratio with-200 order titanium valves, nickel powder, chromium powder, molybdenum powder, copper powder, ball milling mixes, the dress plastic film sleeve, with 220MPa pressure cold isostatic compaction, obtain bar through 1150 ℃/2h vacuum sintering, its performance of sampling and testing obtains following result: density 4.53g/cm
3, hardness Hv422, tensile strength sigma b1050MPa, unit elongation δ 2%, under the normal temperature in 15% hydrochloric acid and 20% sulfuric acid annual corrosion rate be respectively 0.13 and 0.27mm/.
Embodiment 4: this example adopts the powder metallurgy process alloying, specifically weigh in the Ti-1Ni-2Cr-3Mo-1Cu ratio with-200 order titanium valves, nickel powder, chromium powder, molybdenum powder, copper powder, ball milling mixes, dress plastics die sleeve is with 220MPa pressure cold isostatic compaction, obtain bar through 1200 ℃/2h vacuum sintering, its performance of sampling and testing gets following result: density 4.79g/cm
3, hardness Hv487, tensile strength sigma b1070Mpa extends δ 1.5%, under the normal temperature in 15% hydrochloric acid and 20% sulfuric acid annual corrosion rate be respectively 0.021 and 0.025mm/.
Embodiment 5: this example adopts the powder metallurgy process alloying, specifically weigh in the Ti-1.5Ni-0.3Cr-1.5Mo-2Cu ratio with-200 order titanium hydride powders, nickel powder, chromium powder, molybdenum powder, copper powder, ball milling mixes, dress plastics die sleeve is with 220MPa pressure cold isostatic compaction, obtain bar through 1100 ℃/2h vacuum sintering, its performance of sampling and testing gets following result: density 4.60g/cm
3, hardness Hv450, tensile strength sigma b1180Mpa extends δ 1.0%, under the normal temperature in 15% hydrochloric acid and 20% sulfuric acid annual corrosion rate be respectively 0.017 and 0.012mm/.
Embodiment 6: this example adopts the powder metallurgy process alloying, specifically weigh in the Ti-3Ni-0.8Cr-0.3Mo-3Cu ratio with-200 order titanium hydride powders, nickel powder, chromium powder, molybdenum powder, copper powder, ball milling mixes, dress plastics die sleeve is with 220MPa pressure cold isostatic compaction, obtain bar through 1050 ℃/2h vacuum sintering, its performance of sampling and testing gets following result: density 4.56g/cm
3, hardness Hv515, tensile strength sigma b1220Mpa, extending δ is 0, under the normal temperature in 15% hydrochloric acid and 20% sulfuric acid annual corrosion rate be respectively 0.015 and 0.010mm/.
Embodiment 7: this example adopts the powder metallurgy process alloying, specifically weigh in the Ti-2Ni-1Cr-0.8Mo-0.5Cu ratio with-200 order titanium hydride powders, nickel powder, chromium powder, molybdenum powder, copper powder, ball milling mixes, dress plastics die sleeve is with 220MPa pressure cold isostatic compaction, obtain bar through 1050 ℃/2h vacuum sintering, its performance of sampling and testing gets following result: density 4.56g/cm
3, hardness Hv430, tensile strength sigma b1290Mpa extends δ 3.8%, under the normal temperature in 15% hydrochloric acid and 20% sulfuric acid annual corrosion rate be respectively 0.008 and 0.013mm/.
Embodiment 8: this example adopts the powder metallurgy process alloying, specifically weigh in the Ti-0.8Ni-0.5Cr-1Mo-0.3Cu ratio with-200 order titanium hydride powders, nickel powder, chromium powder, molybdenum powder, copper powder, ball milling mixes, dress plastics die sleeve is with 220MPa pressure cold isostatic compaction, obtain bar through 1200 ℃/2h vacuum sintering, its performance of sampling and testing gets following result: density 4.48g/m
3, hardness Hv310, tensile strength sigma b780Mpa extends δ 4.2%, under the normal temperature in 15% hydrochloric acid and 20% sulfuric acid annual corrosion rate be respectively 0.16 and 0.11mm/.
Comprehensive above embodiment as can be known, corrosion resistant Ti alloy of the present invention has following advantage with industrially pure titanium and Ti-0.8Ni-0.3Mo alloy phase ratio:
The physical strength aspect: the tensile strength sigma b of industrially pure titanium is 390-540Mpa, Ti-0.8Ni-0.3Mo alloy sigma b is 490-550Mpa, and alloy sigma b of the present invention reaches 666-1290Mpa, apparently higher than industrially pure titanium and Ti-0.8Ni-0.3Mo alloy, has middle high intensity level.
The solidity to corrosion aspect: choose most representative embodiment 2Ti-2Ni-1Cr-0.8Mo-0.5Cu alloy and industrially pure titanium among the present invention in various media, carry out corrosion test the result and with document in the relevant testing data of Ti-0.8Ni-0.3Mo alloy with the Ti-0.5Pd alloy compare (seeing Table one), titanium alloy of the present invention as can be known not only has excellent corrosion resistance nature in solution such as strong corrosive medium of oxidisability such as nitric acid, in solution such as reductibility strong corrosive medium example hydrochloric acid, goodish erosion resistance is arranged also, and the corrosion resistant medium scope of the present invention has been expanded greatly also.Can be no more than 4% by anti-corrosion concentration range industrially pure titanium under the normal temperature in hydrochloric acid, sulfuric acid, the Ti-0.8Ni-0.3Mo alloy is no more than 10%, and alloy of the present invention can reach 15% and 20% respectively.Titanium alloy of the present invention has strengthened the ability of anti-crevice corrosion owing to added an amount of Ni, Mo element simultaneously.Alloy processing characteristics of the present invention in addition is good, do not contain rare precious metal, low cost of manufacture, have stronger competitive power and popularizing value, can be widely used in departments such as chlor-alkali, salt manufacturing, metallurgy, chemical fertilizer, chemical fibre, papermaking, electric power, plating, medicine, food, environmental protection, be particularly suitable for using under the high-intensity situation in unconformable etching condition harshness of pure titanium and Ti-0.8Ni-0.3Mo titanium alloy and the requirement.
Table one:
Alloy Ti-2Ni-1Cr-0.8Mo-0.5Cu of the present invention and industrially pure titanium and the Ti-0.8Ni-0.3Mo alloy corrosion resisting property synopsis in various media
| Test conditions | Annual corrosion rate (mm/) |
| The medium temperature time (h) | Ti-2Ni-1Cr-0.8Mo Ti-0.8Ni-0.3Mo titanium-0.5Cn alloy alloy |
| 40% nitric acid room temperature 480 | 0.00046 0.009 |
| 60 ℃ 144 in 40% nitric acid | 0.0061 0.017 |
| 40% nitric acid boiling 40 | 0.057 0.144 |
| 10% hydrochloric acid room temperature 144 | 0.0065 0.328 0.022 * |
| 12.5% hydrochloric acid room temperature 496 | 0.401 * |
| 15% hydrochloric acid room temperature 288 | 0.0071 0.551 |
| 18% hydrochloric acid room temperature 185 | 0 580 0.78 |
| 20% hydrochloric acid room temperature 240 | 2.69 0.90 |
| 3% hydrochloric acid boiling 40 | 0.178 25.2 10.2 |
| 10% sulfuric acid room temperature 480 | 0.0047 0.307 0.032 * |
| 15% sulfuric acid room temperature 496 | 0.469 * |
| 20% sulfuric acid room temperature 240 | 0.011 0.355 |
| 25% sulfuric acid room temperature 288 | 0.141 0.89 |
| 30% sulfuric acid room temperature 51 | 1.83 2.21 |
| 40% sulfuric acid room temperature 48 | 2.79 2.41 |
| 1% sulfuric acid boiling 40 | 0.0657 16.3 0.038 * |
| 50% formic acid boiling 48 | 0.00383 17.5 0.026 ** |
| 1% oxalic acid boiling 40 | 0.0389 6.24 1.14 ** |
| 50% citric acid boiling 48 | 0.0165 0.84 0.025 ** |
*For quoting data in " Rare Metals Materials and engineering " the 21st volume 1 phase " development of anti-corrosion Ti-0.3Mo-0.8Ni alloy " literary composition
*Be Ti-0.15Pd alloy corrosion testing data
Claims (4)
1, a kind of novel corrosion resistant titanium alloy, the composition (by % weight) that it is characterized in that described titanium alloy is Ni=0.3-3, Cr=0.3-3, Mo=0.3-3, the Ti of Cu=0.3-3 and equal amount.
2, corrosion resistant Ti alloy according to claim 1, the composition (by % weight) that it is characterized in that above-mentioned titanium alloy is Ni=1-2, Cr=0.5-2, Mo=0.5-2, the Ti of Cu=0.5-2.5 and equal amount.
3, corrosion resistant Ti alloy according to claim 2, the composition (by % weight) that it is characterized in that above-mentioned titanium alloy is Ni=2, Cr=1, Mo=0.8, the Ti of Cu=0.5 and equal amount.
4,, it is characterized in that the total amount that above-mentioned titanium alloy contains four kinds of elements of Ni.Cr.Mo.Cu is 2.5%-5.5% according to claim 1 or 2 or 3 described corrosion resistant Ti alloys.
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| CNB971088985A CN1155729C (en) | 1997-04-25 | 1997-04-25 | Novel corrosion resistant titanium alloy |
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| CNB971088985A CN1155729C (en) | 1997-04-25 | 1997-04-25 | Novel corrosion resistant titanium alloy |
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| CN1155729C true CN1155729C (en) | 2004-06-30 |
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| US7273074B2 (en) | 2002-07-24 | 2007-09-25 | Albany International Corp. | On-machine-seamable industrial fabric having seam-reinforcing rings |
| CN101886191B (en) * | 2010-07-14 | 2011-10-12 | 南京信息工程大学 | Corrosion-resistant and abrasion-resistant titanium alloy and preparation method thereof |
| CN107740020A (en) * | 2017-10-24 | 2018-02-27 | 宝鸡市渭滨区怡鑫金属加工厂 | A kind of preparation method of titanium nickel tube material |
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