Boron carbide composite

Abstract

The present disclosure relates to boron carbide (B4C) composite material and the method of making and using the boron carbide (B4C) composite.

Description

TECHNICAL FIELD

The present disclosure relates to novel boron carbide (B₄C) composite material and the method of making and using the novel boron carbide (B₄C) composite.

BACKGROUND

This section introduces aspects that may help facilitate a better understanding of the disclosure. Accordingly, these statements are to be read in this light and are not to be understood as admissions about what is or is not prior art.

Boron carbide is useful for applications where ultra-hard components are needed, such as wear-resistant bearings, sand-blasting nozzles, abrasives and ballistic armor. There are significant challenges, such as the high temperatures required and particle coarsening, associated with the pressureless sintering of boron carbide (B₄C). The strong, stable covalent bonds of B₄C give it notoriously low sintering ability and sintering mechanisms that lead to densification, such as bulk diffusion and grain boundary diffusion, only become effective at temperatures in excess of 2300° C. One important consideration for achieving near theoretical density B₄C components using pressureless sintering is the use of sintering aids. Sintering aids have been widely shown to improve the densification of B₄C at lower temperatures than would be required for non-doped systems. It has also been shown that the addition of sintering aids may be beneficial to both hardness and fracture toughness. See U.S. Pat. No. 7,309,672B2.

While methods/composites in previous disclosures provided some improvements, better boron carbide composite materials and methods of preparing such materials are still needed.

SUMMARY

The present invention provides novel boron carbide (B₄C) composite material and the method of making and using the novel boron carbide (B₄C) composite.

In one embodiment, the present disclosure provides a novel composite material comprising a sintered product of a mixture comprising 70-95 wt. % of boron carbide (B₄C), 2-15 wt. % of tungsten carbide (WC), and 3-15 wt. % of yttrium oxide (Y₂O₃), wherein said boron carbide, tungsten carbide, and yttrium oxide are substantially uniformly distributed in the sintered product.

In one embodiment, the present disclosure provides a method of preparing the novel boron carbide (B₄C) composite material of the present disclosure, wherein the method comprises:

attrition milling boron carbide and tungsten carbide in ethanol to provide an attrition milled powder comprising boron carbide and tungsten carbide, wherein said boron carbide after the attrition milling is substantially free of boron oxide (B₂O₃);

preparing an aqueous suspension comprising the attrition milled boron carbide and tungsten carbide powder, and yttrium oxide powder;

injecting mold said suspension and making it a dried mixture; and

sintering the dried mixture at a temperature range of 1600-2600° C.

DETAILED DESCRIPTION

For the purposes of promoting an understanding of the principles of the present disclosure, reference will now be made to the embodiments illustrated in the drawings, and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of this disclosure is thereby intended.

In the present disclosure the term “about” can allow for a degree of variability in a value or range, for example, within 10%, within 5%, or within 1% of a stated value or of a stated limit of a range.

In the present disclosure the term “substantially” can allow for a degree of variability in a value or range, for example, within 90%, within 95%, or within 99% of a stated value or of a stated limit of a range.

In the present disclosure the term “relative density” refers to a comparison between the bulk density of a material (i.e. the density measured using the Archimedes' technique which includes voids and other defects) compared to the theoretical density of the material (i.e. the density if there were no voids or defects). It is usually expressed as a percentage.

In one embodiment, the present disclosure provides a novel composite material comprising a sintered product of a mixture comprising 70-95 wt. % of boron carbide (B₄C), 2-15 wt. % of tungsten carbide (WC), and 3-15 wt. % of yttrium oxide (Y₂O₃), wherein said boron carbide, tungsten carbide, and yttrium oxide are substantially uniformly distributed in the sintered product.

In one embodiment, the present disclosure provides a novel composite material comprising a sintered product of a mixture comprising 70-90 wt. % of boron carbide (B₄C), 5-15 wt. % of tungsten carbide (WC), and 5-15 wt. % of yttrium oxide (Y₂O₃), wherein said boron carbide, tungsten carbide, and yttrium oxide are substantially uniformly distributed in the sintered product.

In one embodiment, the present disclosure provides a novel composite material comprising a sintered product of a mixture comprising boron carbide (B₄C), tungsten carbide (WC), and yttrium oxide (Y₂O₃), wherein the sintered product has a relative density of 90-99%.

In one embodiment, the present disclosure provides a novel composite material comprising a sintered product of a mixture comprising boron carbide (B₄C), tungsten carbide (WC), and yttrium oxide (Y₂O₃), wherein the sintered product is obtained under substantially pressureless condition at a temperature range of 1600-2600° C.

In one embodiment, the present disclosure provides a novel composite material comprising a sintered product of a mixture comprising boron carbide (B₄C), tungsten carbide (WC), and yttrium oxide (Y₂O₃), wherein said boron carbide is first attrition milled with tungsten carbide in ethanol to provide attrition milled mixture of boron carbide and tungsten carbide, wherein said boron carbide after attrition milled is substantially free of boron oxide (B₂O₃).

In one embodiment, the present disclosure provides a method of preparing the novel boron carbide (B₄C) composite material of the present disclosure, wherein the method comprises:

attrition milling boron carbide and tungsten carbide in ethanol to provide an attrition milled powder comprising boron carbide and tungsten carbide, wherein said boron carbide after the attrition milling is substantially free of boron oxide (B₂O₃);

preparing an aqueous suspension comprising the attrition milled boron carbide and tungsten carbide powder, and yttrium oxide powder;

injecting mold said suspension and making it a dried mixture; and

sintering the dried mixture at a temperature range of 1600-2600° C.

In one embodiment, the present disclosure provides a method of preparing the novel boron carbide (B₄C) composite material of the present disclosure, wherein the sintering is carried out at substantially pressureless condition.

Experimental Sections

Boron carbide (B₄C) powder (H. C. Starck, Germany) with an average particle size of 1.1 micron was used as a starting powder, which had a chemical composition as provided in Table 1:

TABLE 1
Chemical composition of the as-received boron carbide.
Element Wt. %
B       75.8
C       22.3
N       0.5
O       1.3
Fe      0.02
Si      0.06
Al      <0.01

Three different powder treatments were performed. The first was as-received powder with no treatment.

The second kind of treatment was that the as-received boron carbide was treated by washing in ethanol.

The third was attrition milling in ethanol with sintering aids. In the process utilized in the present disclosure, B₄C powder is first attrition milled in ethanol to remove the thin layer of B₂O₃ that forms on the surface of B₄C particles. Due to the extreme hardness of B₄C, the WC—Co milling media is slowly eroded and mixed into the B₄C powder during attrition milling. As a result, the attrition milled powder is about 2-15% by weight WC—Co. The using of attrition milling increases final densities when compared to using as-received or ethanol washed powders. However, it was noticed the relative density is still below 85% with only WC addition (Table 2).

B₄C powder was suspended in ethanol and attrition milled with ⅛″ 94% tungsten carbide-6% cobalt (WC—Co) milling media for 2 hours at 50 rpm. The milling media to powder ratio was 6.7:1. The powders were dried overnight and then ball milled for 24 hours. During attrition milling, an amount of the WC—Co milling media was worn away and integrated into the B₄C powder. This amount ranged from 2-10 wt. % depending on the batch. Ethanol washed powder was treated in a manner identical to attrition milling, except no WC—Co milling media was added. Tungsten carbide (WC) powder with an average particle size of 0.75 micron was added to the as-received and ethanol washed powders. Powder mixtures with the compositions provided in Table 2 were prepared, with variation of the quantity of sintering aids from 0-20 wt. %.

TABLE 2
Samples 1-9
Sample	Powder	B4C	WC—Co	WC	Relative
No.	Preparation	(wt. %)	(wt. %)	(wt. %)	Density (%)
1	As-received	100	NA	NA	76.63
2	As-received	90	NA	10	77.85
3	As-received	85	NA	15	78.83
4	As-received	80	NA	20	78.79
5	Ethanol	100	NA	NA	78.23
	washed
6	Ethanol	90	NA	10	79.03
	washed
7	Ethanol	85	NA	15	79.86
	washed
8	Ethanol	80	NA	20	79.92
	washed
9	Attrition	85	15	NA	81.13
	milled

Pellets of each composition were uniaxially pressed at 34.5 MPa for 20 seconds in a steel die with a diameter of 15 mm. Pellets were placed in a graphite crucible and sintered in a flowing argon atmosphere for 1 hour at 2000° C. with a ramp rate of 25° C./min. After cooling, the pellets were removed and cleaned. Density was measured using Archimedes' method (ASTM C373-14a).

The data of samples 1-9 in Table 2 showed that the addition of WC is beneficial to the pressureless sintering of B₄C. Ethanol washing is also beneficial, as the layer of boric oxide (B₂O₃) found on the surface of B₄C particles dissolves in ethanol. Attrition milling has a significant benefit over ethanol washing, even when WC is intentionally added to match the WC—Co concentration from attrition milling.

Samples 10-31 were prepared in a manner similar to examples 1-9 except yttrium oxide (Y₂O₃) powder with a specific surface area of 6.49 m²/g was also used as a sintering aid. Powder mixtures with the compositions provided in Table 3 were prepared. Powders were mixed in a planetary mixer (Flacktek, South Carolina) at 800 rpm to ensure even mixing.

Sample 32 was prepared by first mixing a highly loaded (>50 vol. %) aqueous suspension using the attrition milled B₄C/WC—Co powder, Y₂O₃ powder, concentrated 12M HCl, and small amount of branched polyethylenimine (PEI, M_w=25,000 g/mol) for improved green body strength. The suspension is then injection molded at room temperature. Afterwards, the component is allowed to dry before undergoing binder burnout and sintering. The final composition of the sintered components is 70-95% B₄C, 2-15% WC—Co, and 3-15% Y₂O₃ by weight. The addition of Y₂O₃ significantly increases the final density of B₄C over a wide variety of compositions and outperforms traditional B₄C sintering aids over much of that range (Table 3). Sample 33-35 are made essentially the same as Sample 32.

TABLE 3
Samples 10-35
						Sintering	Relative
Sample	Powder	B4C	WC—Co	Y2O3	WC	aids total	density
No.	Preparation	(wt. %)	(wt. %)	(wt. %)	(%)	(wt. %)	(%)
10	As-received	90		10		10	86.65
11	As-received	87.5		10	2.5	12.5	86.94
12	As-received	85		10	5	15	86.96
13	As-received	82.5		10	7.5	17.5	88.18
14	As-received	80		10	10	20	88.18
15	As-received	77.5		10	12.5	22.5	89.3
16	As-received	75		10	15	25	89.51
17	Ethanol	90		10		10	87.27
	washed
18	Ethanol	87.5		10	2.5	12.5	87.1
	washed
19	Ethanol	85		10	5	15	87.58
	washed
20	Ethanol	82.5		10	7.5	17.5	89.24
	washed
21	Ethanol	80		10	10	20	88.37
	washed
22	Ethanol	77.5		10	12.5	22.5	89.1
	washed
23	Ethanol	75		10		25	89.92
	washed
24	Attrition	85	5	10		15	87.73
	milled
25	Attrition	82.5	7.5	10		17.5	88.71
	milled
26	Attrition	80	5.08	10	4.92	20	89.49
	milled
27	Attrition	77.5	5.08	10	7.67	22.5	89.48
	milled
28	Attrition	75	5.08	10	9.92	25	91.17
	milled
29	Attrition	90	5	5		10	86.45
	milled
30	Attrition	85	5	10		15	90.98
	milled
31	Attrition	80	5	15		20	93.81
	milled
32	Attrition	84	6	10		16	97.28
	milled
33	Attrition	82.79	7.21	10		17.21	97.67
	milled
34	Attrition	90.34	4.66	5		9.66	94.06
	milled
35	Attrition	78.59	5.91	15		21.41	95.43
	milled

The data of samples 10-35 in Table 3 showed that Y₂O₃ has a strong beneficial effect on densification of B₄C over a wide variety of compositions, regardless of powder treatment. In addition, adding 10 wt. % Y₂O₃ increases the effect of WC additions. This suggests that there is a synergic benefit to using both sintering aids simultaneously.

To compare the performance of the composites of the present disclosure and the performance of the composites of U.S. Pat. No. 7,309,672B2, a comparison study was carried out. The results can be found in Table 4.

TABLE 4
Samples 36*-37*
					Sintering	Relative
Sample	Powder	B4C	Al2O3	Y2O3	aids total	density
No.	Preparation	(wt. %)	(wt. %)	(wt. %)	(wt. %)	(%)
36*	As-received	95	3	2	5	85.22
37*	As-received	98	1.2	0.8	2.0	83.12

Samples 36* and 37* are made corresponding to the method of preparing the Examples 5 and 7 in the U.S. Pat. No. 7,309,672B2. It is clear that composites of the present disclosure provided higher relative density. For example, sample 32 had over 97% relative density, which is more than 10% improvement.

Pellets of each composition was uniaxially pressed at 34.5 MPa for 20 seconds in a steel die with a diameter of 15 mm. Pellets were placed in a graphite crucible and sintered in a flowing argon atmosphere for 1 hour at 2000° C. with a ramp rate of 25° C./min. After cooling, the pellets were removed and cleaned. Density was measured using Archimedes' method (ASTM C373-14a).

Those skilled in the art will recognize that numerous modifications can be made to the specific implementations described above. The implementations should not be limited to the particular limitations described. Other implementations may be possible.

Claims

1. A composite material comprising a sintered product of a mixture comprising 70-95 wt. % of boron carbide (B4C), 2-15 wt. % of tungsten carbide-cobalt (WC—Co), and 3-15 wt. % of yttrium oxide (Y2O3), wherein said boron carbide, tungsten carbide-cobalt (WC—Co), and yttrium oxide are substantially uniformly distributed in the sintered product, wherein the sintered product has a relative density of 90-99%.

2. The composite material of claim 1, wherein the mixture comprises 70-90 wt. % of boron carbide (B4C), 5-15 wt. % of tungsten carbide-cobalt (WC—Co), and 5-15 wt. % of yttrium oxide (Y2O3).

3. The composite material of claim 1, wherein the sintered product has a relative density of 97-99%.

4. The composite material of claim 1, wherein the sintered product is obtained under substantially pressureless condition at a temperature range of 1600-2600° C.

5. The composite material of claim 1, wherein said boron carbide is first attrition milled with tungsten carbide in ethanol to provide attrition milled mixture of boron carbide and tungsten carbide-cobalt (WC—Co), wherein said boron carbide after attrition milled is substantially free of boron oxide (B2O3).

6. A method of preparing the composite material of claim 1, comprising: attrition milling boron carbide and tungsten carbide in ethanol to provide an attrition milled powder comprising boron carbide and tungsten carbide-cobalt (WC—Co), wherein said boron carbide after the attrition milling is substantially free of boron oxide (B2O3);preparing an aqueous suspension comprising the attrition milled boron carbide and tungsten carbide-cobalt (WC—Co) powder, and yttrium oxide powder;injecting mold said suspension and making it a dried mixture; andsintering the dried mixture at a temperature range of 1600-2600° C. to provide the composite material.

7. The method of claim 6, wherein the sintering is carried out at substantially pressureless condition.