CN103276323A - Preparation method of high-strength and corrosion-resistant composite heat exchanger tube - Google Patents
Preparation method of high-strength and corrosion-resistant composite heat exchanger tube Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-strength and corrosion-resistant composite heat exchanger tube. The composite heat exchanger tube consists of a copper base, alloy metal and filling particles, wherein the alloy metal comprises the following components in percentage by weight: 0.5-0.6% of magnesium, 0.08-0.09% of silver, 0.2-0.4% of tin, 0.012-0.014% of zirconium, 0.012-0.014% of niobium, 0.05-0.06% of nickel, 0.005-0.008% of titanium and 0.02-0.04% of mixed rare earth; the mixed rare earth consists of yttrium, berkelium and lanthanum at a mass ratio of 1: (0.15-0.2): (0.4-0.5); and the filling particles comprise the following components in percentage by weight: 0.010-0.012% of tetrapod-like zinc oxide whiskers, 0.008-0.009% of silicon carbide, 0.005-0.006% of aramid fiber, 0.004-0.005% of glass fiber and 0.002-0.003% of nano titanium oxide. The oxygen content of the prepared composite heat exchanger tube is in an oxygen-free copper level; the crystal grain is tiny; and the mechanical strength, the high-temperature resistance, the corrosion resistance and the wear resistance are improved greatly compared with the existing copper tube.
Description
Technical field
The present invention relates to the heat exchanging apparatus field, be specially the preparation method of the compound heat exchanger tube of a kind of high-strength corrosion-resisting.
Background technology
At present, along with the development of power station, boats and ships, refrigeration industry, need to seek a kind of corrosion resistance nature and the good heat exchange tube material of processing characteristics.Originally the heat transfer tube of Shi Yonging mostly is brazed copper tube, nickelic White Copper Tubes or copper tube.But brazed copper tube, nickelic White Copper Tubes and copper tube have its deficiency, and existing division is as follows: the brazed copper tube cost is lower, but corrosion resistance nature and processing characteristics do not have copper-nickel alloy to run well, just wants maintain and replace a collection of in general about 3 years.Power station, the boats and ships maintenance cost of suspending is big, and the influence of refrigeration shutdown maintenance is big.Nickelic White Copper Tubes: corrosion resistance nature is better, but nickel content height, material cost is big, and processing characteristics is relatively poor.Along with the nonferrous materials price significantly rises.Increase is difficult to bear to cost for power station, boats and ships, especially refrigeration industry.Copper tube: processing characteristics is relatively good, but corrosion resistance nature is poor.The physical strength deficiency of existing heat-exchanger brass pipe in addition, the increase along with the running pressure of refrigeration agent needs the ancient piece of jade, round, flat and with a hole in its centre of thickening copper pipe thick, and one has improved cost greatly, and it two also must influence heat conductivility.Present production of copper compo pipe, main method is extrusion process, adopts alternate manner such as oblique casting perforation, and continuous casting rolls and draws seldom, the extrusion process production process is: the circle of batching casting earlier base, through sawing, letter sorting, heating, extruding, pickling, then through rolling, be stretched to production tube.Its defective is: (1) production process is numerous and diverse, and off-set facility is many, maintenance die cost height, and floor space is big, and personnel require many competency profilings height; (2) scale of investment is big, more than one hundred million units at least, several hundred million yuan at most; (3) justify the base second-heating, need extrusion molding, container, pin need energy consumption height such as preheating before the work; Operation metal losses such as (4) stirring, ingot casting, sawing, heating, pressure are surplus, decortication, pickling are big, and yield rate is low, for base yield rate＜90%; (5) adopt single-unit furnace semicontinuous casting or the founding of split stove, the production poor continuity, efficient is low; (6) the zinc scaling loss is big, stir, and second-heating, extruding and the lubricated smog that waits are big, seriously polluted; (7) pipe is eccentric big, influences follow-up cold working, and especially the extrusion yield of the large-caliber thin-walled brazed copper tube of forward extrusion is 40%～60%.
Summary of the invention
Order of the present invention provides the preparation method of the compound heat exchanger tube of high-strength corrosion-resisting that a kind of production process is simple and continuity is strong, yield rate is high, and the product rotproofness of its preparation is strong, physical strength is high and good processability.
The concrete technical scheme of the present invention is: described compound heat exchanger tube is made up of copper base, alloyed metal and filler grain; The weight percent of described alloyed metal is as follows: magnesium 0.5-0.6%, silver 0.08-0.09%, tin 0.2-0.4%, zirconium 0.012-0.014%, niobium 0.012-0.014%, nickel 0.05-0.06%, titanium 0.005-0.008%, mishmetal 0.02-0.04%, described mishmetal is made up of yttrium, berkelium and lanthanum, three's mass ratio is 1:(0.15-0.2): (0.4-0.5); The weight percent of described filler grain is as follows: four acicular type zinc oxide crystal whisker 0.010-0.012%; Silicon carbide 0.008-0.009%, aramid fiber 0.005-0.006%, glass fibre 0.004-0.005% and nano titanium oxide 0.002-0.003%; Preparation process is as follows:
(1), copper material, each alloyed metal and filler grain are divided into many parts, evenly putting into the interior melting of undercurrent type induction stirring line-frequency induction combined electric furnace in proportion at interval is liquation, and cover charcoal on the copper liquid, feed argon gas and form atmosphere protection, draw by the crystallizer cooling and through towing mechanism then and obtain pipe; Concrete control parameter is as follows: copper liquid temperature is 1150-1180 ℃ during melting, on to draw temperature be 1120-1140 ℃; Pulling speed is 400-450mm/min, and copper liquid liquid level is 360-380mm; It is 20-22mm that crystallizer inserts the liquation degree of depth; The crystallizer inflow temperature is that 28-38 ℃, leaving water temperature(LWT) are no more than 55 ℃; Charcoal on the copper liquid is covered as 22-25cm; The oxygen level of pipe should be controlled below 10ppm;
(2), pipe is through cut-out, milling the induction heater that enters by argon shield behind the face and be preheated to 340-350 ℃, enters three-roller planetary rolling mill continuous rolling then and obtains shell, rolling temperature is controlled to be 750-760 ℃, roll speed 18-20m/min;
(3), shell is cooled off fast the back by cold drawing bench cold-drawn moulding, mix as lubricant by weight 1:0.08:0.12 with machine oil, nano molybdenum disulfide, nanometer polytetrafluoroethylcomposite during drawing, wherein the particle diameter of nano molybdenum disulfide is 20-30nm, and the particle diameter of nanometer polytetrafluoroethylcomposite is 60-80nm.
Above scheme also comprises:
Described four acicular type zinc oxide crystal whisker length 12-14 μ m, base diameter 3-5 μ m, described aramid fiber length is 2-2.5mm, filament diameter 8-10 μ m, and described glass fibre is 120-140 purpose glass fibre powder, and described nano titanium oxide particle diameter is 15-30nm; Described silicon carbide is that mean particle size is α-SiC particle of 16-17 μ m.
Described four acicular type zinc oxide crystal whisker need carry out modification in accordance with the following methods: weighing 0.5-0.8 g silane coupling agent is dissolved in the 60-70ml acetone, drips oxalic acid again and regulates PH to 5～6, leaves standstill 20-25 minute; Weighing 12-14g four acicular type zinc oxide crystal whisker places above-mentioned solution then, under 55-58 ℃ of temperature to stirring 5-6 hour; It is standby that suction filtration, dry out solvent obtain the modification four acicular type zinc oxide crystal whisker then; Described aramid fiber need carry out following pre-treatment: aramid fiber was soaked in acetone 8-10 hour, boiled 2-3 hour dry for standby then respectively in water and ethanol; Described glass fibre need carry out modification in accordance with the following methods: weighing 1-1.2g silane coupling agent is dissolved in the 40-50 ml acetone, and weighing 8-10g glass fibre places above-mentioned solution then, under 25-30 ℃ of temperature to stirring 0.5-1 hour; And then 70-75 ℃ dry 2-3 hour, standby after 1-1.5 hour 110-112 ℃ of activation; Described nano titanium oxide need carry out modification in accordance with the following methods: take by weighing the 1-1.5g silane coupling agent and be blended in the 80-120g water; Nano titanium oxide and trolamine are according to mass ratio 1:0.5-1 mixed grinding; Take by weighing abrasive 15-20g and be distributed in the above-mentioned water body that contains silane coupling agent, regulate PH to 8.5-8.8, stirred 3-4 hour, then suction filtration, dry that to obtain modified nano-titanium dioxide standby; Need to carry out following pre-treatment before described α-SiC particle mixes: chlorohydric acid pickling: the SiC particle is joined in the hydrochloric acid of massfraction 15-18%, and soaked 4-5 hour down at 28-30 ℃, till filtration and washing SiC particle were 6-7 to PH, the oven dry back was standby; High temperature oxidation: 950-980 ℃ of following oxidation of SiC particle that oven dry is obtained 5 hours, the cooling back is standby; The nitrate sensitization: the SiC particle that cooling is obtained soaked 3 hours in the magnesium nitrate solution of massfraction 20-22%, then in 3 hours with the ammonia water titration solution PH of massfraction 10-20% most till 9.2, filter and 420 ℃ of following dry for standby.
Described undercurrent type induction stirring line-frequency induction combined electric furnace adopts W type channel; The silane coupling agent of described four acicular type zinc oxide crystal whisker modification is KH-570, and the silane coupling agent of described glass fibre modification is KH-550; Described nano-titanium dioxide modified silane coupling agent is KH-560.Undercurrent type induction stirring line-frequency induction combined electric furnace adopts W type channel; Make copper liquid in channel, form directed flow at high speed, sufficient heat exchange is arranged, make various dystectic oxidation sludges and the quartz sand that deteriorated flow out channel with liquid stream.Add flowing of the interior copper liquid of fast thawing copper, this not only can shorten smelting time, improves electric furnace throughput, and has reduced the temperature in the channel, avoids slag to stop up, thus the working life of raising stove, and realized energy-saving and cost-reducing more than 30%.
This processing method adopts continuous up-casting-rolling-drawing to replace technological processs such as the casting in the traditional technology, sawing, heating, extruding, pickling, thereby simplified technical process greatly, realized continuous with short production cycle, the efficient height, metal loss reduces greatly, less energy consumption can reach 99% for the base yield rate, reduces priming cost more than 60%.The moulding of this technology copper alloy fusing crystallisation by cooling is plumbness, molten alloyed copper is even to the graphite jig pressure distribution, whole section cooling evenly, partly solidify also basically identical, i.e. pipe even particle distribution radially, dense internal organization, do not have loose, pore, smooth surface non-oxidation crackle, cold-forming property is better than extrusion billet.
Alloyed metal has following effect: one, by increasing the physical strength that metals such as tin, magnesium, zirconium, silver can increase substantially copper pipe, such as tensile strength, silver has good sterilization, antibacterial effect in addition, can suppress the breeding of bacterium, virus, algae and fungi.Two, by increasing acid-alkali-corrosive-resisting, high-temperature corrosion resistance and the welding property that zirconium, titanium, nickel, niobium etc. can improve copper pipe, zirconium, niobium can also be used as " VITAMIN " of metallurgical industry in addition, easy sulphur, nitrogen, foster, the direct chemical combination of carbon under the high temperature, with have deoxidation, denitrogenate, the effect of desulfuration, reduce the content of oxygen, nitrogen, sulphur in the copper pipe; Titanium, zirconium and the easy combination of niobium three, the intensity of raising copper pipe and resistance to compression, wear-resisting, corrosion resistance nature; And the ability that has " memory " after titanium, the nickel combination, and memory is very strong, improves the toughness of copper pipe.Three, rare earth metal yttrium, berkelium and lanthanum play the deoxidization desulfuration effect in casting, both content all is reduced to below 0.001%, and changes the state of inclusion, crystal grain thinning, thereby improve the processing characteristics of copper pipe, improve intensity, toughness, corrosion-resistant and oxidation-resistance etc.
The effect of filler ion is as follows:
(1) by in matrix material, adding grit SiC, not only can improve size thermostability, mechanical property and the wear resistance of copper base, but also can improve thermotolerance and the creep-resistant property of copper base, and can reduce thermal expansivity.Strengthen the reductor that particle silicon carbide can be used as casting simultaneously.
(2) because fiber high-strength degree and rigidity and good thermal conductivity are utilized these advantages, aramid fiber and glass fibre are compound in the copper base matrix, improve frictional behaviour and the mechanical property of copper base.Studies show that owing to matrix contacts with other material when friction taking place producing wearing and tearing, fiber can play good carrying effect, can form even continuous transfer film on the mating plate surface, thereby the wear resistance of matrix material is significantly improved.
(3) four acicular type zinc oxide crystal whisker (T-ZnO
w) have the performance that general common one dimension whisker does not possess, T-ZnO with the isotropy characteristics of transitivity because of its special three-dimensional space physical structure
wEvenly distribute in matrix than being easier to, the performance of composites for preparing has isotropy, and this is that one dimension crystal whisker materials and granular filler are unapproachable, T-ZnO
wExcept being used to strengthen the mechanical mechanics property effect of body material as wild phase, also have a lot of the application such as vibration and noise reducing, antistatic, antibiotic etc.The present invention is by mixing T-ZnO
wAfter can be to the copper base matrix, especially antistatic application facet promotes to some extent in the electrical applications field on the one hand, also can make moderate progress aspect thermal property on the other hand, improves its thermal conductivity and reduces thermal expansivity.Make this matrix material that certain using value can be arranged in the electric works field.
(4), nano titanium oxide (TiO
2) have distinctive nanometer size effect, big specific surface area, with polymkeric substance stronger interfacial interaction arranged, it can combine with aramid fiber, glass fibre and fill copper base, plays synergy, TiO
2Can improve the supporting capacity of matrix material, remedy fibre fractionation fill less than barren pars fibrosa, thereby improve the wear resisting property of matrix material.
The compound heat exchanger tube oxygen level of the present invention preparation is the oxygen free copper level, and physical strength, high temperature resistant, corrosion-resistant and wear resisting property are compared with existing heat exchange copper pipe and be improved largely.
Embodiment
Embodiment 1
The preparation method of the compound heat exchanger tube of a kind of high-strength corrosion-resisting, compound heat exchanger tube is made up of copper base, alloyed metal and filler grain; The weight percent of alloyed metal is as follows: magnesium 0.5-0.6%, silver 0.08-0.09%, tin 0.2-0.4%, zirconium 0.012-0.014%, niobium 0.012-0.014%, nickel 0.05-0.06%, titanium 0.005-0.008%, mishmetal 0.02-0.04%, mishmetal is made up of yttrium, berkelium and lanthanum, three's mass ratio is 1:(0.15-0.2): (0.4-0.5); The weight percent of filler grain is as follows: four acicular type zinc oxide crystal whisker 0.010-0.012%; Silicon carbide 0.008-0.009%, aramid fiber 0.005-0.006%, glass fibre 0.004-0.005% and nano titanium oxide 0.002-0.003%; Surplus is copper, the cathode copper of copper preferred content 〉=99.95%; Preparation process is as follows:
(1), copper material, each alloyed metal and filler grain are divided into many parts, evenly putting into the interior melting of undercurrent type induction stirring line-frequency induction combined electric furnace in proportion at interval is liquation, and cover charcoal on the copper liquid, feed argon gas and form atmosphere protection, draw by the crystallizer cooling and through towing mechanism then and obtain pipe; Concrete control parameter is as follows: copper liquid temperature is 1150-1180 ℃ during melting, on to draw temperature be 1120-1140 ℃; Pulling speed is 400-450mm/min, and copper liquid liquid level is 360-380mm; It is 20-22mm that crystallizer inserts the liquation degree of depth; The crystallizer inflow temperature is that 28-38 ℃, leaving water temperature(LWT) are no more than 55 ℃; Charcoal on the copper liquid is covered as 22-25cm; The oxygen level of pipe should be controlled below 10ppm;
(2), pipe is through cut-out, milling the induction heater that enters by argon shield behind the face and be preheated to 340-350 ℃, enters three-roller planetary rolling mill continuous rolling then and obtains shell, rolling temperature is controlled to be 750-760 ℃, roll speed 18-20m/min;
(3), shell is cooled off fast the back by cold drawing bench cold-drawn moulding, mix as lubricant by weight 1:0.08:0.12 with machine oil, nano molybdenum disulfide, nanometer polytetrafluoroethylcomposite during drawing, wherein the particle diameter of nano molybdenum disulfide is 20-30nm, and the particle diameter of nanometer polytetrafluoroethylcomposite is 60-80nm.
Embodiment 2
The preparation method of the compound heat exchanger tube of a kind of high-strength corrosion-resisting, compound heat exchanger tube is made up of copper base, alloyed metal and filler grain; The weight percent of alloyed metal is as follows: magnesium 0.5-0.6%, silver 0.08-0.09%, tin 0.2-0.4%, zirconium 0.012-0.014%, niobium 0.012-0.014%, nickel 0.05-0.06%, titanium 0.005-0.008%, mishmetal 0.02-0.04%, mishmetal is made up of yttrium, berkelium and lanthanum, three's mass ratio is 1:(0.15-0.2): (0.4-0.5); The weight percent of filler grain is as follows: four acicular type zinc oxide crystal whisker 0.010-0.012%; Silicon carbide 0.008-0.009%, aramid fiber 0.005-0.006%, glass fibre 0.004-0.005% and nano titanium oxide 0.002-0.003%; Surplus is copper, the cathode copper of copper preferred content 〉=99.95%; Four acicular type zinc oxide crystal whisker length 12-14 μ m, base diameter 3-5 μ m, aramid fiber length is 2-2.5mm, filament diameter 8-10 μ m, and glass fibre is 120-140 purpose glass fibre powder, and the nano titanium oxide particle diameter is 15-30nm; Silicon carbide is that mean particle size is α-SiC particle of 16-17 μ m.
Compound heat exchanger tube preparation process is as follows:
(1), copper material, each alloyed metal and filler grain are divided into many parts, evenly putting into the interior melting of undercurrent type induction stirring line-frequency induction combined electric furnace in proportion at interval is liquation, and cover charcoal on the copper liquid, feed argon gas and form atmosphere protection, draw by the crystallizer cooling and through towing mechanism then and obtain pipe; Concrete control parameter is as follows: copper liquid temperature is 1150-1180 ℃ during melting, on to draw temperature be 1120-1140 ℃; Pulling speed is 400-450mm/min, and copper liquid liquid level is 360-380mm; It is 20-22mm that crystallizer inserts the liquation degree of depth; The crystallizer inflow temperature is that 28-38 ℃, leaving water temperature(LWT) are no more than 55 ℃; Charcoal on the copper liquid is covered as 22-25cm; The oxygen level of pipe should be controlled below 10ppm;
(2), pipe is through cut-out, milling the induction heater that enters by argon shield behind the face and be preheated to 340-350 ℃, enters three-roller planetary rolling mill continuous rolling then and obtains shell, rolling temperature is controlled to be 750-760 ℃, roll speed 18-20m/min;
(3), shell is cooled off fast the back by cold drawing bench cold-drawn moulding, mix as lubricant by weight 1:0.08:0.12 with machine oil, nano molybdenum disulfide, nanometer polytetrafluoroethylcomposite during drawing, wherein the particle diameter of nano molybdenum disulfide is 20-30nm, and the particle diameter of nanometer polytetrafluoroethylcomposite is 60-80nm.
Embodiment 3
The preparation method of the compound heat exchanger tube of a kind of high-strength corrosion-resisting, compound heat exchanger tube is made up of copper base, alloyed metal and filler grain; The weight percent of alloyed metal is as follows: magnesium 0.5-0.6%, silver 0.08-0.09%, tin 0.2-0.4%, zirconium 0.012-0.014%, niobium 0.012-0.014%, nickel 0.05-0.06%, titanium 0.005-0.008%, mishmetal 0.02-0.04%, mishmetal is made up of yttrium, berkelium and lanthanum, three's mass ratio is 1:(0.15-0.2): (0.4-0.5); The weight percent of filler grain is as follows: four acicular type zinc oxide crystal whisker 0.010-0.012%; Silicon carbide 0.008-0.009%, aramid fiber 0.005-0.006%, glass fibre 0.004-0.005% and nano titanium oxide 0.002-0.003%; Surplus is copper, the cathode copper of copper preferred content 〉=99.95%; Four acicular type zinc oxide crystal whisker length 12-14 μ m, base diameter 3-5 μ m, aramid fiber length is 2-2.5mm, filament diameter 8-10 μ m, and glass fibre is 120-140 purpose glass fibre powder, and the nano titanium oxide particle diameter is 15-30nm; Silicon carbide is that mean particle size is α-SiC particle of 16-17 μ m.Four acicular type zinc oxide crystal whisker need carry out modification in accordance with the following methods: weighing 0.5-0.8 g silane coupling agent is dissolved in the 60-70ml acetone, drips oxalic acid again and regulates PH to 5～6, leaves standstill 20-25 minute; Weighing 12-14g four acicular type zinc oxide crystal whisker places above-mentioned solution then, under 55-58 ℃ of temperature to stirring 5-6 hour; It is standby that suction filtration, dry out solvent obtain the modification four acicular type zinc oxide crystal whisker then; Aramid fiber need carry out following pre-treatment: aramid fiber was soaked in acetone 8-10 hour, boiled 2-3 hour dry for standby then respectively in water and ethanol; Glass fibre need carry out modification in accordance with the following methods: weighing 1-1.2g silane coupling agent is dissolved in the 40-50 ml acetone, and weighing 8-10g glass fibre places above-mentioned solution then, under 25-30 ℃ of temperature to stirring 0.5-1 hour; And then 70-75 ℃ dry 2-3 hour, standby after 1-1.5 hour 110-112 ℃ of activation; Nano titanium oxide need carry out modification in accordance with the following methods: take by weighing the 1-1.5g silane coupling agent and be blended in the 80-120g water; Nano titanium oxide and trolamine are according to mass ratio 1:0.5-1 mixed grinding; Take by weighing abrasive 15-20g and be distributed in the above-mentioned water body that contains silane coupling agent, regulate PH to 8.5-8.8, stirred 3-4 hour, then suction filtration, dry that to obtain modified nano-titanium dioxide standby; Need to carry out following pre-treatment before α-SiC particle mixes: (1), chlorohydric acid pickling: the SiC particle is joined in the hydrochloric acid of massfraction 15-18%, and soaked 4-5 hour down at 28-30 ℃, till filtration and washing SiC particle were 6-7 to PH, the oven dry back was standby; (2), high temperature oxidation: 950-980 ℃ of following oxidation of SiC particle that step (2) oven dry is obtained 5 hours, the cooling back is standby; (3), nitrate sensitization: the SiC particle that step (3) cooling is obtained soaked 3 hours in the magnesium nitrate solution of massfraction 20-22%, then in 3 hours with the ammonia water titration solution PH of massfraction 10-20% most till 9.2, filter and 420 ℃ of following dry for standby;
Compound heat exchanger tube preparation process is as follows:
(1), copper material, each alloyed metal and filler grain are divided into many parts, evenly putting into the interior melting of undercurrent type induction stirring line-frequency induction combined electric furnace in proportion at interval is liquation, and cover charcoal on the copper liquid, feed argon gas and form atmosphere protection, draw by the crystallizer cooling and through towing mechanism then and obtain pipe; Concrete control parameter is as follows: copper liquid temperature is 1150-1180 ℃ during melting, on to draw temperature be 1120-1140 ℃; Pulling speed is 400-450mm/min, and copper liquid liquid level is 360-380mm; It is 20-22mm that crystallizer inserts the liquation degree of depth; The crystallizer inflow temperature is that 28-38 ℃, leaving water temperature(LWT) are no more than 55 ℃; Charcoal on the copper liquid is covered as 22-25cm; The oxygen level of pipe should be controlled below 10ppm;
(2), pipe is through cut-out, milling the induction heater that enters by argon shield behind the face and be preheated to 340-350 ℃, enters three-roller planetary rolling mill continuous rolling then and obtains shell, rolling temperature is controlled to be 750-760 ℃, roll speed 18-20m/min;
(3), shell is cooled off fast the back by cold drawing bench cold-drawn moulding, mix as lubricant by weight 1:0.08:0.12 with machine oil, nano molybdenum disulfide, nanometer polytetrafluoroethylcomposite during drawing, wherein the particle diameter of nano molybdenum disulfide is 20-30nm, and the particle diameter of nanometer polytetrafluoroethylcomposite is 60-80nm.
The compound heat exchanger tube that embodiment 1-3 prepares respectively, the copper pipe that with the diameter is 10mm is example tensile strength following (MPa): embodiment 1 is 385, embodiment 2 is 456, embodiment 3 is 564, by above data as can be known, the heat-exchanger brass pipe 200-300MPa that the tensile strength of the compound heat exchanger tube that embodiment 1-3 makes is comparatively better than existing performance is taller, mechanical property the best of the compound heat exchanger tube of embodiment 3 preparation wherein, owing to added the SiC particle, four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre and nano titanium oxide, and after the process pre-treatment of filler ion or the modification, the disperse more that in the copper matrix, distributes of filler ion, evenly, strengthened the tensile property of compound heat exchanger tube greatly; The raising of above-mentioned tensile strength causes the corresponding raising of the compressive strength of the compound heat exchanger tube of the present invention, and the burstpressures of the compound heat exchanger tube through testing the present invention's preparation is all greater than 22 MPa, and elongation after fracture is also all greater than 16%.By under equal conditions doing corrosion-resistant experiment at fresh water, seawater and steam condensate respectively, the corrosion speed of the compound heat exchanger tube of the present invention's preparation is less than 10% of conventional copper pipe (such as C71500) speed.Because enhancing particle SiC particle, four acicular type zinc oxide crystal whisker and aramid fiber, glass fibre all have preferable wear resistance, prove that through rub(bing)test the more existing copper pipe of compound heat exchanger tube wear rate reduces greatly.
Claims (4)
1. the preparation method of the compound heat exchanger tube of high-strength corrosion-resisting, it is characterized in that: described compound heat exchanger tube is made up of copper base, alloyed metal and filler grain; The weight percent of described alloyed metal is as follows: magnesium 0.5-0.6%, silver 0.08-0.09%, tin 0.2-0.4%, zirconium 0.012-0.014%, niobium 0.012-0.014%, nickel 0.05-0.06%, titanium 0.005-0.008%, mishmetal 0.02-0.04%, described mishmetal is made up of yttrium, berkelium and lanthanum, three's mass ratio is 1:(0.15-0.2): (0.4-0.5); The weight percent of described filler grain is as follows: four acicular type zinc oxide crystal whisker 0.010-0.012%; Silicon carbide 0.008-0.009%, aramid fiber 0.005-0.006%, glass fibre 0.004-0.005% and nano titanium oxide 0.002-0.003%; Preparation process is as follows:
(1), copper material, each alloyed metal and filler grain are divided into many parts, evenly putting into the interior melting of undercurrent type induction stirring line-frequency induction combined electric furnace in proportion at interval is liquation, and cover charcoal on the copper liquid, feed argon gas and form atmosphere protection, draw by the crystallizer cooling and through towing mechanism then and obtain pipe; Concrete control parameter is as follows: copper liquid temperature is 1150-1180 ℃ during melting, on to draw temperature be 1120-1140 ℃; Pulling speed is 400-450mm/min, and copper liquid liquid level is 360-380mm; It is 20-22mm that crystallizer inserts the liquation degree of depth; The crystallizer inflow temperature is that 28-38 ℃, leaving water temperature(LWT) are no more than 55 ℃; Charcoal on the copper liquid is covered as 22-25cm; The oxygen level of pipe should be controlled below 10ppm;
(2), pipe is through cut-out, milling the induction heater that enters by argon shield behind the face and be preheated to 340-350 ℃, enters three-roller planetary rolling mill continuous rolling then and obtains shell, rolling temperature is controlled to be 750-760 ℃, roll speed 18-20m/min;
(3), shell is cooled off fast the back by cold drawing bench cold-drawn moulding, mix as lubricant by weight 1:0.08:0.12 with machine oil, nano molybdenum disulfide, nanometer polytetrafluoroethylcomposite during drawing, wherein the particle diameter of nano molybdenum disulfide is 20-30nm, and the particle diameter of nanometer polytetrafluoroethylcomposite is 60-80nm.
2. the preparation method of the compound heat exchanger tube of high-strength corrosion-resisting according to claim 1, it is characterized in that: described four acicular type zinc oxide crystal whisker length 12-14 μ m, base diameter 3-5 μ m, described aramid fiber length is 2-2.5mm, filament diameter 8-10 μ m, described glass fibre is 120-140 purpose glass fibre powder, and described nano titanium oxide particle diameter is 15-30nm; Described silicon carbide is that mean particle size is α-SiC particle of 16-17 μ m.
3. the preparation method of the compound heat exchanger tube of high-strength corrosion-resisting according to claim 1 and 2, it is characterized in that: described four acicular type zinc oxide crystal whisker need carry out modification in accordance with the following methods: weighing 0.5-0.8 g silane coupling agent is dissolved in the 60-70ml acetone, drip oxalic acid again and regulate PH to 5～6, left standstill 20-25 minute; Weighing 12-14g four acicular type zinc oxide crystal whisker places above-mentioned solution then, under 55-58 ℃ of temperature to stirring 5-6 hour; It is standby that suction filtration, dry out solvent obtain the modification four acicular type zinc oxide crystal whisker then; Described aramid fiber need carry out following pre-treatment: aramid fiber was soaked in acetone 8-10 hour, boiled 2-3 hour dry for standby then respectively in water and ethanol; Described glass fibre need carry out modification in accordance with the following methods: weighing 1-1.2g silane coupling agent is dissolved in the 40-50 ml acetone, and weighing 8-10g glass fibre places above-mentioned solution then, under 25-30 ℃ of temperature to stirring 0.5-1 hour; And then 70-75 ℃ dry 2-3 hour, standby after 1-1.5 hour 110-112 ℃ of activation; Described nano titanium oxide need carry out modification in accordance with the following methods: take by weighing the 1-1.5g silane coupling agent and be blended in the 80-120g water; Nano titanium oxide and trolamine are according to mass ratio 1:0.5-1 mixed grinding; Take by weighing abrasive 15-20g and be distributed in the above-mentioned water body that contains silane coupling agent, regulate PH to 8.5-8.8, stirred 3-4 hour, then suction filtration, dry that to obtain modified nano-titanium dioxide standby; Need to carry out following pre-treatment before described α-SiC particle mixes: chlorohydric acid pickling: the SiC particle is joined in the hydrochloric acid of massfraction 15-18%, and soaked 4-5 hour down at 28-30 ℃, till filtration and washing SiC particle were 6-7 to PH, the oven dry back was standby; High temperature oxidation: 950-980 ℃ of following oxidation of SiC particle that oven dry is obtained 5 hours, the cooling back is standby; The nitrate sensitization: the SiC particle that cooling is obtained soaked 3 hours in the magnesium nitrate solution of massfraction 20-22%, then in 3 hours with the ammonia water titration solution PH of massfraction 10-20% most till 9.2, filter and 420 ℃ of following dry for standby.
4. the preparation method of the compound heat exchanger tube of high-strength corrosion-resisting according to claim 3 is characterized in that: described undercurrent type induction stirring line-frequency induction combined electric furnace employing W type channel; The silane coupling agent of described four acicular type zinc oxide crystal whisker modification is KH-570, and the silane coupling agent of described glass fibre modification is KH-550; Described nano-titanium dioxide modified silane coupling agent is KH-560.
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| CN105399164A (en) * | 2015-11-30 | 2016-03-16 | 江苏润海能源科技有限公司 | Method for preparing heat exchange mechanism for desalination evaporator |
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