CN109735754A - A kind of heat-resisting Mg-Sn-Ca system magnesium alloy of suitable continuous casting and preparation method thereof - Google Patents
A kind of heat-resisting Mg-Sn-Ca system magnesium alloy of suitable continuous casting and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of heat-resisting Mg-Sn-Ca system magnesium alloy and preparation method thereof of suitable continuous casting.Design of alloy is instructed with scientific algorithm, Sn and Ca content is in the specific phase region of Mg-Sn-Ca phasor.Alloy of the present invention is solidification primary phase and matrix, Ca with Mg2‑ xMgx(0≤x≤1) second Sn is mutually tiny, and in≤30 DEG C of narrow warm area, fluidity of alloy melt and cavity filling are good for solid-liquid two-phase region, is suitble to liquid processing.In alloy structure temperature-rise period of the present invention, can just occur liquid phase at 600 DEG C or more, alloy heat resistance is high.Alloy of the present invention can be again containing at least one of Zn, Mn, Cu, Na, Li, Sr, Si, Zr element, and the good combination property of alloy can be used for preparing human body implantable medical device.
Description
Technical field
The present invention relates to the ingredient of a kind of heat resistance magnesium alloy designs and preparation method thereof, belong to nonferrous materials and metallurgy
Field.
Background technique
The density of Mg is only 1.74g/cm3, about 22%, the Mg of 64%, the Fe of Al and its alloy have specific strength height, ratio
The advantages that rigidity is high, density is low, good biocompatibility, in fields such as defence and military, communications and transportation, telecommunications and medical instruments
Have wide practical use.Commercial magnesium alloy most common at present is AZ31 and AZ91 in Mg-Al-Zn system (AZ system) magnesium alloy
The magnesium alloy of the trades mark is waited, the Mg in their tissues17Al12The thermal stability of second phase is low, and eutectic temperature is 437 DEG C, the clothes of alloy
It uses as a servant temperature and is no more than 150 DEG C, otherwise mechanical property significantly deteriorates.Most classic in heat resistance magnesium alloy is using WE43 and WE54 as generation
The Mg-RE (RE represents rare earth) of table is magnesium alloy, and up to 250~300 DEG C, this has benefited from alloy their service temperature
The second phase of Mg-RE thermal stability is high, and for eutectic temperature at 500~600 DEG C, the thermal stability of alloy structure is high.But Mg-RE system
Magnesium alloy contains a large amount of rare earth elements, and Gao Chengben hinders its commercialization and promotes.
Main second phase is the high Mg of thermal stability in traditional Mg-Sn system magnesium alloy2Sn, eutectic temperature are 561 DEG C, with
The eutectic temperature of Mg-RE system magnesium alloy is in same level, and therefore, it is to have very much that the thermal stability of Mg-Sn system Magnesium Alloy is high
Wish the low cost for substituting Mg-RE system magnesium alloy, the heat resistance magnesium alloy without rare earth element.It is added in Mg-Sn bianry alloy
Ca may generate Ca in alloy2-xMgxSn and Mg2Second phase containing Ca such as Ca, wherein Ca2-xMgx(this is mutually that Mg enters Ca to Sn2Sn
The solid solution of formation, as x=1 be CaMgSn phase) thermal stability ratio Mg2Sn is higher, can further increase Mg-Sn alloy
Heat resistance.But Ca2-xMgxSn is easily precipitated during magnesium alloy fused mass solidifies first, forms coarse Ca2-xMgxAt the beginning of Sn
Raw phase, isolates magnesium matrix, deteriorates the mechanical property of casting processing performance and alloy.The solid-liquid two-phase region of Mg-Sn-Ca system magnesium alloy
Temperature gap is difficult to prepare by continuous casting at this time up to 125 DEG C, so that the lumber recovery of alloy and production efficiency are difficult to significantly mention
It is high.
Document 1 discloses plus the method for Y thinning CaMgSn phase in Mg-Sn-Ca magnesium alloy, the method pass through in Mg-
The rare earth element y that 0.5~1.5wt.% is added in Sn-Ca system magnesium alloy realizes, the casting side of the Mg-Sn-Ca-Y alloy
Method is casting.The ingredient for the Mg-Sn-Ca base alloy that embodiment includes in the document are as follows: Mg-3Sn-2Ca, Mg-4Sn-
1.5Ca-0.25Mn and Mg-5Sn-2.5Ca.
Document 2 discloses plus the method for Sr thinning CaMgSn phase in Mg-Sn-Ca magnesium alloy, the method pass through in Mg-
The Sr member of 0.05~0.15wt.% of addition is usually realized in Sn-Ca system magnesium alloy, the casting side of the Mg-Sn-Ca-Sr alloy
Method is casting.The ingredient for the Mg-Sn-Ca base alloy that embodiment includes in the document are as follows: Mg-3Sn-1Ca, Mg-3Sn-
2Ca, Mg-4Sn-1.5Ca-0.25Mn, Mg-5Sn-1.5Ca and Mg-5Sn-2.5Ca.
Document 3 discloses plus the method for Ce thinning CaMgSn phase in Mg-Sn-Ca magnesium alloy, the method pass through in Mg-
The rare earth element ce that 0.5~1.5wt.% is added in Sn-Ca system magnesium alloy realizes, the casting of the Mg-Sn-Ca-Ce alloy
Method is casting.The ingredient for the Mg-Sn-Ca base alloy that embodiment includes in the document are as follows: Mg-3Sn-2Ca, Mg-4Sn-
1.5Ca-0.25Mn and Mg-5Sn-2.5Ca.
Document 4 discloses a kind of high intensity Mg-Sn-Ca-Ag system magnesium alloy and preparation method thereof, each alloy in the alloy
The mass percent of elemental composition are as follows: Sn:4~10%, Ca:0.5~3%, Ag:0.5~2.5%, remaining is Mg and micro miscellaneous
Matter, the casting method of the alloy are casting.The alloying component of the alloy is in the range in addition to requiring Ca/Sn mass ratio
≤ 30%, without other qualifications.The alloying component that embodiment includes in the document are as follows: Mg-5Sn-1Ca-0.5Ag, Mg-
5Sn-1.5Ca-0.5Ag、Mg-7Sn-1Ca-1Ag、Mg-7Sn-1Ca-2Ag、Mg-7Sn-2Ca-1Ag、Mg-8Sn-2.3Ca-
0.5Ag, Mg-9Sn-2Ca-1Ag and Mg-10Sn-2.6Ca-1Ag.
Document 5 discloses a kind of Mg-Sn-Ca heat-conductive cast magnesium alloy, the ingredient percent of the alloy are as follows: Sn:
0.2~5%, Ca:0.5~2%, Zn:0.5~5%, Zr:0.2~1%, remaining is Mg, and the casting method of the alloy is to pour
Casting.The alloying component that embodiment includes in the document are as follows: Mg-1Sn-0.5Ca, Mg-3Sn-1.5Ca-0.5Zn, Mg-3Sn-
1.5Ca-1.5Zn and Mg-3Sn-1.5Ca-0.5Zr.
Document 6 discloses a kind of degradable high-strength anticorrosion biological medical magnesium alloy and preparation method thereof, the alloy
Ingredient percent are as follows: Sn:4~7%, Ca:0.5~5%, Zr:0.3~0.7%, remaining is Mg and inevitable impurity
Element, the casting method of the alloy are casting.The alloying component that embodiment includes in the document are as follows: Mg-4Sn-5Ca-
0.3Zr, Mg-5Sn-4Ca-0.6Zr, Mg-6Sn-3Ca-0.7Zr, Mg-7Sn-1Ca-0.5Zr, Mg-7Sn-2Ca-0.5Zr and
Mg-7Sn-3Ca-0.5Zr。
Document 7 disclose it is a kind of can crushing failure at high speed forming magnesium alloy and preparation method thereof, the composition quality hundred of the alloy
Divide ratio are as follows: Sn:0.1~1%, Ca:0.1~1%, Mn:0.1~0.5%, Ce:0.1~0.5%, and their total amount≤2%,
Remaining is Mg, and the casting method of the alloy is continuous casting.The alloying component that embodiment includes in the document are as follows: Mg-0.1Sn-
1Ca-0.5Mn-0.1Ce、Mg-0.1Sn-1Ca-0.1Mn-0.5Ce、Mg-0.5Sn-0.5Ca-0.3Mn-0.25Ce、Mg-
0.5Sn-1Ca-0.1Mn-0.25Ce and Mg-1Sn-0.5Ca-0.1Mn-0.1Ce.
Existing technical literature
Document 1 (patent): CN101440441B adds the method for Y thinning CaMgSn phase in Mg-Sn-Ca magnesium alloy,
Document 2 (patent): CN101985713A adds the method for Sr thinning CaMgSn phase in Mg-Sn-Ca magnesium alloy,
Document 3 (patent): CN101440438B adds the method for Ce thinning CaMgSn phase in Mg-Sn-Ca magnesium alloy,
Document 4 (patent): CN106834840B, a kind of high intensity Mg-Sn-Ca-Ag system magnesium alloy and preparation method thereof,
Document 5 (patent): CN102560210A, a kind of Mg-Sn-Ca heat-conductive cast magnesium alloy,
Document 6 (patent): CN105401033B, a kind of degradable high-strength anticorrosion biological medical magnesium alloy and its preparation side
Method,
Document 7 (patent): CN108486445A, it is a kind of can crushing failure at high speed forming magnesium alloy and preparation method thereof.
Summary of the invention
The invention solves project: design and prepare the heat resistance Mg-Sn system magnesium alloy of suitable continuous casting, in the alloy
Introduce thermal stability ratio Mg2The higher Ca of Sn2-xMgxSn further increases the heat resistance of alloy.It is avoided by ingredient design coarse
Ca2-xMgxSn primary phase is first precipitated from alloy melt in process of setting, and the solid-liquid two-phase region of alloy is controlled narrow
Within the scope of narrow temperature, Mg-Sn-Ca system magnesium alloy is made to be suitble to continuous casting preparation.This will also improve such alloy in common casting, pressure
Fluidity of molten and cavity filling in other liquid processing techniques such as casting reduce the casting flaws such as loose, shrinkage cavity, generally improve
Their liquid processing performance.
It is as described below as the gist of the invention of target to solve the above subject.Unless otherwise instructed, percentage composition is equal
It is defaulted as mass percent.L represents the liquid phase in phase transformation reaction.
A kind of heat-resisting Mg-Sn-Ca system magnesium alloy of suitable continuous casting, it is characterised in that alloy structure is characterized in alloy graining mistake
Mg primary phase, not coarse Ca are initially formed in journey2-xMgxSn (0≤x≤1) phase, narrow temperature of the solid-liquid two-phase region at≤30 DEG C
In area, to meet above-mentioned requirements, ingredient is instructed to design according to scientific algorithm, the ingredient of the alloy meets following require simultaneously:
(1) it is 0.001~1.05% that Sn content, which is 0.01~10%, Ca content, remaining is Mg and other micro or a small amount of alloying members
Element；(2) as 0.01%≤Sn≤3.5%, Ca content meets 0.001%≤y of equation≤0.3013x, wherein x and y generation respectively
Table Sn and Ca content, it is same as below；(3) as 3.5%≤Sn≤10%, Ca content meet 0.001%≤y of equation≤
3.4802x-0.953。
Above-mentioned alloying component is fallen in Fig. 1 in the R1 of Composition Region, and according to above-mentioned mathematical description, alloying component can be in Composition Region
On the boundary line of R1, for convenience of describing, hereinafter referred to as in the R1 of Composition Region.It should be noted that alloying component can also be used
Atomic percent (at.%) indicates that essence is identical as with mass percent (wt.%) expression, the side proposed according to the present invention
Method, researcher in this field are readily available the mathematic(al) representation of the Composition Region R1 indicated with atomic percent, herein no longer
It repeats.
Design of alloy, the alloy are carried out by the Mg-Sn-Ca ternary phase diagrams based on scientific algorithm and experimental verification
In ingredient Composition Region R1 shown in Fig. 1.The horizontal axis x-axis of Fig. 1 represents the mass percent of Sn in alloy, and longitudinal axis y-axis represents alloy
The mass percent of middle Ca.The Composition Region R1 is defined by 4 boundary lines, their mathematic(al) representation are as follows: (1) x-axis, it is corresponding
Linear equation is y=0；(2) boundary line B1, physical significance are eutectic reaction L → Mg+Ca2-xMgxSn, corresponding curvilinear equation are
Y=3.4802x-0.953；(3) boundary line B2, physical significance are narrow temperature model of the solid-liquid two-phase region of restriction alloy at≤30 DEG C
In enclosing, corresponding linear equation is y=0.3013x；(4) it is parallel to boundary line on the right of Fig. 1 of y-axis, corresponding linear equation is x=
10.X=0~10 in the R1 of Composition Region, y=0~1.05, wherein the friendship of (x, y)=(3.5,1.05) corresponding boundary line B1 and B2
Point.
According to the thermodynamics calculation results and experimental verification, the melt of the Mg-Sn-Ca alloy in the Composition Region R1 works as temperature
Degree occurs the liquid-solid phase transformation of L → Mg, Mg is first precipitated in process of setting as primary phase at 640~650 DEG C.Similarly,
Mg primary phase is also precipitated in Mg-Sn-Ca alloy in Fig. 1 in the R2 of Composition Region in process of setting.But in Fig. 1 in the R3 of Composition Region
Mg-Sn-Ca alloy Ca is first precipitated in process of setting2-xMgxSn primary phase, most first occurred phase transformation is L → Ca2-xMgxSn's
Liquid-solid phase transformation, Ca2-xMgxSn (0≤x≤1) primary phase is grown rapidly in the melt, this is that occur in Mg-Sn-Ca system magnesium alloy
Coarse Ca2-xMgxThe essential reason of Sn phase.Alloy of the present invention avoids Composition Region R3, is not in coarse Ca in alloy2-xMgxSn
Phase.Therefore, different from document 1~3, alloy of the present invention is not necessarily to refine CaMgSn by the way that RE (rare earth element) or Sr is added
Phase.
According to the thermodynamics calculation results and experimental verification, the solid-liquid two-phase region of the Mg-Sn-Ca alloy in the Composition Region R1
Temperature range≤30 DEG C, the mobility and cavity filling of alloy melt are higher, are suitable for a variety of liquid processing such as continuous casting, casting, die casting
Technique, especially being capable of continuous casting.Alloy of the present invention avoids Composition Region R2 and R3, the Mg-Sn-Ca alloy in these Composition Regions
Solid-liquid two-phase region temperature range is greater than 30 DEG C, and some is even greater than 100 DEG C, is formed in very wide warm area in alloy graining process
Mushy zone, mobility and cavity filling are poor, easily occur the defects of loose and shrinkage cavity in casting, by bleedout or drawing easily in continuous casting
It is disconnected, be not suitable for continuous casting.For example, according to calculation of thermodynamics, the solid-liquid two-phase region temperature of Mg-5Sn-1.5Ca base alloy in document 4
Range is 46 DEG C, and the solid-liquid two-phase region temperature range of Mg-3Sn-1.5Ca base alloy is 80 DEG C in document 5, therefore they are all
Casting preparation.
Because the liquid-solid phase transformation of L → Mg occurs in 640~650 DEG C of narrow warm area for alloy of the present invention, continuous casting, casting,
In a variety of liquid processing such as die casting, it is contemplated that the degree of superheat of needs is melted, it can be in 670~699 DEG C of relatively low-temperature space to the present invention
The melt of alloy is kept the temperature or is refined.Alloy in Fig. 1 in the R3 of Composition Region, may be in 700 DEG C or more generation L → Ca2- xMgxThe liquid-solid phase transformation of Sn, therefore, melt heat preservation or refining not preferably less than 700 DEG C of temperature.It is thus understood that in document 1~7
Alloy melt heat preservation or refining temperature at 700~850 DEG C.Alloy of the present invention is in 670~699 DEG C of progress melt heat preservations or essence
The time of refining is 3~19min, and to keep alloy melt ingredient uniform, using pure magnesium, Mg-37Sn eutectic intermediate alloy, (amount containing Sn is
37wt.%) and Mg-16Ca eutectic intermediate alloy (amount containing Ca is 16wt.%) is that raw material carries out alloy melting.Mg-37Sn eutectic
Intermediate alloy and Mg-16Ca eutectic intermediate alloy respectively correspond Mg-Sn alloy and the minimum alloying component of Mg-Ca alloy melting point,
Fusing point is respectively 561 DEG C and 517 DEG C, and the fusing point of pure magnesium is 650 DEG C, is sufficiently melted when raw material is warming up to 670~699 DEG C.
In the Composition Region R1, ternary eutectic reaction L → Mg+Ca occurs in process of setting for Mg-Sn-Ca alloy2- xMgxSn+Mg2Sn or solid-state phase changes react Mg based solid solution → Mg2Sn forms Mg in alloy2The second phase of Sn.But in Composition Region R2
Interior, ternary eutectic reaction L → Mg+Ca occurs in process of setting for Mg-Sn-Ca alloy2-xMgxSn+Mg2Ca or solid-state phase changes reaction
Mg based solid solution → Mg2Ca forms Mg in alloy2The second phase of Ca.By the effect that Magnesium Alloy thermal stability is improved from height to
Low sequence: Ca2-xMgxSn (fusing point > 900 DEG C) > Mg2Sn (771 DEG C of fusing point) > Mg2Ca (715 DEG C of fusing point).Alloy structure of the present invention
In introduce the highest Ca of thermal stability2-xMgxThe second phase of Sn, is different from Mg2Sn is traditional Mg-Sn system magnesium of Main Second Phase
Alloy.Second phase size is tiny in alloy of the present invention, Ca2-xMgxThe average length of Sn is distributed in grain boundaries less than 20 μm；Mg2Sn
Average diameter less than 5 μm, be distributed in transgranular or grain boundaries.
Further, alloy of the present invention also contains at least one of Zn, Mn, Cu, Na, Li, Sr, Si, Zr element, content
Are as follows: Zn:0.1~7%, Mn:0.1~0.5%, Cu:0.1~1%, Na:0.1~0.3%, Li:0.1~0.5%, Sr:0.01
~0.08%, Si:0.15~0.35%, Zr:0.3~1.0%.The purpose that Zn is added is to form Mg-Zn (such as MgZn2、
Mg4Zn7Deng) precipitated phase, improve alloy strength；The purpose that Mn is added is possible Fe impurity in removal raw material, and it is resistance to improve alloy
Corrosion；The purpose that Cu, Na, Li is added is refinement Mg2Sn phase；The effect that Sr, Si, Zr is added is refinement crystal grain.
Further, Mg-Sn-Ca alloy of the present invention, equilibrium at room temperature phase composition are Mg+Ca2-xMgxSn+Mg2Sn,
Middle Mg is matrix, Ca2-xMgxSn and Mg2Sn is the second phase, Ca2-xMgxThe average length of Sn is distributed in grain boundaries less than 20 μm；
Mg2The average diameter of Sn is distributed in transgranular or grain boundaries less than 5 μm.
Further, the alloy is suitable for commonly casting, die-casting process simultaneously, due in 640~650 DEG C of generation L → Mg
Liquid-solid-phase changeable, the liquid processing technique is characterized in can be in the heat preservation or essence of 670~699 DEG C of 3~19min of low-temperature spaces progress
Refining.
A kind of heat-resisting Mg-Sn-Ca system magnesium alloy of suitable continuous casting as described above, it is characterised in that slab can be by rolling
The subsequent solid-states such as system, extruding, drawing, forging and heat treatment are processed into the product of a variety of shapes and sizes.Since the present invention closes
Payment organization heat resistance is high, and during room temperature, the temperature that liquid phase occurs can be greater than 600 DEG C, the spy of the solid-state processing
Sign is that the holding temperature and processing temperature before processing may be up to 530~600 DEG C.
Further, alloy of the present invention, room-temperature yield strength be 40~420MPa, tensile strength be 100~
460MPa, elongation after fracture are 1~25%, and the stable state under 200~300 DEG C and 15~35MPa plus load action conditions is compacted
Variable Rate is 0.2~35 × 10-7/ s, biocompatibility are good.
Further, after obtaining the slab of alloy of the present invention by liquid processing techniques such as continuous casting, casting, die casting, may be used also
To be processed into the product of a variety of shapes and sizes by subsequent solid-state, and realize the regulation of alloy structure and performance.Described
After solid-state processing, the tissue and performance of alloy can also be further regulated and controled by being heat-treated.The solid-state processing includes rolling, squeezes
At least one of pressure, drawing, forging and heat treatment.The heat treatment includes solid solution, quenching and timeliness.According to calculation of thermodynamics
As a result and experimental verification, alloy structure of the present invention liquid phase can just occur from room temperature at 600 DEG C or more, and liquid phase occurs most
High-temperature is 640 DEG C, close to 650 DEG C of pure magnesium fusing point, approaches the heat-resistant limit temperature of magnesium alloy.Therefore, alloy of the present invention is in institute
Holding temperature, processing temperature and solid solubility temperature before stating solid-state processing is up to 530~600 DEG C.And all implementations in document 1~7
The ingredient of the Mg-Sn-Ca base alloy of example alloy is all fallen in Fig. 1 in Composition Region R2 or R3, and heating may go out at 550 DEG C or less
Existing liquid phase, limits the processing and heat-treatment temperature range of alloy.For example, the Mg- according to calculation of thermodynamics, in document 1~3
It is 528 DEG C that temperature, which occurs, in the heating liquid phase of 3Sn-2Ca base alloy.The maximum temperature that solid-state is processed in document 1~7 is 520 DEG C.
The Mg-Sn-Ca system magnesium alloy that Mg-Sn-Ca system provided by the invention magnesium alloy and existing technical literature 1~7 provide
Significant difference and thus bring advantage is at least following one:
(1) alloy of the present invention is without rare earth element and other your dilute elements, such as Ag, Sc etc., at low cost, good economy performance,
It is promoted suitable for commercialization.Document 1 contains rare earth element y, and document 3 and document 7 contain rare earth element ce, and document 4 contains your dilute element
Ag。
(2) primary phase in alloy graining process of the present invention is Mg, rather than Ca2-xMgxSn is instructed by scientific algorithm
Ingredient design avoid and occur coarse Ca in alloy structure2-xMgxSn.And institute in document 1, document 3, document 4 and document 6
The ingredient of the Mg-Sn-Ca base alloy of some embodiment alloys is all fallen in Fig. 1 in the R3 of Composition Region, is analysed in alloy graining process
Coarse Ca out2-xMgxSn primary phase, therefore these documents refine Ca by further alloying2-xMgxSn phase.It is similar
The ingredient of the Mg-Sn-Ca base alloy of most of embodiment alloys is also fallen in the R3 of Composition Region in ground, document 2 and document 5.
(3) the equilibrium at room temperature phase composition of alloy of the present invention is Mg+Ca2-xMgxSn+Mg2Sn, wherein Mg is matrix, Ca2- xMgxSn and Mg2Sn is the second phase.And the ingredient of the Mg-Sn-Ca base alloy of all embodiment alloys all falls in Fig. 1 in document 7
In middle Composition Region R2, the equilibrium at room temperature phase composition of alloy is Mg+Ca2-xMgxSn+Mg2Ca, thermal stability are lower than alloy of the present invention.
Similarly, the ingredient of the Mg-Sn-Ca base alloy of a small number of embodiment alloys is also fallen in the R2 of Composition Region in document 2 and document 5.
(4) for alloy structure of the present invention during from room temperature, the temperature that liquid phase occurs can be greater than 600 DEG C, be higher than
With Mg2Sn is for traditional Mg-Sn based alloy (be warming up to 561 DEG C and liquid phase occur) of Main Second Phase and with Mg2Ca is Main Second Phase
Mg-Ca based alloy (be warming up to 517 DEG C and liquid phase occur).Therefore, the military service, hot-working of alloy of the present invention and the temperature of heat treatment
Range is wider.
(5) solid-liquid two-phase region of alloy of the present invention is in≤30 DEG C of narrow temperature, fluidity of alloy melt and fills
The defects of type is good, and loose and shrinkage cavity is less prone in the liquid processing techniques such as casting, die casting, be not easy in continuous casting bleedout or
It breaks, is particularly suitable for continuous casting preparation.The ingredient of the Mg-Sn-Ca base alloy of embodiment alloy is in the Composition Region Fig. 1 in document 1~6
In R3 and R2, solid-liquid two-phase region temperature range is wide, is not suitable for continuous casting preparation, therefore prepare alloy with casting in the above documents
Slab.
(6) alloy of the present invention, which rests on a scientific basis to calculate, carries out ingredient design, is different from traditional " trial and error based on testing
The design of method " ingredient.The mathematical description and physical significance in alloying component area proposed by the present invention be document 1~7 not it is proposed that.This
The ingredient of invention alloy does not have the basis Mg-Sn-Ca of any embodiment alloy in Fig. 1 in the R1 of Composition Region in document 1~7
The ingredient of alloy is in the R1 of Composition Region.
(7) alloying element of alloy of the present invention be human body must or harmless element, the biocompatibility of alloy
Well, in addition to can be used for application of the conventional magnesium alloy as structural material, it may also be used for human body implantable medical device is prepared,
Including but not limited to: bone nail, spicule, bone plate, intravascular stent and intracranial stent.
Detailed description of the invention
Fig. 1 is the Composition Region R1 of the heat-resisting Mg-Sn-Ca system magnesium alloy of the suitable continuous casting determined based on scientific algorithm, in figure
R1~R3 is 3 different Composition Regions, and B1 and B2 are Composition Region boundary line, and L represents liquid phase, wt.% representation quality percentage.
Specific embodiment
In the following, clearly illustrating effect of the invention by embodiment.In addition, the invention is not limited to below
Embodiment can appropriately be changed in the range of not changing main idea and is implemented.
Following alloying component is defaulted as mass percent.The test of alloy mechanical property is all in room in all embodiments
Temperature carries out.Alloying component can also indicate that any researcher of this field can be according to quality hundred using atomic percent
Divide than deriving that mathematics of the Composition Region R1 as unit of atomic percent is retouched in Fig. 1 with the conversion relation between atomic percent
It states, is repeated no more in the present invention.
Embodiment 1: narrow solid-liquid two-phase region Mg-Sn-Ca ternary magnesium alloy continuous casting wire rod is prepared
The ingredient of example alloy is in the R1 of the Composition Region Fig. 1, as shown in table 1-1.To be closed among pure magnesium, Mg-37Sn eutectic
Gold and Mg-16Ca eutectic intermediate alloy are that raw material prepares example alloy.By being put into continuous casting after the composition proportion raw material in table 1-1
It in machine, vacuumizes after filling protection against oxidation gas, induction heating melts raw material, starts after 670~699 DEG C of heat preservation 15min
Throwing, drawing speed are 1~10mm/min, and cooling water temperature is 10~15 DEG C, and casting mold outlet temperature is 430~500 DEG C.Continuous casting
The diameter for obtaining surface-brightening is the alloy wire slab of 5~10mm.Slab is using Mg column crystal as matrix, containing tiny
CaMgSn and Mg2The second phase of Sn.The average length of CaMgSn is distributed in grain boundaries less than 20 μm；Mg2The average diameter of Sn is less than 5
μm, it is distributed in transgranular or grain boundaries.
Table 1- is measured according to national standard GB/T 228.1-2010 " metal material stretching test part 1, room temperature test method "
In 1 the room-temperature yield strength of example alloy be 40~80MPa, tensile strength be 100~130MPa, elongation after fracture be 5~
25%.Example alloy is measured in table 1-1 200 according to GB/T 2039-1997 " metal stretching creep and duration running method "
Secondary creep rates under~300 DEG C and 15~35MPa plus load action conditions are 0.2~35 × 10-7/s.According to GB/T
16886.5-2017 " the 5th part of BiologicalEvaluationofMedicalDevice: vitro cytotoxicity test " measures example alloy in table 1-1
Leaching liquor it is free of toxic effects to L929 cell and Human umbilical vein endothelial cells (HUVEC), biocompatibility is good.
Table 1-1
Embodiment 2: microalloying Mg-Sn-Ca system quaternary magnesium alloy rolling wire rod is prepared
The ingredient of the Mg-Sn-Ca base alloy of example alloy further adds on this basis in the R1 of the Composition Region Fig. 1
Add a kind of micro-alloying elements, as shown in table 2-1.Alloying component is indicated using international practice in table, is with example alloy 12
Example illustrates, in the alloy: Sn 2.5%, Ca 0.7%, Zn 0.1%, surplus Mg similarly know other example alloys
Ingredient.Micro alloying element is also added in the form of Mg base intermediate alloy, continuous casting billet is made according to the method for embodiment 1, so
Pass is rolled into finished wire rod afterwards.Rolling temperature is 25~350 DEG C, and total deformation is 60~98%.
The room-temperature yield strength for measuring alloy finished product wire rod in table 2-1 according to the method for embodiment 1 is 115~230MPa,
Tensile strength is 143~460MPa, and elongation after fracture is 1~25%, is acted in 200~300 DEG C and 15~35MPa plus load
Under the conditions of secondary creep rates be 0.2~35 × 10-7/ s, biocompatibility are good.
Table 2-1
| Example | Alloying component (mass percent, wt.%) |
| 12 | Mg-2.5Sn-0.7Ca-0.1Zn |
| 13 | Mg-3.5Sn-1Ca-0.1Mn |
| 14 | Mg-4.5Sn-0.5Ca-0.1Cu |
| 15 | Mg-0.2Sn-0.06Ca-0.1Na |
| 16 | Mg-1.5Sn-0.4Ca-0.1Li |
| 17 | Mg-5.5Sn-0.6Ca-0.01Sr |
| 18 | Mg-6.5Sn-0.5Ca-0.15Si |
| 19 | Mg-7.5Sn-0.3Ca-0.3Zr |
Embodiment 3: novel Mg-Sn-Ca system complex magnesium alloy plate is prepared
The ingredient of the Mg-Sn-Ca base alloy of example alloy further adds on this basis in the R1 of the Composition Region Fig. 1
Add at least one kind of alloy element, as shown in table 3-1.Alloying element is added all in the form of Mg base intermediate alloy, uses casting side
Legal system obtains slab, carries out homogenization heat treatment to slab, and plate then is made by rolling or extrusion process, then sends out part
Bright example alloy is dissolved, is quenched and aging strengthening model.
The casting refining temperature is 670~699 DEG C, and soaking time is 3~19min, casts in and is preheated to 200~300
DEG C high purity graphite mold in, be cooled to room temperature obtain slab.
The temperature of the homogenization heat treatment is 400~600 DEG C, and soaking time is 30min~48h.
The temperature of the rolling is 25~350 DEG C, and total deformation is 40~98%.
The temperature of the extruding is 150~250 DEG C, and extrusion ratio is 9~36.
Example alloy 20 and 25~28 is carried out to be dissolved → quench → timeliness.The temperature of the solid solution is 300~600
DEG C, soaking time is 5~15min；Immediately by the example alloy in cold quenching-in water after solid solution；The aging temp
It is 180~250 DEG C, soaking time is 5~100h.
The room-temperature yield strength for measuring alloy finished product wire rod in table 3-1 according to the method for embodiment 1 is 134~420MPa,
Tensile strength is 152~460MPa, and elongation after fracture is 1~20%, is acted in 200~300 DEG C and 15~35MPa plus load
Under the conditions of secondary creep rates be 0.2~35 × 10-7/ s, biocompatibility are good.
Table 3-1
| Example | Alloying component (mass percent, wt.%) |
| 20 | Mg-2.5Sn-0.7Ca-7Zn |
| 21 | Mg-3.5Sn-1Ca-0.5Mn |
| 22 | Mg-4.5Sn-0.5Ca-1Cu |
| 23 | Mg-0.2Sn-0.06Ca-0.3Na |
| 24 | Mg-1.5Sn-0.4Ca-0.5Li |
| 25 | Mg-5.5Sn-0.6Ca-0.08Sr |
| 26 | Mg-6.5Sn-0.5Ca-0.35Si |
| 27 | Mg-7.5Sn-0.3Ca-1Zr |
| 28 | Mg-6Sn-0.6Ca-6Zn-0.2Mn |
| 29 | Mg-3Sn-0.9Ca-0.2Na |
Embodiment 4: novel Mg-Sn-Ca system complex magnesium alloy extruded bars are prepared
The ingredient of the Mg-Sn-Ca base alloy of example alloy further adds on this basis in the R1 of the Composition Region Fig. 1
Add at least two kinds of alloy elements, as shown in table 4-1.Alloying element is added all in the form of Mg base intermediate alloy, according to embodiment
The continuous casting billet that diameter is 20mm is made in 1 method, then obtains finished product bar by squeezing.The extruding is according to embodiment 3
Method carries out.
The room-temperature yield strength for measuring alloy finished product wire rod in table 4-1 according to the method for embodiment 1 is 120~420MPa,
Tensile strength is 150~460MPa, and elongation after fracture is 1~25%, is acted in 200~300 DEG C and 15~35MPa plus load
Under the conditions of secondary creep rates be 0.2~35 × 10-7/ s, biocompatibility are good.
Table 4-1
| Example | Alloying component (mass percent, wt.%) |
| 30 | Mg-8Sn-0.4Ca-3Zn-0.3Na |
| 31 | Mg-6Sn-0.5Ca-6Zn-0.5Mn |
| 32 | Mg-9.5Sn-0.3Ca-0.5Sr-0.5Li |
| 33 | Mg-5.5Sn-0.5Ca-1Cu-0.8Zr |
| 34 | Mg-4Sn-0.9Ca-3Zn-0.2Mn |
| 35 | Mg-3Sn-0.5Ca-0.3Mn-0.2Si-0.5Cu |
| 36 | Mg-5Sn-0.5Ca-5Zn-0.3Mn-0.02Sr |
| 37 | Mg-4Sn-0.8Ca-3Zn-0.4Mn-0.15Si |
| 38 | Mg-2Sn-0.6Ca-1Zn-0.2Mn-0.3Cu-0.2Na-0.3Zr |
| 39 | Mg-1Sn-0.3Ca-0.15Si-0.12Cu |
| 40 | Mg-0.5Sn-0.1Ca-0.1Li-0.01Sr |
Claims (6)
1. a kind of heat-resisting Mg-Sn-Ca system magnesium alloy of suitable continuous casting, it is characterised in that alloy structure is characterized in alloy graining process
In be initially formed Mg primary phase, not coarse Ca2-xMgxSn (0≤x≤1) phase, narrow warm area of the solid-liquid two-phase region at≤30 DEG C
Interior, the ingredient of the alloy meets following require simultaneously: (1) Sn content be 0.01~10%, Ca content be 0.001~
1.05%, remaining is Mg and other micro or a small amount of alloy elements；(2) as 0.01%≤Sn≤3.5%, Ca content meets
0.001%≤y of equation≤0.3013x, wherein x and y respectively represents Sn and Ca content, same as below；(3) when 3.5%≤Sn≤
When 10%, Ca content meets 0.001%≤y of equation≤3.4802x-0.953。
2. a kind of heat-resisting Mg-Sn-Ca system magnesium alloy of suitable continuous casting as described in claim 1, it is characterised in that the present invention closes
Gold is also containing at least one of Zn, Mn, Cu, Na, Li, Sr, Si, Zr element, content are as follows: and Zn:0.1~7%, Mn:0.1~
0.5%, Cu:0.1~1%, Na:0.1~0.3%, Li:0.1~0.5%, Sr:0.01~0.08%, Si:0.15~
0.35%, Zr:0.3~1.0%.
3. a kind of heat-resisting Mg-Sn-Ca system magnesium alloy of suitable continuous casting as claimed in claim 1 or 2, it is characterised in that alloy
Mg-Sn-Ca alloy, equilibrium at room temperature phase composition are Mg+Ca2-xMgxSn+Mg2Sn, wherein Mg is matrix, Ca2-xMgxSn and Mg2Sn
For the second phase, Ca2-xMgxThe average length of Sn is distributed in grain boundaries less than 20 μm；Mg2The average diameter of Sn is less than 5 μm, distribution
In transgranular or grain boundaries.
4. a kind of preparation method of the heat-resisting Mg-Sn-Ca system magnesium alloy of suitable continuous casting as claimed in claim 1 or 2, feature exist
Be suitable for commonly casting simultaneously in the alloy, die-casting process, 670~699 DEG C of low-temperature spaces carry out 3~19min heat preservation or
Refining.
5. a kind of preparation method of the heat-resisting Mg-Sn-Ca system magnesium alloy of suitable continuous casting as claimed in claim 1 or 2, feature exist
The product of a variety of shapes and sizes can be processed by rolling, extruding, drawing, forging and the subsequent solid-state of heat treatment in slab.
6. a kind of preparation method of the heat-resisting Mg-Sn-Ca system magnesium alloy of suitable continuous casting as claimed in claim 5, it is characterised in that
The Alloy At Room Temperature yield strength is 40~420MPa, and tensile strength is 100~460MPa, and elongation after fracture is 1~25%,
Secondary creep rates under 200~300 DEG C and 15~35MPa plus load action conditions are 0.2~35 × 10-7/ s, biology
Compatibility is good.
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| CN113684406A (en) * | 2021-08-26 | 2021-11-23 | 承德石油高等专科学校 | Scandium-containing high-strength extruded Mg-Sn-Ca alloy and preparation method thereof |
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| CN113684406A (en) * | 2021-08-26 | 2021-11-23 | 承德石油高等专科学校 | Scandium-containing high-strength extruded Mg-Sn-Ca alloy and preparation method thereof |
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