TW200302285A - Magnesium-zirconium alloying - Google Patents

Abstract

Zirconium sponge can be chemically depassivated by treatment with hydrofluoric acid to improve the ability of molten magnesium/magnesium alloy to dissolve zirconium from the treated zirconium sponge and to form a melt containing substantially evenly distributed particles of zirconium.

Description

200302285 发明 、 Explanation of the invention == Ming: Inventing the dirty surface field, advanced technology, content, implementation, and drawings [Technical field to which the invention belongs] Afternoon " x knife) The present invention is about adding rhenium to pure magnesium or magnesium alloy Technology, and the preparation of a magnesium-zirconium (Mg_Zr) alloy that has a delta-staggered master alloy. [Prior art] For magnesium alloys that contain trace elements such as Ming, Shi Xi, Iron, Lu, Gu, Tin, and Ship, and rhenium forms a stable compound, rhenium is a kind of = standing in this magnesium alloy 'In a 1% weight ratio, = the particle size is easily reduced at a normal cooling rate = even more. This special particle refining ability makes it an important alloying element that is not related to the alloys of the two alloys in the two Shaoxing alloys. For example, faults containing alloys such as Ε × 33 (Town_3 3 chain_2 7 Tit and ZE41 (Town-1 · 2 Baht-4.2Zinc_〇7Zirconium) will provide Zhen Er-Zinc alloys. A special combination of high temperature and room temperature properties that cannot be achieved. The solubility of 、, 鍅 in pure molten magnesium is approximately 06% °, and the melting temperature increases with a slight increase. Solubility of two percentages has been reported Wrong magnesium alloy 'has the largest feature of its microstructure. Most of the particles in the town are rich in recorded cores. This hammer-rich calibration is believed to be a solidified product. In order to achieve commercial production 'It has excellent particle refining effect', so we hope to dissolve all the miscible content (ie, about 0.6%) in the magnesium melt. [Also, for decades, various miscibility has been introduced into the melting, among which Includes: J Wanzai Yumu (a) alloyed with different forms of hafnium metal; (b) alloyed with zirconium metal wool; v Continued pages ((Send bribes to make ends meet, please note and use continuation pages) ) 200302285 Description of Invention Continued (C) Alloying with Zinc-Material Alloy; (d) Alloying with Oxidation Hammer; (e) and Each Alloying zirconium, compound, or compound and / or compound with different salts such as sodium chloride, potassium chloride, barium chloride, sodium fluoride, potassium fluoride, etc .; and (f) Alloying with a magnesium-zirconium master alloy. The advantages and disadvantages of the above-mentioned tin technology have been developed by Mr. WP Saunders and Mr. F. P. Strieter at the American Foundrymen's Society, 60, 1952, pp. 581-594. The "Alloying Zirconium to Magnesium" report and the "Principles of Magnesium Technology" quoted by Mr. E. F. Emley, Oxford Pergamon Publication, 1966, pp. 127-155 — have been discussed in detail. Since about 1960, Only the magnesium-wrong master alloy has been widely used commercially as a source of zirconium metal alloyed with magnesium. This zirconium-rich magnesium-zirconium master alloy is based on some fluorinated hammers or zirconium chloride. It is made by chemical reduction reaction of magnesium salt mixture. The two types of master alloys are essentially the same and contain one third of the weight ratio. Among them, Magnesium Elektron Corporation (MEL) The technology developed for the chemical reduction reaction of zirconium fluoride and molten magnesium has been known as Zirmax (trade name). The same type of magnesium-hammer master alloy was developed in the reduction process based on the chloride salt, which was developed in the United States .

Zirmax-type master alloys are still the primary alloys used in the commercial production of junction-containing ballast alloys. Zirmax contains about 33% magnesium and 67% magnesium, and most of them are hammer particles of various sizes (most of them are in the range of 200200285 Invention _ Continued from the range of microns to 10 # m) in the magnesium matrix. . Before Zirmax-type master alloys became the standard source of zirconium for ytterbium-containing magnesium alloys, alloying with various forms of mismatch metals has been studied.

Sauerwald published the alloying of zirconium metal powder and magnesium in 1947 (V · F · Sauerwald, " Dus Zustandsdiagram Magnesium-Zirkonnium 丨 ', Zeitschrift for anorganische Chemie ·, 1947, Vol. 255, pages 212_220), He added 5wt% zirconium metal powder to magnesium at various temperatures between 680 and 1100 ° C and an argon atmosphere. Soluble content of more than 0.5% by weight (sample decomposed in hydrochloric acid) was obtained at all temperatures tested. In the same year, a report published by Mr. J.P. Ball in 1947 " Metallurgia ", Vol. 35, pp. 125-129, and 211, stated that" the state of the metal is distorted in an argon atmosphere at 900-1100 ° C. Dissolved in magnesium, but this is a difficult and expensive procedure. Operating at this temperature is not commercially viable because of the vaporization of magnesium. Mr. EF Emley in 1948 in `` Discussions of the Faraday Society, '' A report published in Vol. 47, No. 4, p. 219 states that because hammer metal powders are expensive and highly flammable, it is natural to consider the possibility of alloying with reducible wrong compounds. Saunders, 1952 In the research published by Mr. and Mr. Strieter, different forms of metal rhenium (ie, hammer metal wool, molten zirconium, iodide-decomposable ductile zirconium, and zirconium powder) were used with rhenium at 760 ° C. (1400 ° F) alloyed materials were studied. This melted block was distorted, and it was added to a small steel barrel with 6.35 mm (1/4 pair) pieces, and a steel rod Stirring. After stirring for 30 minutes, there is no obvious dissolution. 200302285 Invented. Analyze the dissolved material, the result shows that the content of soluble error is 0.03% when 1% is added. 6.35mm (1/4 hour) small pieces, add its plate similar to the way used in the molten block hammer. Stir in a bucket for several minutes. After holding at this temperature for 65 minutes, add 1% 鍅 when it is The soluble content is only 0.1%. The powder is evaluated in a variety of ways: Yes, because the powder is self-igniting, and some method must be applied to protect the powder from oxidation. The powder is based on Various binders are used to make ingot pellets, zirconium powder is sealed in a tight magnesium capsule, hafnium powder is tightly combined with magnesium powder, and zirconium powder is used in the form of sintered zirconium powder compacts. % Hammer added to a magnesium_5 zinc melt, the hafnium content indicated in the literature varies between 0.7 to 0.85%. The solubility of zirconium in magnesium will be affected by the presence of a third element. Some reports indicate that In the presence of 3-4% zinc, the solubility of zirconium in magnesium can be from 0.6% Increased to slightly more than 0.7%, and 5% of the word can increase the solubility of the wrong in magnesium to about 0. 8%. According to the report of Mr. Saunders and Mr. Strieter, test hammers of various metal forms, and hammer metal wool. Alloying shows the best results. The metal wool used is produced by the Kr0U program. (A) The four gaseous samarium system acts on the oxidizing hammer by chlorine and carbon, such as vermiculite (Zircon). (ZrSi04) Baddeleyite (Zr02) Zr02 + 2C12 + 2C (900. . ) -► ZrCl4 + 2CO, or

ZrSi04 + 4Cl2 + 4C (900 ° C) -► ZrCl4 + SiCl4 + 4CO; (b) The generated tetragas tritium is produced by fractional distillation with iron trichloride (from iron impurities) and silicon tetrachloride (If present) separately; and 200302285 Description of the invention $ 卖 页 (C) The purified zirconium tetrachloride is reduced by reaction with molten magnesium under argon to produce "zirconium metal wool"

ZrCl4 + 2Mg (1100 ° Zr + 2MgCl2. In the above experiment, the metal wool was basically ground to reduce the average size to about 12.7 μm or 0.0005 inch. The results show that the addition of 3 to the magnesium-5 alloy % Zirconium, and after stirring for 3-4 minutes, the zirconium metal wool produces soluble zirconium with a content of about 0.62 to 0.66%. When 1% rhenium metal wool is added, the soluble hafnium content can reach the range of 0.32 to 0.52%. In addition, the author of the above report found that as the size of the metal wool fragments shrinks, the alloying efficiency will decrease, because when the particles become a finer powder, the material will burn out before immersing in the melt. Therefore, it is bound to Some protection methods are used to keep the powder from being oxidized. Although Saunders and Mr. Strieter showed excellent alloying results with zirconium metal wool by the Kroll procedure, the alloying of stuttered metal and magnesium is still largely limited to experiments The size of the room. As Mr. Saunders and Mr. Strieter understand and point out, "In the magnesium alloying industry, an important disadvantage of the commercial use of metal wool is that it requires considerable labor to alloy this material." Because the alloying process, that is, 3-4 minutes of stirring, is obviously very simple, the labor demand is obviously related to its grinding process. In addition, the inevitable pollution problem caused by the grinding process is Another important disadvantage of commercial use of zirconium metal wool. In the Principles of Magnesium Technology article, Mr. Emley made a similar comment on the alloying of zirconium metal with magnesium, "No 200302285

The pure wrong metal obtained by any method is very responsible, and its powder form is very flammable, and it is easily contaminated by oxygen, hydrogen, and nitrogen. For these reasons, the zirconium metal method is obviously not the best one. Some experiments have pointed out that in the commercial production of magnesium alloys, when Zirmax is dissolved in a magnesium melt at a commercially available addition rate, some undissolved can be easily observed in the microstructure of the magnesium alloy produced: Wrong particles (see Ma Qian, L. Zheng, D Graham, D j

"SetUing 〇f undissolved zirconium particles in pure, magnesium melts" by Journal of Mr. St John and M. T. Frost, etc., Journal of Light Metals, 2001, Vol. 3, No. 3, pp. 157-165 and Y. Tamura, Ν · κ_ ， τ Μ〇 ^ _ e

Sato et al. &Quot; Grain refining ___ _ casting structure of Mg-Zr alloys-, j〇urnal 〇f Japan

Institute of Light Metals, 1998, Vol. 48, No. 4, p. 185_189). Many of these residual (undissolved) wrong particles have an average size of about 5 μm. The density of zirconium is 6.5 g / cm3, and the density of molten magnesium is 16 g / cm3. Therefore, unless vigorously stirred, zirconium particles will have a strong tendency to settle in the magnesium melt. The larger the particles, the faster the sedimentation speed to the bottom of the melt. For example, 15 μηι of zirconium particles at 7 80 C will precipitate to the bottom of the ballast at a rate of about 40 mm / min, so it is difficult to maintain these particles suspended in the melt at this temperature. status. In contrast, when its particle size is less than 3 µm, it can be easily suspended in a magnesium melt at the same temperature. π 200302285 __Explanation continued

The Chambers Science and Technology Dictionary (1991) defines " passivity " as a " metal or mineral surface that does not respond to chemical attack, even with clean, newly exposed surfaces. Because of various factors, including aging, Oxidation or pollution caused by insoluble film, etc., the surface energy at the discontinuous lattice becomes lower; the thin layer of adsorption · _ ,. Throughout the specification, the term "depassivate (depassivate wide," "Depassivated", and "heart-to-heart, heart-to-heart (depassivation), should be understood as having the meaning derived from the aforementioned definition of" passivity, "(bluntness). Spring [Abstract] Article In one aspect, the present invention provides a method for processing hafnium metal, which method comprises chemically depassivating zirconium metal. The zirconium metal is preferably a zirconium metal wool formed by the above-mentioned method related to the treated hafnium metal. This zirconium metal wool can be chemically depassivated by treatment with a fluoride ion source. The fluoride ion source can be hydrofluoric acid. This fluoride ion source can be hydrofluoric acid and Mixture of nitric acid. The above-mentioned hydrofluoric acid, the preferred concentration is between 0.10% and 500%, more preferably between 0.50% and 5.0%, and most preferably between Between 2 5% and 2.5%, the calculation of this acid concentration will be described later in this manual. This acid concentration range is equivalent to 0.05-5 mol concentration, ^ • 25-2.63 mol concentration, respectively. And 〇.76_128 Molar concentration, the range of vocational ear concentration &, can be regarded as 005_500 Molar concentration, 0.25_3 Molar concentration and 0.75-1.5 Molar concentration. Also in the first aspect In the present invention, a square 12 for treating zirconium metal is provided.

Invention I ---- Method This method involves the treatment of wrong metal wool with a solution containing fluorine ions to form a treated wrong metal brocade. Said rhenium metal is preferably porous agglomerates of wrong particles. The metal wool is preferably formed by the Kroll procedure. This metal bond preferably contains only faults with inseparable impurities. Giving is a common impurity in mistakes. Relatively speaking, iron, iron, metal, stone, carbon, and iron: tin and copper are undesirable, because these will inhibit alloying, and their total concentration is preferably less than 1%. Less than 5%. Preferably, the knotted metal wool is in the form of small particles and has a polymorphic structure. Although the material has the following properties:-The average size of these particles is between G1 and 10 mm, and more preferably between 0.5 and 5 mm;-the minimum wealth of these females is w, Qiqi imm, and its maximum size is 10mm, more preferably 5mm;-Density of metal wool = 5.2_6.3 g / cm3 'better is 5.5-5.8 fine 3 ❿ Porosity of metal 4 (L metal wool density / Density of solid faults) = 0.08 ~ 0.2, more preferably 0.11-0.15; -The size of the gap above the polished cross section of each-wrong metal wool particles is generally between 5 and 60 // m. In the third aspect, the present invention provides a method for processing a metal complex, which is prepared according to the first or second aspect of the present invention. When compared to untreated (as obtained) metal wool, the metal wool treated according to the present invention has been found to improve the molten state 13 200302285

Magnesium / magnesium gold / gut error-solving ability is formed in the melt of large particles. In the above 3 samples of zirconium particles with uniform distribution, the present invention provides a wrong metal wool, which contains the wrong ', and has at least a part coated on at least one of the particles, and the service The gaseous compound is preferably a compound having a gasification complex &quot; Chemical formula may be ZrxFy.nH20. In the fifth aspect, the present invention proposes a method. There are four kinds of domain master alloys in the branch ω: = the wrong metal wool treated in the third aspect of the invention, or according to the author: The mixed metal wool 'is mixed with the molten ballast / ballast alloy to form a ballast dissolving material containing dissolved particles and malocclusions; and (b) the ballast material is solidified and cast into ballast. Master alloy. Metallographic ΓΓ 疋 This metal wool is a sample towel made by mixing with _ molten magnesium / magnesium by searching and mixing. The present invention provides a fifth aspect according to the present invention. Spoon = gold. Among the magnesium alloys, the master alloy is preferably a tr5 t% hammer, and even more preferably contains a %% error. The mystery is that at least 90% of the wrong particles in gold have a size smaller than _㈣ and smaller than 3 _. Its average particle size is up to 5 μηι 〇 帛. Sample invention provides-a kind of magnesium alloy containing dissolved dislocations and wrong particles &quot; 'and substantially free of dentate inclusions, straight middle, 90%, its size is less than one, more preferably two: :. 14 200302285 Preferably, the parent alloy is cast into an ingot, which term should be understood to include bdqUette, peUet, and the like. In an eighth aspect, the present invention provides a method for adding a hammer to a molten magnesium / magnesium alloy as an alloyed vanillin, the method comprising treating the wrong metal wool processed according to the third aspect of the present invention, or According to a fourth aspect of the present invention, the metal wool is mixed with the magnesium / magnesium alloy described above. In a ninth aspect, the present invention provides a method for adding zirconium as an alloying element to a hafnium magnesium / ballast alloy, the method comprising adding a magnesium hafnium master alloy according to the seventh or seventh feature of the present invention, Mix with molten ore / ballast alloy as described above. Preferably, the amount of zirconium added to the axial lock / money alloy at the temperature of the molten material is greater than the amount of zirconium required to saturate the magnesium / magnesium alloy. In a tenth aspect, the present invention provides a magnesium alloy containing zirconium, which is prepared according to the method of the eighth or ninth aspect of the present invention. In order that the present invention may be more fully understood, reference will be made to the exemplified drawings mentioned below, which are merely examples to illustrate preferred embodiments of the present invention and other elements. [Embodiment] Comparative test The untreated (as obtained) hammer metal wool is selected from cool metal wool particles with a solid shape of only 1-10 mm. The main impurity in this metal wool is 给. Its impurity concentration is: 铪 (hydrofluoric acid) = 0.8% (approximate value) iron (Fe) + chromium (Cr) = 0.1% 200302285 carbon (C) = 0.004% hydrogen (H) = 0.00 1% nitrogen (N ) = 0.002% and added to molten magnesium samples at 7300 and 780 ° C under the treatment.扃 Collect cone-shaped samples (ρ30χρ 20x25 mm) at different times and inspect the agency Mo Nengyi. ",,, 0 fruit", and even if the melt is kept at 780 C for 2 to 6 hours, there is almost no sign of particle refinement (see the first and second graphs). Use 15% hydrochloric acid The wet-chemical analysis of the samples with soluble fault content showed a very small amount of fault content (&lt; 0.05%). The treated hammer metal wool _ _ will be the same zirconium metal used in the comparative test Cotton, first immersed in an acidic solution, the preparation method of this acidic solution is as follows: 45ml of concentrated hydrofluoric acid (68 · 5% _69 · 5%) and "M concentrated nitric acid (50%), and diluted with water to form a total The volume is 100m. This will produce an acidic solution containing approximately 3% and 2% hydrofluoric acid which is approximately equal to 1.1 moles of hydrofluoric acid and 0.5 moles of nitric acid. The stiff metal wool was left in this acidic solution for 5 minutes. Observation of bubbling indicates that the acid solution may have at least partially removed the hafnium oxide layer and is dissolving some zirconium metal beneath it. After the zirconium metal wool was removed from the acidic solution, it was washed with ethanol, and the temperature was about 50. Dry under the heat lamp of 〇. Water was also found to be a suitable cleaning agent. Treated wrong metal used in the alloy as described in Figures 4-5. 16 200302285 The preparation was made by immersing the same wrong metal weft as used in the comparative test: immersed in a hydrofluoric acid solution for up to 5 minutes , Then washed with water and dried. The hydrofluoric acid solution was diluted with 45 ml of concentrated hydrofluoric acid (鄕) and water to a total volume of 1000 ml to produce approximately 225% hydrofluoric acid, which is approximately equal to 1 mole of hydrogen. Fluoric acid. Another successfully used acidic solution is 0.07_0.25% hydrofluoric acid. This is a very dilute solution of hydrofluoric acid and is easy to handle. The treated wrong metal wire was immersed in a 2% hydrofluoric acid solution for 4 minutes by immersing the same wrong metal wool 'used in the comparative test, then washed with water and dried. The processed reaction product is the white phase above the metal wool particles in Figure 16. Although the success of the above treatment is considered to involve the dissolution of the oxide from the wrong surface or some physical removal of the oxide, we do not wish to be limited by any theory of how such treatment is effective. The χρ8 analysis of the treated and untreated metal wool particles is shown in Table-. Difficulty lies in the place, soaked in hydrofluoric acid for 4 minutes, washed with water and dried. For each of the listed analyses, the φ-lean signal was collected at a depth of 5 nm or 10 atomic layers above the surface of six different large particles. According to the energy levels measured per-element debt, in the three cases studied, oxygen exists in the form of KK) 2, and the fluorine detected in the treated particles is in the form of ZrxFy. ΗΗ2〇 Exist, such as ZrF4. It has been observed in all experiments that the weight of metal brocade particles decreases with increasing treatment time in acidic solutions, until all 17 200302285 Panming · Explanation Continuation Sheets disappear, or fluoric acid is depleted . Although we do not want to be bound by any theory, the reaction mechanism of the currently thought of tadpole is that this treatment allows the oxide film on each metal wool particle to be partially or completely removed, and on these particles To form a continuous or discontinuous reaction product layer (possibly ZrxFy · nH20). As these metal brocade particles form ZrxFy · ηΗ20 fragments or coatings, the oxidation of zirconium under the fragments or coatings can be avoided after treatment. . These fragments are thought to dissolve into the molten magnesium as described above, leaving a portion of the hafnium surface exposed to the molten magnesium, thereby providing a fresh contact location to the molten town. BSE imaging has revealed that there are many very small channels in each metal wool particle, which can provide an explanation of the dispersion of these metal wool particles. The reaction mechanism suggested above is only for a possible explanation of the above experimental results', and there may be other reaction mechanisms among them. The invention may be incorporated but should not be viewed as being limited to the reaction mechanisms described above. Magnesium-rhenium alloy f is borrowed from a small piece of magnesium ingot to make a hole, and the required processed metal-bonded piece is placed in the hole as shown in the ninth figure. This ingot was then quickly immersed under the surface of the magnesium melt. This allows the treated zirconium metal wool to be guided directly into the melt without the possibility of staying on the surface of the melt. This solution can prevent the treated metal wool from being trapped in the dross, and avoid the treated metal wool from being wetted by the molten material. The metal wool can be added to the melt in a variety of other ways, such as by adding a compacted metal wool particle, as long as it can be successfully guided below its surface. 200302285 Alternatively, the zirconium metal wool particles were found to be directly added to the above-mentioned solvent in some cases. An example is if the surface of the above-mentioned magnesium melt is protected by a covering gas such as 1% sulfur hexafluoride (SF6) (the rest is: 49.5% carbon dioxide and 49.5% dry air), so the magnesium melt is above the surface The oxygen concentration is very low, and the metal wool particles can be successfully added directly, as long as it is completed quickly. For example, the zirconium metal wool particles can be added through a steel funnel at a height of 800 mm from the surface of the melt, and the bottom of the funnel is positioned just above the surface of the melt. This allows the metal wool particles to quickly enter the melt without being oxidized. This has proven to be a very convenient method for adding small (<5mm) metal wool particles to magnesium frit. After adding 1% by weight of the treated zirconium metal wool, the melt was left for several minutes, reheated to the correct temperature, and then stirred for 30 minutes. Three temperatures were used: 680 ° C, 730 ° C, and 800 ° C. After adding the treated zirconium metal wool, conical samples were collected at different times. The third to fifth figures show typical views of the particle structure obtained from the above three experiments. The results of the wet chemical analysis are summarized in Table 2, which lists the results of the wet chemical analysis of the soluble zirconium content sampled from the three alloying tests. As you can see, after 30 minutes of stirring, the soluble zirconium content reached 0.56% at 730 ° C and 800 ° C. This value is very close to the limit of the solubility of zirconium in molten pure magnesium, i.e. 0-6 wt%. Soluble miscibility achieved by adding the same amount of faults from the Zirmax master alloy in the literature report 200302285 Description of the invention Continuation pages, usually less than 0.5%, typically around 0.4% at 720 ° C_ See γ

By Tamura, Mr. Kono, Mr. Motegi and Mr. Sato, &quot; Grain refining mechanism and casting structure of

Mg-Zr alloys \ Journal of Japan Institute of Light Metals, 1998, Vol. 48 No. 4 pp. 185-189. Compared to using

The Zirmax master alloy, using pre-treated zirconium metal wool, shows better recovery. Stabilized hafnium treated with zirconium metal brocade

A 0.4% hydrofluoric acid solution was prepared by adding 40 ml of 10% hydrofluoric acid to 960 ml of water. Using the same hammer metal wool as in the comparative test, it was immersed in 0.4% hydrofluoric acid for 5 minutes at room temperature, then washed in water and dried. Store the dried zirconium metal wool in a plastic bag. 'After four weeks of storage, 300 g of treated metal wool particles were added to 30 kg of pure magnesium at 680 ° C and stirred. After 30 minutes of stirring and 60 minutes of stirring, add the treated

Before the zirconium metal wool particles, some samples of cold-cast rods (25mm diameter) were cast. After 30 minutes of stirring, a very good level of difficulty can be achieved. Its solubility and total # content were 0.38% and 0.069% after 3 G minutes of rhenium, respectively, and after 60 minutes of stirring, it was increased by 0.42% and 0.8% by 〇. The preparation will be a total of 50g and the size range is about "Working Process Shot 20 200302285 Description of the invention / continued sheet metal wool particles, added to 550g magnesium melt at 730 ° C. The nominal amount of 鍅 is about 25wt %. These rhenium particles are added in two batches. It is continuously stirred during the entire alloying process. After 60 minutes of stirring, the melt is cast into a steel ingot mold. The seventh and eighth figures show the treated A typical view of the microstructure of the zirconium metal wool. Due to the gradual dissolution of its porous structure, each hammer metal wool particle will eventually be dispersed into many fine particles with a size of about 2-3 // m. Maintaining mild agitation from beginning to end can strengthen the suspension of fine hammer particles in the above-mentioned melt. The magnesium-zirconium frit produced as described above can be cast into different molds, preferably into cold-cast molds. Unless the mold used has excellent cooling effect As a result, the height of each ingot is preferably not more than 500 mm. Where possible, a washing and casting temperature of 680 ° C or lower is preferred. During the casting, a covering gas should be used. Figures 10 and 11 show typical views of the microstructure of an ingot produced by adding a 25% cone as described above. The white phase is the zirconium particles. Figures 12 and 13 show typical views of the Zirmax master alloy of MEL As you can see, the zirconium particles that appear in the master alloy of the present invention are generally smaller than those that appear in Zirmax. As discussed earlier, small hammer particles are always more advantageous. By treating 440g at 700 ° C, The zirconium metal wool particles were added to 440 g of molten magnesium, and slowly manually stirred for 90 minutes to prepare a magnesium hammer master alloy containing about 50 wt% of zirconium. Figures 14 and 15 are cast when the stirring is completed A typical view of the microstructure of Chengzhi's ingot, where the gray particles are wrong and the white phase is the town. 21 200302285 Description Continued The preparation of a magnesium-zirconium alloy from a magnesium-zirconium master alloy at 730 ° C will contain about 25% by weight Zirconium Magnesium Zirconium Master Alloy (prepared according to the present invention Add to a crucible containing 30kg of molten magnesium. Before adding the master alloy to the crucible, preheat it to about 175 ° C, and add sufficient master alloy to generate about 1wt% zirconium. After the addition of the master alloy, the melt was mixed with a mechanical stirrer at 150 rpm for 5 minutes. After that, the melt was allowed to stand for 15 minutes, and then a 30 mm thick mold was cast at 730 ° C with a sand mold. Plate sample (160mm x 140mm). Before adding the master alloy, a pure magnesium plate sample was also cast with a sand mold at 730 ° C. The average particle size of this pure magnesium plate sample was approximately 10,000 / / m. After alloying with the master alloy, the resulting plate samples had an average particle size of 98 // m, a soluble hafnium content of 0.49%, and a total zirconium content of 0.58%. It should be understood that the words &quot; comprise "(inclusive) and other Wncomprisesn * &quot; comprising" variants used in this description, unless the context requires otherwise, are intended to implicitly incorporate a stated Characteristics, but does not exclude the existence of other characteristics. Any reference in this specification to prior art is not, and should not be taken as, an acknowledgement or any form of suggestion that such prior art forms part of the common sense in Australia or elsewhere. 22 200302285 Description of the invention [Simplified description of the drawings] Figure-Figure ⑷-⑷ is a photomicrograph of the particle refining ability of 纟 78 (TC, the obtained and untreated metal wool, when added to pure magnesium. III The micrographs are all at the same magnification. The first picture is pure magnesium, the first picture (b) is manually added for 3G minutes after adding iwt% untreated wrong metal wool, and the first picture is added again. lwt% untreated wrong metal wool, and then manually stirred for 30 minutes. The first picture (aHc) is the obtained and untreated zirconium metal wool at 780 艽. Photomicrograph of the ability. The three photomicrographs have the same magnification as in the first picture (aHc). The second picture (a) is pure magnesium, and the second picture (b) is 1% added without correction. After processing the wrong metal wool, it was manually stirred for 2 minutes and held at 7 ° C for 30 minutes, and the second picture (c) is after 210 minutes at 78 ° C. Second pictures (a)-(c) It is a photomicrograph of the particle refining ability of the rubidium metal sponge treated by the present invention when added to pure magnesium at 68 °. (Three microphotographs The same magnifications are used for each of the images described above. The third image (a) is pure magnesium, and the second image (b) is after adding iwt% treated zirconium metal wool, and then manually stirred for 20 minutes, and the first The third image (c) is after manual stirring for another 10 minutes. The fourth image OHc) is a photomicrograph of the particle refining ability of the samarium metal, and the name ', which have been treated by the present invention at 730 ° C when added to the pure town. Two photomicrographs, with the same magnification as the previous figures. 23 200302285 Instructions for Posting S Continuation The fourth picture (a) is pure magnesium, and the fourth picture (b) is added with lwt% treated metal wool. After 30 minutes of manual stirring, and the fourth figure (c) is after 2 minutes of manual stirring. The fifth figure (a) e (c) shows that at 800 ° C, the treated zirconium metal wool is added to pure Photomicrograph of the particle refining ability of the town. The three photomicrographs are the same magnifications as the previous images. The fifth image (&amp;) is pure and the fifth image (b) is the addition of lwt% The treated metal wool is manually stirred for 30 minutes, and the fifth figure (c) is manually stirred for another 2 minutes. The sixth figure is one of the present invention. Photograph of the physical form of the untreated (as obtained) hammer metal wool particles used in the examples. The seventh figure is a typical microstructure of the zirconium metal wool particles as shown in the sixth figure after treatment according to the present invention. A photomicrograph of the view. Figure 8 is a photomicrograph of another microstructure view of the hafnium metal wool particles shown in Figure 6 after treatment according to the present invention. Figure 9 is a treated zirconium metal sponge. The schematic diagram of the method to the molten magnesium. The tenth figure is a typical view of the microstructure of the ingot of the master alloy produced according to the present invention. The eleventh figure is the development of the ingot of the master alloy produced according to the present invention Typical view of microstructure. Figure 12 is a typical view of a commercially available Zirmax master alloy. Brother Twelve is a typical view of a commercially available Zirmax master alloy. The fourteenth figure is a typical view of the microstructure of the master alloy produced in accordance with the present invention. Fig. 15 is a typical view of the microstructure of an ingot of a master alloy produced according to the present invention. Figure 16 is a photomicrograph of the reaction product remaining on the zirconium metal wool particles after the treatment according to the present invention.

25 200302285 Pickup, diagrammatic symbol description 1. Table block 2. Pin metal wool 200302285 Table 1. XPS analysis of treated and untreated metal wool particles Surface composition of carbon brocade particles in atomic percentage (carbon) C) Oxygen (〇) Zirconium (Zr) Iron (Fe) Silicon (Si) Fluorine (F) Chlorine (C1) Magnesium (Mg) Thorium (Hf) Untreated 30.5 49.2 16.2 1.1 3.0 0 0 0 0 Treated particles (Black) 10.3 43.3 14.9 1.3 2.3 27.8 0 0 0 Treated particles (gray) 26.0 41.1 15.6 1.1 1.7 27.4 0 0 200302285 Table 2. Wet chemical analysis of soluble and total error content of the sample (%) Alloying Temperature 680 ° C lwt% metal wool added 730 ° C lwt% metal wool added 800 ° C lwt% metal wool added soluble $ Total amount ** Total soluble amount Total soluble amount before adding <0.005 &lt; 0.005 &lt; 0.005 &lt; 0.005 &lt; 0.005 &lt; 0.005 Stir for 30 minutes 0.48 0.93 0.56 0.76 0.54 0.92 Hold for 30 minutes 0.56 0.85 0.56 0.66 Stir for another 2 minutes 0.56 0.97 0.57 0.74 * Soluble: 15% hydrochloric acid ** total : 50% hydrochloric acid plus 6% hydrofluoric acid

Claims (1)

200302285 Scope of Patent Application 1 · A method for treating zirconium metal, the method includes chemically depurifying the wrong metal. 2-A method for treating hafnium metal, which method comprises chemically depassivating the hammer metal wool to form a treated hammer metal wool. 3. The method for treating zirconium metal as described in item 2 of the scope of patent application, wherein the hammer metal sponge is chemically depurated by treatment with a fluoride ion source. 4. The method for treating thallium metal as described in item 3 of the scope of patent application, wherein the fluoride ion source is an acidified solution containing fluoride ions. 5. The method for treating zirconium metal according to item 3 of the scope of patent application, wherein the fluoride ion source is hydrofluoric acid. 6. A method for treating a hafnium metal wool, the method comprising treating the zirconium metal wool with a solution containing fluorine ions to form a treated zirconium metal wool. 7. A treated zirconium metal wool prepared by a method as described in any one of claims 2 to 6 of the scope of patent application. 8. A zirconium metal wool comprising agglomerates of hafnium particles and a surface layer of a fluorine-containing compound at least partially coated on at least some of the particles. 9. The zirconium metal wool according to item 8 of the scope of patent application, wherein the fluoride-containing compound comprises a fluorinated compound. 10. The zirconium metal wool according to item 9 of the scope of the patent application, wherein the chemical formula of the fluoride-containing compound is ZrxFy · nH20. 1 L A method for manufacturing a magnesium-zirconium master alloy, the method comprising the following steps: (a) treating the rhenium metal wool as described in the scope of patent application item 7 or any of the scope of patent application items 8-10 The zirconium metal wool described in item 1 is mixed with molten magnesium / magnesium alloy to form a magnesium-zirconium frit containing dissolved zirconium and zirconium particles; (Please note and use continuation pages) Rhenium casting blue rectifier material, so that Rhenium into a secret mother alloy. _ ° The magnesium-zirconium master alloy produced by the method for manufacturing a staggered master alloy as described in item 11 of the Stomach Patent. It is stated that the magnesium alloy described in item 12 of the patent patent, which contains 10-50% by weight of the fault. The ship mother alloy described in item 12 of the patent π patent rail enclosure contains 20-40% zirconium by weight. Apply for &quot; Monthly Patent | &amp; around the 12th and 14th any-item of the mismatched master alloy, 90% of the wrong particles, its size is less than 5 mm. 16. A magnesium-zirconium master alloy 'comprising dissolved dissociated and disproportionate particles and substantially free of dentate inclusions, and 90% of the disproportioned particles are smaller than 5 #m in size. 17. The masterbatch alloy as described in Patent Application No. 12 &lt; 16, wherein 90% of the zirconium particles are smaller in size. A method for adding gadolinium to a molten magnesium / magnesium alloy as an alloying element, the method comprising: treating the wrong metal, cotton as described in Application No. 7 or the scope of patent application; ] The zirconium metal wool according to any one of the items, mixed with the molten magnesium / magnesium alloy. 19 · —A method for adding a wrong alloy as an alloying element to a smelting long-term alloy, the method includes adding a magnesium-zirconium master alloy as described in item 12-17 of the patent application scope to the molten magnesium / magnesium alloy mixing. 20. An error-containing magnesium alloy prepared by a method as described in item 18 or item 19 of the scope of patent application. 27