CN112779445A - Heat-resistant cast aluminum-zinc alloy and preparation method thereof - Google Patents
Heat-resistant cast aluminum-zinc alloy and preparation method thereof Download PDFInfo
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Abstract
The invention provides a heat-resistant cast aluminum-zinc alloy and a preparation method thereof. The invention comprises the following elements: 4.0-5.3% of Zn, 1.5-2.9% of Si, 1.5-2.3% of Cu, 0.3-0.6% of Mg, 1.5-2.5% of Ca, 0.2-0.6% of Ba, less than or equal to 0.2% of impurities and the balance of Al; wZn/(WSi+WCa+WBa) Less than or equal to 1.19; the invention also provides a preparation method of the alloy, which comprises the steps of adding raw materials, smelting and casting. The invention forms a dense eutectic reticular Al-Zn-Cu-Ca-Mg-Ba precipitated phase, effectively strengthens the matrix structure of the alloy, obviously improves the tensile strength of the alloy, and ensures that the alloy has good heat resistance, and the tensile strength can reach 310-320 MPa; keeping the temperature at 220 DEG CThe tensile strength does not decline after 200h, and the product can be used for a long time at 220 ℃.
Description
Technical Field
The invention relates to the technical field of aluminum-zinc alloy, in particular to a heat-resistant cast aluminum-zinc alloy and a preparation method thereof.
Background
The aluminum-zinc alloy is a casting aluminum alloy which is light and can be strengthened without heat treatment, has good casting performance, is suitable for various casting methods, is commonly used for manufacturing complex thin-wall airplane accessories, instrument parts and the like, and is popularized and applied in the fields of aviation and vehicles. Compared with the traditional cast aluminum alloy, the cast aluminum-zinc alloy can reach certain strength without heat treatment. The working temperature of the existing cast aluminum-zinc alloy is lower, and generally can not exceed 180 ℃, and the strength of the existing cast aluminum-zinc alloy is lower; however, in some special industries, for example: the engine comprises parts such as a base plate of a special engine, an engine sound-proof housing and the like, wherein the special parts usually require the service temperature to be 200 ℃; therefore, the existing cast aluminum-zinc alloy can not meet the use requirement of the special part, which limits the development and application of the cast aluminum-zinc alloy to a certain extent.
Disclosure of Invention
The invention aims to provide a heat-resistant cast aluminum-zinc alloy and a preparation method thereof, and aims to solve the problem that the application of the cast aluminum-zinc alloy is limited because the cast aluminum-zinc alloy cannot meet the service temperature requirements of parts such as a base disc of a special engine, an engine sound-proof housing and the like due to low working temperature and strength in the prior art.
In order to solve the technical problem at the last time, the technical scheme of the invention is realized as follows:
in one aspect, the heat-resistant cast aluminum-zinc alloy comprises the following elements in percentage by weight: 4.0 to 5.3 percent of Zn, 1.5 to 2.9 percent of Si, 1.5 to 2.3 percent of Cu, 0.3 to 0.6 percent of Mg, 1.5 to 2.5 percent of Ca, 0.2 to 0.6 percent of Ba, less than or equal to 0.2 percent of impurities and the balance of Al.
In the heat-resistant cast aluminum-zinc alloy, Al, Zn, Cu, Ca, Mg and Ba elements form dense eutectic net-shaped Al-Zn-Cu-Ca-Mg-Ba precipitated phases in an alloy matrix, and the net-shaped precipitated phases effectively strengthen the matrix structure of the alloy and obviously improve the tensile strength of the alloy; meanwhile, the net precipitated phases have good high-temperature stability, so that the alloy has good heat resistance. When the heat-resistant cast aluminum-zinc alloy is in an as-cast state, the tensile strength can reach 310-320MPa, and the elongation is 3.0-3.8%; the heat preservation treatment is carried out for 2 hours at the temperature of 220 ℃, and the tensile strength is still maintained at 317MPa of 310-; keeping the temperature at 220 ℃ for 200h, and basically not reducing the tensile strength; keeping the temperature at 220 ℃ for 200h, and keeping the tensile strength unchanged; therefore, the heat-resistant cast aluminum-zinc alloy can be used for a long time at a high temperature of 220 ℃, is widely applied to parts with higher requirements on service temperature, such as a base plate of a special engine, an engine sound-proof housing and the like, and expands the application range.
As a preferred embodiment, the impurities comprise the following elements in weight percent: fe is less than or equal to 0.10 percent, Sn is less than or equal to 0.05 percent, and Pb is less than or equal to 0.05 percent. The impurities of the invention are mainly derived from raw materials of elements, the content of the impurities is better, and the impurities are iron elements, tin elements and lead elements. In the cast aluminum-zinc alloy, when the iron content is high, the iron element and aluminum easily form a thick and thick insoluble strip compound, and a matrix is cut in the stretching process, so that the strength and the elongation of the alloy are reduced; when the content of tin or lead element exceeds 0.05%, tin atoms and lead atoms enter the middle of aluminum atoms, the average atomic distance of the aluminum atoms is increased, stress is generated on the surface layer of the crystal, and the elastic modulus and the elongation of the alloy are also reduced.
As a preferred embodiment, the alloy comprises the following elements in percentage by weight: 4.5 to 5.1 percent of Zn, 1.9 to 2.7 percent of Si, 1.5 to 1.8 percent of Cu, 0.3 to 0.4 percent of Mg, 1.8 to 1.9 percent of Ca, 0.3 to 0.4 percent of Ba, less than or equal to 0.1 percent of impurities and the balance of Al. The invention has low zinc element content, improves the corrosion resistance of the cast copper-zinc alloy; the heat-resistant cast aluminum-zinc alloy also contains silicon, copper, magnesium, calcium and barium, and can react with zinc element to produce stable net precipitated phase in the solidification process, and the net precipitated phase can effectively strengthen a matrix; meanwhile, proper silicon element can effectively improve the fluidity of the aluminum melt, improve the feeding capacity and improve the internal quality of the alloy; the copper, the magnesium, the calcium and the barium jointly act on the reticular precipitated phase, and the thermal stability of the reticular precipitated phase is improved.
As a preferred embodiment, the impurities comprise the following elements in weight percent: fe is less than or equal to 0.07 percent, Sn is less than or equal to 0.02 percent, and Pb is less than or equal to 0.01 percent. The invention further controls the content of impurities, improves the purity of the heat-resistant casting aluminum-zinc alloy and further reduces the influence of impurity elements on the performance of the heat-resistant casting aluminum-zinc alloy.
In a preferred embodiment, the heat-resistant cast aluminum-zinc alloy contains the following elements in percentage by weight: wZn/(WSi+WCa+WBa) Less than or equal to 1.19; wherein, WZnIs the weight percentage content of Zn element; wSiIs the weight percentage content of Si element; wCaThe weight percentage of Ca element; wBaIs the weight percentage of Ba element. The invention controls the weight percentage content of Zn, Si, Ca and Ba elements, thereby controlling the precipitated phase of eutectic net Al-Zn-Cu-Ca-Mg-Ba; when W isZn/(WSi+WCa+WBa) When the temperature is more than 1.19, the eutectic net Al-Zn-Cu-Ca-Mg-Ba precipitated phase begins to grow and has microcracks, which has adverse effect on the comprehensive mechanical properties of the heat-resistant cast aluminum-zinc alloy.
As a preferred embodimentAccording to the scheme, in the heat-resistant cast aluminum-zinc alloy, the weight percentage content of Zn, Si, Ca and Ba elements meets the following requirements: wZn/(WSi+WCa+WBa) Less than or equal to 1.05; wherein, WZnIs the weight percentage content of Zn element; wSiIs the weight percentage content of Si element; wCaThe weight percentage of Ca element; wBaIs the weight percentage of Ba element. W in the inventionZn/(WSi+WCa+WBa) When the temperature is more than 1.41, the precipitation phase of the eutectic net Al-Zn-Cu-Ca-Mg-Ba begins to be obviously coarsened, cracks begin to appear in the precipitation phase of the eutectic net Al-Zn-Cu-Ca-Mg-Ba, the tensile strength of the heat-resistant cast aluminum-zinc alloy is obviously reduced, and the elongation is also obviously reduced; therefore, the present invention requires controlling the weight percentage of the elements Zn, Si, Ca and Ba.
In another aspect, the invention provides a method for preparing a heat-resistant cast aluminum-zinc alloy, comprising the following steps: 1) firstly, heating a smelting furnace to raise the temperature of the smelting furnace to 280 ℃ of 200-; 2) cooling to reduce the temperature of the melting furnace to 700-; 3) keeping the temperature of the furnace at 700-710 ℃, adding the raw material containing Mg, stirring for 3-5min, adopting inert gas for rotary blowing for 10-15min, standing for 5-8min, and pouring to obtain the heat-resistant cast aluminum-zinc alloy.
The preparation method of the heat-resistant cast aluminum-zinc alloy comprises the steps of firstly heating a smelting furnace, adding raw materials containing aluminum, zinc, silicon, copper and calcium elements, then heating to melt the raw materials, then adding the raw materials containing barium elements and a refining agent, adding the raw materials containing magnesium elements, and finally, blowing, standing and pouring to obtain the heat-resistant cast aluminum-zinc alloy; according to the invention, the magnesium element is added after the refining agent, so that the burning loss of the magnesium element can be reduced, the cost is reduced, and meanwhile, the content of the magnesium element can be accurately controlled; the preparation method of the heat-resistant cast aluminum-zinc alloy is simple, low in cost, convenient to operate, easy to master and easy to realize industrialization.
As a preferred embodiment, in the step 1), the Al-containing material is pure aluminum metal, the Zn-containing material is pure zinc metal, and the Ca-containing material is pure calcium metal; in the step 3), the raw material containing Mg element is pure magnesium metal. In the invention, the aluminum element is used as a matrix, the content of the aluminum element is the maximum, and the aluminum element is added in a pure metal form; the zinc metal and the magnesium metal are more and easily obtained, and the zinc element and the magnesium element are also added in a pure metal form; the calcium element is also added in the form of pure calcium metal; the pure metal has wide source, low price, easy obtaining and convenient use.
As a preferred embodiment, the purity of the pure aluminum metal is not less than 99.993%, the purity of the pure zinc metal is not less than 99.95%, the purity of the pure calcium metal is not less than 99.99%, and the purity of the pure magnesium metal is not less than 99.95%. The pure metal aluminum is Al99.993, and the element content requirement meets the GB/T8644-2000 requirement; the pure metal zinc of the invention is Zn99.95, and the element content requirement meets the GB/T470-2008 requirement; the pure metal calcium is Ca99.99, and the element content requirement meets the GB/T4864-2008 requirement; the pure magnesium metal is Mg99.95, and the element content requirement meets the requirement of GB/T3499-; the impurity elements of the obtained heat-resistant casting aluminum-zinc alloy are controlled by strictly controlling the purity of each element raw material, so that the performance of the heat-resistant casting aluminum-zinc alloy is improved.
In a preferred embodiment, in the step 1), the Si-containing material is a silicon alloy, and the Cu-containing material is a copper alloy. In the invention, the raw materials of the silicon and the copper elements are added in the form of the intermediate alloy, and because the content of the silicon and the copper elements is low, the silicon and the copper elements added in the form of the intermediate alloy are easy to mix with the raw materials of other elements, thereby improving the uniformity of the heat-resistant cast aluminum-zinc alloy.
In a preferred embodiment, the silicon alloy is AlSi12 and the copper alloy is AlCu 50. The silicon alloy AlSi12 meets the requirement of GB/T27677-2011 on the element content; the copper alloy AlCu50 meets the requirement of GB/T27677-2011 on element content; the silicon intermediate alloy is aluminum-silicon alloy, the copper intermediate alloy is aluminum-copper alloy, and the intermediate alloys do not contain elements irrelevant to heat-resistant cast aluminum-zinc alloy, so that the purity of the heat-resistant cast aluminum-zinc alloy is further improved.
As a preferred embodiment, in the step 2), the Ba-containing raw material is a barium salt, preferably, the barium salt is BaCl2. In the invention, the raw material of Ba element is added in a salt mode, barium salt covers the surface of the aluminum melt, reacts with aluminum continuously to replace Ba atoms, and is suspended in the aluminum melt, and the Ba element added in the mode is distributed more uniformly. In general, barium chloride is adopted as the barium salt, and the technical requirement meets the requirements of class I superior products in GB/T1617-2014.
In a preferred embodiment, in the step 2), the refining agent is a mixture of hexachloroethane and titanium dioxide in a mass ratio of 2: 1. The refining agent in the invention is commonly used in the cast aluminum industry, namely hexachloroethane (C)2Cl6) And titanium dioxide (TiO)2) A mixture of components. The refining agent has wide source, convenient acquisition and convenient use.
In a preferred embodiment, in step 3), the inert gas is any one or more of nitrogen, helium, argon and neon. The aluminum alloy obtained in the smelting furnace needs to be blown by inert gas in a rotating mode, the inert gas floats upwards in the alloy melt after being sprayed out of the rotating graphite nozzle, the hydrogen partial pressure in the bubbles of the inert gas just coming out of the graphite nozzle is 0, the hydrogen in the alloy melt diffuses into the bubbles of the inert gas in the bubble floating process, and floats upwards to the surface along with the bubbles, so that the hydrogen is discharged; therefore, the inert gas in the present invention has an effective degassing effect.
Compared with the prior art, the invention has the beneficial effects that: in the heat-resistant cast aluminum-zinc alloy, Al, Zn, Cu, Ca, Mg and Ba elements form dense eutectic net-shaped Al-Zn-Cu-Ca-Mg-Ba precipitated phases in an alloy matrix, and the net-shaped precipitated phases effectively strengthen the matrix structure of the alloy and obviously improve the tensile strength of the alloy; meanwhile, the net precipitated phases have good high-temperature stability, so that the alloy has good heat resistance. The heat-resistant cast aluminum-zinc alloy has low zinc element content, and improves the corrosion resistance of the cast copper-zinc alloy; when in an as-cast state, the tensile strength can reach 310-320MPa, and the elongation is 3.1-3.8%; the heat preservation treatment is carried out for 2h at 220 ℃, the tensile strength is still maintained at 317MPa of 310-; therefore, the high-temperature-resistant heat-insulating material can be used for a long time at the high temperature of 220 ℃, is widely applied to parts with higher requirements on service temperature, such as a base plate of a special engine, an engine sound-insulating cover and the like, and expands the application range. The preparation method of the heat-resistant cast aluminum-zinc alloy is simple, low in cost, convenient to operate, easy to master and easy to realize industrialization.
Drawings
FIG. 1 is a scanning electron micrograph of a heat-resistant cast Al-Zn alloy according to an embodiment of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention relates to a heat-resistant casting aluminum-zinc alloy which comprises the following elements in percentage by weight: 4.0 to 5.3 percent of Zn, 1.5 to 2.9 percent of Si, 1.5 to 2.3 percent of Cu, 0.3 to 0.6 percent of Mg, 1.5 to 2.5 percent of Ca, 0.2 to 0.6 percent of Ba, less than or equal to 0.2 percent of impurities and the balance of Al.
Preferably, the impurities comprise the following elements in percentage by weight: fe is less than or equal to 0.10 percent, Sn is less than or equal to 0.05 percent, and Pb is less than or equal to 0.05 percent.
Preferably, the alloy comprises the following elements in percentage by weight: 4.5 to 5.1 percent of Zn, 1.9 to 2.7 percent of Si, 1.5 to 1.8 percent of Cu, 0.3 to 0.4 percent of Mg, 1.8 to 1.9 percent of Ca, 0.3 to 0.4 percent of Ba, less than or equal to 0.1 percent of impurities and the balance of Al.
Further, the impurities comprise the following elements in percentage by weight: fe is less than or equal to 0.07 percent, Sn is less than or equal to 0.02 percent, and Pb is less than or equal to 0.01 percent.
Preferably, in the heat-resistant casting aluminum-zinc alloy, the weight percentage content of Zn, Si, Ca and Ba elements satisfies: wZn/(WSi+WCa+WBa) Less than or equal to 1.19; wherein, WZnIs the weight percentage content of Zn element; wSiIs the weight percentage content of Si element; wCaThe weight percentage of Ca element; wBaIs the weight percentage of Ba element.
Further, in the heat-resistant cast aluminum-zinc alloy, the weight percentage content of Zn, Si, Ca and Ba elements satisfies: wZn/(WSi+WCa+WBa) Less than or equal to 1.05; wherein, WZnIs the weight percentage content of Zn element; wSiIs the weight percentage content of Si element; wCaThe weight percentage of Ca element; wBaIs the weight percentage of Ba element.
The invention relates to a preparation method of heat-resistant cast aluminum-zinc alloy, which comprises the following steps:
1) firstly, heating a smelting furnace to raise the temperature of the smelting furnace to 280 ℃ of 200-;
2) cooling to reduce the temperature of the melting furnace to 700-;
3) keeping the temperature of the furnace at 700-710 ℃, adding the raw material containing Mg, stirring for 3-5min, adopting inert gas for rotary blowing for 10-15min, standing for 5-8min, and pouring to obtain the heat-resistant cast aluminum-zinc alloy.
Preferably, in the step 1), the raw material containing the Al element is pure aluminum metal, the raw material containing the Zn element is pure zinc metal, and the raw material containing the Ca element is pure calcium metal; in the step 3), the raw material containing Mg element is pure magnesium metal.
Further, the purity of the pure aluminum metal is not less than 99.993%, the purity of the pure zinc metal is not less than 99.95%, the purity of the pure calcium metal is not less than 99.99%, and the purity of the pure magnesium metal is not less than 99.95%.
Preferably, in the step 1), the Si-containing material is a silicon alloy, and the Cu-containing material is a copper alloy. .
Further, the silicon alloy is AlSi12, and the copper alloy is AlCu 50.
Preferably, in the step 2), the raw material containing Ba element is a barium salt; further, the barium salt is BaCl2。
Preferably, in the step 2), the refining agent is a mixture of hexachloroethane and titanium dioxide according to the mass ratio of 2: 1.
Preferably, in the step 3), the inert gas is any one or more of nitrogen, helium, argon and neon.
Example one
The invention relates to a preparation method of heat-resistant cast aluminum-zinc alloy, which comprises the following steps:
1) weighing the raw materials according to the following weight percentage of the elements of Zn 4.5%, Si 1.9%, Cu 1.8%, Mg 0.4%, Ca 1.9%, Ba 0.3%, impurities less than or equal to 0.2% and the balance of Al;
wherein Al, Zn, Ca and Mg are pure metals, the pure metal aluminum is Al99.993, and the element content requirement meets the GB/T8644-2000 requirement; the pure metal zinc is Zn99.95, and the element content requirement meets the GB/T470-2008 requirement; the pure metal calcium is Ca99.99, and the element content requirement meets the GB/T4864-2008 requirement; the pure metal magnesium is Mg99.95, and the element content requirement meets the requirement of GB/T3499-; si adopts AlSi12 intermediate alloy, and the element content requirement meets the GB/T27677-2011 requirement; cu adopts AlCu50 intermediate alloy, and the element content requirement meets the GB/T27677-2011 requirement; ba adopts barium chloride, and the technical requirements meet the requirements of I-class superior products in GB/T1617-;
2) firstly, heating a smelting furnace to raise the temperature of the smelting furnace to 200 ℃, preserving heat for 35min, then adding pure metal Al, AlCu50 intermediate alloy, AlSi12 intermediate alloy, pure metal Ca and pure metal Zn, smelting, continuing to heat to raise the temperature of the smelting furnace to 720 ℃, preserving heat for 1.3h, and stirring for 25min to obtain an aluminum alloy melt;
3) cooling to reduce the temperature of the smelting furnace to 700 ℃, adding barium chloride, stirring for 14min, adding a refining agent, wherein the addition amount of the refining agent is 0.5 percent of the total weight of the aluminum alloy melt, and stirring for 5 min;
4) keeping the temperature of the smelting furnace at 700 ℃, adding pure metal Mg, stirring for 4min, adopting argon gas to carry out rotary blowing for 10min, carrying out stokehole composition analysis, standing for 6min, and pouring to obtain the heat-resistant cast aluminum-zinc alloy.
Example two
The invention relates to a preparation method of heat-resistant cast aluminum-zinc alloy, which comprises the following steps:
1) weighing the raw materials according to the following weight percentage of the elements of 5.1 percent of Zn, 2.7 percent of Si, 1.5 percent of Cu, 0.3 percent of Mg, 1.8 percent of Ca, 0.3 percent of Ba, less than or equal to 0.2 percent of impurities and the balance of Al;
wherein Al, Zn, Ca and Mg are pure metals, the pure metal aluminum is Al99.993, and the element content requirement meets the GB/T8644-2000 requirement; the pure metal zinc is Zn99.95, and the element content requirement meets the GB/T470-2008 requirement; the pure metal calcium is Ca99.99, and the element content requirement meets the GB/T4864-2008 requirement; the pure metal magnesium is Mg99.95, and the element content requirement meets the requirement of GB/T3499-; si adopts AlSi12 intermediate alloy, and the element content requirement meets the GB/T27677-2011 requirement; cu adopts AlCu50 intermediate alloy, and the element content requirement meets the GB/T27677-2011 requirement; ba adopts barium chloride, and the technical requirements meet the requirements of I-class superior products in GB/T1617-;
2) firstly, heating a smelting furnace to raise the temperature of the smelting furnace to 250 ℃, preserving heat for 20min, then adding pure metal Al, AlCu50 intermediate alloy, AlSi12 intermediate alloy, pure metal Ca and pure metal Zn, smelting, continuing to heat to raise the temperature of the smelting furnace to 725 ℃, preserving heat for 1.0h, and stirring for 30min to obtain an aluminum alloy melt;
3) cooling to 705 ℃, adding barium chloride, stirring for 13min, adding a refining agent, wherein the addition amount of the refining agent is 0.4 percent of the total weight of the aluminum alloy melt, and stirring for 8 min;
4) keeping the temperature of the smelting furnace at 705 ℃, adding pure Mg metal, stirring for 3min, adopting nitrogen to carry out rotary blowing for 12min, carrying out stokehole component analysis, standing for 5min, and pouring to obtain the heat-resistant cast aluminum-zinc alloy.
EXAMPLE III
The invention relates to a preparation method of heat-resistant cast aluminum-zinc alloy, which comprises the following steps:
1) weighing the raw materials according to the following weight percentage of the elements of 4.0 percent of Zn, 2.9 percent of Si, 2.3 percent of Cu, 0.6 percent of Mg, 1.5 percent of Ca, 0.2 percent of Ba, less than or equal to 0.1 percent of impurities and the balance of Al;
wherein Al, Zn, Ca and Mg are pure metals, the pure metal aluminum is Al99.993, and the element content requirement meets the GB/T8644-2000 requirement; the pure metal zinc is Zn99.95, and the element content requirement meets the GB/T470-2008 requirement; the pure metal calcium is Ca99.99, and the element content requirement meets the GB/T4864-2008 requirement; the pure metal magnesium is Mg99.95, and the element content requirement meets the requirement of GB/T3499-; si adopts AlSi12 intermediate alloy, and the element content requirement meets the GB/T27677-2011 requirement; cu adopts AlCu50 intermediate alloy, and the element content requirement meets the GB/T27677-2011 requirement; ba adopts barium chloride, and the technical requirements meet the requirements of I-class superior products in GB/T1617-;
2) firstly, heating a smelting furnace to raise the temperature of the smelting furnace to 280 ℃, preserving heat for 25min, then adding pure metal Al, pure metal Zn, AlSi12 intermediate alloy, AlCu50 intermediate alloy and pure metal Ca, continuing to heat to raise the temperature of the smelting furnace to 730 ℃, preserving heat for 2.0h, and stirring for 20min to obtain an aluminum alloy melt;
3) cooling to 710 ℃, adding barium chloride, stirring for 10min, adding a refining agent, wherein the addition amount of the refining agent is 0.6 percent of the total weight of the aluminum alloy melt, and stirring for 10 min;
4) keeping the temperature of the smelting furnace at 710 ℃, adding pure Mg metal, stirring for 5min, adopting helium gas for rotary blowing for 15min, carrying out stokehole composition analysis, standing for 8min, and pouring to obtain the heat-resistant cast aluminum-zinc alloy.
Example four
The invention relates to a preparation method of heat-resistant cast aluminum-zinc alloy, which comprises the following steps:
1) weighing the raw materials according to the following weight percentage of the elements of 5.3 percent of Zn, 1.5 percent of Si, 2.0 percent of Cu, 0.5 percent of Mg, 2.5 percent of Ca, 0.6 percent of Ba, less than or equal to 0.1 percent of impurities and the balance of Al;
wherein Al, Zn, Ca and Mg are pure metals, the pure metal aluminum is Al99.993, and the element content requirement meets the GB/T8644-2000 requirement; the pure metal zinc is Zn99.95, and the element content requirement meets the GB/T470-2008 requirement; the pure metal calcium is Ca99.99, and the element content requirement meets the GB/T4864-2008 requirement; the pure metal magnesium is Mg99.95, and the element content requirement meets the requirement of GB/T3499-; si adopts AlSi12 intermediate alloy, and the element content requirement meets the GB/T27677-2011 requirement; cu adopts AlCu50 intermediate alloy, and the element content requirement meets the GB/T27677-2011 requirement; ba adopts barium chloride, and the technical requirements meet the requirements of I-class superior products in GB/T1617-;
2) firstly, heating a smelting furnace to raise the temperature of the smelting furnace to 250 ℃, preserving heat for 25min, then adding pure metal Al, pure metal Zn, AlSi12 intermediate alloy, AlCu50 intermediate alloy and pure metal Ca, continuing to heat to raise the temperature of the smelting furnace to 725 ℃, preserving heat for 1.5h, and stirring for 25min to obtain an aluminum alloy melt;
3) cooling to 705 ℃, adding barium chloride, stirring for 15min, adding a refining agent, wherein the addition amount of the refining agent is 0.5 percent of the total weight of the aluminum alloy melt, and stirring for 8 min;
4) keeping the temperature of the smelting furnace at 705 ℃, adding pure Mg metal, stirring for 4min, adopting argon gas to carry out rotary blowing for 12min, carrying out stokehole component analysis, standing for 7min, and pouring to obtain the heat-resistant cast aluminum-zinc alloy.
The heat-resistant cast aluminum-zinc alloy obtained in example one was observed on a scanning electron microscope of SIGMA 300 type manufactured by Zeiss. As can be seen from the attached figure 1, the internal structure of the heat-resistant cast aluminum-zinc alloy obtained by the method of the invention is in a net structure, and a stable net eutectic phase is distributed on the grain boundary.
The contents of the elements in the four parts of heat-resistant casting aluminum-zinc alloy obtained in the first to fourth examples and the conventional ZL401 alloy (control) were measured according to the method for measuring the components of the aluminum alloy in GB/T6987-.
TABLE 1 analysis results of alloy compositions
As can be seen from Table 1, the heat-resistant cast aluminum-zinc alloy obtained by the method of the invention contains 7 effective elements, namely Al, Zn, Si, Cu, Mg, Ca and Ba, wherein the content of Zn element is 4.0-5.3%, and the content of Zn element is low; 1.5 to 2.9 percent of Si element, 1.5 to 2.3 percent of Cu element, 0.3 to 0.6 percent of Mg element, 1.5 to 2.5 percent of Ca element, 0.2 to 0.6 percent of Ba element, less than or equal to 0.2 percent of impurity and the balance of Al. The ZL401 alloy selected as the reference sample meets the GB/T1173-2013 standard, and the zinc content in the ZL401 alloy is as high as 12.1 percent; besides zinc element, the zinc-containing alloy also contains two elements of Si and Mg, and the content of silicon element is as high as 7.5%; the content of magnesium element is low, only 0.2%; the impurity element content is high, wherein the iron element content is 0.43 percent, the tin element content is 0.13 percent, and the lead element content is 0.08 percent.
The tensile strength and the elongation of four parts of the heat-resistant casting aluminum-zinc alloy obtained in the first to fourth examples and the conventional ZL401 alloy (control) are respectively measured according to the measuring method of the tensile strength and the elongation of the alloy of GB/T228-.
TABLE 2 mechanical and Corrosion resistance Properties of the alloys
| Sample name | Tensile strength (MPa) | Elongation (%) | Mass loss rate (%) |
| Example one | 316 | 3.3 | 10.9 |
| Example two | 319 | 3.0 | 11.0 |
| EXAMPLE III | 310 | 3.8 | 9.8 |
| Example four | 320 | 3.1 | 10.6 |
| Control sample | 271 | 1.8 | 16.3 |
As can be seen from Table 2, the tensile strength of the heat-resistant cast aluminum-zinc alloy obtained by the method of the invention is between 310 and 320MPa, which is obviously higher than that of the control sample; the elongation of the heat-resistant cast aluminum-zinc alloy obtained by the method is between 3.0 and 3.8 percent, which is obviously higher than that of a control sample; therefore, the heat-resistant cast aluminum-zinc alloy obtained by the method has better tensile strength. In a salt spray test with the pH value of 6.5-7.2, the spray pressure of 84KPa and the spray time of 96h, the heat-resistant cast aluminum-zinc alloy obtained by the method has the mass loss rate of 9.8-11.0 percent, which is obviously less than that of a reference sample under the same condition; therefore, the heat-resistant cast aluminum-zinc alloy obtained by the method has better corrosion resistance.
Taking 4 parts of each of four parts of the heat-resistant casting aluminum-zinc alloy obtained in the first to fourth examples and the conventional ZL401 alloy (a comparison sample), and respectively keeping the four parts at 220 ℃ for 2h, 100h and 200 h; then, the alloy was taken out and the tensile strength of four parts of the heat-resistant cast aluminum-zinc alloy and the conventional ZL401 alloy (control) was measured again according to the measuring method of the tensile strength and elongation of the alloy of GB/T228-2010 and the experimental results are shown in Table 3.
TABLE 3 high temperature resistance of the alloy at 220 deg.C
As can be seen from Table 3, in the process of keeping the temperature of the heat-resistant cast aluminum-zinc alloy at 220 ℃ for 200 hours, the standard deviation of the tensile strength is less than 5, and the coefficient of variation is less than 1.5%; therefore, the tensile strength of the heat-resistant cast aluminum-zinc alloy obtained by the method is basically kept unchanged in the heat preservation process, and the heat-resistant cast aluminum-zinc alloy obtained by the method has good heat resistance, can be used for a long time at a high temperature of 220 ℃, and is widely applied to parts with high service temperature requirements, such as base discs of special engines, engine sound-proof covers and the like. However, in the process of keeping the temperature of the control sample at 220 ℃ for 200 hours, the standard deviation of the tensile strength is more than 40, and the coefficient of variation is about 20%; the tensile strength of the control sample is significantly reduced during the incubation.
Taking 1 part of each of four parts of the heat-resistant casting aluminum-zinc alloy obtained in the first to fourth examples and the conventional ZL401 alloy (control sample), and respectively keeping the samples at 300 ℃ for 2 hours; then, the alloy was taken out and the tensile strength of four parts of the heat-resistant cast aluminum-zinc alloy and the conventional ZL401 alloy (control) was measured again according to the measuring method of the tensile strength and elongation of the alloy of GB/T228-2010 and the experimental results are shown in Table 4.
TABLE 4 high temperature resistance of the alloys at 300 deg.C
As can be seen from Table 4, the tensile strength of the heat-resistant cast Al-Zn alloy obtained by the method of the present invention is slightly reduced after heat preservation at 300 ℃ for 2 hours, but the reduction of the tensile strength of the heat-resistant cast Al-Zn alloy is small, and the tensile strength is still between 298-303 MPa. However, the tensile strength of the control sample is obviously reduced after the control sample is kept at 300 ℃ for 2h, and the tensile strength is only 176 MPa.
Therefore, compared with the prior art, the invention has the beneficial effects that: in the heat-resistant cast aluminum-zinc alloy, Al, Zn, Cu, Ca, Mg and Ba elements form dense eutectic net-shaped Al-Zn-Cu-Ca-Mg-Ba precipitated phases in an alloy matrix, and the net-shaped precipitated phases effectively strengthen the matrix structure of the alloy and obviously improve the tensile strength of the alloy; meanwhile, the net precipitated phases have good high-temperature stability, so that the alloy has good heat resistance. The heat-resistant cast aluminum-zinc alloy has low zinc element content, and improves the corrosion resistance of the cast copper-zinc alloy; when in an as-cast state, the tensile strength can reach 310-320MPa, and the elongation is 3.0-3.8%; the heat preservation treatment is carried out for 2h at 220 ℃, the tensile strength is still maintained at 317MPa of 310-; therefore, the high-temperature-resistant heat-insulating material can be used for a long time at the high temperature of 220 ℃, is widely applied to parts with higher requirements on service temperature, such as a base plate of a special engine, an engine sound-insulating cover and the like, and expands the application range. The preparation method of the heat-resistant cast aluminum-zinc alloy is simple, low in cost, convenient to operate, easy to master and easy to realize industrialization.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The heat-resistant cast aluminum-zinc alloy is characterized by comprising the following elements in percentage by weight:
4.0 to 5.3 percent of Zn, 1.5 to 2.9 percent of Si, 1.5 to 2.3 percent of Cu, 0.3 to 0.6 percent of Mg, 1.5 to 2.5 percent of Ca, 0.2 to 0.6 percent of Ba, less than or equal to 0.2 percent of impurities and the balance of Al.
2. The heat resistant cast aluminum zinc alloy of claim 1, wherein the impurities comprise the following elements in weight percent:
Fe≤0.10％，Sn≤0.05％，Pb≤0.05％。
3. the heat resistant cast aluminum zinc alloy of claim 1, comprising the following elements in weight percent:
4.5 to 5.1 percent of Zn, 1.9 to 2.7 percent of Si, 1.5 to 1.8 percent of Cu, 0.3 to 0.4 percent of Mg, 1.8 to 1.9 percent of Ca, 0.3 to 0.4 percent of Ba, less than or equal to 0.1 percent of impurities and the balance of Al.
4. The heat resistant cast aluminum zinc alloy of claim 3, wherein the impurities comprise the following elements in weight percent:
Fe≤0.07％，Sn≤0.02％，Pb≤0.01％。
5. the heat resistant cast aluminum zinc alloy of any one of claims 1 to 4, wherein:
in the heat-resistant cast aluminum-zinc alloy, the weight percentage content of Zn, Si, Ca and Ba elements meets the following requirements: wZn/(WSi+WCa+WBa)≤1.19；
Wherein, WZnIs the weight percentage content of Zn element;
WSiis the weight percentage content of Si element;
WCathe weight percentage of Ca element;
WBais the weight percentage of Ba element.
6. The heat resistant cast aluminum zinc alloy of claim 5, wherein:
in the heat-resistant cast aluminum-zinc alloy, the weight percentage content of Zn, Si, Ca and Ba elements meets the following requirements: wZn/(WSi+WCa+WBa)≤1.05；
Wherein, WZnIs the weight percentage content of Zn element;
WSiis the weight percentage content of Si element;
WCathe weight percentage of Ca element;
WBais the weight percentage of Ba element.
7. The method of making a heat resistant cast aluminum zinc alloy as claimed in any one of claims 1 to 6 including the steps of:
1) firstly, heating a smelting furnace to raise the temperature of the smelting furnace to 280 ℃ of 200-;
2) cooling to reduce the temperature of the melting furnace to 700-;
3) keeping the temperature of the furnace at 700-710 ℃, adding the raw material containing Mg, stirring for 3-5min, adopting inert gas for rotary blowing for 10-15min, standing for 5-8min, and pouring to obtain the heat-resistant cast aluminum-zinc alloy.
8. The method of preparing a heat resistant cast aluminum zinc alloy as claimed in claim 7, characterized in that:
in the step 1), the raw material containing Al element is pure aluminum metal, the raw material containing Zn element is pure zinc metal, and the raw material containing Ca element is pure calcium metal; in the step 3), the raw material containing Mg element is pure magnesium metal;
preferably, the purity of the pure aluminum metal is not less than 99.993%, the purity of the pure zinc metal is not less than 99.95%, the purity of the pure calcium metal is not less than 99.99%, and the purity of the pure magnesium metal is not less than 99.95%.
9. The method of preparing a heat resistant cast aluminum zinc alloy as claimed in claim 7, characterized in that:
in the step 1), the raw material containing Si element is silicon alloy, and the raw material containing Cu element is copper alloy;
preferably, the silicon alloy is AlSi12 and the copper alloy is AlCu 50.
10. The method of preparing a heat resistant cast aluminum zinc alloy as claimed in claim 7, characterized in that:
in the step 2), the raw material containing Ba element is barium salt; preferably, the barium salt is BaCl2；
Preferably, in the step 2), the refining agent is a mixture of hexachloroethane and titanium dioxide according to the mass ratio of 2: 1;
preferably, in the step 3), the inert gas is any one or more of nitrogen, helium, argon and neon.
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