CN102676865A - Method for manufacturing palladium alloy and palladium alloy - Google Patents
Method for manufacturing palladium alloy and palladium alloy Download PDFInfo
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Abstract
The present invention aims at providing a method for manufacturing a palladium alloy and the palladium alloy. In the method for manufacturing the palladium alloy, not only a surface but also an inner part of the palladium alloy has the hardness suitable for processing, and has a uniform composition. The method comprises the step of: a first process, wherein, 94.5-97.6wt% palladium and 2.4-5.5wt% boron are melt in a water-cooling crucible to manufacture a master alloy having a uniform composition; and a second process, wherein, the master alloy manufactured by the first process and specified amount of palladium are melted in the water-cooling crucible to manufacture the palladium alloy at least containing 0.03-1.40wt% boron and more than 95.0wt% palladium.
Description
Technical field
The present invention relates to a kind of method of manufacture and palldium alloy of palldium alloy.
Background technology
Such as in as the ring of jewelry, necklace etc.; Though do not have clear and definite difference, but can be divided into: the commodity that are called jewelry (Jewelry Accessories) that adopt advanced material (high-quality platinum, platinum alloy, gold, au-alloy, natural gemstone diamond etc.) as classification roughly; Adopt the commodity of the material of less expensive (silver, silver alloys, low-quality au-alloy, artificial gem etc.).
In recent years, receive the surging influence of price of precious metal material, adopt the price of the jewelry of platinum or platinum alloy, gold or au-alloy to improve, the consumption market of jewelry shows the tendency of dwindling.Particularly, influenced by it bigger for high-quality Jewelry Accessories.
Therefore, for to should environmental change, when keeping material value, begin to seek than platinum alloy, ornamental material that au-alloy is more cheap with high-quality precious metal.
Again, in writing appliance, in order to produce value added; Adopt au-alloy etc. at the parts of ornamental gold ring, nib etc., when guaranteeing mechanical properties, the stationery that produces feeling of high class exists; But; Even in writing appliance so,, begin to discuss and replace platinum alloy or au-alloy and make with new precious metal material like above-mentioned reason or corresponding client's appealing.
Under background so, recently, be all precious metal, but price is about 5 one-tenth of the platinum price, cheap a lot of palladium (Pd) of 6 one-tenth of price of gold lattice is much accounted of, and adopts the jewelry of new palldium alloy manufacturing to be developed, and on market, goes into circulation.
In this palldium alloy, imported the product of a part of so-called Pd990, still, the palldium alloy of being made at home is a main flow with the purity that reaches Pd950.Its reason is that the purity of palladium is too high, adds at ornaments and not only is difficult to guarantee required mechanical properties man-hour, and is soft as if too, can easy deformation, injured easily.Specifically such as in ring etc., as realistic problem, Vickers' hardness is asked to more than 80Hv, if but palladium purity is high more, and its Vickers' hardness will be low more, and the Vickers' hardness of pure palladium (containing unavoidable impurities) can be low to moderate about 40Hv.
Therefore, for example in the patent documentation 1, as the method for sclerosis palladium, motion has the technology of the surface being carried out boronation.This method makes its surface carry out the hardened method for boron (B) is penetrated into as the employed palladium of Jewelry Accessories or by the surface of the palldium alloy of alloying.
The prior art document
[patent documentation]
No. 2987314 communique of [patent documentation 1] japanese
Summary of the invention
, in above-mentioned surface treatment method, the amount on the surface of boron infiltration palladium etc. is difficult to control, and it is difficult making the boron that contains desired amount in the palladium.
Again, hardened in the surface of the palladium of infiltration boron etc., and Vickers' hardness improves, and still, there is not boron in the inside of palladium etc., so inner Vickers' hardness is not improved, for example, is processed into the isochronous anti-deformation performance of ring by sheet material and can not be referred to as fully.
Again, in aforesaid method, though can be hardened in the surface of palladium etc., still, be easy to generate coarsely on the surface, when for example making ring etc., the back operations polished in the surface of needing also can produce the problem that related manufacturing cost improves more after processing.
To this, be considered to:, then be not only the surface of palladium if form inside, the even palldium alloy of forming that boron contains palladium equably; Its inner Vickers' hardness also is enhanced; Or, can not produce the coarse of surface, and then solve the problems referred to above because the surface is not carried out necessity of boronation.
But, also realize to obtain the scheme of following palldium alloy, in this palldium alloy, the inside that obtains making boron contain palladium equably, form uniformly.Its reason is: even want palladium is fused with boron, both fusing point differences are very big, and boron is HMP (about 2092 ℃), oxidation easily, the alloy that is difficult to evenly formed.
In the occasion of the general precious metal of fusion, for example use and contain ZrO again,
2, SiO
2Deng the crucible (ceramic crucible) of oxide compound, even so the heat-resistant limit of crucible heats up just about 2000 ℃, relative therewith, the fusing point of boron is 2092 ℃, also oxidation easily.Therefore, has following problems: in these crucibles,, fuse, can not stably dissolve, be difficult to obtain even matter alloy even palladium and boron are put into the ratio of regulation.
Therefore, in palldium alloy, obtain the also palldium alloy more than 80Hv of inner Vickers' hardness, the present inventor has carried out all research, and its result learns, in palldium alloy, in order to improve Vickers' hardness, preferably contains boron, element silicon.But distinguish: the purchase price of boron is high, element silicon is lower than the purchase price of boron, relative therewith, if same amount; Compare with boron, the Vickers' hardness of palldium alloy does not improve, and if the content of element silicon is too much; Then alloy shows the tendency that becomes fragile, and thus, obtains the present invention.
Problem of the present invention is, a kind of method of manufacture and palldium alloy of palldium alloy is provided, and in this palldium alloy, is not only the surface, even the inner hardness that also has suitable processing contains boron equably from the surface to inside, is formed uniformly.
In order to solve above-mentioned problem; The invention that technical scheme 1 is put down in writing provides a kind of method of manufacture of palldium alloy, it is characterized in that, in the method for manufacture of this palldium alloy, has: first operation; Wherein, Account for the proportion of composing that 94.5～97.6 quality %, boron account for 2.4～5.5 quality % with palladium, palladium and boron are fused with cold-crucible, make the mother alloy of evenly forming; Second operation wherein, is fused the above-mentioned mother alloy of making in first operation and the palladium of specified amount with cold-crucible, make following palldium alloy: contain the boron in 0.03～1.40 quality % scope at least, and contain the above palladium of 95.0 quality %.
Again, in the invention that technical scheme 2 is put down in writing, a kind of palldium alloy is provided, it is characterized in that, contain the boron in 0.03～1.40 quality % scope at least, and contain the above palladium of 95.0 quality %, and, boron contained equably to inside from its surface.
Add the mother alloy that first operation that adopts the invention in the technical scheme 1 is carried out alloying, the occasion in that second operation is fused again for example contains SiO in use
2The occasion of crucible, the element silicon that this crucible contained (Si) is reduced stripping, or contains the occasion of the crucible of zircon in use; Zirconium that this crucible contains (Zr) is reduced stripping, and the composition that constitutes crucible is sneaked into inevitably, and it is difficult that this mixed volume is controlled; Can not obtain the palldium alloy of desirable proportion of composing; In second operation,, be important constitutive requirements to have used cold-crucible for palladium fusion with mother alloy that obtains in first operation and specified amount.
Again; A kind of method of manufacture of palldium alloy is provided in the invention that technical scheme 3 is put down in writing, it is characterized in that, in the method for manufacture of this palldium alloy, have: first operation; Wherein, Account for the proportion of composing that 94.5～97.6 quality %, boron account for 2.4～5.5 quality % with palladium, palladium and boron are fused with cold-crucible, make the mother alloy of evenly forming; Second operation; Wherein, the mother alloy of making to above-mentioned first operation of major general's specified amount mixes, fuses with palladium and silicon, makes following palldium alloy: boron and silicon add up to and contain 0.04～1.0 quality %; At least contain the silicon of the scope of 0.01～0.4 quality %, and contain the above palladium of 99.0 quality %.
Again; A kind of method of manufacture of palldium alloy is provided in the invention that technical scheme 4 is put down in writing, it is characterized in that, in the method for manufacture of this palldium alloy, have: first operation; Wherein, Account for the proportion of composing that 94.5～97.6 quality %, boron account for 2.4～5.5 quality % with palladium, palladium and boron are fused with cold-crucible, make the mother alloy of evenly forming; Second operation, wherein, the mother alloy of making to above-mentioned first operation of major general's specified amount mixes with palladium, adopt and contain SiO
2Crucible fusion, make following palldium alloy: boron adds up to silicon and contains 0.04～1.0 quality %, contains the silicon of the scope of 0.01～0.4 quality % at least, and contains the palladium more than the 99.0 quality %.
Again; A kind of method of manufacture of palldium alloy is provided in the invention that technical scheme 5 is put down in writing, it is characterized in that, in the method for manufacture of this palldium alloy, have: first operation; Wherein, Account for the proportion of composing that 94.5～97.6 quality %, boron account for 2.4～5.5 quality % with palladium, palladium and boron are fused with cold-crucible, make the mother alloy of evenly forming; Second operation; Wherein, the casting that constitutes with the Si oxide compound with crucible in, the mother alloy of making to above-mentioned first operation of major general's specified amount mixes with palladium; Adopt the fusion of high-frequency melting stove; The casting article that manufacturing is made up of following palldium alloy: boron and silicon add up to and contain 0.04～1.0 quality %, contain the silicon of the scope of 0.01～0.4 quality % at least, and contain the above palladium of 99.0 quality %.
Again, in the invention that technical scheme 6 is put down in writing, a kind of palldium alloy is provided, it is characterized in that, in this palldium alloy, boron and silicon add up to and contain 0.04～1.0 quality %, contain the silicon of the scope of 0.01～0.4 quality % at least, and contain the above palladium of 99.0 quality %.
Generally speaking,, also contain unavoidable impurities respectively even say " palladium ", " boron " or " silicon " separately again.For example, even pure palladium also contains unavoidable impurities, the ratio of the palladium that contains in the palldium alloy among the present invention is: containing of palladium on the basis of unavoidable impurities is proportional containing.Again, same boron and silicon also are in the ratio that contains on the basis of unavoidable impurities.
In the present invention, if form inside, the even palldium alloy of forming that boron is evenly contained palladium, then be not only the surface, even the raising of the Vickers' hardness in inside also is possible.
In the invention of the method for manufacture of the palldium alloy that technical scheme 3 is put down in writing, though detail in the back,, at first obtain boron is contained the inside of palladium, the mother alloy of forming uniformly equably, in second operation, add silicon.
In order to obtain this mother alloy, be necessary near the eutectic point of palladium and boron, to make alloy (mother alloy), the eutectic point of palladium and boron exists near two positions of content 3.1 quality %, 5.3 quality % of boron.When fusion palladium and boron, for example, use the general SiO that contains as fusion usefulness
2The occasion of crucible; The element silicon that this crucible contained (Si) is reduced stripping; Or contain the occasion of the crucible of zircon in use; Zirconium that this crucible contains (Zr) is reduced stripping, can distinguish through experimental result: the composition that constitutes crucible is sneaked into mother alloy inevitably, and the proportion of composing of boron reduces.It is difficult that the mixed volume of the reduction of this boron, silicon, zirconium is controlled, and in order to obtain the mother alloy of correct proportion of composing, using cold-crucible is important constitutive requirements.
For example; The occasion that the Pd990 alloy of the boron that is combined with 1.0 quality % in the palladium is fused with the ceramic crucible that contains silicon; The amount of boron reduces to the scope of 0.66～0.95 quality %; The amount of silicon contains with the scope of 0.02～0.41 quality %, distinguishes not to be that the silicon suitable with the reduction of boron is contained by displacement and by alloying.
In order to obtain the alloy that palladium-boron-silicon constitutes, do not make even do not add the silicon of positive trace, contained SiO through what technical scheme 2 put down in writing
2Crucible make (for example according to method manufacturings such as castings), silicon (Si) is reduced stripping, the part of replacement boron by being sneaked in the alloy, therefore can easily obtain the alloy that palladium-boron-silicon constitutes.
According to the present invention, boron is contained from the surface to inside equably, therefore, can make the highly purified palldium alloy of following even composition, and it is not only the surface, even inner also can have processing suitable hardness.
And because be so highly purified palldium alloy, for example, as the material of the jewelry of ring or necklace etc., or parts such as the nib of writing appliance, ornamental Jin Huan can use in wide purposes.
Again, the occasion of using at the Jin Huan that equips as the ring of jewelry etc., writing appliance etc., becoming is difficult to distortion, injured man-hour adding; Therefore; Do not carry out necessity of back operation because of distortion, scar, not only quality improves, but and also Be Controlled of manufacturing cost.
Again, aspect color, compare, the not inferior jewelry that reduces Master Cost also can be provided with platinum alloy.
Again, because of having kept high purity, so when having given the feeling of high class impression of client, the more cheap jewelry of making than platinum alloy can be provided as precious metal.
Description of drawings
Fig. 1 representes the equilibrium diagram of Pd-B binary alloy.Binary alloy state graph (" BINARY ALLOY PHASE DIAGRAMS [SECOND EDITION] Voluume 1, distribution: the 518th page of record of ASM INTERNATINAL The Materials Information Society)
Embodiment
Below, form of implementation of the present invention is at length explained.
(first form of implementation)
Palldium alloy among the present invention for example is suitable for following field, such as as the material of the jewelry of ring, necklace etc. or as parts such as the nib of writing appliance, ornamental Jin Huan.
This palldium alloy is following formation, contains the boron in 0.03～1.40 quality % scope at least, and contains the above palladium of 95.0 quality %.
Through the content with boron is more than the 0.03 quality %, and the surface and the inner Vickers' hardness of palldium alloy can be for more than the 80Hv.In addition, Vickers' hardness is 80Hv when above, then is the mutually equal hardness of jewelry material Pt900 (Pd of 10 quality %) with market circulation, and that for example can guarantee ring etc. adds desired mechanical properties in man-hour.That is, because have this Vickers' hardness, palldium alloy becomes the material that has suitable hardness man-hour adding, and can think and improve: if the purity of palladium uprises, and then easy deformation, easy injured shortcoming.
On the other hand, if the content of boron is more than 1.40 quality %, then in following occasion, the hardness that work hardening produces rises and will increase, and this occasion for example is: when the manufacturing of ring etc.Alloy is hoped the rolling processing of thickness and carried out in order to obtain the processing of desirable shape.Thus, for the processing that obtains product just become difficulty, add and can be easy to generate crackle man-hour, therefore, produce the problem that productivity descends, not preferred.
And then, the content of the boron in the above-mentioned palldium alloy, in 0.03～0.30 quality % scope for more preferably.
As the reason of content more than 0.03 quality % of boron, same as described above.
On the other hand; Content the reasons are as follows below 0.30 quality % as boron; In the following occasion of imagination; In order to be suitable for the palldium alloy of various purity, this is combined into: when the application of this specification sheets at present, detect effective situation in the palladium of being implemented, Bureau of Standards carries out in Japan.
Specifically, in Japan, as the purity guarantee of present precious metal; Detection system with Bureau of Standards, for example, in the occasion of Pt1000; By the tolerance of approval 0.30 quality %, so long as the above purity of 99.70 quality %, just can access the mark of Pt1000.
For example,, approved ± tolerance of 0.50 quality %, so long as more than the 89.50 quality %, just can access the mark of Pt900 in the occasion of Pt900 again.
At this; Detect about palladium, in Japan also do not implementing now, implement if consider benchmark same as described above; The tolerance of the purity of palladium is identical with pure platinum; Be set in advance below the 0.30 quality %, the occasion that then implement to detect with same datum is thought the mark that can obtain Pd1000 (pure palladium).
Again, also have as content other reason below 0.30 quality % of boron, if the content of boron below 0.30 quality %, then palldium alloy can be not really up to the mark, has the hardness of easy processing, and is therefore preferred.
Then, the method for manufacture to above-mentioned palldium alloy of the present invention describes.
In the method for manufacture of palldium alloy of the present invention, comprise first operation of making the mother alloy of evenly forming, second operation that the above-mentioned mother alloy of employing is made highly purified palldium alloy.
In this method of manufacture; As palladium is evenly contained boron and the method for alloying from the surface to inside; Focusing on palladium and boron has on this starting point of eutectic point; At first, near eutectic point, make alloy (mother alloy), then use the palladium of the proportioning that even matter alloy (mother alloy) manufacturing of fusing point reduction is stipulated and the alloy (the highly purified palldium alloy of hope) of boron.
Again, the eutectic point of palladium and boron is present near two positions 3.1 quality %, the 5.3 quality %, below, be that example describes just with near the eutectic point the 3.1 quality %.
At first; In first operation; Palladium is mixed with the ratio of boron with near the composition the eutectic point in the equilibrium diagram (Fig. 1) of this two metaclass alloy; This ratio is: the boron of the palladium of 96.90 quality %-3.10 quality %, and adopt cold-crucible to fuse then, obtain boron is evenly contained the inner mother alloy of palladium.
At this, so-called cold-crucible, the crucible for forming with the good metal of heat conductivity forms with copper generally speaking.When adopting the cold-crucible fusion to be received thing (various metal), for example, carry out simultaneously carrying out refrigerative according to the heat-eliminating medium of water etc. on one side.As the thermal source of cold-crucible, can adopt for example electric arc, plasma body, electron beam, high frequency etc.
If be this cold-crucible, can be warmed up to the high temperature more than 3000 ℃, so, can the boron of palladium and HMP (2092 ℃) be fused equably.
Again, if palladium-boron class alloy for example uses ceramic crucible to fuse, then the crucible composition is reduced; Be blended in the alloy in the fusion, will become ternary alloy, if cold-crucible; Then the composition of crucible can not be blended in the alloy, can make the binary palldium alloy of even matter.
According to cold-crucible so, palladium fuses in fusion processes with both of boron and alloying is so carried out, and the eutectic point identical with liquidus line in solidus curve becomes fusing point for 1065 ℃.Near eutectic point, solidification temperature range narrows down, and is difficult to produce so-called " lever principle ", is difficult to carry out segregation, through repeating fusion, can obtain uniform alloy at eutectic point.
At this moment, the palladium in mother alloy and the ratio of boron, be difficult in fact just in time to carry out alloying in the ratio of eutectic point, carry out some skews from eutectic point and have no idea.Through with keen determination result of experiment and know, about 115 ℃, be no problem as solidification temperature range.
In fact, for eutectic point, be maintained at about under 115 ℃ solidification temperature range, the situation at 5.50 quality % of the boron content of maximum; After making mother alloy 50g; Broken and be divided into 4, from each piece sampling, implement icp analysis; Its result, the analytical value of boron are that 5.25 quality %～5.42 quality %, maximum error rate are 4.5 quality %.Equally, make the mother alloy 50g of 2.40 quality % of minimum boron amount after, carry out fragmentation, be divided into 5, from each piece sampling, implement icp analysis, its as a result the analytical value of boron be that 2.29 quality %～2.37 quality %, maximum error rate are 4.6 quality %.
Again, use boron is that the mother alloy of 5.5 quality % ratios fuses, and with the alloy of formation palladium-1 quality % boron, but the analytical value of the boron of actual mother alloy is the occasion of 5.25 quality %, becomes the alloy of palladium-0.96 quality % boron.Using boron is the mother alloy of 2.4 quality % ratios; Fuse; To form the alloy of palladium-1 quality % boron; But the analytical value of the boron of actual mother alloy is the occasion of 2.29 quality %, becomes the alloy of palladium-0.95 quality % boron, and the skew of 0.05 quality % level of boron amount can be referred to as mechanical properties is not almost had the level of influence.
Again, use boron is that the mother alloy of 5.5 quality % ratios fuses, and with the alloy of formation palladium-0.03 quality % boron, but the analytical value of the boron of actual mother alloy is the occasion of 5.25 quality %, becomes the alloy of palladium-0.029 quality % boron.Using boron is the mother alloy of 2.4 quality % ratios; Fuse; To form the alloy of palladium-0.03 quality % boron; But the analytical value of the boron of actual mother alloy is the occasion of 2.29 quality %, becomes the alloy of palladium-0.029 quality % boron, and the skew of 0.001 quality % level of boron amount can be referred to as mechanical properties is not almost had the level of influence.
Therefore; If the solidification temperature range about 115 ℃; The mother alloy that does not have problem in the actual production can be made,, stable mother alloy can be made if the boron amount is the scope of 2.4 quality %～5.5 quality %; Palladium is in the scope of 94.5～97.6 quality %, and boron can cooperate in the scope of 2.4～5.5 quality %.
Further preferred temperature of solidification is below 50 ℃.
In fact; For eutectic point, have 50 ℃ solidification temperature range, make after the mother alloy 50g with the boron amount 5.40 quality % of maximum, broken and be divided into 4; From each piece sampling; Implement icp analysis, its result, the analytical value of boron are that 5.29 quality %～5.35 quality %, maximum error rate are 2.0 quality %.Equally, make the mother alloy of 2.80 quality % of minimum boron amount after, carry out fragmentation and be divided into 5, from each piece sampling, implement icp analysis, its as a result the analytical value of boron be that 2.74 quality %～2.77 quality %, maximum error rate are 2.1 quality %.Therefore, if the solidification temperature range about 50 ℃ can be made stable mother alloy,, can make stable mother alloy if the boron amount is the scope of 2.8 quality %～3.9 quality %, 5.0 quality %～5.4 quality %.
Therefore, can cooperate in following ranges: palladium is when the scope of 94.6～95.0 quality %, and boron is in the scope of 5.0～5.4 quality %; Palladium is when the scope of 96.1～97.2 quality %, and boron is in the scope of 2.8～3.9 quality %.
Again, as eutectic point, be considered to boron be near the 3.1 quality % with 5.3 quality % near, preferably use near the eutectic point of 3.1 quality %.There is Pd near the eutectic composition that boron is in the 5.3 quality %
5B
2With β B two mutually, have β B.On the other hand, boron is near the eutectic composition of 3.1 quality % by Pd soluble solids and Pd
5B
2Or Pd
3B or Pd
16B
3Deng the formation mutually of intermetallic compound.
Near the eutectic composition that boron is in the 5.3 quality % contains β B, thus there is the one side of easy oxidation, still; 3.1 near the eutectic composition the quality % for only by palladium as the constituting mutually of principal constituent, be difficult to oxidation, perhaps the rising of solidification temperature range is slow; Manageable, so preferred.
Then, in second operation, the mother alloy of making in above-mentioned first operation and the palladium of specified amount are fused with cold-crucible, the palldium alloy of manufacturing contains the boron in 0.03～1.40 quality % scope at least, and contains the above palladium of 95.0 quality %.
Promptly; The palladium that the mother alloy of making in first operation is added specified amount; Adopt cold-crucible to fuse; In the palladium more than containing 95.0 quality %, contain the boron (more preferably adding the boron in 0.03～0.30 quality % scope) in 0.03～1.40 quality % scope at least, make the palldium alloy of evenly forming.
In addition, in the invention of technical scheme 1, in order to obtain the mother alloy of even matter; It is necessary fusing with near the binary alloy of the eutectic of palladium and boron, forming, still, and in second operation; Contain the mother alloy of in first operation, making; The purity that is conceived to for the normalization of corresponding Pd990, Pd950 etc. is adjusted the purity of palladium, and for example can adding, other elements such as Pt, Au, Ag, Ru, Cu carry out the purity adjustment.Again, in the palldium alloy of the invention of technical scheme 2, also can be at the palladium of above-mentioned amount and beyond the boron, trace adds other element of above-mentioned that kind.
As above, can boron be contained from the surface to inside equably according to the present invention, therefore, can make the highly purified palldium alloy of even composition, it is not only the surface, even the inner hardness that also has suitable processing.
And, because be so highly purified palldium alloy,, or, can use in wide purposes as parts such as the nib of writing appliance, ornamental Jin Huan as the material of the jewelry of for example ring, necklace etc.
Again, be used for as the ring of jewelry etc., be equipped on the occasion of the Jin Huan etc. of writing appliance, adding and be not easy distortion, injured man-hour,, can suppress manufacturing cost therefore not because of the necessity of distortion and the injured back operation that causes.
Again, can reduce under the situation of materials cost, be provided at the color aspect also not inferior jewelry of comparing with platinum alloy.
Because kept high purity, when can give the impression of client, the more cheap jewelry of making than platinum alloy can be provided as the feeling of high class of precious metal again.
[embodiment]
Below, through embodiment, palldium alloy of the present invention is explained particularly.
(embodiment 1～15)
At first; With purity is that palladium 48.45g, purity more than the 99.95 quality % is that boron 1.55g more than the 99.9 quality % places on the cold-crucible made of copper (Ha one ス), carry out vacuum exhaust after, with the electric arc furnace after the argon replaces (below; Be referred to as vacuum displacement type electric arc furnace) fuse; Produce the mother alloy 50g of the even composition of following palladium and boron formation, it contains 3.1 quality % boron, and it is positioned at the eutectic point of palladium and boron.
Then; (containing palladium is 0.465g with the mother alloy 0.480g that makes; Boron is 0.015g) place on the cold-crucible made of copper with the above palladium 49.52g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.03 quality % is as embodiment 1.
Identical with embodiment 1; (containing palladium is 0.785g with the mother alloy 0.810g that makes; Boron is 0.025g) place on the cold-crucible made of copper with the above palladium 49.19g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.05 quality % is as embodiment 2.
Identical with embodiment 1; (containing palladium is 1.085g with the mother alloy 1.120g that makes; Boron is 0.035g) place on the cold-crucible made of copper with the above palladium 48.88g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.07 quality % is as embodiment 3.
Identical with embodiment 1; (containing palladium is 1.395g with the mother alloy 1.440g that makes; Boron is 0.045g) place on the cold-crucible made of copper with the above palladium 48.56g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.09 quality % is as embodiment 4.
Identical with embodiment 1; (containing palladium is 1.56g with the mother alloy 1.61g that makes; Boron is 0.05g) place on the cold-crucible made of copper with the above palladium 48.39g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.10 quality % is as embodiment 5.
Identical with embodiment 1; (containing palladium is 3.13g with the mother alloy 3.23g that makes; Boron is 0.10g) place on the cold-crucible made of copper with the above palladium 46.77g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.20 quality % is as embodiment 6.
Identical with embodiment 1; (containing palladium is 4.69g with the mother alloy 4.84g that makes; Boron is 0.15g) place on the cold-crucible made of copper with the above palladium 45.16g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.30 quality % is as embodiment 7.
Identical with embodiment 1; (containing palladium is 6.25g with the mother alloy 6.45g that makes; Boron is 0.20g) place on the cold-crucible made of copper with the above palladium 43.55g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.40 quality % is as embodiment 8.
Identical with embodiment 1; (containing palladium is 9.38g with the mother alloy 9.68g that makes; Boron is 0.30g) place on the cold-crucible made of copper with the above palladium 40.32g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.60 quality % is as embodiment 9.
Identical with embodiment 1; (containing palladium is 12.50g with the mother alloy 12.90g that makes; Boron is 0.40g) place on the cold-crucible made of copper with the above palladium 37.10g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.80 quality % is as embodiment 10.
Identical with embodiment 1; (containing palladium is 15.63g with the mother alloy 16.13g that makes; Boron is 0.50g) place on the cold-crucible made of copper with the above palladium 33.87g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 1.00 quality % is as embodiment 11.
Identical with embodiment 1; (containing palladium is 18.75g with the mother alloy 19.35g that makes; Boron is 0.60g) place on the cold-crucible made of copper with the above palladium 30.65g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 1.20 quality % is as embodiment 12.
Identical with embodiment 1; (containing palladium is 21.88g with the mother alloy 22.58g that makes; Boron is 0.70g) place on the cold-crucible made of copper with the above palladium 27.42g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 1.40 quality % is as embodiment 13.
Identical with embodiment 1; (containing palladium is 7.81g with the mother alloy 8.06g that makes; Boron is 0.25g) place on the cold-crucible made of copper with above palladium 39.69g, the silver-colored 2.25g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.50 quality % is as embodiment 14.
Identical with embodiment 1; (containing palladium is 16.13g with the mother alloy 16.63g that makes; Boron is 0.50g) place on the cold-crucible made of copper with above palladium 31.37g, the silver-colored 2.00g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 1.00 quality % is as embodiment 15.
(comparative example 1～4)
With the sheet material of the palladium 50g more than the purity 99.95 quality %, as comparative example 1.
Identical with embodiment 1; (containing palladium is 0.155g with the mother alloy 0.160g that makes; Boron is 0.005g) place on the cold-crucible made of copper with the above palladium 49.84g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 0.01 quality % is as comparative example 2.
Identical with embodiment 1; (containing palladium is 25.01g with the mother alloy 25.81g that makes; Boron is 0.80g) place on the cold-crucible made of copper with the above palladium 24.19g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 1.60 quality % is as comparative example 3.
Identical with embodiment 1; (containing palladium is 28.13g with the mother alloy 29.03g that makes; Boron is 0.90g) place on the cold-crucible made of copper with the above palladium 20.97g of purity 99.95 quality %; Fuse with vacuum displacement type electric arc furnace, the sheet material of the palldium alloy 50g of the even composition of making boracic 1.80 quality % is as comparative example 4.
< evaluation method >
(1. hardness)
About the sheet material of embodiment 1～15 and comparative example 1～4, three the position measurement Vickers' hardnesses (Hv) on the surface are obtained its MV.
Again, each sheet material is cut off, three the position measurement Vickers' hardnesses (Hv) in inside are obtained its MV.Its result is as shown in table 1.
(2. processibility)
About the sheet material of embodiment 1～15 and comparative example 1～4, carry out rolling processing, visual inspection has flawless, carries out following evaluation.Its result that kind as shown in table 1.
Do not crack ... Zero
Crack ... *
(3. condition of surface)
About the sheet material of embodiment 1～15 and comparative example 1～4, the coarse state on visual observation surface, the condition of surface of each sheet material is all good, does not find the difference of embodiment and comparative example.
Table 1
In comparative example 1 and the comparative example 2; Surface in palldium alloy sheet material and the inner not enough 80Hv of Vickers' hardness are under the occasion of for example using as the material of the ring of ornamental, when making according to the casting ring; Have injured problem easily as product, not preferred.
In comparative example 3 and the comparative example 4, hardness is excessive, in the manufacturing of ring etc., exists rolling to add the problem that cracks man-hour, and is not preferred.
(second form of implementation)
Palldium alloy in the present invention is for example as the material of the jewelry of ring, necklace etc. or as the parts of the nib of writing appliance, ornamental Jin Huan etc. and suitable use.
This palldium alloy constitutes, and total contains boron and silicon is 0.04～1.0 quality %, contains the silicon of 0.01～0.4 quality % scope at least.
Contain boron and silicon is more than the 0.04 quality % through total, the surface and the inner Vickers' hardness of palldium alloy can be more than 80Hv.Again, Vickers' hardness more than 80Hv, then have with in the equal hardness of the jewelry material Pt900 (10%Pd) of market circulation, for example, that guarantees ring for example etc. adds desired mechanical properties in man-hour.That is, because have this Vickers' hardness, palldium alloy becomes the material that has suitable stiffness man-hour adding, and can think and improve drawback: if the purity of palladium is high, and easy deformation, injured easily then.
On the other hand; Surpass 1.0 quality % if boron and silicon add up to contain, when then for example making ring etc., carrying out the man-hour that adds of alloy with the rolling processing of the thickness of hope, desirable shape with cut etc.; The hardness that is accompanied by work hardening and produces rises, and resistance to deformation also increases.Thus, the processing of the manufacturing articles difficulty that becomes is easy to generate crackle adding to become man-hour, has produced the low problem of productivity thus, and is not preferred thus.
More specifically, when using palldium alloy to make manufacture, comprise following method of manufacture: according to cutting, press the method for manufacture of the mechanical workout of processing etc.; According to casting mold be shaped, make based on the casting method of manufacture.In the former method of manufacture, as previously mentioned, for carrying out the mechanical workout of rolling, pressure processing etc.; Palldium alloy is carried out work hardening, and hardness increases, for the processing that forms product becomes difficult; But, in the latter's method of manufacture, can obtain complicated and very thin shape as manufacture; There is no need to carry out rolling processing, the cut in the above-mentioned post-treatment, even the surface of alloy and inner Vickers' hardness are than higher also no problem, but because also there is operation that the surface of manufacture is ground etc.; So should not make Vickers' hardness too high, see that from this some boron and silicon add up in the scope of 1.0 quality % to preferred.
Again, if silicone content is more than the 0.01 quality %, then as after state shown in the reference example 8 of [table 3] such, with pure palladium (comparative example 1) relatively, the Vickers' hardness height is to more than the 10Hv, the hardness height has arrived more than the measuring error, so obtained the rising of hardness really.If silicone content surpasses 0.4 quality %, then become fragile, be the processing of the purpose difficulty that becomes to form product, add and be easy to generate crackle man-hour, produce the low problem of productivity thus, thus, not preferred.
Again, another reason that contains silicon is that machinability improves in the isochronous cut of ring in order to make.
The manufacturing of ring generally is made up of following operation.
A. at first, make the operation of the ingot casting of palldium alloy etc.;
B. above-mentioned sheet material is repeated rolling, annealing, obtain the operation of regulation thickness of slab.
C. be stamped into circularly, press machine-shaping, form the operation of ring.
D. carry out annealed as required simultaneously, enlarge the operation of ring size.
E. reduce width cutting (adopting lathe that the width of ring is processed as specified dimension) and external diameter cutting (adopting lathe is the shape of semicircle or planar shaped with the shape cutting of ring for the cross section), make the operation of ring.
In above-mentioned cutting process,, in the cutting process of the manufacturing of each ring of the alloy of the alloy of palladium-boron, palladium-boron-silicon, the alloy of palladium-silicon, distinguish that the machinable ring quantity of each cutter there are differences though be to adopt diamond tool to cut.Its result representes with table 2.
Table 2
In table 2, so-called [with reference to hardness] measuring method is following, is that 3 positions of upper layer of the ring of semicircular ring (internal diameter size is No. 18) are measured with Vickers' hardness (Hv) with forming cross section behind the above-mentioned external diameter cutting process, obtains this MV.According to rolling process, cutting process, the hardness during than the sheet material after the annealing of palldium alloy is higher.So-called [plastic working evaluation] is illustrated in the manufacturing procedure among above-mentioned b～d, through visual inspection whether crackle arranged, and is O if situation about not cracking is given a definition, and is X if situation about cracking is given a definition.
As shown in table 2; At the boron that contains 0.2 quality % that carries out reference example 1 that kind; All the other are the ring (Vickers' hardness of upper layer: during 204Hv) manufacturing, when carrying out the external diameter cutting with above-mentioned cutter, just need change carrying out about about 200 cutting of the palldium alloy of palladium.Again, carrying out the such boron that contains 1.0 quality % of reference example 2, all the other are the ring (Vickers' hardness of upper layer: during 356Hv) manufacturing, also just need change carrying out about about 250 cutting of the palldium alloy of palladium.Carrying out such boron that contains 0.05 quality % of reference example 3 and the silicon of 0.05 quality %, all the other are the ring (Vickers' hardness of upper layer: during 212Hv) manufacturing, also just need change carrying out about about 200 cutting of the palldium alloy of palladium.
Relative therewith, at the boron that 0.17 quality % is arranged of reference example 4 and the silicon of 0.13 quality %, all the other are the ring (Vickers' hardness of upper layer: in manufacturing 282Hv), can carry out about about 300 cutting of the palldium alloy of palladium.Again, the silicon that contains 0.09 quality % of reference example 5, all the other are the ring (Vickers' hardness of upper layer: in manufacturing 164Hv), can carry out about about 300 cutting of the palldium alloy of palladium.The silicon that contains 0.4 quality % of reference example 6, all the other are the ring (Vickers' hardness of upper layer: in manufacturing 285Hv), can carry out about about 400 cutting of the palldium alloy of palladium.
Therefore, if contain the silicon of 0.09～0.4 quality %, then can find the raising of machinability.Again, such shown in reference example 7, if the content of silicon is 0.6 quality %, then become fragile, in the rolling process, can crack on the sheet material.
Then, the method for manufacture to above-mentioned palldium alloy of the present invention describes.
In the method for manufacture of palldium alloy of the present invention, comprise first operation of making the mother alloy of evenly forming, adopt above-mentioned mother alloy to make second operation of high purity palldium alloy.
In this method of manufacture; As the method that boron is contained, carries out alloying from the palladium surface to inside equably, be absorbed in the situation that palladium and boron have eutectic point, at first; Near eutectic point, make alloy (mother alloy); Then, use the alloy (mother alloy) of the even matter that fusing point is descended, make the palladium and the boron alloy (the highly purified palldium alloy of hope) of regulation ratio.
Again, the eutectic point of palladium and boron is near near two places the 3.1 quality %, the 5.3 quality %, below describes about near the eutectic point the 3.1 quality %.
At first; In first operation; With near the composition the eutectic point in the equilibrium diagram (Fig. 1) of this two metaclass alloy, promptly the ratio of the boron of the palladium of 96.90 quality %-3.10 quality % cooperates with palladium and boron, adopts cold-crucible to fuse; Thus, obtain boron is evenly contained the inner mother alloy of palladium.
At this, so-called cold-crucible, the crucible for adopting the good metal of heat conductivity to form generally speaking, forms with copper.When adopting the cold-crucible fusion to be received thing (various metal), for example can carry out refrigerative and carry out simultaneously according to the heat-eliminating medium of water etc.As the thermal source of cold-crucible, adopt for example electric arc, plasma body, electron beam, high frequency etc.
If use this cold-crucible, can liquefactent be warmed up to the high temperature more than 3000 ℃, so, can the boron of palladium and HMP (2092 ℃) be fused equably.
Again, if palladium-boron class alloy for example uses ceramic crucible to fuse, then the crucible composition is reduced; Be blended in the alloy in the fusion; Will become ternary alloy, if use cold-crucible, crucible can not react with boron; Then the composition of crucible can not be blended in the alloy, can make the binary palldium alloy of even matter.
According to cold-crucible so, palladium is with both of boron weldings and alloying is so carried out in fusion processes, and the eutectic point identical with liquidus line in solidus curve becomes fusing point for 1065 ℃.Near eutectic point, solidification temperature range narrows down, and is difficult to produce so-called " lever principle ", is difficult to carry out segregation, through repeating fusion, can obtain uniform alloy at eutectic point.
At this moment, the palladium in mother alloy and the ratio of boron, be difficult in fact just in time to carry out alloying in the ratio of eutectic point, carry out some skews from eutectic point and have no idea.Knowing through deep result of experiment, is no problem as solidification temperature range about 115 ℃.
It is identical that reason and form of implementation 1 are put down in writing.
Further, solidification temperature range is preferably below 50 ℃.
It is identical that reason and form of implementation 1 are put down in writing.
Again, as eutectic point, be considered to boron be near the 3.1 quality % with 5.3 quality % near, preferably use near the eutectic point of 3.1 quality %.
It is identical that reason and form of implementation 1 are put down in writing.
Then; In second operation; The mother alloy of making in above-mentioned first operation and the palladium and the silicon of specified amount are mixed, adopt the cold-crucible fusion, make following palldium alloy: contain the silicon of the scope of 0.01～0.4 quality % at least, and contain the above palladium (technical scheme 3) of 99.0 quality %.
Again, the palladium employing with mother alloy of making in above-mentioned first operation and specified amount contains SiO
2Crucible fusion, make following palldium alloy: contain the silicon of the scope of 0.01～0.4 quality % at least, and contain the above palladium (technical scheme 4) of 99.0 quality %.
Again; The casting that constitutes with the Si oxide compound with crucible in; The mother alloy of making to above-mentioned first operation of major general's specified amount mixes with palladium, adopts the fusion of high-frequency melting stove, makes the casting article that following palldium alloy constitutes: boron and silicon total contain 0.04～1.0 quality %; At least contain the silicon of the scope of 0.01～0.4 quality %, and contain the above palladium (technical scheme 5) of 99.0 quality %.
In technical scheme 3～5,, be necessary that near the binary alloy of the eutectic of palladium and boron, forming fuses in order to obtain the mother alloy of even matter again.But, in second operation, contain the mother alloy of making in first operation, in order to adjust the purity of palladium, can for example add Ag, Cu, Ni, carry out the adjustment of purity.Again, even in the palldium alloy of the invention of technical scheme 3, the palladium of above-mentioned amount and beyond the boron trace contain other above-mentioned element and also be fine.
Adopt the manufacture of above-mentioned palldium alloy, for example ring is such, through the gained alloy being carried out rolling, press the mechanical workout of processing etc., or is based on the casting that is shaped in the casting mold and makes.
[embodiment]
Below, according to embodiment palldium alloy of the present invention is specified.
(embodiment 16)
At first 48.45g palladium, 1.55g boron are placed on the cold-crucible made of copper; After the vacuum exhaust; Fuse with the electric arc furnace after the argon displacement (below, be called vacuum displacement type electric arc furnace), produce the mother alloy 50g of the even composition of following palladium and boron formation; It contains 3.1 quality % boron, its be positioned at palladium and boron eutectic point near.
Then; (containing palladium is 0.465g with the mother alloy 0.48g that makes; Boron is 0.015g) place on the cold-crucible made of copper with palladium 49.485g, silicon 0.035g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.90 quality %, boron is that 0.03 quality %, silicon are the sheet material of the palldium alloy 50g of 0.07 quality %, as embodiment 16.
(embodiment 17)
Identical with embodiment 16; (containing palladium is 0.785g with the mother alloy 0.81g that makes; Boron is 0.025g) place on the cold-crucible made of copper with palladium 49.165g, silicon 0.025g; Fuse with vacuum displacement type electric arc furnace, making contains palladium 99.90 quality %, boron is that 0.05 quality %, silicon are the sheet material of the palldium alloy 50g of 0.05 quality %, as embodiment 17.
(embodiment 18)
Identical with embodiment 16; (containing palladium is 1.095g with the mother alloy 1.13g that makes; Boron is 0.035g) place on the cold-crucible made of copper with palladium 48.86g, silicon 0.01g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.91 quality %, boron is that 0.07 quality %, silicon are the sheet material of the palldium alloy 50g of 0.02 quality %, as embodiment 18.
(embodiment 19)
Identical with embodiment 16; (containing palladium is 1.405g with the mother alloy 1.45g that makes; Boron is 0.045g) place on the cold-crucible made of copper with palladium 48.545g, silicon 0.005g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.90 quality %, boron is that 0.09 quality %, silicon are the sheet material of the palldium alloy 50g of 0.01 quality %, as embodiment 19.
(embodiment 20)
Identical with embodiment 16; (containing palladium is 4.69g with the mother alloy 4.84g that makes; Boron is 0.15g) place on the cold-crucible made of copper with palladium 45.06g, silicon 0.10g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.50 quality %, boron is that 0.3 quality %, silicon are the sheet material of the palldium alloy 50g of 0.2 quality %, as embodiment 20.
(embodiment 21)
Identical with embodiment 16; (containing palladium is 7.81g with the mother alloy 8.06g that makes; Boron is 0.25g) place on the cold-crucible made of copper with palladium 41.69g, silicon 0.08g, each a kind of 0.17g of from Ag, Cu, Ni, selecting as other additive, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.00 quality %, boron is that 0.5 quality %, silicon are the sheet material of the palldium alloy 50g of 0.16 quality %, as embodiment 21.
(embodiment 22)
Identical with embodiment 16; (containing palladium is 9.38g with the mother alloy 9.68g that makes; Boron is 0.30g) place on the cold-crucible made of copper with palladium 40.12g, silicon 0.20g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.00 quality %, boron is that 0.6 quality %, silicon are the sheet material of the palldium alloy 50g of 0.4 quality %, as embodiment 22.
(embodiment 23)
Identical with embodiment 16; (containing palladium is 12.50g with the mother alloy 12.90g that makes; Boron is 0.40g) place on the cold-crucible made of copper with palladium 37.01g, silicon 0.05g, each a kind of 0.04g of from Ag, Cu, Ni, selecting as other additive, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.02 quality %, boron is that 0.8 quality %, silicon are the sheet material of the palldium alloy 50g of 0.1 quality %, as embodiment 23.
(embodiment 24)
Identical with embodiment 16; (containing palladium is 12.50g with the mother alloy 12.90g that makes; Boron is 0.40g) place on the cold-crucible made of copper with palladium 37.0g, silicon 0.10g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.00 quality %, boron is that 0.8 quality %, silicon are the sheet material of the palldium alloy 50g of 0.2 quality %, as embodiment 24.
(embodiment 25)
Identical with embodiment 16; (containing palladium is 0.469g with the mother alloy 0.484g that makes; Boron is 0.015g) place on the cold-crucible made of copper with palladium 49.511g, silicon 0.005g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.96 quality %, boron is that 0.03 quality %, silicon are the sheet material of the palldium alloy 50g of 0.01 quality %, as embodiment 25.
(comparative example 5)
With the sheet material of the 50g of pure palladium as comparative example 5.
(comparative example 6)
Identical with embodiment 16; (containing palladium is 0.155g with the mother alloy 0.16g that makes; Boron is 0.005g) place on the cold-crucible made of copper with palladium 49.835g, silicon 0.005g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.98 quality %, boron is that 0.01 quality %, silicon are the sheet material of the palldium alloy 50g of 0.01 quality %, as comparative example 6.
(comparative example 7)
Identical with embodiment 16; (containing palladium is 0.31g with the mother alloy 0.32g that makes; Boron is 0.01g) place on the cold-crucible made of copper with palladium 49.675g, silicon 0.005g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.97 quality %, boron is that 0.02 quality %, silicon are the sheet material of the palldium alloy 50g of 0.01 quality %, as comparative example 7.
(comparative example 8)
Identical with embodiment 16; (containing palladium is 1.56g with the mother alloy 1.61g that makes; Boron is 0.05g) place on the cold-crucible made of copper with palladium 47.99g, silicon 0.40g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.10 quality %, boron is that 0.1 quality %, silicon are the sheet material of the palldium alloy 50g of 0.8 quality %, as comparative example 8.
(comparative example 9)
Identical with embodiment 16; (containing palladium is 14.07g with the mother alloy 14.52g that makes; Boron is 0.45g) place on the cold-crucible made of copper with palladium 35.23g, silicon 0.25g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 98.60 quality %, boron is that 0.9 quality %, silicon are the sheet material of the palldium alloy 50g of 0.5 quality %, as comparative example 9.
(comparative example 10)
Identical with embodiment 16; (containing palladium is 18.75g with the mother alloy 19.35g that makes; Boron is 0.60g) place on the cold-crucible made of copper with palladium 30.35g, silicon 0.3g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 98.2 quality %, boron is that 1.2 quality %, silicon are the sheet material of the palldium alloy 50g of 0.6 quality %, as comparative example 10.
(reference example 8)
At first; Palladium 48.0g, silicon 2.0g are placed on the cold-crucible made of copper, after the vacuum exhaust, with the electric arc furnace after the argon replaces (below; Be referred to as vacuum displacement type electric arc furnace) fuse; Produce the mother alloy 50g of the even composition of following palladium and silicon formation, it contains the silicon of 4.0 quality %, and it is positioned near the eutectic point of palladium and silicon.
Then; (containing palladium is 0.12g with the mother alloy 0.125g that makes; Silicon is 0.005g) place on the cold-crucible made of copper with palladium 49.875g, fuse with vacuum displacement type electric arc furnace, carry out rolling, annealing; Making contains palladium 99.99 quality %, silicon is the sheet material of the palldium alloy 50g of 0.01 quality %, as a reference example 8.
< evaluation method >
(1. hardness)
About the sheet material of embodiment 16～25 and comparative example 5～10,, obtain its MV in three position measurement Vickers' hardnesses (Hv) of upper layer.
Again, each sheet material is cut off, three the position measurement Vickers' hardnesses (Hv) in inside are obtained its MV.Its result is as shown in table 3.
(2. rolling job evaluation)
For the sheet material of embodiment 16～25 and comparative example 5～10 and reference example 8, carry out rolling processing, visual inspection has flawless, carries out following evaluation.Its result that kind as shown in table 3.
Do not crack ... O
Crack ... X
(3. condition of surface)
Though there is not mark, about the sheet material of embodiment 16～25, comparative example 5～10 and reference example 8, the coarse state on visual observation surface, the condition of surface of each sheet material is all good, does not find the difference of embodiment and comparative example.
In embodiment 21; The ratio of palladium, boron and silicon is identical, and a kind of even other additive adds each that from Ag, Cu, Ni, select as M, Vickers' hardness does not separately have difference yet; The Vickers' hardness of upper layer is at 303Hv, and inner Vickers' hardness is 300Hv.Equally, in embodiment 8, the ratio of palladium, boron, silicon is also identical; Even other additive adds each that from Ag, Cu, Ni, select as M a kind of; Vickers' hardness does not separately have difference yet, and the Vickers' hardness of upper layer is at 308Hv, and inner Vickers' hardness is 310Hv.
In comparative example 5～7; Surface in the sheet material of palldium alloy and the inner not enough 80Hv of Vickers' hardness, the occasion of for example using as the material of the ring of ornamental has following problems: when making ring through casting; Injured easily as product, therefore not preferred.
In comparative example 8～9, have the above Vickers' hardness of 245Hv, but the amount of silicon is too much, adds in rolling to have produced crackle man-hour.
In the comparative example 10, the Vickers' hardness height is to more than the 380Hv, and the amount of silicon is too much, adds in rolling to have produced crackle man-hour.
In reference example 8, though adding man-hour, rolling do not crack, to compare with the pure palldium alloy of comparative example 5, Vickers' hardness has improved more than the 10Hv, though so, does not still expire 80Hv.
(embodiment 26)
At first; Identical with embodiment 16; With the mother alloy 4.84g (containing palladium is 4.69g, and boron is 0.15g) that makes with, mix in silicon oxide crucibles for the ratio that makes the boron in the calculating reaches the palladium 45.16g that 0.3 quality % adds, the employing centrifugal casting machine is cast; Make ring thus, as embodiment 26.
(embodiment 27)
At first, identical with embodiment 16, palladium 145.35g, boron 4.65g are placed on the cold-crucible made of copper; After the vacuum exhaust; Fuse with the electric arc furnace after the argon replaces (below, be referred to as vacuum displacement type electric arc furnace), produce the mother alloy 150g of the even composition that following palladium and boron constitutes; It contains the boron of 3.1 quality %, and it is positioned near the eutectic point of palladium and boron.
Then; With the mother alloy 11.64g (containing palladium is 11.29g, and boron is 0.35g) that makes with, mix in silicon oxide crucibles for the ratio that makes the boron in the calculating reaches the palladium 58.36g that 0.5 quality % adds, the employing centrifugal casting machine is cast; Make ring thus, as embodiment 27.
(embodiment 28)
Identical with embodiment 27; (containing palladium is 15.81g with the mother alloy 16.30g that makes; Boron is 0.49g) with, mix in silicon oxide crucibles for the ratio that makes the boron in the calculating reaches the palladium 53.70g that 0.7 quality % adds; Adopt centrifugal casting machine to cast, make ring thus, as embodiment 28.
(embodiment 29)
Identical with embodiment 27; (containing palladium is 18.06g with the mother alloy 18.62g that makes; Boron is 0.56g) with, mix in silicon oxide crucibles for the ratio that makes the boron in the calculating reaches the palladium 51.38g that 0.8 quality % adds; Adopt centrifugal casting machine to cast, make ring thus, as embodiment 29.
(embodiment 30)
Identical with embodiment 27; (containing palladium is 22.58g with the mother alloy 23.28g that makes; Boron is 0.70g) with, mix in silicon oxide crucibles for the ratio that makes the boron in the calculating reaches the palladium 46.72g that 1.0 quality % add; Adopt centrifugal casting machine to cast, make ring thus, as embodiment 30.
(comparative example 11)
Identical with embodiment 27; (containing palladium is 31.61g with the mother alloy 32.59g that makes; Boron is 0.98g) with, mix in silicon oxide crucibles for the ratio that makes the boron in the calculating reaches the palladium 37.41g that 1.4 quality % add; Adopt centrifugal casting machine to cast, make ring thus, as comparative example 11.
(comparative example 12)
Identical with embodiment 27; (containing palladium is 45.16g with the mother alloy 46.56g that makes; Boron is 1.40g) with, mix in silicon oxide crucibles for the ratio that makes the boron in the calculating reaches the palladium 23.44g that 2.0 quality % add; Adopt centrifugal casting machine to cast, make ring thus, as comparative example 12.
The boron of the reality in each ring of the foregoing description 26～30 and comparative example 11～12 and the ratio of silicon are obtained with the ICP apparatus for analyzing luminosity.Rest part is as the ratio of palladium, and its result is presented in the table 4.
< evaluation method >
(1. hardness)
About the ring of embodiment 26～30 and comparative example 11～12, three the position measurement Vickers' hardnesses (Hv) on the surface are obtained its MV.
Again, cut off each ring, three the position measurement Vickers' hardnesses (Hv) in inside are obtained its MV.Its result is as shown in table 4.
[table 4]
In comparative example 11 and comparative example 12, the surface of ring is more than the 385Hv with inner Vickers' hardness, and surface hardness is 500Hv.To in the ring of need in the type that jewel is installed on ring thereafter etc., need carry out jewel processing is installed, if hardness is too high, then can produce the problem that processing becomes difficulty.If the hardness on the surface of ring etc. is too high, then in the process of ring surface grinding, can grind the problem of difficulty again.
Again, in the ring about embodiment 26～30 and comparative example 11～12, the hardness on the surface of each ring is more than the 400Hv; High more a lot of than inner Vickers' hardness; Its reason is not also confirmed, is considered to owing to following result: the section bar of shaping ring is formed with the silica-based coverture of non-binding type, thus; The silicon (Si) that forms section bar is reduced stripping, replaces the part of boron to sneak into the surface of ring.
Claims (6)
1. the method for manufacture of a palldium alloy is characterized in that, in the method for manufacture of this palldium alloy, has: first operation; Wherein, Account for the proportion of composing that 94.5～97.6 quality %, boron account for 2.4～5.5 quality % with palladium, palladium and boron are fused with cold-crucible, make the mother alloy of evenly forming; Second operation wherein, is fused the palladium of mother alloy of making in first operation and specified amount with cold-crucible, make following palldium alloy: contain the boron in 0.03～1.40 quality % scope at least, and contain the above palladium of 95.0 quality %.
2. a palldium alloy is characterized in that, contains the boron in 0.03～1.40 quality % scope at least, and contains the above palladium of 95.0 quality %, and, contain boron equably to inside from its surface.
3. the method for manufacture of a palldium alloy is characterized in that, in the method for manufacture of this palldium alloy, has: first operation; Wherein, Account for the proportion of composing that 94.5～97.6 quality %, boron account for 2.4～5.5 quality % with palladium, palladium and boron are fused with cold-crucible, make the mother alloy of evenly forming; Second operation; Wherein, the mother alloy of making to above-mentioned first operation of major general's specified amount mixes, fuses with palladium and silicon, makes following palldium alloy: boron and silicon add up to and contain 0.04～1.0 quality %; At least contain the silicon of the scope of 0.01～0.4 quality %, and contain the above palladium of 99.0 quality %.
4. the method for manufacture of a palldium alloy is characterized in that, in the method for manufacture of this palldium alloy, has: first operation; Wherein, Account for the proportion of composing that 94.5～97.6 quality %, boron account for 2.4～5.5 quality % with palladium, palladium and boron are fused with cold-crucible, make the mother alloy of evenly forming; Second operation, wherein, the mother alloy of making to above-mentioned first operation of major general's specified amount mixes with palladium, adopt and contain SiO
2Crucible fusion, make following palldium alloy: boron adds up to silicon and contains 0.04～1.0 quality %, contains the silicon of the scope of 0.01～0.4 quality % at least, and contains the palladium more than the 99.0 quality %.
5. the method for manufacture of a palldium alloy is characterized in that, in the method for manufacture of this palldium alloy, has: first operation; Wherein, Account for the proportion of composing that 94.5～97.6 quality %, boron account for 2.4～5.5 quality % with palladium, palladium and boron are fused with cold-crucible, make the mother alloy of evenly forming; Second operation; Wherein, the casting that constitutes with the Si oxide compound with crucible in, the mother alloy of making to above-mentioned first operation of major general's specified amount mixes with palladium; Adopt the fusion of high-frequency melting stove; The casting article that manufacturing is made up of following palldium alloy: boron and silicon add up to and contain 0.04～1.0 quality %, contain the silicon of the scope of 0.01～0.4 quality % at least, and contain the above palladium of 99.0 quality %.
6. a palldium alloy is characterized in that, in this palldium alloy, boron and silicon add up to and contains 0.04～1.0 quality %, contain the silicon of the scope of 0.01～0.4 quality % at least, and contains the above palladium of 99.0 quality %.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2011046282A JP5771026B2 (en) | 2011-03-03 | 2011-03-03 | Method for producing palladium alloy |
| JP2011-046282 | 2011-03-03 | ||
| JP2011134045A JP5755514B2 (en) | 2011-06-16 | 2011-06-16 | Method for producing palladium alloy |
| JP2011-134045 | 2011-06-16 |
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| CN115927890A (en) * | 2022-12-19 | 2023-04-07 | 深圳市赛欧珠宝首饰有限公司 | Hard gold joint coating material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56123338A (en) * | 1980-03-03 | 1981-09-28 | Tanaka Kikinzoku Kogyo Kk | Electrical contact material |
| RU2132885C1 (en) * | 1995-08-08 | 1999-07-10 | Институт химии силикатов РАН | Palladium-based composition |
| US20020114725A1 (en) * | 2000-05-19 | 2002-08-22 | Miles Melvin H. | Palladium-boron alloys and methods for making and using such alloys |
| US20050230009A1 (en) * | 2000-05-19 | 2005-10-20 | Miles Melvin H | Palladium-boron alloys and methods for making and using such alloys |
| CN101906550A (en) * | 2010-07-09 | 2010-12-08 | 深圳市吉盟首饰有限公司 | Palladium alloy and production method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56123338A (en) * | 1980-03-03 | 1981-09-28 | Tanaka Kikinzoku Kogyo Kk | Electrical contact material |
| RU2132885C1 (en) * | 1995-08-08 | 1999-07-10 | Институт химии силикатов РАН | Palladium-based composition |
| US20020114725A1 (en) * | 2000-05-19 | 2002-08-22 | Miles Melvin H. | Palladium-boron alloys and methods for making and using such alloys |
| US20050230009A1 (en) * | 2000-05-19 | 2005-10-20 | Miles Melvin H | Palladium-boron alloys and methods for making and using such alloys |
| CN101906550A (en) * | 2010-07-09 | 2010-12-08 | 深圳市吉盟首饰有限公司 | Palladium alloy and production method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115927890A (en) * | 2022-12-19 | 2023-04-07 | 深圳市赛欧珠宝首饰有限公司 | Hard gold joint coating material and preparation method thereof |
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