Patent Application
20140217883
The present invention, in a first aspect thereof, relates to an improved mercury dosing composition, in a second aspect thereof to a method for mercury dosing and in a third aspect thereof to a discharge lamp containing the improved mercury dosing composition.
Fluorescent lamps require for their operation the introduction of controlled, small amounts of mercury, however, due the toxicity of mercury, the regulations and constraints on its use have become more stringent with time. This requires to adopt better and more efficient methods for its dosing, both to minimize its use and also to have safer processes to avoid unwanted and premature mercury release.
Improved methods to introduce mercury in lamps exploit the use of dispensers based on mercury compounds that are stable at relatively low temperatures but can release the mercury by means of specific thermal activation just when the lamp is sealed. In particular, the release of mercury shall be avoided in the intermediate manufacturing steps that in the case of linear fluorescent lamps production may envision heating of the mercury dispenser to 400-500° C., while in the case of circular fluorescent lamps such temperature may be up to 600-650° C.
In this regard one of the earliest solutions adopted is the one described in U.S. Pat. No. 3,657,589, in the applicant's name, which showed a composition consisting of TixZryHgz compounds. This solution, although innovative when made, showed some limits and improvements to it where made in the following years.
In particular, EP 0691670 and U.S. Pat. No. 7,674,428, both in the applicant's name, disclose improvements of the above-mentioned TixZryHgz compounds by adding copper and additional elements, namely silicon in EP 0691670, while in U.S. Pat. No. 7,674,428 the additional elements are chosen from silicon, tin and chromium. Although the solution disclosed in U.S. Pat. No. 7,674,428 achieves improvements with respect to the hazards posed by the use of mercury and mercury compounds, there is still a need to improve this characteristic.
Avoiding or minimizing to the maximum extent the mercury release in high temperature intermediate process phases, i.e. 400-500° C. and up to 650° C. such as in the case of circular fluorescent lamps, ensures that the contamination risks and environmental hazards are minimized. However, at the same time there is the need to have solutions capable to guarantee a fast and efficient release of mercury when the temperature is raised at or above a certain threshold (i.e. 800° C.) by the heating means typically adopted (usually Radio Frequency heating systems).
The purpose of the present invention is to improve the results obtained with the compounds known in the art in terms of guaranteeing a high mercury yield and at the same time minimizing the premature release of mercury, and in a first aspect consist in a mercury dosing composition consisting of titanium, copper, silicon and mercury wherein:
A mercury dosing composition according to the present invention will be also defined in the following as a composition having the correct weight ratio, as per above specification.
Also, the mercury dosing composition according to the present invention although consisting of titanium, copper, silicon and mercury, may comprise and contain traces of unavoidable impurities (for example Fe, Mn, Zn as the most common ones) whose overall cumulative contribution is not higher than half of the minimum possible level for the elements of the dispensing composition, i.e. equal to or less than 0.5 wt %.
The invention will be further illustrated with the help of the following figures where:
The inventors have found that by choosing the proper element to be added, silicon, with the Cu/Ti weight ratio in a much narrower and specific interval with respect to what is disclosed in U.S. Pat. No. 7,674,428, it is possible to obtain a high mercury yield, higher than 90% at 800° C., and at the same time an improved stability at 400-500° C., therefore enhancing the safety of the industrial processes using such compositions.
The compositions of the present invention may be made by pre-alloying all the components, with the exception of mercury, and then exposing to mercury such pre-alloyed composition as described in U.S. Pat. No. 7,674,428, or by mixing powders of titanium, copper and silicon in the correct weight ratio and then exposing them to mercury.
All the mercury dosing compositions made according to the present invention are obtained after a conditioning process for the removal of excess mercury, such as for example the process described in U.S. Pat. No. 7,674,428.
In general the conditioning process envisions heating the mercury dosing composition under vacuum. Temperatures and especially heating times may vary a lot, with temperatures that typically range from 300° C. to 500° C., while times range from 1 to 300 min. Usually shorter times are used with higher temperatures and viceversa.
In a second aspect thereof the invention consists in a method for mercury dosing by heating for at least 15 seconds at a temperature of at least 800° C. a system comprising a metallic holder and at least a deposit of a mercury dosing composition consisting of titanium, copper, silicon and mercury wherein:
The method according to the present invention is not limited to a specific form or structure of the holder, even though the use of some type of supports acting as powders holder, such as the one based on flat metallic surfaces, is particularly advantageous.
Such metallic supports are known in the technical field and represent an advantageous means to incorporate the mercury source within the fluorescent lamps; they are described, for example, in WO 97/019461 in the applicant's name and in U.S. Pat. No. 5,825,127, whose teachings are herein incorporated by reference. One advantage of the compositions according to the invention is related to the fact that the adhesion of these mercury releasing powders on the metallic support is better than that of compounds known in the prior art. This feature allows a more stress-free and reliable handling and activation of the new dispensers without problems of possible particle loss.
Another particularly advantageous holder shape for systems for carrying out the method according to the present invention is described in WO 98/053479 in the applicant's name with particular reference to the embodiment shown in
Other materials, such as getter materials for the removal of impurities, may be deposited in the holder (in the case of wire-shaped holders) or on the holder (in the case of flat supports), together with the mercury dosing composition according to the present invention.
The term “deposit” is intended in its widest conception of aggregate, meaning that the mercury dosing composition according to the present invention may be present in the form of a layer (on flat supports) or a filler (in wire-shaped holders).
Examples of suitable getter materials are for example those described in U.S. Pat. No. 3,203,901 (Zr—Al alloys), U.S. Pat. No. 4,306,887 (Zr—Fe alloys), U.S. Pat. No. 5,961,750 (Zr—Co-Rare earths alloy). For hydrogen sorption, particularly at high temperatures, it is also known to use yttrium alloys, as described in WO 2007/099575 and WO 2010/105945, or a suitable mix of different getter material powders as described in the Italian patent application number MI2011A001870 in the applicant's name. The above-mentioned getter alloys are those preferably used with the mercury dosing composition according to the present invention, but any getter alloy used in powder form may be employed with the inventive concept herein disclosed.
Concerning the temperature for the mercury release from the system containing the mercury releasing composition according to the present invention, in general it is preferred not to exceed 920° C. in order to avoid significant outgassing from the metallic part of the support that may contaminate the lamp environment or, in the case of a getter material present on the support or on another lamp part, may prematurely reduce its gas sorption capacity.
Number and arrangement of the tracks and of the fastening means for the support can vary without departing from the scope of the present invention. For example a first possible equivalent variant is shown in
Another advantageous variant with regards to the given shape of the system is shown in
The tracks of the mercury dosing composition according to the present invention and the optional tracks of the getter material can be deposited by various means onto the flat metallic surfaces of the support before giving it its final shape. One of the preferred ways to produce the support is to deposit the tracks by means of the cold rolling technique, i.e. by depositing tracks of the materials in powder form on a substrate and then by passing over a compressing roll. The support is then cut in the desired length and given its final shape. The substrate is typically made of a metallic material, for example suitable materials are nickel-plated iron, nickel-iron alloys, stainless steel.
With this technique it is particularly advantageous to have the size of the powders (to be intended as maximum transverse dimension of the powders) equal to or less than 300 μm. Such powder grain size can be easily selected by means of a simple sieving operation and the use of sieves with smaller openings enables to select particles distribution with a lower grain size.
As to the tracks width this is advantageously comprised between 1 and 10 mm, being intended as an average width since it is slightly non-uniform due to the fact that is defined by discrete particles. As to the tracks height this is advantageously less than 0.5 mm, the lowest limit being given by the height of a particle monolayer.
Another variant of the support is shown in
Another advantageous variant for a system 30 comprising the mercury dosing composition to carry out the method according to the present invention is shown in
In a third aspect thereof the invention consists in a lamp containing a system comprising a metallic holder that carries a deposit of a mercury dosing composition consisting of titanium, copper, silicon and mercury wherein:
The system may also comprise other materials, advantageously getter materials as previously defined. The support may have various shapes and forms, even though the most useful ones are those previously described.
In particular,
The invention will be further illustrated with the help of the following non-limiting example.
100 grams of a mercury dosing composition 51 according to the present invention made of 32.2 wt % Ti, 36.4 wt % Cu, 1.4 wt % Si, 30 wt % Hg are prepared according to the following process:
Then after opening of the furnace the compact body of the composition is extracted from the crucible. Finally, the mercury dosing composition is subjected to a treatment for the removal of non-binded mercury, obtaining the reported weight ratio. Such treatment consists in heating at 320° C. for 4 hours under vacuum (pressure below 1*10−3 mbar) after a long ramp-up time of about 6 hours.
The same process is used to obtain a sample of another mercury dosing composition S2 made according to the present invention and comparative samples C1, C2 and C3, whose characteristics are reported in table 1.
Samples S1 and S2 have a Cu/Ti weight ratio according to the present invention, while samples C1 and C2 are comparative examples since their Cu/Ti weight ratio is higher than 1.2; C3 is also a comparative example because its Cu/Ti weight ratio is lower than 0.95.
The five compositions are then evaluated in terms of Hg yield at 800° C. and Hg loss at 400° C. In order to measure Hg yield and Hg loss, six specimens for each composition are prepared by pressing the powders in small metallic rings. For each composition three specimens are inductively heated in a glass bulb under vacuum (pressure below 1*10−3 mbar) at 800° C. for 20 seconds after a ramp-up time of 10 seconds. The weight difference of the specimen after the applied heating process indicates the mercury release and, knowing the initial Hg content, the Hg yield is thus determined.
For the other three specimens for each composition the Hg loss is determined in the same way by weight difference: in this case the rings are heated in a glass bulb under vacuum at 400° C. for 2 minutes after a ramp-up time of 10 seconds. The sensitivity limit of the weight difference measurement technique is about 0.3% and in some cases the results of Hg loss tests are below this limit. Data of average Hg yield obtained during activation at 800° C. and of average Hg loss at 400° C. are reported in table 2.
All the samples show very good Hg yields, with the exception of C3 that has a Hg yield lower than 90%, however only the samples made according to the present invention show a Hg yield higher than 93% combined with a negligible mercury loss at 400° C.
It has to be underlined that comparative samples C1 and C2 are made according to the previously mentioned U.S. Pat. No. 7,674,428, according to example 1 with the only difference that the pre-conditioning step was milder (320° C. instead of 500° C.).
This shows that the alloys of the present invention are less dependent from the pre-conditioning step characteristic, resulting in more stable alloys, and this result is achieved without compromising the yield at 800° C.
| Number | Date | Country | Kind |
|---|---|---|---|
| MI2012A000940 | May 2012 | IT | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/IB2013/053876 | 5/13/2013 | WO | 00 | 2/20/2014 |
