CN1153853C

CN1153853C - Manufacture of nanometer material reinforced electroformed crystalline metal product

Info

Publication number: CN1153853C
Application number: CNB011133279A
Authority: CN
Inventors: 坚徐; 徐坚; 王一建
Original assignee: Individual
Current assignee: Xu Jian
Priority date: 2001-07-09
Filing date: 2001-07-09
Publication date: 2004-06-16
Anticipated expiration: 2021-07-09
Also published as: CN1332272A

Abstract

The present invention relates to a manufacturing method of a nanometer-material reinforced electroformed crystalline metal product, which is characterized in that one of the nanometer materials of alpha-Al2O3, gamma-Al2O3 and TiO2 is added into electroformed liquid, the added amount of the nanometer materials is from 1.5 to 7.0% of volume of a metal layer, and the metal product is formed by stirring under ultrasonic waves; the formed metal product is heated to 500 to 800 DEG C in the normal-pressure protecting gas of N2 and Ar or the vacuum of 10<-1> to 10<-2> Pa, and then heat preservation lasts for 15 to 45 minutes. Compared with the prior art, the present invention has the obvious advantages that because the nanometer materials are added and are treated by a crystalline process, the mechanical performance of a product is obviously enhanced, and for example, the hardness of the product at room temperature can still maintain HV110 after the product is heated at 800 DEG C. The product can be used for automotive air conditioners, domestic air conditioners and the metal pipe pieces of refrigerator refrigerating systems.

Description

The manufacture method of nano material enhanced electroformed crystalline metal product

The present invention relates to a kind of electrocasting method of ducted body, particularly a kind of manufacture method of novel nano material enhanced electroformed crystalline metal product.

The great advantage of electrocasting method is can be with the form of no weld seam, one-step moulding, produces the metal parts of the complicated special shape of precision height, interior external form surface that surfaceness is low, and this is that the general machining method is difficult to realize.Because no weld seam just can be accomplished compact construction with this class parts such as reducing multi-way pipe fittings, volume-diminished, weight saving and cost reduce.The greatest drawback of this traditional electroforming metal goods is that intensity is lower, and pipe fitting is not withstand voltage, easily produces and is similar to " piping " of dam in big flood.Therefore, still can only make as this classes such as waveguide, Venturi meter, screen cloth and disc pressing molds the less demanding part of intensity (or pressure) so far.To requiring the pipe fitting of certain intensity or the anti-certain pressure of need, now still adopt the machining process manufacturing both at home and abroad, for example when manufacturing was led to reducing fittings more, the straight pipe that is about to different diameter adopted operations such as blanking, punching, expansion (contracting) mouth, bending, welding to finish.Owing to limit by the characteristics of these manufacturing process own, the product that is processed into has many unsurmountable defectives, when connecting as cross pipe, has unnecessary pipe end insertion and welding slag to remain in the inner chamber, and it is not smooth to cause liquid in pipe to flow, and working efficiency reduces.In addition, if when having welding flaw such as lack of penetration, slag inclusion, when this part is welded on other parts again, can make former defective produce " secondary sealing-off ".Mechanically vibrative when especially being used in as this class operation of automobile, above-mentioned fault location then easily shakes and splits, and causes the accident.With the part that welding processing becomes, the intensity of its weld seam and heat affected zone material is significantly less than all the other partly, has formed a weak band.For some complicated special-shaped multi-way pipe fittings,, owing to limit by weldprocedure, must keep suitable distance during adjacent sealing of tube, thereby make the pipe fitting volume too huge as double above special-shaped many logical (more than the four-way) pipe fittings.Therefore, industrial sector wishes to seek a kind of advantage that can have electroforming and mechanical workout goods simultaneously for a long time, and overcomes the manufacture method of the metal products of their shortcomings.

The object of the present invention is to provide a kind of manufacture method of nano material enhanced electroformed crystalline metal product, overcome the existing in prior technology defective, make the metal products of making both have the intensity and the withstand voltage properties of (or surpass) rolling stock, have no weld seam, compact construction, fatigue resistance is good, precision is high, surfaceness is low advantages such as the baroque special shape of interior external form again.Realize that key problem in technology of the present invention is: in the electrotyping forming process, add an amount of nano material in the electroforming solution, nano material is evenly distributed in the metal level of electrolytic deposition, make the article construction densification, reduced porosity, improved mechanical property; To carry out the crystalline state processing by the goods that the electroforming once shaped makes again, make the packed particle of its microstructure, and change uniform fine crystalline structure into, and eliminated internal stress from galvanic deposit.

Below be described in detail particular content of the present invention:

A kind of manufacture method of nano material enhanced electroformed crystalline metal product, it comprises the core manufacturing, pre-treatment, electrotyping forming is sloughed core, aftertreatment.It is characterized in that: in copper electroforming or nickel goods, add nanometer Al ₂O ₃Or TiO ₂Strengthen, moulding is after the crystalline state processing; Add nano material in the composition of the electroforming solution of the copper of electrotyping forming or nickel, this nano material is selected α-Al for use ₂O ₃, γ-Al ₂O ₃, TiO ₂In a kind of, the particle diameter d≤10nm of nano material, length-to-diameter ratio l/d=5～10, content is 1.5～7.0% of volume in metallic copper or nickel dam, and codeposition moulding under ultrasonic stirring; The crystalline state processing of being carried out behind copper electroforming or the nickel product molding is at non-pressurized N ₂Perhaps in the protection gas of Ar, perhaps 10 ^-1～10 ^-2In the vacuum of Pa, be heated to 500～800 ℃, insulation 15～45min.Core manufacturing, pre-treatment, slough core, aftertreatment is same as the prior art.

With prior art relatively, the outstanding advantage that the present invention has is owing to the adding nano material and through the crystalline state processing, the microstructure and the mechanical property that has improved product of product have been improved significantly, microstructure as copper electroforming goods of the present invention is uniform close grain, the hardness of these goods reaches HV110 simultaneously, after 800 ℃ of heating, its at room temperature hardness still keep HV110, and original copper electroforming goods, its hardness is HV100, after 250～300 ℃ of heating, its hardness is at room temperature reduced to HV25.

Embodiment 1: produce a kind of nanometer Al ₂O ₃Enhanced crystalline state electroforming reducing multi-path copper pipe fitting, its geometrical shape as shown in Figure 1,1 is house steward among the figure, 1a is house steward's import, 2 for being in charge of, 2a is for being in charge of outlet, its processing step is as follows:

Coremaking mould and pre-treatment are made the inner core steel die by the shape and size of this pipe fitting inner core earlier, and the low melting point alloy (65%Pb, 30%Sn, 5%Zn) that fusing is good pours in the core, and core is taken out in the cooling back.It is in the 5g/L chromatedsolution in concentration that core takes out the back, floods 20 seconds, makes mandrel surface form one deck stripping film.

Electrotyping forming formulation of electroforming solution and processing condition are as follows: copper sulfate 190g/L, sulfuric acid 70g/L, M 0.0007g/L, N 0.0005g/L, SP 0.015g/L, polyoxyethylene glycol 0.1g/L; Sodium lauryl sulphate 0.08g/L, Cl-0.08g/L; 15～25 ℃, cathode current density 5A/dm ², anode is T2 electrolytic copper and the PVC millipore filtration net circulating filtration that 15 μ m are housed, and enters electroforming solution to prevent anode sludge slag.Before the beginning electroforming, in electroforming solution, add Al ₂O ₃Nano material, add-on are that to make its content in the copper electroforming layer be 3.0% (Vol).In the electroforming process, adopt the ultrasonic stirring device to stir electroforming solution, and make Workpiece Rotating, so that Al ₂O ₃Be evenly distributed in electroformed layer, the wall thickness of product is 1.5mm, and the electroforming depositing time is 24～25 hours.Its microstructure as shown in Figure 2.

Slough the reducing multi-path copper pipe fitting of core after with moulding, be heated to 230 ℃, the core alloy melting makes it to separate with the copper electroforming pipe fitting and reclaim stand-by.

The crystalline state processing is put into non-pressurized N with the reducing multi-path copper pipe fitting that obtains ₂In the process furnace of gas shiled, under 550 ℃, insulation 15min makes its microstructure change uniform fine grained texture into, as shown in Figure 3.

The reducing multi-path copper pipe fitting of aftertreatment after with the crystalline state processing carries out shaping earlier, surface finish (as needs), and putting it into concentration again is in the BAT solution of 2～5g/L, 60 ℃ of dipping 5min down.Take out after after clear water cleaned, dries up, check, packing can be dispatched from the factory.

Hardness and temperature relation curve with original copper electroforming pipe fitting and copper electroforming pipe fitting of the present invention is shown in Fig. 4 after tested.Ordinate zou is a hardness among the figure, and X-coordinate is a Heating temperature, and the A curve is the relation of hardness and Heating temperature under the room temperature of original copper electroforming pipe fitting, and the B curve is the relation of hardness under the copper electroforming pipe fitting room temperature of the present invention and Heating temperature.

Embodiment 2: produce a kind of nanometer Al ₂O ₃Enhanced crystalline state electroforming reducing multi-path copper pipe fitting, its processing step is as follows:

The prescription and the processing condition of electrotyping forming electroforming solution are as follows: copper sulfate 150g/L, sulfuric acid 50g/L, M 0.0005g/L, N 0.0003g/L, SP 0.01g/L, polyoxyethylene glycol 0.07g/L, sodium lauryl sulphate 0.05g/L, Cl ^-0.05g/L all the other are identical with embodiment 1.

The crystalline state processing puts into 10 with the reducing multi-path copper pipe fitting that obtains ^-1～10 ^-2In the vacuum oven of Pa, at 600 ℃, insulation 20min.

Make core and pre-treatment, slough core, aftertreatment is identical with embodiment 1.

This pipe fitting hardness value is HV105 after tested.

Embodiment 3: produce a kind of nano-TiO ₂Enhanced crystalline state electroformed nickel pipe fitting, concrete steps are as follows:

The core material that manufacturing core and pre-treatment are selected for use is low melting point (240 ℃) alloy of 92%Sn, 8%Zn.Press the identical method of embodiment 1, also can be in 10%NaOH solution, 6V anode electrolysis 10～40 seconds during electrolysis treatment, is made negative electrode with common iron plate.They all can form one deck stripping film at mandrel surface.

Electrotyping forming formulation of electroforming solution and processing condition are as follows: Ni (NH ₂SO ₃) ₂4H ₂O300g/L, NiCl ₂6H ₂O 15g/L, H ₃BO ₃40g/L, pH 4.0,40 ℃ of temperature, cathode current density 15A/dm ², make anode (adding the Ti basket) with electrolysis Ni plate.Used nano material is TiO ₂, add-on is that to make its content in the electroforming nickel dam be 2.5% (Vol), all the other press embodiment 1.

Slough the nickel product of core film after, be heated to 250 ℃, the Sn-Zn low melting point core alloy of fusing can be separated and reclaim moulding.

The crystalline state processing will with the electroformed nickel pipe fitting behind the core membrane sepn, put into non-pressurized Ar protection gas, at 750 ℃ of insulation 20min, make its microstructure change uniform fine grained texture into.

Aftertreatment again with product through shaping, surface finish, cleaning, oven dry, check back packing.

Claims

1. the manufacture method of a nano material enhanced electroformed crystalline metal product comprises the core manufacturing, pre-treatment, and electrotyping forming is sloughed core, and aftertreatment is characterized in that: added nanometer Al in the goods of copper electroforming or nickel ₂O ₃Or TiO ₂Strengthen, moulding is after the crystalline state processing.

2. manufacture method according to claim 1 is characterized in that: add nano material in the composition of the electroforming solution of the copper of electrotyping forming or nickel, this nano material is selected α-Al for use ₂O ₃, γ-Al ₂O ₃, TiO ₂In a kind of, the particle diameter d≤10nm of nano material, length-to-diameter ratio l/d=5～10, content is 1.5～7.0% of volume in metallic copper or nickel dam, and codeposition moulding under ultrasonic stirring.

3. manufacture method according to claim 1 is characterized in that: the crystalline state processing of being carried out behind copper electroforming or the nickel product molding is at non-pressurized N ₂Perhaps in the protection gas of Ar, perhaps 10 ^-1～10 ^-2In the vacuum of Pa, be heated to 500～800 ℃, insulation 15～45min.