# Patent

## Title
Ceramic-coated tungsten powder

## Abstract

The coating the tungsten powder particles with a ceramic barrier suppresses the leachability of tungsten in aqueous media. Preferably, the ceramic coating substantially encapsulates each particle of tungsten and has a thickness of at least about 30 nm and, more preferable, from about 200 nm to about 500 nm. Examples of ceramic coatings that may be used include, but are not limited to, aluminum oxide (alumina), aluminum oxyhydroxide (AlOOH), zirconium oxide (zirconia), cerium oxide (ceria), hafnium oxide (hafnia), and magnesium oxide (magnesia).

## Background
CROSS REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Application No. 60/593,534, filed Jan. 24, 2005.


BACKGROUND OF THE INVENTION
The use of tungsten powder or pressed tungsten powder compacts in pure or mixtures with other powders under natural conditions in the presence of water and oxygen (e.g., air or dissolved oxygen) leads to the formation of a water-soluble, tungsten-containing species. The first step of the reaction can be described as follows:

W+H2O+1.5O2-->WO42−+2H+.

The monotungstate ion, WO42−, reacts with H+, resulting in the formation of the soluble metatungstate anion [H2W12O40]6−:

12WO42−+18H+-->[H2W12O40]6−+8H2O.

The formation of this polyoxometalate anion is detectable by its typical UV absorption maximum at 256 nm (molar extinction coefficient, ε256=3.8×104 L(mol·cm)−1).
SUMMARY OF THE INVENTION
By coating the tungsten powder particles with a ceramic barrier such as alumina, the leachability of tungsten is prevented or greatly reduced. Preferably, the ceramic coating substantially encapsulates each particle of tungsten and has a thickness of at least about 30 nm and, more preferable, from about 200 nm to about 500 nm. Examples of ceramic coatings that may be used include, but are not limited to, aluminum oxide (alumina), aluminum oxyhydroxide (AlOOH), zirconium oxide (zirconia), cerium oxide (ceria), hafnium oxide (hafnia), and magnesium oxide (magnesia). Preferably, the coating is applied in a fluidized bed of tungsten particles using a chemical vapor deposition (CVD) reaction. Similar methods have been used for coating phosphor particles. Examples of these methods are described in U.S. Pat. Nos. 5,220,243, 5,244,750, 6,309,700, and 6,064,150.


DETAILED DESCRIPTION OF THE INVENTION
For a better understanding of the present invention, together with other and further objects, advantages and capabilities thereof, reference is made to the following disclosure and appended claims.
A spheroidized tungsten powder of (particle size >3 micrometers) was coated with a ceramic material in a fluidized bed reactor using a CVD reaction of trimethylaluminum (TMA) and water vapor. The hydrolyzed TMA coating and CVD process are described in U.S. Pat. Nos. 5,080,928 and 5,220,243 which are incorporated herein by reference. The hydrolyzed TMA coating is believed to be an aluminum oxyhydroxide, but may be varied in composition between aluminum oxide and aluminum hydroxide depending upon the reaction conditions. The CVD reaction can be described as follows:

Al(CH3)3+(3+n)/2H2O-->AlO(3−n)/2(OH)n+3CH4(0≦n≦3)

The tungsten particles were coated in the fluidized bed reactor for various lengths of time (from 0.5 hours to 3.5 hours) in order to produce coating thicknesses from 30 nm-500 nm.
Coated and uncoated tungsten powders were subjected to a leach test performed in an aqueous buffer solution. The buffer solution having a pH of 7.2 was prepared by dissolving 4.03 mg KCl, 50.6 mg CaSO4.2H2O, 123.2 mg MgSO4.7H2O, 96.0 mg NaHCO3, and 209.3 mg of a noncomplexing tertiary amine, 3-(N-morpholino) propanesulfonic acid (MOPS) per liter of water. Ten-gram amounts of the powders were added to 500-ml volumes of the aqueous buffer solution in 1-liter NALGENE© (PP) Erlenmeyer flasks.
The 1-liter flasks containing the samples were loosely covered with an aluminum foil and continuously shaken in a dark, thermostated room (72° F.) with a LAB-LINE® Force orbital open air shaker, Model 4690, for a period of 28 days. Periodic 25-ml samples of the leachate solutions were taken and analyzed for pH, oxygen content, and tungsten content at 7, 14, 21, and 28 days. A constant oxygen concentration of 8.3±0.2 mg/liter was observed for the entire testing period of 28 days.
The results of the leach tests are shown in Table I. Coating thickness was determined using a sputtering rate of approximately 0.1 nm/s (based on a tantalum oxide depth-profiling standard). The completeness of the ceramic coating on the particles was evaluated using x-ray photoelectron spectroscopy by observing the attenuation of the tungsten photoelectron peak. In each case, the coating attenuated the W signal by at least 99% indicating that the coating substantially encapsulated the individual tungsten particles.
As can be seen, the amount of tungsten in the leachate of the uncoated spheroidized tungsten powder (uncoated control) increases from 0.43% of the initial tungsten amount at 7 days to 0.75% at 28 days. Whereas, in all cases, the ceramic coating suppressed the leachability of tungsten as compared to the uncoated control and in fact the amount of leached tungsten becomes almost undetectable as coating thickness increases.







TABLE I







Effect of ceramic coatings on tungsten leachability (in % of initial tungsten)














Coating
Approx. Coating







Time
Thickness
% W
% W
% W
% W


Sample
(hours)
(nm)
7-day
14-day
21-day
28-day





Spheroidized W
—
—
0.43
0.54
0.59
0.75


powder (uncoated


control)


Coated Spheroidized W
0.5
 30
0.04
0.05
—
—


powder


Coated Spheroidized W
2.0
200
0.00
0.08
0.11
0.13


powder


Coated Spheroidized W
3.5
500
0.00
0.00
0.01
0.05


powder









While there has been shown and described what are at the present considered the preferred embodiments of the invention, it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the scope of the invention as defined by the appended claims.

## Claims

1. A tungsten powder having a coating of a ceramic material that substantially encapsulates each individual tungsten particle, wherein the coating is hydrolyzed trimethylaluminum.

2. A tungsten powder having a coating of a ceramic material that substantially encapsulates each individual tungsten particle, wherein the coating is selected from aluminum oxide, aluminum oxyhydroxide, zirconium oxide, cerium oxide, hafnium oxide, and magnesium oxide.

3. The tungsten powder of claim 1, wherein the coating has a thickness of at least about 30 nm.

4. The tungsten powder of claim 1, wherein the coating has a thickness of from about 200 nm to about 500 nm.

5. The tungsten powder of claim 2, wherein the coating has a thickness of at least about 30 nm.

6. The tungsten powder of claim 2, wherein the coating has a thickness of from about 200 nm to about 500 nm.