Marmem is subjected to stress can induce parent phase to change to martensitic phase, meanwhile on the part macroscopic view that alloy is done certain deformation has taken place.Take a turn for the worse more than the alternating temperature degree if above-mentioned part is heated to, martensitic phase reverses and becomes parent phase, and correspondingly part has also recovered original shape thereupon.This alloy with shape memory function is called marmem.In the iron-base marmem, the martensite of deironing palldium alloy has the fct structure, and the martensite of iron platinum and ferro-nickel-cobalt-titanium alloy is outside the bct structure, and general iron-base marmem martensite is hcp type 2H structure mostly, is commonly referred to ε martensite.We have found this martensitic 4H, 6H, 8H structure again recently.Parent phase γ is a fcc type 3R structure, also can be described as alloy austenite.The Martensitic transformation of γ → ε, its essence are the changes of atom stacking sequence.Martensitic phase has dissimilar combination faults for parent phase.
Fault low temperature propagation and fault high temperature are degraded and have been constituted martensitic phase transformation and reversed the elementary process that becomes.Though the marmem of non-iron-based such as NiTi and copper base alloy are used already, cost an arm and a leg.The iron-base marmem cost is low, and operating temperature is moderate, and vast potential for future development is arranged.
Patent and feature thereof associated before the present invention are listed below:
CN 1064319A composition (wt%) is characterized as: Mn:15-35%, Si:0.2-6.5%, Al:0.2-8%, Cu:0-0.5, Pr, Pm, Eu, Gd, Td, Dy, Ho, Er, Tm, Yb, Lu, La, Ce, Nd, Sm one or two or more kinds, amount is at 0.008-0.12%, and all the other are iron and inevitable impurity element.
One of JP170457 composition characteristics is: Mn:15-40%, Cr, Co one or both, the amount at 1-20%, Si, Al, Ge, Ga, Nb, V, Ti, Cu, Ni, Mo one or more, addition≤15%, La, Ce, Nd, Sm, Y one or more, addition≤2%.
JP2270938A (USP 5032195) composition characteristics: Mn:15-20%, Si≤3%, Cr≤10%, all the other are iron and inevitable impurity element.
JP216946 composition characteristics: Mn:15-30%, Cr, Ni one or both, addition≤15%, Si, Co one or both ,≤6%.
JP271761 (USP4780154) composition characteristics is: Mn:20-40%; Si:3.5-8%, following element comprises one: Cr≤10% at least, Ni≤10%, Co≤10%, Mo≤2%, C≤1%, Al≤1%, Cu≤1%, all the other are iron and inevitable impurity element.
More than three patent Mn content more than 15%, the superheated susceptivity of alloy is all bigger, restive its heat processing technique.Also be difficult for antirustly in addition, also be difficult to significantly improve its decay resistance even add Cr.What relate to below is Mn at patent below 15% and the document delivered:
The JP2301514 composition characteristics is: Cr:10-17%, Si:3.0-6.0%, following element at least one: Mn:10-25.0%, Ni≤7.0%, Co:2.0-10.0, Ti, Zr, V, Nb, Mo, Cu etc. are a small amount of, all the other be iron and inevitable impurity element.
B.E.Wilde, Corrosion-Nace (1986), Vol.42, the composition of P.678. delivering are Cr:17-19%, Si:0.35-4.79%, Ni:8.83-9.07%, Mn:1.30-1.53%, Cu:0.009-0.20%, N:0.011-0.040%, Mo:0.019-0.21%.
EP 336157A (JP 2030734A, USP 4929289A) composition characteristics is: Cr:0.1-5.0%, Si:2.0-8.0%, Mn:0.1-14.8%, Co:0.1-30%, Ni:0.1-2.0%, Cu:0.1-3%, N:0.01-0.4%, all the other are Fe and inevitable impurity element.
USP 4933027 (EP336175A), its composition range are Cr:5-20%, Si:2.0-8.0%, at least 1 Mn:0.1-14.8% of following element, Ni:0.1-2.0%, Co:0.1-30.0%, Cu:0.1-3.0%, N:0.001-0.4%, all the other are iron and inevitable impurity element.
EP 0506488A1 (claim 4), its composition range is: Cr:16-21%, Si:3.0-7.0%, Ni:11-21%, following element one or more:
Mn:0.1-5.0%, Cu:0.1-1.0%, N:0.001-0.100%, Mo:0.1-3.0%, W:0.1-3.0%, Ti:0.01-1.0%, Zr:0.01-2.0%, Hf:0.01-2.0%, V:0.01-1.0%, Nb:0.01-2.0% and Ta:0.01-2.0%.
As the shape-memory material of practical engineering application, often require yield strength to be higher than 300MPa, reminiscence temperature moderate (As:60-120 ℃), corrosion-resistant and be easy to processing become a useful person.The listed alloy of above-mentioned patent and document is difficult to satisfy simultaneously the requirement of this three aspect.
The purpose of this invention is to provide a kind of shape-memory stainless steel joint for pipeline and chemistry formation thereof, the present invention can overcome the shortcoming of prior art, and this pipe joint structure is simple, practical, economical, easy for installation, uses reliable.
Structure characteristic of the present invention is made up of memory stainless steel or the alloy collar 1, intermediate seal circle 2, ring end sealing compound 3 and connected tube 4.The intermediate seal circle is solid-state high-ductility alloy hoop or rubber ring or other high-ductility material ring that is fixed on memory alloy collar middle inside.The cross section of seal ring can be circle, ellipse, rectangle, trapezoidal or other is special-shaped.Sealing compound then is resin, water glass or plastic inorganic paste thing or the solid that is coated in memory alloy collar inner wall section close end.The sealing compound of the intermediate seal circle of said structure and ring end can use simultaneously, also can use separately.The intermediate seal circle can play axial front and back positioning action at the mounting pipe period of the day from 11 p.m. to 1 a.m, is tightly sealed by the compressing of both sides pipe in the centre during assembling.Sealing compound only is coated near on the inner wall section area of memory alloy ring end.Like this, when guaranteeing sealing, unlikely overflowing in the assembly process to tube interior.Shrink when the memory alloy collar is heated, tighten up pipe and reach purpose of connecting.
For this reason, we propose following novel components and technology, and concrete composition range is as follows:
Cr:12-20%
Si:3-8%
Ni:0.1-8%
Mn:0.1-14.8%
Co:0.1-20%
N:0.05-0.4%
Contain more than one in Ce, La, Sm, Nd, Pm, Eu, Tb, Dy, Pr, Gd, Ho, Er, Tm, Tb, the Lu element, content is 0.01-0.15%.Elements such as Nb, Ti, V, Zr, Ta, Hf, W, Mo, Al, Cu contain more than one, and content is 0.05-2%, and all the other are Fe and unavoidable impurities element.Press the ferro-alloy classification, the invention belongs to stainless steel with shape-memory properties.
The difference of the present invention and patent CN1064319A, JP170457, JP2270938A, JP216946, JP201761 is to contain Mn≤14.8%, has good corrosion resistance to guarantee alloy.One of difference of patent such as the present invention and JP2301514, Wilde, EP336157A, USP4933027, EP0506488A1 and document is to add rare earth elements RE, and main purpose is in order to reduce the dendrite deviation of element, to improve the uniformity of component distributing.Can obviously increase memory effect like this.The difference of the present invention and JP2301514 and the listed alloy of Wilde document is to add 0.05-0.4%N, and purpose is to reduce stacking fault energy, adjustment transformation temperature, also can improve the intensity of material simultaneously.The other difference of the present invention and EP336157A, USP4933027 is to contain carbonitride forming element Nb, Ti, V, Zr, Ta, Hf, W, Mo, can effectively reduce the material superheated susceptivity, and can improve the intensity of material.
To the effect of the alloying element that relates to, do a simple declaration below.
Cr: ferrite former, main effect is to improve the alloy corrosion resistance.It is not remarkable to be lower than 5% corrosion-resistant effect, and general Cr>12.0% can be used as stainless steel and uses.It presents comparatively complicated rule to the influence of stacking fault energy and transformation temperature.Be lower than at 9% o'clock and reduce stacking fault energy, greater than 9%, Cr obviously increases stacking fault energy and reduces transformation temperature, promotes the generation of fragility σ phase simultaneously.
Ni: can promote austenite to form strongly, the effect that reduces yield strength is arranged, so control nickel content is in the 0.1-8% scope.Because of nickel increases stacking fault energy, so should cooperate reduction stacking fault energy elements such as adding a certain amount of Si, Mn.
Si: can obviously reduce stacking fault energy, so generally should increase Si content.Si is lower than 3% to be reduced a little less than the stacking fault energy effect, and content surpasses 7%, and processibility worsens.
N: be austenite former, can obviously reduce stacking fault energy, have the effect of the Ms of stablizing point.Adding N can partly form carbonitride, has the good action that suppresses heat sensitivity.N can improve alloy yield and pitting corrosion resistant performance simultaneously.Be easy to form the volume nitride but surpass 0.4%, make material embrittlement, so N content is controlled at 0.050-0.40%.
Nb: comprise carboritride forming elements such as Ti, Ta, V, Zr, Hf, W, can the fixed carbon element, prevent that the carbide of chromium from separating out, avoid the dilution and the grain boundary corrosion of crystal boundary chromium.Form fine carbonitride simultaneously and can stop grain growth, alloy superheat when preventing high temperature.Addition is crossed conference and is caused along brilliant fragility, so its content is chosen in 0.05-2%.
Mo: the purpose that adds molybdenum is to improve the ability of anti intercrystalline corrosion and stress corrosion, and it is 0.05% inoperative that Mo is lower than, and exceeds 2% and cause memory performance to worsen, so the Mo addition is controlled at 0.05-2%.
Cu: be austenite former, can improve the alloy anti-corrosion capacity, but improve the austenite stacking fault energy simultaneously, cross and to suppress the formation of ε martensite at most and worsen memory performance.The general copper that adds is controlled in 2%.
Al: crystal grain thinning, reduce stacking fault energy, improve the memory performance of alloy, but Al content surpasses 2%, processibility worsens, so Al content should be controlled within 2%.
The effect and the composition range of each element are described above qualitatively.Concrete composition needs to observe following three criterions with collocation:
1. the parent phase that must guarantee alloy is single austenite phase.For this reason, alloying constituent (wt%) should satisfy following relation:
(Ni+0.5Mn+0.4Co+0.06Cu+0.002N+3)≤[0.67(Cr+Mo)+0.804(Si+Ti+Zr+Hf+V+Nb+Ta)]
2. must guarantee that alloy has the ability of stress corrosion resistant and spot corrosion.For this reason, alloying constituent (wt%) should satisfy relation:
Cr+Si>18;Cr+3.3Mo+30N>18
3. must guarantee that alloy has good memory performance and moderate phase transition temperature.For this reason, the alloying element that can reduce stacking fault energy of sufficient amount should be added, following formula need be satisfied:
7Si+Mn+3Co+100N>50
The performance index that memory stainless steel of the present invention reaches are as follows:
1. than higher shape-memory properties.3% tensile buckling, the reminiscence rate can reach 80%.Through the suitable hot mechanical training, linear answer can reach more than 4%.
2. stress corrosion resistant and spot corrosion can be mated with 304 stainless steels.
3. yield strength σ
0.2〉=300MPa, σ
b〉=650MPa, these performance index 304 stainless levels that are above standard.
(304 stainless steel compositions (wt%): C≤0.08, Cr:18-20, Ni:8-12, Mn:1-2, N≤0.03
Mechanical property: σ
0. 2=247MPa, σ
b=541MPa, δ=50%)
4. alloy has good cold and hot pressure machining characteristics.
5. the transformation temperature of alloy is moderate ,-40 ℃≤Ms≤20 ℃.
Table one is as the embodiment of invention alloy.Wherein meet be designated as " zero " of These parameters, the person of not meeting is marked with " * ".Marmem of the present invention, intensity height, good processability, moderate, the corrosion resistance and good of transformation temperature.The shape-memory pipe box that utilizes shape-memory stainless steel of the present invention to make connects pipe and has adopted special linkage structure.JP04069481A proposes to utilize Fe Mn Si alloy pipe to interlock when joining two pipes together to be used for sealing at pipe box coated inner wall epoxy resin.JP05215277CN proposes except that inwall is coated with sealing compound, and also at the inwall rag, purpose is to strengthen to be fastenedly connected effect.In addition, CN2116140 proposes closed coating pipe connecting structure, is used for high reliability and connects.Above-mentioned patent all relates to when installing and will be coated in sealing compound on the pipe box inwall.Construction is complicated like this.The present invention proposes novel simple, practical pipe joint linkage structure, as shown in Figure 1, Fig. 1: utilize the shape-memory stainless steel to connect the structural approach schematic representation of pipe, wherein: the 1-memory stainless steel or the alloy collar, 2-intermediate seal circle, 3-ring end sealing compound, 4-connected tube.