CN1428465A - Surface treatment method of tantalum spinneret for wet spinning - Google Patents
Surface treatment method of tantalum spinneret for wet spinning Download PDFInfo
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Abstract
The surface treatment method of tantalum spinning jet for wet spinning process includes the following steps: (A). making metal tantalum plate into tantalum spinning jet; (B).l making the tantalum spinning jet undergo the process of nitridation treatment, using ion nitridation furnace and forming nitrided layer on the surface of tantalum spinning jet; (C). adopting fused-salt electrochemical process to make the above-mentioned tantalum spinning jet wit hnitrided layer undergo the coating treatment to form a layer of film containing lithium tantalate on its surface; and (d). polishing out-yarn surface of the spinning jet, grinding off the lithium tantalate contained insulated film layer from surface of spinning jet outlet and remaining transition layer. Said invention can obviously raise hardness of tantalum spinning jet.
Description
[technical field] the present invention relates to a kind of surface treatment method that is used for the tantalum spinneret of wet spinning.
[background technology]
Chemical fibre production has obtained vigorous growth in 20 end of the centurys, become an important component part of national economy, and spinning head (plate) is the most accurate, most important parts in the chemical fibre production, and its quality quality directly has influence on labor productivity, cost and the chemical fibre quality that chemical fibre is produced.People are updating spinning head always, to adapt to the development need that chemical fibre is produced.
Produce the process difference of chemical fibre, also different to the requirement of spinning head (plate).In producing, adopts chemical fibre three kinds of explained hereafter usually, i.e. fusion method, dry method (also claiming to do wet method) and wet method.Wherein the fusion method spinnerets pressure that can bear is up to a hundreds of atmospheric pressure, therefore the material that requires to make spinnerets has good physical and mechanical properties, the thickness of spinnerets reaches 1Omm-30mm, and the used required pressure that bears of spinning head of wet spinning is much smaller, generally between 0.2-0.75mm, dry spinning then falls between with spinning head thickness.Because wet spinning is to carry out in the environment of strong acid and strong base, spinning head requires to have strong resistance to corrosion, therefore at the chemical fibre production development initial stage, spinning heads such as most of wet spinnings such as viscose, acrylic silk all adopt noble metal (as the alloy of gold, platinum, rhodium, palladium).Closely during the last ten years, spinning head with tantalum cash equivalent platinum is widely used gradually, wherein the plated film tantalum spinneret of making of electrochemical reaction (seeing Chinese patent ZL 85101505 and ZL86102269 for details) replaces golden platinum spinning head to obtain good effect in wet spinning production because better spinnability is arranged.
The quality quality of so-called spinning head, relate generally to two aspects, the spinnability of first spinning head, the spinning head of good spinnability, it is unplanned to change that a rate is low, the spinning cycle long, the quality of spun chemical fibre silk is good, lousiness rate (in lousiness rate=one working day because the bucket quantity of the silk that lousiness downgrades/the bucket total amount of the silk produced) is low, fault is few etc., these all directly influence to labor productivity, chemical fibre quality, cost and spinning working strength of workers etc. to chemical fibre production.
Suppose that its spinnability is just relevant with the following manufacturing technique of spinning head under all rational situation of design of spinning head:
(1) the good manufacturing technique that meets design requirement.The enough fineness of spinning head micropore inwall and exit face, micro-pore wall and aperture can not be jagged, breach etc.
(2) suitable process of surface treatment, surface treatment is not only in order to obtain enough hardness and mechanical strength to spinning head, to wet spinning, also need obtain a suitable surface property, it is more direct that he says, need obtain a suitable electrode potential by surface treatment as spinning heads such as viscoses to spinning head.
(3) select suitable spinning head material.To fusion method and dry spinning, can meet the demands with stainless steel, but must be with the alloy or the tantalum material of erosion-resisting noble metal to wet spinning that strong acid and strong base is arranged.
Another important aspect of weighing the spinning head quality is the service life of spinning head, and it is main relevant with scratch resistance, resistance to deformation, the resistance to corrosion of spinning head.
(1) non-deformability: under the situation that the spinning head material has been selected, its adequate thickness guarantees that it has enough non-deformabilities.But under the situation that thickness has been selected by the designer, suitable process of surface treatment can make spinning head integral body or top layer obtain enough rigidity and intensity, thereby improves the non-deformability of spinning head.
(2) scratch resistance ability: main relevant with the case hardness of spinning head.Under the situation that material has been selected, it just depends on the surface treatment of spinning head.Because no matter be fusion method, or the spinning head of dry method or wet spinning, spinning head all is to carry out under the situation of material softer attitude after the capillary processing, again through surface treatment, to obtain enough hardness.
(3) resistance to corrosion: this is particularly important in wet spinning, and it is relevant with material.After material was selected, it also has certain relation with process of surface treatment, and was simultaneously, also in use relevant to the suitable cleaning of spinning head with applying unit.
People are being devoted to improve the spinnability of spinning head always, prolong the research of spinning head service life and reduction spinning head cost.
Chemical fibre wet spinning such as spunbond glue fiber, acrylic, polyvinyl chloride fibre etc., because the strong acid and strong base environment, spinning head material people use expensive noble metal always before the 1980s, as the alloy of metals such as golden platinum rhodium palladium.The shortcoming of its maximum is the cost height, and simultaneously because hardness is lower, and its scratch resistance ability is also relatively poor, fragile, thereby service life is shorter.Therefore, the spinning head also always studied with other cheap materials of people replaces the precious metal alloys spinning head.Tantalum spinneret has been to be hopeful to replace the noble metal spinning head most since nineteen seventies comes out, and its corrosion resistance is suitable with noble metal under the condition of chemical fibre wet spinning.Tantalum spinneret reaches about Hv300 through the case hardness after the heat treatment of low vacuum timeliness, and after nitriding is handled the case hardness of tantalum spinneret can be up to Hv700 more than, more much higher than noble metal spinning head case hardness.However,, thereby fail in wet spinning always, replace the noble metal spinning head during especially viscose is produced through the still too late noble metal spinning head of the spinnability of these two kinds of surface-treated tantalum spinnerets.Therefore,, to solve the spinnability of tantalum spinneret in fact exactly, make it reach the level of noble metal spinning head with the research of tantalum cash equivalent.The 1980s, the tantalum spinneret of the oxygenatedchemicals film of making of the melten salt electriochemistry method by patent ZL85101501 and ZL86102269 that has tantalum, solved this key issue of spinnability, the tantalum spinneret that the surface is generated contain lithium tantalate film not only spinnability has reached even has surpassed the noble metal spinning head, and, the hardness of superficial film is also up to Hv700-800, after grinding off superficial film, the hardness of the transition zone of superficial film below also can reach Hv300-Hv600, than noble metal spinning head, hardness Hv180-Hv280 as the plation spinning head is much higher, has strengthened the spinning head scratch resistance, the ability of resistance to deformation.In the applying of more than ten years, obtained good result of use, in wet spinning, replacing golden platinum spinning head to open up broad application prospect with tantalum spinneret.
Yet also there is deficiency in the tantalum spinneret that is coated with lithium tantalate film.Why its spinnability can meet or exceed the noble metal spinning head, obtain by the following method, promptly earlier the whole surface of tantalum spinneret (comprising the micropore inwall) generate equably one deck in conjunction with the firm rete that lithium tantalate is arranged after, the regrind insulating film layer (rete that promptly contains lithium tantalate) of spinning head wire vent face, stay the transition zone of the tantalum of conduction, form special electrode potential between the rete that contains lithium tantalate of the transition zone of wire vent face conduction and the insulation of spinning head micropore inwall, significantly improved spinnability.Practice shows, if keep the lithium tantalate rete of the high insulation of hardness at wire vent face, the spinnability of this plated film tantalum spinneret of result will be very poor, do not reach the noble metal spinning head, therefore, can not replace golden platinum spinning head, and only grind off the high rete of wire vent surface hardness, the transition zone that stays conduction could be realized with tantalum cash equivalent platinum.Although as previously mentioned, though the hardness HV300-600 of transition zone is still much higher than noble metal spinning head, but the hardness Hv700-800 than rete is much lower again, in use still can cause in various degree scuffing and wearing and tearing, especially the plated film tantalum spinneret shows in the practice of viscose filament yarn during the last ten years, and when spinning no optic filament, its service life have only 2-3 generally more than 5-6 its service life when spinning lustrous filament.When main cause is spun dull yarn exactly, mixed a certain proportion of titanium dioxide (TiO2) in the viscose glue stoste, wearing and tearing increase to spinning head, influence service life, therefore further improve plated film spinning head case hardness, to improving the antiwear property of plated film tantalum spinneret, thereby prolong shower nozzle service life, very important meaning is arranged.
Here it is worthy of note, above-mentioned have the spinnability of the tantalum spinneret of lithium tantalate rete why so improvement can be arranged, even surpassed the noble metal spinning head, be by the decision of the factor of following two necessity, it at first is the existence that lithium tantalate film is arranged, rather than the oxide of other dielectric films such as tantalum can replace, and uses in viscose production already because anodic oxidation generates the tantalum spinneret of tantalum pentoxide film, but fails the effect that obtains.Its two, as previously mentioned, grind off the rete of wire vent face, stay the transition zone of tantalum.The combination of these two factors, indispensable.
Improve the case hardness of spinning head, strengthen its scratch resistance ability, not only improved the service life of spinning head, but also helped improving the chemical fibre quality.Because spinning head is scrapped meeting with scuffing or wearing and tearing, just reaching comparatively under the serious situation, just scrap after being above standard, that is to say before scrapping, spinning head is in long-term use (3-6 does not wait), reality is with in various degree slight wound work, and the spinnability that this just will inevitably influence spinning head also will make the chemical fibre degradation.Therefore, improve the hardness on spinning head surface, reduce aforementioned slight scuffing and wearing and tearing, help improving the chemical fibre quality.Because use on the surface of plated film tantalum spinneret is the tantalum transition zone that grinds off behind the rete, and therefore, the hardness that improves transition zone is most important.
Tantalum at high temperature has good absorption gas performance, but material can become fragile behind the gases such as the hydrogen of hyperabsorption, nitrogen, oxygen.Tantalum spinneret processing method the earliest is that the tantalum spinneret that will process is under low vacuum, in thin air, heat in other words, remain on certain temperature, carry out timeliness heat treatment, to reach the purpose that improves tantalum spinneret hardness, this method can make surface of tantalum spinning jet hardness reach about Hv300 usually.
Nitridation technique is used for improving the case hardness of metal works already, thereby improves its anti-wear performance, scratch resistance performance.The 1980s, nitridation technique just has been employed in the surface treatment of tantalum spinneret, and its case hardness is brought up to more than the Hv700.And the method for nitriding also has multiple, with the difference of workpiece mode of heating, ion heating, body of heater heating etc. is arranged.
But the nitriding method that above-mentioned usefulness is simple carries out surface of tantalum spinning jet to be handled, though case hardness can meet the demands, its spinnability of foregoing reason is not as good as the noble metal spinning head, in wet spinning, especially during viscose is produced, can not be used for replacing the noble metal spinning head.
[summary of the invention]
The object of the present invention is to provide a kind of surface treatment method that is used for the tantalum spinneret of wet spinning, can significantly strengthen the scratch resistance of tantalum spinneret, wear-resistant ability, improve the service life of tantalum spinneret, simultaneously, can make tantalum spinneret have good spinnability again, and can replace the noble metal spinning head fully, thereby reduce production costs greatly.
In order to achieve the above object, the invention provides a kind of surface treatment method that is used for the tantalum spinneret of wet spinning, it is characterized in that: comprise the steps:
(a) processing and manufacturing of metal tantalum plate is become tantalum spinneret;
(b) nitriding: tantalum spinneret is carried out nitriding handle, use ion nitriding furnace, with tantalum spinneret is negative electrode, furnace temperature is 500 ℃-1000 ℃, and furnace pressure is 20-2000Pa, and charging into gas is nitrogen, hydrogen, nitrogen: hydrogen=2: 1 to 1: 10, nitriding 0.5-6 hour, make surface of tantalum spinning jet form nitriding layer, surface of tantalum spinning jet hardness reaches Hv400-Hv1100;
(c) plated film: the tantalum spinneret that will handle through nitriding, adopt the melten salt electriochemistry method to carry out coating film treatment, make it generate the rete that one deck contains lithium tantalate; Tantalum spinneret is placed 440 ℃-650 ℃ containing the oxygen inorganic lithium salt or containing the mixed melting thing of oxygen inorganic lithium salt and lithium hydroxide, or in the mixed melting liquid of the mixed melting liquid of other salt and lithium hydroxide or other lithium salts and oxysalt, boost current density be the 1-1000 milliampere/centimetre
2, add the anode voltage that 1-35 lies prostrate, constant voltage 0.5-8 hour, make surface of tantalum spinning jet form the film that one deck contains lithium tantalate;
(d) polishing: the wire vent face of the tantalum spinneret that step (c) was handled carries out polishing, grinds off the rete that contains lithium tantalate of wire vent face surface insulation, stays the transition zone of tantalum.
The described surface treatment method that is used for the tantalum spinneret of wet spinning is characterized in that: the coating process condition of step (c) preferably temperature is 480 ℃～520 ℃, 5～25 volts of anode voltages, 5～20 milliamperes/centimetre of boost current density
2
The described surface treatment method that is used for the tantalum spinneret of wet spinning is characterized in that: supersonic generator can be arranged in the fused solution in step (c).
The present invention also provides a kind of surface treatment method that is used for the tantalum spinneret of wet spinning, it is characterized in that: comprise the steps:
(a) processing and manufacturing of metal tantalum plate is become tantalum spinneret;
(b) nitriding: tantalum spinneret is carried out nitriding handle, use the vacuum nitriding stove, tantalum spinneret is placed the airtight vacuum nitriding furnace, be evacuated to 10Pa～20Pa, be heated to 600 ℃～1000 ℃ of temperature, charge into nitrogen, hydrogen, nitrogen and hydrogen volume are than between 2: 1 to 1: 10, tantalum spinneret in body of heater nitriding 0.5-6 hour, tantalum spinneret hardness is between HV400～1100 after the nitriding;
(c) plated film: the tantalum spinneret that will handle through nitriding, adopt the fusion electrochemical method to carry out coating film treatment, make it generate the rete that one deck contains lithium tantalate; Tantalum spinneret is placed 440 ℃-650 ℃ containing the oxygen inorganic lithium salt or containing the mixed melting thing of oxygen inorganic lithium salt and lithium hydroxide, or in the mixed melting liquid of the mixed melting liquid of other salt and lithium hydroxide or other lithium salts and oxysalt, boost current density be the 1-1000 milliampere/centimetre
2, adding the anode voltage of 1-35 volt, O.5-8 hour constant voltage makes surface of tantalum spinning jet form the film that one deck contains lithium tantalate;
(d) polishing: the wire vent face of the tantalum spinneret that step (c) was handled carries out polishing, grinds off the rete that contains lithium tantalate of wire vent face surface insulation, stays the transition zone of tantalum.
The described surface treatment method that is used for the tantalum spinneret of wet spinning is characterized in that: the coating process condition of step (c) preferably temperature is 480 ℃～520 ℃, 5～25 volts of anode voltages, 5～20 milliamperes/centimetre of boost current density
2
The described surface treatment method that is used for the tantalum spinneret of wet spinning is characterized in that: supersonic generator can be arranged in the fused solution in step (c).
The surface treatment method that is used for the tantalum spinneret of wet spinning of the present invention, adopt the surface carburization technology, at first the tantalum spinneret that processes being carried out surface carburization handles, then tantalum spinneret is inserted the containing in the oxygen inorganic lithium salt of fusion, add anode voltage, make surface of tantalum spinning jet generate the enough thick plated film layer that contains lithium tantalate of one deck, the transition zone hardness of the tantalum under the gained plated film layer has been brought up to Hv700-Hv1300 from original Hv400-Hv600, improved about Hv400～Hv600, significantly strengthened the scratch resistance of plated film tantalum spinneret, wear-resistant ability has improved service life.Simultaneously, not only kept the advantages such as original good spinnability of plated film tantalum spinneret, found that also the spinning contrast test shows, the spinnability of the tantalum spinneret of plated film is better than the plated film tantalum spinneret after the nitriding, sees the comparing result of embodiment table 1 for details.The reason that produces this good result is still waiting research, and this result makes it to replace the noble metal spinning head fully, thereby reduces production costs greatly, improves the chemical fibre quality.
[description of drawings]
Fig. 1 is the overall appearance schematic diagram of tantalum spinneret of the present invention.
Fig. 2 is the flow diagram of the surface treatment method of the tantalum spinneret that is used for wet spinning of the present invention.
Fig. 3 is the local amplification profile schematic diagram of the micropore of tantalum spinneret of the present invention after nitriding.
Fig. 4 is the local amplification profile schematic diagram of the micropore of tantalum spinneret of the present invention after polishing.
[specific embodiment]
With reference to Fig. 2, the surface treatment method that is used for the tantalum spinneret of wet spinning of the present invention, the step of embodiment 1 is as follows:
Step 1, with prior art the processing and manufacturing of metal tantalum plate is become tantalum spinneret, as shown in Figure 1, this tantalum spinneret comprises body 10, and the external diameter of spinning head wire vent face 11 is 12mm, and the quantity of micropore 12 is 30, and the micropore internal diameter is 0.083 ± 0.001mm.
Step 2, nitriding: the LD-25 type ion nitriding furnace that adopts Beijing to produce, the tantalum spinneret of making of step 1 is a negative electrode, furnace temperature is 800 ℃, furnace pressure is 800Pa, charging into gas is nitrogen, hydrogen, nitrogen: hydrogen=1: 3, nitriding two hours, vacuum cooled to 100 ℃ taking-up makes after the nitriding about tantalum spinneret hardness HV500.As shown in Figure 3, surface of tantalum spinning jet forms nitriding layer 20, and inside is spinning head tantalum matrix 21.
Step 3, plated film: add 10 volts of anode voltages in 500 ℃ of fusion lithium nitrate solutions, the constant voltage reaction made the plated film layer 30 that contains lithium tantalate in 6 hours, and the micropore internal diameter is 0.08 ± 0.001mm behind the plated film.
Step 4, polishing tantalum spinneret wire vent face 11: grind off the insulation plated film layer 30 of tantalum spinneret wire vent face 11, stay transition zone 40, as shown in Figure 4, transition zone 40 is actually the outer layer segment that is equivalent to the nitriding layer 20 behind the plated film, and the hardness of transition zone 40 is HV870.
The plated film tantalum spinneret and the plated film tantalum spinneret through nitriding of the present invention that do not carry out nitriding in the above-mentioned prior art are carried out the spinning contrast test at viscose filament yarn, its result such as following table 1, table 1 are two kinds of tantalum spinneret spinning of plated film result contrasts after prior art plated film and the nitriding of the present invention.Table 1
| The tantalum spinneret feature | Change a rate % | Lousiness rate % | Finished product top-quality product rate % |
| Prior art plated film tantalum spinneret | ????1.11 | ????4.06 | ????96.71 |
| The plated film tantalum spinneret that the present invention makes | ????0.93 | ????3.14 | ????98.54 |
As seen from Table 1, use the tantalum spinneret spinning of plated film after the nitriding of the present invention, can make a rate of changing, lousiness rate reduce, the finished product top-quality product rate improves.A rate of changing herein refers to that the unit interval domestic demand changes the quantity of spinning head, lousiness rate=one in the working day because the bucket quantity of the silk that lousiness downgrades/the bucket total amount of the silk produced.
In tantalum spinneret micropore manufacturing process, should be taken into account and generate after the oxygenatedchemicals rete, the thickness of rete will make micropore diminish, in order to guarantee the dimensional tolerance of micropore behind plated film, the micropore size should be reserved the rete size, to offset the thickness of film, it is suitable that this thickness normally is chosen as between the 1-5 micron, and the spinning pressure that general spinning head face bears is little, less thickness can be selected for use, otherwise thicker size can be selected.Because rete is thick, the transition zone of tantalum corresponding with it is also thick, and the pressure that spinning head bears is also big.
Step 2 can adopt glow ion nitridation equipment on sale on the market to carry out, and wherein should note following control of process condition:
Tantalum spinneret is 400 ℃ of beginning absorbed nitrogen atoms in nitriding furnace, and tantalum spinneret can both improve its hardness more than 400 ℃ in nitrogen environment, the reorganization of 1020 ℃-1200 ℃ beginning crystal grain.The furnace temperature height, spinning head hardness height after the nitriding, the length of penetration of nitrogen-atoms is also dark, but furnace temperature is subjected to the restriction of the recrystallization temperature of tantalum material, the tantalum metal is grown up again after the crystal grain reorganization in too high furnace temperature, influence micropore and spinning head surface smoothness, furnace temperature of the present invention can be selected between 500 ℃-1000 ℃.
Furnace pressure height, spinning head nitriding speed in the vacuum nitriding stove is fast, but influences ionisation of gas resistance in the stove, furnace pressure high ionization resistance is little, and the too small easy initiation short circuit current of ionization resistance burns out spinning head, the low ionization resistance of furnace pressure is big, and it is slow to heat up, and furnace pressure of the present invention can be selected between 20Pa-2000Pa.
Nitrogen, hydrogen usage ratio, the nitrogen ratios height, its ionization resistance is little, and programming rate is fast, and nitriding speed is fast, and the too small easy initiation short circuit current of ionization resistance burns out spinning head.Nitrogen hydrogen ratio can be a selection in 2: 1 to 1: 10.
Nitriding time is long more, and it is dark more that nitrogen-atoms infiltrates spinning head, and spinning head hardness is high more, the oversize then tantalum of nitriding time metal grain is grown up again after reorganization, influences micropore and spinning head surface smoothness, and the while nitriding time is temperature influence also, temperature is high more, and nitriding time is wanted corresponding shortening; Temperature is low more, and nitriding time is wanted corresponding growth, and nitriding time can be selected between 0.2-6 hour.
The hardness of tantalum spinneret after nitriding is too high, and then in follow-up step 3, coating growth is slow, and after coating film treatment, causes that spinning head poor surface smoothness, micropore are not justified etc., and tantalum spinneret can be selected between HV400-HV1100 through the hardness after the nitriding.
The gases used carbonaceous gass such as nitrogen, hydrogen, ammonia, argon gas and methane, ethanol, acetylene, interior ketone that can be during glow discharge nitriding.Use nitrogen, hydrogen process stabilizing, reliable in quality.
Described step 2, also can adopt other nitridation technique to carry out, for example: tantalum spinneret is placed the nitriding of airtight vacuum stove high temperature, be about to spinning head and place body of heater, be evacuated to 10Pa～20Pa, be heated to 600 ℃-1000 ℃ of temperature, charge into gas such as nitrogen, hydrogen (nitrogen and hydrogen volume are than between 2: 1 to 1: 10), spinning head nitriding 0.5～6 hour in body of heater, tantalum spinneret hardness is between HV400-HV1100 after the nitriding.
The gases used carbonaceous gass such as nitrogen, hydrogen, ammonia, argon gas and methane, ethanol, acetylene, acetone that can be when tantalum spinneret utilizes the vacuum drying oven heating nitriding.
Because the glow discharge nitriding energy consumption is low, processing speed is fast, is widely being adopted aspect the reinforced metal spare surface.
In the described step 3, current density can be selected the anode voltage of 5-1000 milliampere/square centimeter and the 1-30 that boosts volt, place 440 ℃-650 ℃ contain the oxygen inorganic lithium salt (as lithium nitrate, lithium nitrite etc.) or the fused solution of itself and lithium hydroxide or contain in the oxygen inorganic salts in the mixed melting liquid of (as potassium nitrate etc.) and lithium salts (as lithium chloride etc.), or plated film in the mixed melting liquid of lithium hydroxide and other inorganic salts (as potassium nitrate) etc., adopt mixed melting liquid to reduce fusing point and cost than independent use lithium nitrate fused solution.
Find that after deliberation the tantalum spinneret of nitriding as add 10 volts of anode voltages in 490 ℃ lithium nitrate, did not react 3 hours, the gained rete shows that through the X-ray material phase analysis existing lithium tantalate exists, and the spinning in viscose production shows that spinnability is good.But the tantalum spinneret after nitriding carries out coating film treatment under same condition,, show through the X-ray material phase analysis that the rete composition is the oxide of tantalum though also generated one deck dielectric film at surface of tantalum spinning jet, and do not have the existence of lithium tantalate.And the thickness of rete is also much thin than the former, shows that through chemical fibre spinning practice its spinnability is bad.
Studies show that further the tantalum spinneret after the nitriding generates the condition of lithium tantalate film with above-mentioned electrochemical method,, also can generate the insulating film layer that contains lithium tantalate at the surface of tantalum spinning jet of nitriding if prolong the electro-chemical reaction time.As in above-mentioned condition, tantalum spinneret hardness after nitriding is HV500, adds 10 volts of anode voltages then in 500 ℃ lithium nitrate, and the reaction time was extended to about 6 hours by 3 hours, and the gained rete shows that through the X-ray material phase analysis it contains lithium tantalate.Grind off wire vent and behind the superficial film, the transition zone hardness of the tantalum that stays reach HV870 (ballast 100 grams during measurement) and not the transition zone of (similarity condition) plated film tantalum spinneret of nitriding about HV500.
Test shows that in order to obtain to contain the rete of lithium tantalate, the plated film time of the tantalum spinneret of nitriding needs the tantalum spinneret of more not nitriding to prolong about 1 times, just its spinnability and case hardness can have good effect.
Reaction temperature is one of key condition that generates lithium tantalate film, be lower than 440 ℃ and will can not get lithium tantalate film, but temperature is too high, and reaction speed is fast, and thicknesses of layers is wayward, and the crystal grain of film is thick, and fineness is low, and therefore, maximum temperature is no more than 650 ℃.And need have lithium hydroxide to exist in the liquation, because, the fusing point height of lithium hydroxide.
The tantalum spinneret that nitriding is later, after above-mentioned coating film treatment, grind off the hardness of the transition zone of tantalum behind the wire vent face mask layer, not only much higher than the hardness of the tantalum spinneret that contains lithium tantalate film of nitriding not, and more much higher than the hardness of the tantalum spinneret after the nitriding, common high HV200-300.
As shown in Figure 4, tantalum spinneret is after above-mentioned electrochemical reaction coating film treatment, the surface has formed plated film layer 30, and the tantalum intermediate metal 40 under the plated film layer 30 (is one deck tantalum metal under the plated film layer, because the absorption of the scattering and permeating of molecule and tantalum metal pair gas at high temperature and modification is called transition zone), can be referred to as modified layer.The transition zone 40 of tantalum is still the same with the tantalum metal to conduct electricity, but hardness, tensile strength, elastic limit will have significant increase, and ductility reduces.It is from plated film layer 30, and gradually to the tantalum metal transfer, the thickness of transition zone 40 changes with process conditions in gradient.
The temperature of electrochemical reaction, anode voltage and reaction time are the principal elements of the thickness of decision plated film layer 30 and transition zone 40.Typical temperature raises, and anode voltage raises, and the reaction time prolongs, and modified layer thickens, and the amplitude of performance change increases, and increases as performances such as hardness, elasticity, intensity, insulation, and ductility reduces.But meanwhile, also can make the grain coarsening of forming rete, surface smoothness reduces.Though surface smoothness is not to be unique factor that the decision spinning head can spin part, the surface is too coarse, also influences the spinnability of spinning head to a certain extent.
By reducing reaction temperature, shorten the reaction time, reduce anode voltage and can suitably improve fineness, but this is a contradiction with improving physical and mechanical propertiess such as intensity, hardness, is the SOME METHODS of improving the fineness of film below.
(400 ℃-460 ℃) surface of tantalum spinning jet electro-chemical reaction generates a skim under lower temperature, its fineness is higher, but modification is less, and the film that (480 ℃-520 ℃) generate under higher temperature, crystal grain is thick, surface smoothness is lower, but modification is bigger, combine as both, mutual alternation response, resulting rete, its fineness is than the fineness height that at high temperature reacts the gained rete separately, and modification is also big, in 440 ℃ lithium nitrate, add earlier 15 volts of anode voltage reactions 3 hours as tantalum spinneret, and then in 520 ℃ lithium nitrate, add 15 volts of anode voltage constant voltage reactions 2 hours, and the light activity of gained coated surface is higher than the only plating of gained under a condition (promptly 520 ℃), and another kind of situation is to add earlier 10 volts of anode voltages in 520 ℃ lithium nitrate, constant voltage reaction 2 hours, and then in 440 ℃ lithium nitrate, add 25 volts anode voltage, and constant voltage reaction 2 hours, its surface smoothness is higher than the film that at high temperature generates separately.
As everyone knows, ultrasonic applications can make the grain refinement of plated film layer in electroplating technology, surface smoothness increases, firmly degree also increases, and in the fused solution of above-mentioned electrochemical reaction, introduces ultrasonic vibration, because cavitation effect of ultrasonic waves, can make in the crucible melt composition and temperature more evenly and make the gas of reaction be able to timely eliminating, make rete more evenly firmly, simultaneously also because action of ultrasonic waves, can make grain refinement, improve surface smoothness.
Its equipment preferably adopts the higher water-cooled magnetostriction transducer of efficient.The mode that ultrasonic wave is introduced melt has two kinds: a kind of is ultrasonic generator to be made bar-shaped, introduces the melt from the crucible top of reaction; Another kind of mode is that the crucible of electro-chemical reaction is made generator, introduce from the lower end of electro-chemical reaction stove, and the former more easily realizes, the most handy nickel of material or the stainless steel of generator, the frequency of supersonic generator can be selected at 22.5-27KHZ, and watt level then should design according to the height of crucible size and melt.
Optimised process scope provided by the invention: 460 ℃-520 ℃ of reaction temperatures, anode voltage 5-25 volt, boost current density 5-20 milliampere/square centimeter.
The polishing of described step 4 is meant that the high rigidity plated film tantalum spinneret by step 3 gained polishes the insulation plated film layer 30 that grinds off tantalum spinneret wire vent face 11 again, stay the transition zone 40 of conduction, by the special electrode potential that the transition zone 40 of the tantalum of conduction and insulating film layer in the micropore form, can significantly improve the spinnability of spinning head.Less demanding to spinnability, but the spinning higher to the spinning head requirement of strength can not grind off plated film layer 30, gets final product and only polish a little.
Tantalum and niobium are associated metals, and performance is close, but the corrosion resistance of niobium is not so good as tantalum, and the processing characteristics of making spinning head is also undesirable.If but tantalum and niobium form tantalum-niobium alloy, these two shortcomings can obtain very big overcoming, and the price of niobium is also than tantalum considerably cheaper, tantalum-niobium alloy spinneret also can adopt said method of the present invention, make the tantalum-niobium alloy spinneret of the plated film of nitriding, surface treatment method and technological parameter are basic identical.
Below be the second embodiment of the present invention:
Step 1, with prior art the processing and manufacturing of metal tantalum plate is become tantalum spinneret, as shown in Figure 1, this tantalum spinneret comprises body 10, and the external diameter of spinning head wire vent face 11 is 12mm, and the quantity of micropore 12 is 30, and the micropore internal diameter is 0.083 ± 0.001mm.
Step 2, nitriding: the LD-25 type ion nitriding furnace that adopts Beijing to produce, the tantalum spinneret of making of step 1 is a negative electrode, furnace temperature is 1000 ℃, furnace pressure is 1000Pa, charging into gas is nitrogen, hydrogen, nitrogen: hydrogen=1: 3, nitriding two hours, vacuum cooled to 100 ℃ taking-up makes after the nitriding about tantalum spinneret hardness HV900.As shown in Figure 3, surface of tantalum spinning jet forms nitriding layer 20.
Step 3, plated film: add 10 volts of anode voltages in 500 ℃ of fusion lithium nitrate solutions, the constant voltage reaction made the plated film layer 30 that contains lithium tantalate in 6 hours, and the micropore internal diameter is 0.08 ± 0.001mm behind the plated film.
Step 4, polishing tantalum spinneret wire vent face 11: grind off the insulation plated film layer 30 of tantalum spinneret wire vent face 11, stay transition zone 40, transition zone 40 is actually the outer layer segment that is equivalent to the nitriding layer 20 behind the plated film, and the hardness of transition zone 40 is HV1024.
Final spinning head micropore surface is bright and clean, the rete densification.
With the tantalum spinneret blank that makes in the above-mentioned prior art and do not carry out the plated film tantalum spinneret of nitriding and the hardness through the plated film tantalum spinneret of nitriding of embodiments of the invention 1,2 compares, its result is shown in following table 2.
The wire vent face final hardness of the embodiment of the invention 1 and embodiment 2 is the transition zone hardness that grinds off the tantalum that stays behind the surface insulation plated film in the table 2.
In the table 2 not plated film nitriding tantalum spinneret wire vent face final hardness be wire vent face without the hardness of polishing.
Table 2 (annotate: ballast 100 grams are all adopted in all hardness measurements)
| Treatment process | Handle the hardness of back wire vent face | |
| Wire vent surface hardness after the nitriding | Wire vent face final hardness | |
| The tantalum blank of prior art system | Hv80 | |
| Do not carry out the plated film tantalum spinneret of nitriding in the prior art | Hv500 (tantalum transition zone) | |
| Plated film nitriding tantalum spinneret not | ????Hv850 | Hv850 |
| The product of the embodiment of the invention 1 | ????Hv500 | Hv870 (tantalum transition zone) |
| The product of the embodiment of the invention 2 | ????Hv900 | Hv1204 (tantalum transition zone) |
Plated film tantalum spinneret through nitriding of the present invention, the plated film tantalum spinneret that does not carry out nitriding in its hardness ratio prior art has improved Hv400～Hv600, thereby the scratch resistance of plated film tantalum spinneret, the ability of resistance to deformation have been improved greatly, improve the service life of spinning head, significantly improved the spinnability of plated film tantalum spinneret simultaneously again.
Claims (6)
1, a kind of surface treatment method that is used for the tantalum spinneret of wet spinning is characterized in that: comprise the steps:
(a) processing and manufacturing of metal tantalum plate is become tantalum spinneret;
(b) nitriding: tantalum spinneret is carried out nitriding handle, use ion nitriding furnace, with tantalum spinneret is negative electrode, furnace temperature is 500 ℃-1000 ℃, and furnace pressure is 20-2000Pa, and charging into gas is nitrogen, hydrogen, nitrogen: hydrogen=2: 1 to 1: 10, nitriding 0.5-6 hour, make surface of tantalum spinning jet form nitriding layer, surface of tantalum spinning jet hardness reaches Hv400-Hv1100;
(c) plated film: the tantalum spinneret that will handle through nitriding, adopt the melten salt electriochemistry method to carry out coating film treatment, make it generate the rete that one deck contains lithium tantalate; Tantalum spinneret is placed 440 ℃-650 ℃ containing the oxygen inorganic lithium salt or containing the mixed melting thing of oxygen inorganic lithium salt and lithium hydroxide, or in the mixed melting liquid of the mixed melting liquid of other salt and lithium hydroxide or other lithium salts and oxysalt, boost current density be the 1-1000 milliampere/centimetre
2, add the anode voltage that 1-35 lies prostrate, constant voltage 0.5-8 hour, make surface of tantalum spinning jet form the film that one deck contains lithium tantalate;
(d) polishing: the wire vent face of the tantalum spinneret that step (c) was handled carries out polishing, grinds off the rete that contains lithium tantalate of wire vent face surface insulation, stays the transition zone of tantalum.
2, the surface treatment method that is used for the tantalum spinneret of wet spinning according to claim 1 is characterized in that: the coating process condition of step (c) is that temperature is 480 ℃～520 ℃, 5～25 volts of anode voltages, 5～20 milliamperes/centimetre of boost current density
2
3, the surface treatment method that is used for the tantalum spinneret of wet spinning according to claim 1 and 2 is characterized in that: in step (c) supersonic generator is arranged in the fused solution.
4, a kind of surface treatment method that is used for the tantalum spinneret of wet spinning is characterized in that: comprise the steps:
(a) processing and manufacturing of metal tantalum plate is become tantalum spinneret;
(b) nitriding: tantalum spinneret is carried out nitriding handle, use the vacuum nitriding stove, tantalum spinneret is placed the airtight vacuum nitriding furnace, be evacuated to 10Pa～20Pa, be heated to 600 ℃～1000 ℃ of temperature, charge into nitrogen, hydrogen, nitrogen and hydrogen volume than at 2: 1 to 1: between the 1O, tantalum spinneret in body of heater nitriding 0.5-6 hour, tantalum spinneret hardness is between HV400～1100 after the nitriding;
(c) plated film: the tantalum spinneret that will handle through nitriding, adopt the fusion electrochemical method to carry out coating film treatment, make it generate the rete that one deck contains lithium tantalate; Tantalum spinneret is placed 440 ℃-650 ℃ containing the oxygen inorganic lithium salt or containing the mixed melting thing of oxygen inorganic lithium salt and lithium hydroxide, or in the mixed melting liquid of the mixed melting liquid of other salt and lithium hydroxide or other lithium salts and oxysalt, boost current density be the 1-1000 milliampere/centimetre
2, add the anode voltage that 1-35 lies prostrate, constant voltage 0.5-8 hour, make surface of tantalum spinning jet form the film that one deck contains lithium tantalate;
(d) polishing: the wire vent face of the tantalum spinneret that step (c) was handled carries out polishing, grinds off the rete that contains lithium tantalate of wire vent face surface insulation, stays the transition zone of tantalum.
5, the surface treatment method that is used for the tantalum spinneret of wet spinning according to claim 4 is characterized in that: the coating process condition of step (c) is that temperature is 480 ℃～520 ℃, 5～25 volts of anode voltages, 5～20 milliamperes/centimetre of boost current density
2
6, according to claim 4 or the 5 described surface treatment methods that are used for the tantalum spinneret of wet spinning, it is characterized in that: in step (c), supersonic generator is arranged in the fused solution.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443629C (en) * | 2006-06-22 | 2008-12-17 | 上海交通大学 | Diamond thin-film reinforcement on tantalum spinning head surface by chemical gas phase deposition |
| CN106756844A (en) * | 2016-12-20 | 2017-05-31 | 长沙南方钽铌有限责任公司 | A kind of method for plating DLC film in surface of tantalum spinning jet |
| CN106987911A (en) * | 2017-03-23 | 2017-07-28 | 长沙南方钽铌有限责任公司 | A kind of surface treatment method of tantalum, tantalum-niobium alloy or tantalum niobium tungsten alloy spinning head |
| WO2018157867A1 (en) * | 2017-03-03 | 2018-09-07 | 北京华宇创新钽铌科技有限公司 | Surface processing method for tantalum spinning head |
| CN109023550A (en) * | 2018-07-03 | 2018-12-18 | 湖南华冉科技有限公司 | A kind of modification tantalum spinneret that fibre strength can be improved |
| CN108531906B (en) * | 2017-03-03 | 2020-05-29 | 北京华宇创新钽铌科技有限公司 | Surface treatment method of tantalum spinneret |
-
2001
- 2001-12-27 CN CN 01144879 patent/CN1428465A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443629C (en) * | 2006-06-22 | 2008-12-17 | 上海交通大学 | Diamond thin-film reinforcement on tantalum spinning head surface by chemical gas phase deposition |
| CN106756844A (en) * | 2016-12-20 | 2017-05-31 | 长沙南方钽铌有限责任公司 | A kind of method for plating DLC film in surface of tantalum spinning jet |
| WO2018157867A1 (en) * | 2017-03-03 | 2018-09-07 | 北京华宇创新钽铌科技有限公司 | Surface processing method for tantalum spinning head |
| CN108531906B (en) * | 2017-03-03 | 2020-05-29 | 北京华宇创新钽铌科技有限公司 | Surface treatment method of tantalum spinneret |
| CN106987911A (en) * | 2017-03-23 | 2017-07-28 | 长沙南方钽铌有限责任公司 | A kind of surface treatment method of tantalum, tantalum-niobium alloy or tantalum niobium tungsten alloy spinning head |
| CN109023550A (en) * | 2018-07-03 | 2018-12-18 | 湖南华冉科技有限公司 | A kind of modification tantalum spinneret that fibre strength can be improved |
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