CN101215662A - Tungsten alloy used for jewelry and ornamental article, and preparation method thereof - Google Patents
Tungsten alloy used for jewelry and ornamental article, and preparation method thereof Download PDFInfo
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- CN101215662A CN101215662A CNA2008100451246A CN200810045124A CN101215662A CN 101215662 A CN101215662 A CN 101215662A CN A2008100451246 A CNA2008100451246 A CN A2008100451246A CN 200810045124 A CN200810045124 A CN 200810045124A CN 101215662 A CN101215662 A CN 101215662A
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Abstract
The invention discloses a tungsten alloy for jewelry and decorations and a method for preparation. According to the weight percentages, the compositions of the invention comprise 80-94 percent of tungsten carbide, 6-16 percent of nickel, and 0-4 percent of one or more lutetium, tantalum, niobium, vanadium and strontium. The method for preparation is that the above compositions are mixed through wet milling, adding forming agent, compression molding, removing forming agent and sintering and the like according to proper proportion, and the sintering temperature is 1400-1440 DEG C. Tungsten alloy for jewelry and decorations has high hardness, strong wear resistance, black and bright color, corrosion resistance, oxidation resistance, sweat resistance and no radioactivity, is capable of contacting with human bodies without harm in zero distance, belongs to a best novel decoration material, and has wide market prospect.
Description
Technical field:
The present invention relates to hart metal product and preparation method thereof.Particularly make the hard phase with wolfram varbide, nickel is made the jewellery that are used for that metal binding agent, Chrome, tantalum, niobium, vanadium, strontium, molybdenum or their carbide are made additive. Wimet of ornaments and preparation method thereof.
Background technology:
At present most tungstenalloys all is applied in industrial, and along with people's growth in the living standard, the demand of aesthetic conceptions, the material of jewellery, ornaments develops into from precious metals such as traditional jade and gold and silver, palladium, platinum and begins to use tungsten alloy material.U.S. Pat 6928734 a kind of method for preparing annular jewellery with tungstenalloy of having reported for work.This patent disclosure by weight percentage the amount consist of: wolfram varbide 50-90; Caking agent nickel 2-10; Cobalt 1-2 and chromium carbide 0.5-3.
As seen, this patent weak point is:
At first, described ornaments only limit to annular jewellery;
Secondly, then be that the wolfram varbide lower limit is too low.If wolfram varbide accounts for 50%, the material of configuration has not reached the requirement of tungstenalloy jewellery.We know that tungsten is a kind of very hard material, and its hardness is only second to diamond.People are used for doing cutter, high abrasion resisting material.What of hard phase wolfram varbide are its hardness be decided by.The wolfram varbide weight percent reaches 94%, its hardness (HRA) 〉=93; Wolfram varbide weight percent 80%, its hardness (HRA) 〉=82 (HRC:61).Hardness reduces with the minimizing of wolfram varbide.Wolfram varbide is lower than 70%, no longer includes high rigidity, and wear resistance has also lost the characteristic of tungstenalloy jewellery;
Its three, this patent lacks the requirement that tungsten alloy material is used for ornaments.As requirement to color and luster, light, wear resistance, anti-oxidant, anticorrosive, multiple suitable jewellery material such as " artificial perspiration ", radioactivity.Promptly the selecting for use of material, proportioning, preparation etc. are lacked overall understanding, analyze and refine, to reach the material requirements of tungstenalloy ornaments.Wolfram varbide, caking agent and additive select for use erosion resistance, oxidation-resistance and " artificial perspiration's " influence etc., all lack strong data.Can not make good decoration material by United States Patent (USP);
Its four, cobalt is a kind of radioactive element that is easy to produce, and is extremely dangerous to being used for ornaments. its price also is higher than nickel.
Summary of the invention:
The objective of the invention is to provides a kind of tungsten alloy material of suitable processing ornaments for overcoming above-mentioned the deficiencies in the prior art.Jewellery after the processing, ornaments have the black full color and luster of tungsten, the gloss of bright perpetuity; Have high rigidity, crash resistance, never wornout, anticorrosive, anti-oxidant, anti-" artificial perspiration ", "dead", contact not have with people zero and injures, the jewellery of advantage such as with low cost, the tungsten alloy material and the preparation method of ornaments.
The objective of the invention is to realize by the following technical solutions:
Tungstenalloy consists of by weight percentage:
Wolfram varbide 80-94
Metal binding agent 6-16
Additive 0-4
Described caking agent is a nickel, the preferred carboxyl nickel of the classification of nickel,
Described additive is Chrome, tantalum, niobium, vanadium, strontium, molybdenum or their carbide.
The mean particle size of wolfram varbide is 0.4-1.5um.
Above-mentioned tungstenalloy preferred group by weight percentage becomes:
Wolfram varbide 85-92
Metal binding agent 6-14
Additive 1-4
Described metal binding agent is a nickel.The preferred hydroxyl nickel of the classification of nickel, mean particle size 1.0-2.5um or thinner.
Described additive Tanization Chrome is 1-3, and one or both in tantalum carbide, niobium carbide, vanadium carbide, strontium carbide, the molybdenum carbide are 0-1.
The granularity of wolfram varbide is with above-mentioned.
Above-mentioned tungstenalloy consists of by weight percentage:
Wolfram varbide 90-94
Metal binding agent 6-9
Additive 0-1
Described metal binding agent is a nickel,
Described additive is chromium carbide, tantalum carbide, niobium carbide.
The mean particle size of wolfram varbide is 0.4-1.5um.
Above-mentioned tungstenalloy most preferred group by weight percentage becomes:
Wolfram varbide 90.5
Metal is sticking by agent 8
Additive 1.5
Described metal binding agent is a nickel, the preferred hydroxyl nickel of the classification of nickel, and described additive is chromium carbide, tantalum carbide, niobium carbide.
The mean particle size of wolfram varbide is 0.4-1.5um.
The wolfram varbide technological standard that the present invention selects for use is by GB/T429-1993.Nickel is GB/T5247-1985.Or be higher than above-mentioned standard.
By the tungstenalloy of above-mentioned batching system, wolfram varbide is a principal constituent, and the grain fineness number of wolfram varbide is the essential characteristic that 0.2～1.0 μ m has guaranteed the tungsten metal: the pitch-black light of color and luster, and the hardness of tungstenalloy can reach HRA82-HRA92, and wear resistance is also higher.
The wolfram varbide that identical batching is chosen is the wolfram varbide of inferior thin → superfine nano crystal grain, and its hardness is higher, can reach HRA86-HRA93.5, wear resistance is higher.Because crystal grain is thin, ornaments grinding-polishing rear surface is finer and smoother, and brighter level and smooth, the visual impression of ornaments is more beautiful, tactile feel is better.
Be classified as follows table by WC grain degree difference in the alloy:
| Alloy is by the WC grain classification | Nanocrystal | Superfine crystal particle | Inferior close grain | Close grain | Middle crystal grain | Coarse grain |
| The grain fineness number scope, um | ＜0.2 | 0.2-0.5 | 0.5-0.8 | 0.8-1.0 | 1.0-2.0 | ＞2.0 |
The composition of tungstenalloy of the present invention is wolfram varbide, nickel, carbon Chrome. vanadium carbide, niobium carbide all are to have stable chemical properties, and be anticorrosive, resistance of oxidation is very strong, is far longer than decoration materials such as yellow gold and silver, palladium, platinum.Tungstenalloy is used for jewellery, and is importantly anticorrosive, particularly avoids " artificial perspiration ".So-called " artificial perspiration " is human body surface movement (as corrosive salt sodium-chlor, urea etc.) in fact, to the corrosion of tungstenalloy, makes that its surface smoothness fogs, variable color, loses due light and color and luster.Content by the present invention's strict control additive and caking agent can prevent " artificial perspiration " effectively, and light is brilliant forever can to make the tungstenalloy ornaments.
Cobalt is the unsettled metal of chemical, and careful usefulness can prevent injury and the tungsten corrosion of metal of radioactivity to human body effectively.
The material that the present invention selects for use all is equal to or higher than national standard, can well prevent the influence that impurity is attractive in appearance to ornaments to ornaments purity, luminance brightness and flaw.
The tungstenalloy preparation method of jewellery of the present invention, ornaments, it comprises: batching, wet-milling, drying, mix forming agent, compression molding, take off forming agent, the whole technology of sintering.Suitable with traditional CEMENTED CARBIDE PRODUCTION.The difference is that wet-milling adopted ratio of grinding media to material 5: 1, alloy ball was with diameter 6mm. wet-milling time 72-96 hour.
Sintering temperature is 1400 ℃-1440 ℃.Select different temperature for use according to different batchings.In such production process, must control:
1. the carbon content of alloy is in the C00 scope.Can not decarburization, can not carburizing.Accomplish this point, the total carbon content of wolfram varbide is selected for use suitably, generally adopts the combined carbon+forming agent residual carbon ≈ 6.13 ± 0.02 of wolfram varbide.
Oxygen level and the strict control of the oxygenation in the course of processing to various compositions.Comprise the medium moisture content in the wet-milling, the oxygenation in abrasive material time, temperature, the drying process, material deposit, take off forming agent and vacuum sintering the time vacuum tightness all want strict control oxygenation, oxygen can be captured the carbon in the alloy, and makes the alloy decarburization.
2. the grain fineness number of control alloy is evenly and thin, and wet-milling time, ratio of grinding media to material, rotating speed, sintering temperature all can directly influence the grain fineness number of alloy, also influence the luminance brightness of tungstenalloy.Except that adding the additive (niobium, vanadium, strontium, molybdenum) be no less than 0.5% (weight percent) waits, control the counting for much of wet-milling and sintering temperature well, assurance tungstenalloy grain fineness number is at 1.0um-0.2um.
3. each link in the production technique, strict control is polluted, as dust, impurity, booty cause dirtyization of product, ornaments purely be subjected to polluting, dirtyization.
By above process, make every technical indicator of tungstenalloy ornaments reach:
Hole: A00-A02 (1.0-10um; ) B00-B02 (10um-25um)
Hole: 25-75uml; 75-125um does not have;＞125um does not have.
Carbon: C00. (not decarburization, not carburizing)
Hardness: HRA86-HRA93.5
Density: 13.50～15.1g/cm
3
Magnetic: do not have or a little less than
Grain fineness number: 1.0-0.2um
The tungstenalloy jewellery that obtain, ornaments and other decoration material compare:
| Decoration material | Color and luster | Luminance brightness | Wear resistance | Permanent (antioxidant anticorrosive) | Ductility | The human body infringement | Remarks |
| Diamond | Water white transparency | Light | Good | Good | Difference | Do not have | |
| The tungsten gold | Pitch-black | Light | Good | Good | Difference | Do not have | Suitable with diamond |
| Gold | Golden yellow | Light | Difference | Difference | Good | Do not have | |
| Silver | Silver color | Bright slightly | Difference | Difference | Good | Do not have | |
| Porpezite | White | Bright slightly | Difference | Difference | Good | Do not have | |
| Platinum | White | Bright slightly | Difference | Difference | Good | Do not have |
The advantage that technical solution of the present invention is brought: 1. tungstenalloy has the permanent all suitable with diamond of unique tone, light, wear-resisting, ornaments, deserves to be called good decoration material.2. being of wide application of inexpensive this material of environmental protection .3.. can design difform ornaments according to the market requirement, make different moulds, suppress different shapes, sintering is processed into the ornaments of various forms.As jewellery, ring, ear pendant, pendant, sign (as product or logo), label, souvenir, prize, trophy etc., have extensive market prospects.
Specific embodiment:
Below with specific embodiment technical scheme of the present invention is further described.
Embodiment 1:
With the wolfram varbide 81% (wt) of 1.5um, nickel 18% (wt), surplus Tac, Nbc, through wet-milling, precipitation, drying, mix forming agent, drying, sieve, compacting, sintering (1400 ℃).Make the tungstenalloy decoration material.Hardness HRA is 85.Porosity A02, B00, C00.Grain fineness number is 0.8um, and density is 13.8g/cm
3, ground finish, after the polishing, tungsten is black shinny.Scouring on coarse cement face, wet look have fuzzy vaporific, and slight scratch is arranged, and abrasion resistance is poor slightly.Be made for the garden sheet of φ 63 * 0.6, the 1.2m level freely falls, and does not break, and crash resistance energy is preferably arranged.This material ground finish, after the polishing, on the human sweat of simulation preparation, be placed in the baking oven and keep 40 ℃, steam test (being commonly called as " artificial perspiration's test "), the deepening of ornaments luminance brightness through 48 hours human sweats.The surface is invaded to wet is vaporific, and wiping can't is washed off.Anti-" artificial perspiration " ability of this material is relatively poor.This material can be done less demanding, collides more frequent ornaments.
Embodiment 2:
With the wolfram varbide 84% (wt) of 1.2um-1.5um, hydroxyl nickel 14% (wt), surplus chromium carbide, tantalum carbide.Through wet-milling, mix glue, compacting, sintering (1410 ℃ ± 10 ℃).Make material: hardness HRA87-88, density: 14.1 ± 0.1g/ cubic centimetre, grain fineness number 0.8-0.6um, porosity A02, B00, C00.Ground finish, the polishing back is pitch-black shinny, scouring on coarse cement face, wet look is harmless.Make the garden sheet of φ 63 * 0.6,1.2 meters levels freely fall not have falls damage.Through 40 ℃, 48 hours " artificial perspiration " test does not have and corrodes.Harmless to the contact of human body zero distance through radioassay, this material has certain resistance to corrosion, and anti-preferably falling decreased and abrasion resistance.To make various ornaments and all adapt to, and ornaments effect is preferably arranged. this material is nonmagnetic, as watchband, the accuracy when watchcase does not influence.
Embodiment 3:
With 1.2um wolfram varbide 85% (wt), hydroxyl nickel 12% (wt), chromium carbide 2%, tantalum carbide, niobium carbide, molybdenum carbide 1% (wt),, mix forming agent through wet-milling, compression moulding, take off forming agent, the material that sintering (1420 ℃ ± 10 ℃) makes, hardness HRA90 ± 0.2; Density: 13.9-14.0g/cm
3Grain fineness number 0.6um, porosity A02, B00, C00.Through ground finish, after the polishing, pitch-black light, scouring on coarse cement face, wet look the slightest is harmless.Make the garden sheet of φ 63 * 0.6, the 1.2m level freely falls, and does not have and falls damage.Through 40 degrees centigrade, 48 hours " artificial perspiration " test does not have erosion.Radioassay is harmless. and this material has well anticorrosive, oxidation susceptibility and high hardness.Luminance brightness is fine, does never wornoutly, and never the various ornaments of corrosion are all fine, and this material is nonmagnetic, does not influence punctual timing as watchband, watchcase.
Embodiment 4:
With the wolfram varbide 89% (wt) of 1.5um, nickel 10% (wt), surplus is tantalum carbide, chromium carbide.Through wet-milling, mix forming agent, suppress, take off forming agent, sintering (1420 ℃) makes material hardness HRA:89.5-90; Density 14.1-14.2; Grain fineness number 0.6-0.8um; Porosity A02, B00, C00. ground finish, after the polishing, pitch-black light.In coarse cement face friction, wet look is harmless.Make the garden sheet of φ 63 * 0.6, the 1.2m natural horizontal falls, and does not have and falls damage.Through 40 ℃, 48 hours " artificial perspiration " test does not have and corrodes.No magnetic, this product can be made ornaments, sign label, souvenir, prize etc.
Embodiment 5:
With the wolfram varbide 91% (wt) of 1.2um, nickel 8% (wt), surplus is a chromium carbide.Through wet-milling, mix forming agent, suppress, take off forming agent, sintering (1430 ℃).Make material, hardness HRA92, density 14.7g/cm
3, grain fineness number 0.6um, porosity A02, B00, C00.Behind the grinding-polishing, pitch-black light.Rub on coarse cement face, light face the slightest is harmless, makes φ 63 * 0.6 garden sheets, and 1.2 levels freely fall, and fall damage.Through 48 ℃/hour " artificial perspiration " test, wet look does not have erosion.Nonmagnetic.This material has high abrasion resistance.Have more the color and luster and the light of tungstenalloy.Also have very strong anti-oxidant, erosion resistance.Nonmagnetic, but easily break into pieces.This material can be made the annulation ornaments, overcomes its anti-damage of falling with geometrical shape, also can make ornamentally, and display property ornaments have high enjoying value.
Embodiment 6:
With 1.2um wolfram varbide 93.5% (wt), nickel 6% (wt), tantalum carbide 0.5% (wt), through wet-milling, mix forming agent, compacting sintering (1440 ℃) makes material hardness HRA 93.Density: 14.9g/cm
3, grain fineness number 0.6um, porosity A04, B02, C00.Behind the grinding-polishing, pitch-black light, scouring on coarse cement face, light and corner angle the slightest are harmless, make the garden sheet of φ 63 * 0.6, and the 1.2m level freely falls, and falls damage.Through 48 hours " artificial perspiration " test, wet look has variable color, "dead".This material is to have high rigidity, high-wearing feature, has more tungstenalloy color and luster and bright characteristic, and very strong anti-oxidant, erosion resistance are arranged, and is "dead", but crash resistance is poor.This material can be made ornamental ornaments, jewelry, have the color and luster and the light of real tungstenalloy ornaments.Outward appearance can be made angular, and corner angle show fortitude clearly, and its ornaments have display, preserve. the value of souvenir.
Claims (6)
1. the tungstenalloy that is used for jewellery, ornaments is characterized in that consisting of by weight percentage:
Wolfram varbide 80-94
Metal binding agent 6-16
Additive 0-4
Described caking agent is a nickel
Described additive is road, tantalum, niobium, vanadium, strontium, molybdenum or their carbide.
2. the tungstenalloy that is used for jewellery, ornaments according to claim 1 consists of by weight percentage:
Wolfram varbide 85-92
Metal binding agent 6-14
Additive 1-4
Described metal binding agent is a nickel, and the classification of nickel is a hydroxyl nickel,
Described additive Wei Chrome, tantalum, niobium, vanadium, strontium, molybdenum or their carbide.
3. the tungstenalloy that is used for jewellery, ornaments according to claim 1 and 2 consists of by weight percentage:
Wolfram varbide 90-94
Metal binding agent 6-9
Additive 0-1
Described metal binding agent is a nickel, and the classification of nickel is a hydroxyl nickel.
Described additive is Tanization Chrome, tantalum carbide, niobium carbide.
4. the tungstenalloy that is used for jewellery, ornaments according to claim 1 consists of by weight percentage:
Wolfram varbide 90.5
Metal binding agent 8
Additive 1.5
Described metal binding agent is a nickel, and the classification of nickel is a hydroxyl nickel,
Described additive is carbonization road, tantalum carbide, niobium carbide.
5. the jewellery that are used for according to claim 1. the tungstenalloy of ornaments, the grain fineness number that it is characterized in that wolfram varbide is 0.2-1.0um.
6. tungstenalloy preparation method according to claim 1 comprises batching, wet-milling, drying, mixes forming agent, compression moulding, takes off forming agent, sintering step, and adopting ratio of grinding media to material in wet-milling is 5: 1, used alloy ball is that diameter is 6-8mm.The wet-milling time is greater than 72 hours, sintering temperature 1400-1440.
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