CN1333094C - Environmental protection, healthy new type leadless easy cutting corrosion resistant low boron calcium brass alloy - Google Patents
Environmental protection, healthy new type leadless easy cutting corrosion resistant low boron calcium brass alloy Download PDFInfo
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Abstract
The present invention relates to an environment-protecting healthy novel non-lead free cutting corrosion-resistant low-boron calcium brass alloy. The brass alloy comprises the following components in certain proportion: 55 to 65 wt% of copper, 0.004 to 0.25 wt% of calcium, 0.1 to 0.5 wt% of antimony, 0 to 0.05 wt% of boron, 0.2 to 1.5 wt% of other element, zinc as the rest and inevitable impurities, wherein the other elements are at least two of the following elements: titanium, nickel, ferrum, silicon, stannum, aluminum, phosphorus and rare earth metals. In the manufacture method of the alloy, the components are processed by alloying treatment and smelting with a covering protective method in order to make the metals such as the calcium, the boron and the antimony in a brass melting liquid quickly solidified to form an intermetallic compound; the intermetallic compound is continuously cast into a brass cast ingot at a temperature of 1030 DEG C, and the brass cast ingot is extruded in a high extrusion ratio at a temperature of 680 to 730 DEG C, intermediate heat treatment is carried out under the conditions of cold working at a temperature of 420 to 700 DEG C, and annealing is carried out by relieving stresses at a temperature of less than 400 DEG C. The alloy of the present invention has the advantages of excellent cutting ability, good welding performance, good corrosion resistance, good dezincification resistance property and mechanical property. The alloy is especially suitable for cutting and processing molded components, forged pieces, castings, etc.; the alloy is low in cost, and the alloy completely reaches the requirements of standard specifications for international environmental protection, health and safety.
Description
Technical field
The present invention relates to a kind of lead-free brass alloys, relate in particular to a kind of the have excellent mechanical property and the leadless easy cutting corrosion resistant low boron calcium brass alloy (PWEHSNBRASS) of corrosion resistance nature.It is specially adapted to domestic water supply system pipeline foundry goods, valve member, switch web member; The connector of telecommunications apparatus; Home electric; The optoelectronic components of light fixture and photographic apparatus; Fields such as component manufacturing in toy for children and machinery and the automobile industry.It is a kind of new metallic material that helps human nutrition health and environment protection, also is the meeting of present widespread use causes the leaded brass of baneful influence to human body and environment another new type ideal substitute.
Background technology
Leaded brass has characteristics such as good cold and hot working performance, fabulous cutting ability and self-lubricating, can satisfy the machining of different shape component, so Winn bronze is also just by the wide spectrums such as component manufacturing of optoelectronic components, automobile and the machinery manufacturing industry of universally acknowledged component, light fixture and the photographic apparatus that is widely applied to the pipeline foundry goods of domestic water supply system and accessory, household electrical appliances and toy for children for important base mateiral.
Yet lead is a kind of to environment and harmful element, plumbous particularly can cause irreversible damage to children's kidney and cranial nerve to blood of human body and neural system, serious meeting causes that blood lead, brain lead poisoning, nerve are obstructed, backwardness, dementia, adverse consequences such as active.The medical expert of countries in the world has found that Winn bronze has constituted threat to human health and environmental health in recent years, medical research institutes such as Northern Europe, the U.S., Japan and China have all made the report that leaded brass works the mischief to human environment, thereby the government that national governments have also put into effect in succession to the copper alloy containing lead application orders within a certain time, last year, Japanese government is limited in 0.01mg/L with the leaching amount of lead in water.And Chinese Government has also put into effect in succession in the recent period with the world and has ordered the corresponding to mandatory rules of laws such as " electronics and IT products prevention and cure of pollution management methods " within a certain time.
In view of the foregoing, in recent years particularly since 2003, the U.S., the European Community, Japan, countries such as China have made ordering within a certain time of strict control respectively to the lead content in the copper alloy with in the leaching amount of Pb in Drinking Water, and will constantly reduce wherein lead content (wherein the content of electronics and IT products lead must less than 0.1%), thereby the application of Winn bronze will face strict restriction and challenge, therefore developing Lead free cutting copper alloys in succession substitutes copper alloy containing lead, be the instant key subjects that world today's metallic substance production is faced, also be the international EHS of enforcement plan (E: environmental protection, H: health, S: world's recycling economy safety) the key subjects that must solve.
External at present as the U.S., lead-free brass alloys have also been invented by Germany and Japan, disclosed a kind of patent of invention " leadless free-cutting brass alloy material and its manufacture method " in Chinese patent application number 02121991.5 specification sheets for example wherein, it is the leadless free-cutting brass alloy material of Japanese Mikoshi Metal Co., Ltd. invention, its manufacture method is: this alloy contains weight %: copper: 60.0～62.0%, bismuth: 0.5～2.2%, aluminium: 0.01～0.1%, tin: 0.5～1.6%, phosphorus: 0.04～0.15%, all the other are zinc and unavoidable impurities composition, under 460～600 ℃ of temperature, carry out thermal treatment in 30 minutes～4 hours, with the speed of cooling slow cooling below 70 ℃/hour.The leadless free-cutting brass alloy material of foregoing invention patent is that copper-zinc-bismuth is an alloy, contains bismuth in this alloy, and during fabrication because the cost height of bismuth, and world resource closes on exhaustion, do not have competitive power; Another invention is German Wieland company's research and development " Pb-free copper-alloy and its application " patents, this alloy is made up of following ingredients: copper: 70.0～83.0%, silicon: 1～5%, tin: 0.01～2%, iron: 0.01～0.3% and/or cobalt: 0.01～0.3%, nickel: 0.01～0.3%, manganese: 0.01～0.3%, and surplus is zinc and unavoidable impurities.This alloy belongs to copper-zinc-Si system alloy, because of this alloy copper content height, raw materials cost also corresponding higher (than I the department " environmental protection, healthy new type leadless easy cutting corrosion resistant low boron calcium brass alloy " high more than 10%), the market competitiveness a little less than.
Summary of the invention
The objective of the invention is lead-freely to have excellent in machinability, cold and hot formability and good weldability and good mechanical property and have excellent corrosion resisting property simultaneously again in order to provide a kind of, and can not the causing environmental pollution and help the new type leadless easy cutting corrosion resistant low boron calcium brass alloys of human nutrition health of alternative copper alloy containing lead.
The objective of the invention is by providing leadless easy cutting corrosion resistant low boron calcium brass alloy to realize with following each row alloy composition:
The alloy composition of one of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is: it is by copper, zinc and calcium, boron, alloying elements such as antimony become to be grouped into unavoidable impurities, consisting of of described alloy: copper: 55～65wt%, calcium: 0.004～0.25wt%, antimony: 0.1～0.5wt%, boron: 0～0.05wt%, other element: 0.2～1.5wt%, described other element comprises titanium, nickel, iron, silicon, tin, aluminium, phosphorus, at least two kinds of elements in the rare earth metal, all the other are zinc and unavoidable impurities, and content plumbous in the unavoidable impurities is less than 0.1wt%; The copper zincification adds calcium and adds antimony and add boron greater than 97wt% in the described alloy composition, and wherein zinc greater than 35.5wt%.
The preferable content of boron is 0.0005～0.05wt% (but the content that is used in this alloy boron of undrinkable water engineering also can be 0～0.0005%) in the described alloy.
The preferable of described alloy consists of: copper: 58～63wt%, calcium: 0.005～0.15wt%, antimony: 0.15～0.35wt%, boron: 0.0006～0.03wt%, other element: 0.3～1.2%; The copper zincification adds calcium and adds antimony and add boron greater than 97.5% and be not more than 99% in the alloy composition, and wherein zinc is greater than 35.5%.
The phase composite of one of described leadless easy cutting corrosion resistant low boron calcium brass alloy is: based on α, β two-phase, a small amount of tiny calcic that is uniformly distributed in crystal boundary is with to contain between antimony metal compound etc. hard mutually crisp.
One of described leadless easy cutting corrosion resistant low boron calcium brass alloy is to utilize the calcium of low levels and antimony to substitute plumbous, calcium and antimony element are the easy cutting elements (the patent report is at home and abroad all arranged) in part ferrous metal and the non-ferrous metal, through Alloying Treatment, make the metallic compound of calcic and antimony (nontoxic with solid solution, healthy form is present in the alloy) etc. easily the embrittlement of cutting chip breaking accumulate near the crystal boundary mutually, make alloy have the coppery cutting ability of the lead and yellow-collation of elephant, add simultaneously some crystal grain thinnings again, other element of trace that suppresses dezincify and control alloy brittle failure tendency, and then make calcic, stibiated metallic compound is more tiny to be evenly distributed on the crystal boundary, make alloy in machining, easily form short chip breaking point, increased the cutting ability of alloy effectively, over-all properties such as mechanical property and anti-corrosion anti dezincification character, thus make low boron calcium brass alloy obtain to resemble excellent cutting ability the leaded brass, cold and hot processability and good castability, welding property, mechanical property.Can be widely used in optoelectronic components, electronics telecommunication, the household electrical appliances of tap water engineering, five metals, machinery, photographic apparatus, the component production is easily cut in the casting and the cold and hot moulding of automobile component.
Calcium and antimony are the elements of strengthening and improve the alloy cutting ability, and calcium also is the trophicity element simultaneously, based on calcium, with the auxiliary calcium of antimony.Calcium contents was less than 0.004% o'clock in this alloy, and easily cutting effect is lower, and calcium contents was greater than 0.25% o'clock, and cutting ability is better than leaded brass, but casting crystalline is loose, is prone to be mingled with the resistance to air loss that influences alloy, and the mechanical property of alloy is sharply descended.For making full use of the characteristic that calcium can improve cutting ability, to prevent also that simultaneously excessive calcium from can cause the brittle failure tendency that crystallization is loose and mechanical property descends, we only the content of selected calcium be 0.004～0.25%.Such content is controlled under the condition that does not contain other cutting elements such as antimony, the cutting coefficient of this alloy is reached about 60%, we have also added the antimony element of auxiliary low levels on this basis simultaneously for this reason, make it auxiliary calcium and with it acting in conjunction obtained excellent cutting ability (cutting coefficient is 78～92%), mechanical property and excellent corrosion resistant performance, and then reach the requirement of environmental protection, health, nutrition, novel alloy material.
The auxiliary antimony element that adds proper content mainly has been the effect that auxiliary calcium further improves the cutting ability and the inhibition dezincify performance of alloy.When adding content less than 0.1% the time, auxiliary calcium is improved the cutting ability DeGrain, and the auxiliary content that adds is greater than 0.5% o'clock, though that auxiliary calcium improves cutting ability is bigger, it is also very obvious that the plasticity of this alloy reduces, and also increased cost simultaneously.So through facts have proved that the auxiliary content that adds antimony is 0.1～0.5%, just can play auxiliary calcium and improve the effect of the cutting ability of this alloy, and make this alloy have excellent cutting ability (cutting coefficient is 78～92%), cold and hot processability, anti dezincification character energy and welding property, can polish and electroplate performance and favorable mechanical performance.
The antimony of low levels all has certain solubleness in copper and zinc, so antimony is to be present in the alloy with the nontoxic solid solution attitude of low levels, and is water insoluble, rather than resemble and be present in the alloy with deleterious free state the lead.Through electronic probe and transmission electron microscope observing, preferential and the zinc formation sosoloid of antimony in this alloy, and accumulate near the crystal boundary, free machining short chip breaking point formed, make calcic be evenly distributed on mutually on the crystal boundary, further improved the cutting ability of this alloy with stibiated metallic compound embrittlement.
Adding boron mainly has been the effect that suppresses dezincify, improves corrosion resisting property, and the function of deoxidation, crystal grain thinning, enhancing cutting ability is also arranged simultaneously.Because the boron atomic radius is littler than zinc atom radius; therefore the easier diffusion of boron atom ratio zinc atom when brass is corroded can preferentially be captured the room and then be stopped up the diffusion admittance of zinc atom, increases the resistance of zinc diffusion; form anti-corrosion protective membrane, thereby reach effect as the inhibition Dezincification corrosion of arsenic.
The add-on of boron be advisable 0.0005～0.05% (but the content that is used in this alloy boron of undrinkable water engineering also can be 0～0.0005%).Boron content is less than 0.0005% o'clock, to suppressing dezincify and anti-corrosion DeGrain; Boron content was greater than 0.05% o'clock, and boride is easily separated out at crystal boundary, caused " boron is crisp ", reduced the alloy processability.
Except adding boron, in this brass, add other element such as trace tin and can further improve the anti dezincification character energy, make it to reach the leaching standard and the ISO6509 dezincify standard of coherent element in the copper alloy of international tap water mechanism defined.
Zinc content helps the raising of cutting ability and the enhancing of wear resisting property greater than 35.5%, but too high meeting influence cold forming capability and alloy strength.
At least two kinds of effects that element adds in titanium in described other element, nickel, iron, silicon, tin, aluminium, phosphorus, the rare earth metal, the one, deoxidation, crystal grain thinning; The 2nd, form metallic compound with elements such as lead in the impurity, bismuths, strengthen crystal boundary, and make calcic, stibiated metallic compound embrittlement more tiny being evenly distributed on the crystal boundary mutually, also can suppress the poly-brittle failure tendency of calcic and stibiated embrittlement skew simultaneously, and then satisfy the cutting ability of the excellence of industrial needs, cold and hot processability and welding property; The 3rd, suppress dezincify, strengthen corrosion resisting property and anti-stress fragility energy.Described other element total content does not reach satisfied cutting ability and grain-boundary strengthening effect less than 0.2%; Other element total amount though can make the further refinement of alloy, suppresses dezincify greater than 1.5%, can form other more hard crisp phase, does not satisfy the cold forming capability in back step, has also increased cost simultaneously, and effect is promoted the use of in influence.
Adding titanium mainly has been deoxidation and crystal grain thinning effect, and general addition is 0.001～0.15% to be advisable, and less than 0.001% DeGrain, can increase cost greater than 0.15%, and make the castability reduction.
Nickel is matrix strengthening and the element that prevents dezincify, can suppress grain growth, increase alloy strength, plasticity and solidity to corrosion, also can improve the ability of the stress corrosion resistant of alloy simultaneously.Nickel content is difficult to satisfy every performance requriements of industrial needs less than 0.1%; Nickel content can increase manufacturing cost again greater than 0.6%, and can cause the back too high sclerosis of cold-forming in step, so nickel content should be controlled at 0.1～0.6%.
Add silicon, the one, be used for improving casting and welding flowability, improve the welding technological properties of this alloy, particularly silicon can also suppress zinc evaporation and oxide inclusion in welding process; The 2nd, strengthen density and withstand voltage, the wear resisting property and the cutting ability of alloy, rather than make alloy generate the hard crisp phase of γ of high silicon.General add-on is 0.1～0.7%, when silicone content above-mentioned action effect less than 0.1% time not obvious; When silicone content can generate more embrittlement phases such as iron silicide greater than 0.7%, and make alloy brittle failure enhancing, cutting resistance increases.
Iron mainly has been crystal grain thinning with rare earth metal, has stoped grain growth, control β to change the effect of quantity mutually, can improve softening temperature, strengthen intensity, improves cold and hot processability.Iron level generally is controlled at 0.1～0.3%, and iron level is less than 0.1%, and grain refinement effect is not obvious; Iron level can reduce corrosion resisting property and electrodepositable performance greater than 0.3%.Rare earth metal is good alterant and refining scavenging agent, solid solution is in copper hardly, its can form high melting point metal compound with the elements such as impurity lead, bismuth in the alloy, is distributed in intracrystalline, improves plasticity, the wear resistance of alloy, impel grain refining, facilitate the more tiny uniform distribution of metallic compound on the crystal boundary, general add-on is 0.003～0.4%, and adding with the lanthanum is the mishmetal better effects if of base, can increase electric conductivity and anti-dezincify ability, the too high flowability that can reduce alloy.
Add tin, aluminium, phosphorus and mainly be auxiliary boron and strengthen the performance that anti-dezincify, anti-stress split and improve the thermo forming performance, make it to reach the standard of international environment protection health security regulations.Secondly in this brass, add the flowability of tin, aluminium, all right deoxidation of phosphorus, increase alloy, improve the cutting ability and the intensity of alloy.Tin is solution strengthening and the element that suppresses dezincify, strengthen matrix together with boron, aluminium, phosphorus, help being uniformly dispersed and the formation of strengthening phase of each phase, help the raising of intensity, wear resistance and cutting ability, particularly help anti dezincification character can and the raising of thermoforming performance.The content of phosphorus generally is controlled at 0.005～0.2% and is advisable.The content of tin generally is controlled at 0.2～0.6% and is advisable.Aluminium content is generally 0.02～0.3% in this alloy, the aluminium too high levels can reduce cutting ability and performance is electroplated in polishing.Aluminium, phosphorus and tin too high levels can reduce the back cold and hot processability in step.
Even lead and cadmium are as the unavoidable impurities element, the lead content in the impurity must be less than 0.1%, and cadmium content must be less than 0.001%.According to the leaching amount detected result of the correlation detection standard in the international tap water engineering, this lead, cadmium content had both met international environmental protection and had ordered requirement within a certain time, caused public hazards can for again environment and human health.
One of above-mentioned leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is to have excellent cutting ability, anti dezincification character energy, an anti-stress corrosion performance, the new type leadless easy cutting brass alloys that help environmental protection, health, nutrition of good mechanical property and cold and hot processability and good welding property.Can be widely used in optoelectronic components, the household electrical appliances of tap water engineering, five metals, machinery, photographic apparatus, the component production is easily cut in the casting and the cold and hot moulding of automobile component.
Two alloy composition of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is: copper: 55～63wt%, calcium: 0.004～0.25wt%, antimony: 0.1～0.5wt%, boron: 0～0.05wt%, other element: 0.3～1.6wt%, described other element comprises at least two kinds of elements in titanium, nickel, iron, silicon, tin, phosphorus, the rare earth metal, all the other are zinc and unavoidable impurities, and content plumbous in the unavoidable impurities is less than 0.1wt%; The copper zincification adds calcium and adds antimony and add boron greater than 97wt% in the described alloy composition, and wherein zinc greater than 36.5wt%.
The preferable content of boron is 0.0005～0.05wt% (but the content that is used in this alloy boron of undrinkable water engineering also can be 0～0.0005%) in the described alloy.
The preferable of described alloy consists of: copper: 57～62wt%, calcium: 0.005～0.15wt%, antimony: 0.15～0.35wt%, boron: 0.0006～0.03wt%, other element: 0.4～1.4wt%; The copper zincification adds calcium and adds antimony and add boron greater than 97.5% and be not more than 99.2% in the described alloy composition, and wherein zinc is greater than 36.5%.
Two phase composite of described leadless easy cutting corrosion resistant low boron calcium brass alloy is: based on α, β two-phase, a small amount of tiny calcic that is uniformly distributed in crystal boundary is with to contain between antimony metal compound etc. hard mutually crisp.
Two of described leadless easy cutting corrosion resistant low boron calcium brass alloy is to utilize the calcium of low levels and antimony to substitute plumbous, calcium and antimony element are the easy cutting elements (the patent report is at home and abroad all arranged) in part ferrous metal and the non-ferrous metal, through Alloying Treatment, make the metallic compound of calcic and antimony (nontoxic with solid solution, healthy form is present in the alloy) etc. easily the embrittlement of cutting chip breaking accumulate near the crystal boundary mutually, make alloy have the coppery cutting ability of the lead and yellow-collation of elephant, add simultaneously some crystal grain thinnings again, other element of trace that suppresses dezincify and control alloy brittle failure tendency, and then make calcic, stibiated metallic compound is more tiny to be evenly distributed on the crystal boundary, make alloy in machining, easily form short chip breaking point, increased the cutting ability of alloy effectively, over-all properties such as mechanical property and anti-corrosion anti dezincification character, thus make low boron calcium brass alloy obtain to resemble excellent cutting ability the leaded brass, the thermoforming performance, easily performance is electroplated in polishing, good castability and good welding property, mechanical property.Calcium and antimony are the elements of strengthening and improve the alloy cutting ability, and calcium also is the trophicity element simultaneously, based on calcium, with the auxiliary calcium of antimony.Calcium contents was less than 0.004% o'clock in this alloy, easily cutting effect is lower, calcium contents was greater than 0.25% o'clock, free cutting property is better than leaded brass, but casting crystalline is loose, be prone to and be mingled with the resistance to air loss that influences alloy, and the mechanical property of alloy is sharply descended, for making full use of the characteristic that calcium can improve cutting ability, to prevent also that simultaneously excessive calcium from can cause the brittle failure tendency that crystallization is loose and mechanical property descends, we only the content of selected calcium be 0.004～0.25%, such content is controlled under the condition that does not contain other cutting elements such as antimony, the cutting coefficient of this alloy is reached about 60%, we have also added the antimony and the boron of auxiliary low levels on this basis simultaneously for this reason, make it auxiliary calcium and with it acting in conjunction obtained excellent cutting ability (cutting coefficient is 78～92%), excellent corrosion resistant performance and mechanical property, and then reach environmental protection, healthy, nutrition, the requirement of novel alloy material.
The auxiliary antimony element that adds proper content mainly has been the effect that auxiliary calcium further improves the cutting ability and the inhibition dezincify performance of alloy.When adding content less than 0.1% the time, auxiliary calcium is improved the cutting ability DeGrain, and the auxiliary content that adds is greater than 0.5% o'clock, though that auxiliary calcium improves cutting ability is bigger, it is also very obvious that the plasticity of this alloy reduces, and also increased cost simultaneously.So through facts have proved that the auxiliary content that adds antimony is 0.1～0.5%, just can play auxiliary calcium and improve the effect of the cutting ability of this alloy, and make this alloy have excellent cutting ability (cutting coefficient is 78～92%), thermoforming performance, anti dezincification character energy and favorable mechanical performance, welding property.
The antimony of low levels all has certain solubleness in copper and zinc, so antimony is to be present in the alloy with the nontoxic solid solution attitude of low levels, and is water insoluble, rather than resemble and be present in the alloy with deleterious free state the lead.Through electronic probe and transmission electron microscope observing, preferential and the zinc formation sosoloid of antimony in this alloy, and accumulate near the crystal boundary, free machining short chip breaking point formed, make calcic be evenly distributed on mutually on the crystal boundary, further improved the cutting ability of this alloy with stibiated metallic compound embrittlement.
Adding boron mainly has been the effect that suppresses dezincify, improves corrosion resisting property, and the function of deoxidation, crystal grain thinning, enhancing cutting ability is also arranged simultaneously.Because the boron atomic radius is littler than zinc atom radius; therefore the easier diffusion of boron atom ratio zinc atom when brass is corroded can preferentially be captured the room and then be stopped up the diffusion admittance of zinc atom, increases the resistance of zinc diffusion; form anti-corrosion protective membrane, thereby reach effect as the inhibition Dezincification corrosion of arsenic.
The add-on of boron be advisable 0.0005～0.05% (but the content that is used in this alloy boron of undrinkable water engineering also can be 0～0.0005%).Boron content suppressed dezincify and anti-corrosion DeGrain less than 0.0005% o'clock; Boron content was greater than 0.05% o'clock, and boride is easily separated out at crystal boundary, caused " boron is crisp ", reduced anti-dezincify and processability.
Except adding boron, in this brass, add other element such as trace tin and can further improve the anti dezincification character energy, make it to reach the leaching standard and the IS06509 dezincify standard of coherent element in the copper alloy of international tap water defined.
Zinc content helps the raising of cutting ability and the enhancing of wear resisting property greater than 36.5%, but too high meeting influence cold forming capability and alloy strength.
At least two kinds of effects that element adds in titanium in described other element, nickel, iron, silicon, tin, phosphorus, the rare earth metal, the one, deoxidation, crystal grain thinning; The 2nd, form metallic compound with elements such as lead in the impurity, bismuths, strengthen crystal boundary, and make calcic, stibiated metallic compound embrittlement more tiny being evenly distributed on the crystal boundary mutually, also can suppress the poly-brittle failure tendency of calcic and stibiated embrittlement skew simultaneously, and then satisfy the cutting ability of the excellence of industrial needs, cold and hot processability and welding property; The 3rd, suppress dezincify, strengthen corrosion resisting property and anti-stress fragility energy.Described other element total content does not reach satisfied cutting ability and grain-boundary strengthening effect less than 0.3%; Other element total amount though can make the further refinement of alloy, suppresses dezincify greater than 1.6%, can form other more hard crisp phase, does not satisfy the cold forming capability in back step, has also increased cost simultaneously, and effect is promoted the use of in influence.
Adding titanium mainly has been deoxidation and crystal grain thinning effect, and general addition is 0.001～0.15% to be advisable, and less than 0.001% DeGrain, can increase cost greater than 0.15%, and make the castability reduction.
Nickel is matrix strengthening and the element that prevents dezincify, can suppress grain growth, increase alloy strength, plasticity and solidity to corrosion, also can improve the ability of the stress corrosion resistant of alloy simultaneously.Nickel content is difficult to satisfy every performance requriements of industrial needs less than 0.1%; Nickel content can increase manufacturing cost again greater than 0.6%, and can cause the back too high sclerosis of cold-forming in step, so nickel content should be controlled at 0.1～0.6%.
Add silicon, the one, be used for improving casting and welding flowability, improve the welding technological properties of this alloy, particularly silicon can also suppress zinc evaporation and oxide inclusion in welding process; The 2nd, strengthen density and withstand voltage, the wear resisting property and the cutting ability of alloy, rather than make alloy generate the hard crisp phase of γ of high silicon, general add-on is 0.1～0.7%, when silicone content above-mentioned action effect less than 0.1% time not obvious; When silicone content can generate more embrittlement phases such as iron silicide greater than 0.7%, and make alloy brittle failure enhancing, cutting resistance increases.
Iron mainly has been crystal grain thinning with rare earth metal, has stoped grain growth, control β to change the effect of quantity mutually, can improve softening temperature, strengthen intensity, improves cold and hot processability.Iron level generally is controlled at 0.1～0.3% (to plated item, best iron level is 0.1～0.2%).Iron level is less than 0.1%, and grain refinement effect is not obvious; Iron level can reduce corrosion resisting property and electrodepositable performance greater than 0.3%.Rare earth metal is good alterant and refining scavenging agent, solid solution is in copper hardly, its can form high melting point metal compound with the elements such as impurity lead, bismuth in the alloy, is distributed in intracrystalline, improves plasticity, the wear resistance of alloy, impel grain refining, facilitate the tiny more distribution equably of metallic compound on the crystal boundary, general add-on is 0.003～0.4%, and adding with the lanthanum is the mishmetal better effects if of base, can increase electric conductivity and anti-dezincify ability, the too high flowability that can reduce alloy.
Adding tin, phosphorus and mainly be auxiliary boron increases the performance that anti-dezincify, anti-stress split and improves the thermo forming performance, makes it to reach the standard of international environment protection health security regulations.Secondly in this brass, add the flowability of tin, all right deoxidation of phosphorus, increase alloy, improve the cutting ability and the intensity of alloy.Tin is solution strengthening and the element that suppresses dezincify, strengthen matrix together with boron, phosphorus, help being uniformly dispersed and the formation of strengthening phase of each phase, help the raising of intensity, wear resistance and cutting ability, particularly help anti dezincification character energy, thermoforming performance and can polish the raising of electroplating performance.The content of phosphorus generally is controlled at 0.005～0.2% and is advisable.The content of tin generally is controlled at 0.2～0.6% and is advisable, in preferably getting, the upper limit.Phosphorus and tin too high levels can reduce the back cold and hot processability in step.
Even lead and cadmium are as the unavoidable impurities element, the lead content in the impurity must be less than 0.1%, and cadmium content must be less than 0.001%.According to the leaching amount detected result of the correlation detection standard in the international tap water engineering, this lead, cadmium content had both met international environmental protection and had ordered requirement within a certain time, caused public hazards can for again environment and human health.
Two of above-mentioned leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is to have excellent cutting ability, anti-Dezincification corrosion performance, thermoforming performance and easily polish the plating performance, good castability, the new type leadless easy cutting brass alloys that help environment protection health, safety, nutrition of favorable mechanical performance and welding property.The casting and the forge hot heat type of being washed into that can be widely used in tap water engineering, five metals, machinery, household electrical appliances, automobile component can polish easily cutting component production of plating.
Three alloy composition of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is: copper: 56～64wt%, calcium: 0.004～0.25wt%, antimony: 0.1～0.5wt%, boron: 0～0.05wt%, other element: 0.2～1.5wt%, described other element comprises at least two kinds of elements in titanium, nickel, iron, silicon, tin, aluminium, phosphorus, the rare earth metal, all the other are zinc and unavoidable impurities, as content plumbous in the unavoidable impurities less than 0.03wt%; The copper zincification adds calcium and adds antimony and add boron greater than 97wt% in the described alloy composition, and wherein zinc is greater than 35.5wt%.
The preferable content of boron is 0.0005～0.05wt% (but the content that is used in this alloy boron of undrinkable water engineering also can be 0～0.0005%) in the described alloy.
The preferable of described alloy consists of: copper: 58～63wt%, calcium: 0.005～0.15wt%, antimony: 0.15～0.35wt%, boron: 0.0006～0.03wt%, other element: 0.4～1.4wt%, described other element comprises at least two kinds of elements in titanium, nickel, iron, silicon, tin, aluminium, phosphorus, the rare earth metal, all the other are zinc and unavoidable impurities, as content plumbous in the unavoidable impurities less than 0.03wt%; The copper zincification adds calcium and adds antimony and add boron greater than 97.5wt% and be not more than 99wt% in the described alloy composition, and wherein zinc is greater than 35.5wt%.
Three phase composite of described leadless easy cutting corrosion resistant low boron calcium brass alloy is: based on α, β two-phase, a small amount of tiny calcic that is uniformly distributed in crystal boundary is with to contain between antimony metal compound etc. hard mutually crisp.
Three of described leadless easy cutting corrosion resistant low boron calcium brass alloy is to utilize the calcium of low levels and antimony to substitute plumbous, calcium and antimony element are the easy cutting elements (the patent report is at home and abroad all arranged) in part ferrous metal and the non-ferrous metal, through Alloying Treatment, make the metallic compound of calcic and antimony (nontoxic with solid solution, healthy form is present in the alloy) etc. easily the embrittlement of cutting chip breaking accumulate near the crystal boundary mutually, make alloy have the coppery cutting ability of the lead and yellow-collation of elephant, add simultaneously some crystal grain thinnings again, other element of trace that suppresses dezincify and control alloy brittle failure tendency, and then make calcic, stibiated metallic compound is more tiny to be evenly distributed on the crystal boundary, make alloy in machining, easily form short chip breaking point, increased the cutting ability of alloy effectively, over-all properties such as mechanical property and anti-corrosion anti dezincification character, thus make low boron calcium brass alloy obtain to resemble good cutting performance the leaded brass, excellent corrosion resisting property, cold and hot processability and good castability, welding property, mechanical property.
Calcium and antimony are the elements of strengthening and improve the alloy cutting ability, and calcium also is the trophicity element simultaneously, based on calcium, with the auxiliary calcium of antimony.Calcium contents was less than 0.004% o'clock in this alloy, easily cutting effect is lower, calcium contents was greater than 0.25% o'clock, free cutting property is better than leaded brass, but casting crystalline is loose, be prone to and be mingled with the resistance to air loss that influences alloy, and the mechanical property of alloy is sharply descended, for making full use of the characteristic that calcium can improve cutting ability, to prevent also that simultaneously excessive calcium from can cause the brittle failure tendency that crystallization is loose and mechanical property descends, we only the content of selected calcium be 0.004～0.25%, such content is controlled under the condition that does not contain other cutting elements such as antimony, the cutting coefficient of this alloy is reached about 60%, we have also added the antimony and the boron of auxiliary low levels on this basis simultaneously for this reason, make it auxiliary calcium and with it acting in conjunction obtained good cutting performance (cutting coefficient is 78～92%), mechanical property and excellent corrosion resisting property, and then reach present and environmental protection in the future, healthy, nutrition, the requirement of novel alloy material.
The auxiliary antimony element that adds proper content mainly has been the effect that auxiliary calcium further improves the cutting ability and the inhibition dezincify performance of alloy.When antimony content less than 0.1% the time, auxiliary calcium is improved the cutting ability DeGrain, and the auxiliary content that adds is greater than 0.5% o'clock, though that auxiliary calcium improves cutting ability is bigger, it is also very obvious that the plasticity of this alloy reduces, and also increased cost simultaneously.So through facts have proved that the auxiliary content that adds antimony is 0.1～0.5%, just can play auxiliary calcium and improve the effect of the cutting ability of this alloy, and make this alloy have good cutting performance (cutting coefficient is 78～92%), cold and hot processability, anti dezincification character energy and welding property, good mechanical property.
The antimony of low levels all has certain solubleness in copper and zinc, so antimony is to be present in the alloy with the nontoxic solid solution attitude of low levels, and is water insoluble, rather than resemble and be present in the alloy with deleterious free state the lead.Through electronic probe and transmission electron microscope observing, preferential and the zinc formation sosoloid of antimony in this alloy, and accumulate near the crystal boundary, free machining short chip breaking point formed, make calcic be evenly distributed on mutually on the crystal boundary, further improved the cutting ability of this alloy with stibiated metallic compound embrittlement.
Adding boron mainly has been the effect that suppresses dezincify, improves corrosion resisting property, and the function of deoxidation, crystal grain thinning, enhancing cutting ability is also arranged simultaneously.Because the boron atomic radius is littler than zinc atom radius; therefore the easier diffusion of boron atom ratio zinc atom when brass is corroded can preferentially be captured the room and then be stopped up the diffusion admittance of zinc atom, increases the resistance of zinc diffusion; form anti-corrosion protective membrane, thereby reach effect as the inhibition Dezincification corrosion of arsenic.
Containing into amount of boron is advisable 0.0005～0.05%.Boron content is less than 0.0005% o'clock, to suppressing dezincify and anti-corrosion DeGrain; Boron content was greater than 0.05% o'clock, and boride is easily separated out at crystal boundary, caused " boron is crisp ", reduced anti-dezincify and processability.
Except adding boron, in this brass, add other element such as trace tin and can further improve the anti dezincification character energy, make it to reach the leaching standard and the IS06509 dezincify standard of coherent element in the copper alloy of international tap water defined.
Zinc content helps the raising of cutting ability and the enhancing of wear resisting property greater than 35.5%, but too high meeting influence cold forming capability and alloy strength.
At least two kinds of effects that element adds in titanium in described other element, nickel, iron, silicon, tin, aluminium, phosphorus, the rare earth metal, the one, deoxidation, crystal grain thinning; The 2nd, form metallic compound with elements such as lead in the impurity, bismuths, strengthen crystal boundary, and make calcic, stibiated metallic compound embrittlement more tiny being evenly distributed on the crystal boundary mutually, also can suppress the poly-brittle failure tendency of calcic and stibiated embrittlement skew simultaneously, and then satisfy the good cutting performance of industrial needs, cold and hot processability and welding property; The 3rd, suppress dezincify, strengthen corrosion resisting property and anti-stress fragility energy.Described other element total content does not reach satisfied cutting ability and grain-boundary strengthening effect less than 0.2%; Other element total amount though can make the further refinement of alloy, suppresses dezincify greater than 1.5%, can form other more hard crisp phase, does not satisfy the cold forming capability in back step, has also increased cost simultaneously, and effect is promoted the use of in influence.
Adding titanium mainly has been deoxidation and crystal grain thinning effect, and general addition is 0.001～0.15% to be advisable, and less than 0.001% DeGrain, can increase cost greater than 0.15%, and make the castability reduction.
Nickel is matrix strengthening and the element that prevents dezincify, can suppress grain growth, increase alloy strength, plasticity and solidity to corrosion, also can improve the ability of the stress corrosion resistant of alloy simultaneously.Nickel content is difficult to satisfy every performance requriements of industrial needs less than 0.1%; Nickel content can increase manufacturing cost again greater than 0.6%, and can cause the back too high sclerosis of cold-forming in step, so nickel content should be controlled at 0.1～0.6%.
Add silicon, the one, be used for improving casting and welding flowability, improve the welding technological properties of this alloy, particularly silicon can also suppress zinc evaporation and oxide inclusion in welding process; The 2nd, strengthen density and withstand voltage, the wear resisting property and the cutting ability of alloy, rather than make alloy generate the hard crisp phase of γ of high silicon.General add-on is 0.1～0.7%, when silicone content above-mentioned action effect less than 0.1% time not obvious; When silicone content can generate more embrittlement phases such as iron silicide greater than 0.7%, and make alloy brittle failure enhancing, cutting resistance increases.
Iron mainly has been crystal grain thinning with rare earth metal, has stoped grain growth, control β to change the effect of quantity mutually, can improve softening temperature, strengthen intensity, improves cold and hot processability.Iron level generally is controlled at 0.1～0.3% (to plated item, the best is 0.1～0.2%).Iron level is less than 0.1%, and grain refinement effect is not obvious; Iron level can reduce corrosion resisting property and electrodepositable performance greater than 0.3%.Rare earth metal is good alterant and refining scavenging agent, solid solution is in copper hardly, its can form high melting point metal compound with the elements such as impurity lead, bismuth in the alloy, is distributed in intracrystalline, improves plasticity, the wear resistance of alloy, impel grain refining, facilitate the tiny more distribution equably of metallic compound on the crystal boundary, general add-on is 0.003～0.4%, and adding with the lanthanum is the mishmetal better effects if of base, can increase electric conductivity and anti-dezincify ability, but the too high flowability that can reduce alloy.
Add tin, aluminium, phosphorus and mainly be auxiliary boron and strengthen the performance that anti-dezincify, anti-stress split and improve the thermo forming performance, make it to reach the standard of international environment protection health security regulations.Secondly in this brass, add the flowability of tin, aluminium, all right deoxidation of phosphorus, increase alloy, improve the cutting ability and the intensity of alloy.Tin is solution strengthening and the element that suppresses dezincify, strengthen matrix together with boron, aluminium, phosphorus, help being uniformly dispersed and the formation of strengthening phase of each phase, help the raising of intensity, wear resistance and cutting ability, particularly help anti dezincification character can and the raising of thermoforming performance.The content of phosphorus generally is controlled at 0.005～0.2% and is advisable.The content of tin generally is controlled at 0.2～0.6% and is advisable.Aluminium content is generally 0.02～0.3% in this alloy, the aluminium too high levels can reduce cutting ability and performance is electroplated in polishing.Aluminium, phosphorus and tin too high levels can reduce the back cold and hot processability in step.
Even lead and cadmium are as the unavoidable impurities element, the lead content in the impurity must be less than 0.03%, and cadmium content must be less than 0.001%.This lead, cadmium content had both met international environmental protection and had ordered requirement within a certain time, caused public hazards can for again the environment and the mankind, and adapt to environmental friendly material development trend in the future.According to the leaching amount detected result of the correlation detection standard in the international tap water engineering, this lead, cadmium content had both met international environmental protection and had ordered requirement within a certain time, caused public hazards can for again the environment and the mankind.
Three of above-mentioned leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is to have good cutting performance, excellent anti-Dezincification corrosion performance, an anti-stress corrosion performance, the new type leadless easy cutting brass alloys that help environmental protection, health, nutrition of excellent mechanical property and cold and hot processability and good welding property.Can be widely used in optoelectronic components, electronics telecommunication, toy for children, the household electrical appliances of tap water engineering, five metals, machinery, photographic apparatus, the component production is easily cut in the casting and the cold and hot moulding of automobile component.
After adding elements such as calcium, boron, antimony three kinds of leadless easy cutting corrosion resistant low boron calcium brass alloys invention of three from one of above-mentioned leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention to above-mentioned leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention, machinability, solidity to corrosion and anti dezincification character improve widely.The brass alloys that these copper contents are lower contain the α phase, β is a spot of hard mutually crisp with other mutually, hard crisp mutually tinyly be evenly distributed on crystal boundary and intracrystalline and the precipitation strength effect is arranged, improved the cutting ability of alloy, increase the chip breaking point of short bits, also strengthened solidity to corrosion, anti dezincification character, wear resistance, mechanical property and the cold and hot processability of alloy simultaneously.
The manufacture method of described alloy is with weight %: copper: 55～65%; calcium: 0.004～0.25%; antimony: 0.1～0.5%; boron: 0.0005～0.05%; other element: 0.2～1.5%; all the other are the alloying constituent that zinc and unavoidable impurities are constituted; adopt Alloying Treatment and covering protection method melting low boron calcium brass alloy; make calcium metal; boron; antimony quick solid solution in the brass liquation is an intermetallic compound; and (the whole fusion process top temperature of this brass is 1080 ℃ to be continuously cast into the brass ingot casting under 1030 ℃; do not reach 1675 ℃ of boiling temperatures that make metallic antimony evaporation far away; so work the mischief can not for the mankind and environment); under 680～730 ℃ of temperature, carry out the large extrusion ratio extruding; intermediate heat treatment is carried out under 420～700 ℃ of temperature by cold worked condition, is being lower than the annealing that eliminates stress under 400 ℃ the temperature.
Compared with prior art, the invention has the advantages that: 1. have excellent cutting ability, excellent anti dezincification character energy, good welding property, good solidity to corrosion, mechanical property and can polish the plating performance, be specially adapted to the component, forging, foundry goods of machining moulding and as the component material of other manufacture method; 2. low cost of manufacture only is equivalent to the manufacturing cost of the leaded brass of prior art, thereby has market competition advantage; 3. can reach international environmental protection, health, safety standards code requirement fully, and the leadless easy cutting corrosion resistant low boron calcium alloy material of another novel environment friendly, nutrition, health is provided for world's recycling economy.
Description of drawings
Fig. 1, be the car of alloy of the present invention bits pattern synoptic diagram, the turning back engagement of the cutting edge is 0.5mm, and the speed of mainshaft is 1120rpm/min, and the amount of feed is 0.08mm/rev.
Embodiment
Below in conjunction with embodiment invention is described in further detail:
Embodiment forms ingot casting, pushes, is drawn into pole by the alloy ingredient in following each table leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention; The contrast sample is the Winn bronze trade mark C36000 alloy of the U.S., and it is the universally acknowledged best Winn bronze of machinability, also carries out same shaping.
Its technological process of production method is as follows:
Starting material are prepared, and---------------stretching,------------aligning polishing---stress relieving---check finished product packing stretches in pickling in thermal treatment in extruding in the ingot casting heating in continuous casting in the Alloying Treatment melting.
Specifically can be expressed as follows: adopt Alloying Treatment and covering protection method melting low boron calcium brass alloy; making the quick solid solution in the brass liquation of calcium metal, boron, antimony is intermetallic compound; and under 1030 ℃, be continuously cast into the brass ingot casting; under 680～730 ℃ of temperature, carry out the large extrusion ratio extruding; intermediate heat treatment is carried out under 420～700 ℃ of temperature by cold worked condition, is being lower than the annealing that eliminates stress under 400 ℃ the temperature.
Wherein changing process of thermal treatment flow implementation process over to proves, thermal treatment is lower than 400 ℃ stress relieving and must carries out, and that intermediate heat treatment needs to be annealed under 420～700 ℃ of temperature according to cold worked condition is suitable, but warm brittle zone annealing in should as far as possible avoiding (its flow process is produced identical with the lead brass alloy of routine substantially).
It is of a size of Φ 170*400～500 millimeter the ingot casting of the various serial invention alloy of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention, under 680 ℃～730 ℃ of identical appointed condition and different extrusion temperatures, be squeezed into the wire rod of 10 millimeters of Φ 8, Φ, its concrete component content sees Table 11, (seeing the 17th page) shown in the table 12, table 13.
The performance test of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is as follows:
1. machinability experiment
Estimate by turning that the experiment of machinability is performed such:
Under identical mechanical workout condition, (see Table 14), adopt the cutting force experiment instrument to record the cutting force of each invention alloy, and calculate the machinability index of each invention alloy phase thus for C36000, C36000 is the universally acknowledged best Winn bronze of machinability, and its machinability is considered to 100%.The results are shown in Table 15, the car bits pattern of the correspondence that obtains as shown in Figure 1.
Table 14 is estimated the mechanical workout condition of machinability
| The lathe model | Diameter of work (mm) | Back engagement of the cutting edge (mm) | The amount of feed (mm/r) | Cutting speed (m/min) | The speed of mainshaft (r/min) | Cut count (point) | Cutting state |
| CA6140 | Φ4.75 | 0.5 | 0.08 | 16.713 | 1120 | 3 | Do |
Table 15 machinability evaluation result
| Alloy | Machinability index (%) |
| C36000 | 100 |
| Invent an alloy | ＞86 |
| Invent two alloys | ＞80 |
| Invent three alloys | ＞78 |
Annotate: cutting resistance * 100% of [machinability index]=[cutting resistance of C36000]/each invention alloy, each cutting resistance are according to the measured cutting force mean value value of experiment.
As seen, the machinability of alloy of the present invention can reach 78～92% of traditional Winn bronze C36000, the cutting ability excellence.
Except C36000, alloy of the present invention is that the Cu-Zn-Si of alloy, Japanese Triratna company is that alloy contrasts with the Cu-Zn-Bi of U.S. NAKAYAMA company also, by cutting, boring processing, obtain the comprehensive cutting ability of machining of invention alloy, the results are shown in Table 16 (seeing the 19th page).
From table 16, can find out significantly: invent the close of the cutting ability of an alloy and traditional Winn bronze C36000, than the like product excellence of Japan, the U.S..
2. thermo compression experiment
From first to the 3rd invention alloy extrudes respectively to be got Φ 8*20mm and makees sample on the product, contrast sample C36000 in addition and also get same size, does the thermo compression test.Sample axially loads then 670 ℃ of heating 30 minutes, and deflection is 70%, and length is reduced to 6mm by 20mm, observes its distortion rear surface crackle situation under 5～10 times of magnifying glasses.
We can see that after the thermo compression experiment, the surface of invention alloy and C36000 alloy is flawless all.As seen the hot workability of invention alloy and C36000 quite or better are fit to industrial processes.
3. dezincify experiment
Three carried out the dezincify experiment according to IS06509 dezincify experimental technique from one of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention invention to invention, contrasting sample is the C36000 Winn bronze, and the maximum Dezincification corrosion degree of depth that records sees Table 17:
Table 17: the maximum Dezincification corrosion depth correlation of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention and C36000 Winn bronze
| Alloy | The maximum Dezincification corrosion degree of depth (μ m) | |
| Laterally | Vertically | |
| C36000 | 560 | 610 |
| One of the present invention | 20 | 50 |
| The present invention's two | 65 | 85 |
| The present invention's three | 30 | 70 |
As seen from Table 17, the anti dezincification character of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention all is better than the C36000 Winn bronze.
4. stress etching experiment
We have also carried out stress etching experiment to leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention, and experimental technique is ISO6957, and the contrast sample is the C36000 Winn bronze.
After the test of 24 hours ammonia cures, take out sample, several minutes is fully cleaned in rinsing in distilled water water earlier then in the sulphuric acid soln 5% under the room temperature, at last washing and drying up in distilled water again.Through the specimen surface behind 10 times the amplifications observation ammonia cure, can see that behind stress etching experiment, leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention and C36000 surface condition are all fine, flawless.
5. normal temperature tension experiment
Getting one of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is the finished product of Φ 7.4*140mm to three specification of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention, carries out the normal temperature tension test, and the contrast sample is the C36000 Winn bronze.Test the unit elongation and the tensile strength of each invention alloy, the results are shown in Table 18.
Table 18: the normal temperature mechanical property contrast of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention and C36000 Winn bronze
| Alloy | Specification/state | Unit elongation (%) | Tensile strength (MPa) |
| C36000 | Φ7.4Y/2 | 16 | 526 |
| One of invention | Φ7.4Y/2 | 14 | 542 |
| Two of invention | Φ7.4Y/2 | 10 | 569 |
| Three of invention | Φ7.4Y/2 | 15 | 540 |
As seen from Table 18, C36000 is higher for the strength ratio of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention tradition Winn bronze, and unit elongation is low slightly.
6. conductivity test
Get leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention and C36000 Winn bronze, test its conductivity at room temperature rate, test result such as table 19:
The conductivity at room temperature rate contrast of table 19 leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention and C36000 Winn bronze
| Alloy | IACS(％) |
| C36000 | 23.64 |
| One of invention | 22.53 |
| Two of invention | 22.98 |
| Three of invention | 24.02 |
7. differential thermal analysis (DTA)
Get leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention and C36000 and make differential thermal analysis, record fusing point and see Table 20:
The fusing point contrast of table 20 leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention and C36000 Winn bronze
| Alloy | Fusing point (℃) |
| C36000 | 900 |
| One of invention | 906 |
| Two of invention | 899 |
| Three of invention | 902 |
8. wholesomeness check
According to " Drinking Water transmission ﹠ distribution wetting system and protective material hygienic safety value disciplines " (2001), three of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention has been carried out the wholesomeness check, assay sees Table 21:
Table 21 non-leaded easily-cutting brass-corrosion resistant low boron calcium brass immersion test increases survey project result
| Sequence number | Analysis project | The hygienic practice requirement | Assay |
| 1 | Copper | Increasing amount≤0.2mg/L | Qualified |
| 2 | Zinc | Increasing amount≤0.2mg/L | Qualified |
| 3 | Antimony | Increasing amount≤0.0005mg/L | Qualified |
Take all factors into consideration various experimental results, we think that leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is close with traditional Winn bronze cutting ability, the cutting ability of the external recent bismuth yellow brass of researching and developing of ratio, siliceous 3% brass is excellent or suitable, and phase composite also has its unique distinction in formation mechanism of the cutting of alloy of the present invention reinforcement simultaneously and the alloy.
Above-mentioned various experimental result also proves, the cutting ability of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention, physical strength and excellent corrosion-proof performance.And raw materials cost is lower more than 5% than the generic no lead brass alloy (Cu-Zn-Bi alloy) of the U.S.; Generic no lead brass alloy (Cu-Zn-Si alloy) than Japanese Triratna is low more than 10%; But than traditional C36000 Winn bronze raw materials cost slightly high 2%.
Therefore leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is a kind of no lead brass alloy with excellent in machinability energy, corrosion resisting property, anti dezincification character energy, higher-strength.Can be widely used in the component, heat exchanger web member, light fixture spare, gasburner of the foundry goods of component, domestic water supply system of the fastening piece of high-strength abrasion-proof of electronics telecommunication, household electrical appliances, five metals cutting component, forging, foundry goods and other purposes and hydraulic efficiency plant and valve, switch, water tap, automobile and instrument industries etc., all have very high use value, also satisfied the standard-required of international ecological environment protection health safety and sanitation standards simultaneously.
Table 11: the composition of one of invention of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is formed example: (weight %)
Table 12: two composition of the invention of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is formed example: (weight %)
Table 13: three composition of the invention of leadless easy cutting corrosion resistant low boron calcium brass alloy of the present invention is formed example: (weight %)
The comprehensive cutting ability contrast of the machining of table 16 invention alloy and comparative alloy
Claims (7)
1. leadless easy cutting corrosion resistant low boron calcium brass alloy, it is characterized in that: it is become to be grouped into by copper, zinc and calcium, boron, antimony alloy element and unavoidable impurities, consisting of of described alloy: copper: 55～65wt%, calcium: 0.004～0.25wt%, antimony: 0.1～0.5wt%, boron: 0.0005～0.05wt%, other element: 0.2～1.5wt%, described other element is at least two kinds of elements in titanium, nickel, iron, silicon, tin, aluminium, phosphorus, the lanthanum, all the other are zinc and unavoidable impurities, and content plumbous in the unavoidable impurities is less than 0.1wt%; The copper zincification adds calcium and adds antimony and add boron greater than 97wt% in the described alloy composition, and wherein zinc greater than 35.5wt%.
2. leadless easy cutting corrosion resistant low boron calcium brass alloy according to claim 1, it is characterized in that: the consisting of of described alloy: copper: 58～63wt%, calcium: 0.005～0.15wt%, antimony: 0.15～0.35wt%, boron: 0.0006～0.03wt%, other element: 0.3～1.2%; The copper zincification adds calcium and adds antimony and add boron greater than 97.5% and be not more than 99% in the described alloy composition, and wherein zinc is greater than 35.5%.
3. leadless easy cutting corrosion resistant low boron calcium brass alloy, it is characterized in that: the consisting of of described alloy: copper: 55～63wt%, calcium: 0.004～0.25wt%, antimony: 0.1～0.5wt%, boron: 0.0005～0.05wt%, other element: 0.3～1.6wt%, described other element is at least two kinds of elements in titanium, nickel, iron, silicon, tin, phosphorus, the lanthanum, all the other are zinc and unavoidable impurities, and content plumbous in the unavoidable impurities is less than 0.1wt%; The copper zincification adds calcium and adds antimony and add boron greater than 97wt% in the described alloy composition, and wherein zinc greater than 36.5wt%.
4. leadless easy cutting corrosion resistant low boron calcium brass alloy according to claim 3 is characterized in that: the consisting of of described alloy: copper: 57～62wt%, calcium: 0.005～0.15wt%, antimony: 0.15～0.35wt%, boron: 0.0006～0.03wt%, other element: 0.4～1.4wt%; The copper zincification adds calcium and adds antimony and add boron greater than 97.5% and be not more than 99.2% in the described alloy composition, and wherein zinc is greater than 36.5%.
5. leadless easy cutting corrosion resistant low boron calcium brass alloy, it is characterized in that: the consisting of of described alloy: copper: 56～64wt%, calcium: 0.004～0.25wt%, antimony: 0.1～0.5wt%, boron: 0.0005～0.05wt%, other element: 0.2～1.5wt%, described other element is at least two kinds of elements in titanium, nickel, iron, silicon, tin, aluminium, phosphorus, the lanthanum, all the other are zinc and unavoidable impurities, as content plumbous in the unavoidable impurities less than 0.03wt%; The copper zincification adds calcium and adds antimony and add boron greater than 97wt% in the described alloy composition, and wherein zinc is greater than 35.5wt%.
6. leadless easy cutting corrosion resistant low boron calcium brass alloy according to claim 5, it is characterized in that: the consisting of of described alloy: copper: 58～63wt%, calcium: 0.005～0.15wt%, antimony: 0.15～0.35wt%, boron: 0.0006～0.03wt%, other element: 0.4～1.4wt%, described other element is at least two kinds of elements in titanium, nickel, iron, silicon, tin, aluminium, phosphorus, the lanthanum, all the other are zinc and unavoidable impurities, as content plumbous in the unavoidable impurities less than 0.03wt%; The copper zincification adds calcium and adds antimony and add boron greater than 97.5wt% and be not more than 99wt% in the described alloy composition, and wherein zinc is greater than 35.5wt%.
7. method for preparing as claim 1 or 3 or 5 described leadless easy cutting corrosion resistant low boron calcium brass alloys; it is characterized in that: adopt Alloying Treatment and covering protection method melting low boron calcium brass alloy; making the quick solid solution in the brass liquation of calcium metal, boron, antimony is intermetallic compound; and under 1030 ℃, be continuously cast into the brass ingot casting; under 680～730 ℃ of temperature, carry out the large extrusion ratio extruding; intermediate heat treatment is carried out under 420～700 ℃ of temperature by cold worked condition, is being lower than the annealing that eliminates stress under 400 ℃ the temperature.
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| CN1557981A (en) * | 2004-01-15 | 2004-12-29 | 宁波博威集团有限公司 | Non-lead free cutting antimony yellow copper alloy |
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| DE102022120122A1 (en) | 2022-08-10 | 2024-02-15 | Diehl Brass Solutions Stiftung & Co. Kg | Lead-free brass alloy |
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