The mechanical properties of pressed PBX are mainly related to the explosive crystals, the interface effect of binders, and explosive particles. The surface morphology of crystals will affect the adhesion between crystals and binders, thus resulting in changes in the mechanical properties of PBX. Since the surface of H-RDX is smoother and the morphology is more regular than that of raw RDX, the influence of H-RDX on the mechanical properties of pressed PBX was explored.
3.3.1. Effect of Different RDX on Compressive Strength of Pressed PBX
The compressive strength (
Sc) of different RDX-based PBX prepared by 3 # and 4 # formulations with an applied pressure of 200 MPa was tested. The comparison of the samples before and after the test is shown in
Figure 3. It can be observed that the surface cracks of H-RDX-based PBX are obvious after the test, while the surface of raw RDX is almost no cracks. A plot of the measured compressive stress as a function of the displacement is shown in
Figure 4, and the test results are listed in
Table 5. The compressive stress of H-RDX-based PBX is significantly lower than that of raw RDX-based PBX, and the compressive strength decreases by 36%. However, the fluctuation of compressive stress of H-RDX-based PBX is relatively small, due to its standard deviation and range being reduced by more than 60% compared with raw RDX-based PBX. In other words, the compressive strength consistency of H-RDX-based PBX is significantly better than that of raw RDX-based PBX.
In order to investigate the reason for the decline of compressive strength caused by H-RDX, we use the interfacial wetting theory [
27,
28] to deduce it. Since the surface roughness of H-RDX is different from that of raw RDX, the Young equation [
29,
30,
31] is applied to the rough surface system. Combined with the Young equation and Wenzel equation [
32], we can obtain Equation (3):
where
r is a rough factor,
θ′ is the apparent contact angle of solid–liquid phase (°), and
θ is the solid–liquid contact angle (°).
Equation (3) shows that the cos
θ′ of a rough surface is always greater than that of a smooth surface. The apparent morphology analysis of RDX proves that the surface of H-RDX is smoother than that of raw RDX; thus, we have the following.
Reference [
18] shows that the liquid surface tension of PVAc, FKM DS2603, and VITON A is always greater than 0, for the use of the same binder in PBX. Combined with Equation (4) and Young equation, we obtain the following:
where
Wa is the adhesion work (mJ•m
−2). According to Equation (5), the adhesion work between H-RDX with smooth surface and binder is smaller than that of raw RDX and binder, which means that the interface effect between H-RDX crystal and binder is weaker; thus, the compressive strength of pressed H-RDX-based PBX is lower.
On the other hand, the irregularity of the surface, such as uneven peak valley or loose pore structure, is conducive to the filling of the adhesive. After curing, the adhesive and the surface are bitten and fixed. In the process of coating RDX with a water suspension granulation method, the binder wets or spreads on the irregular surface of RDX crystal, which plays the role of filling peak valleys and gaps and makes the surface of RDX crystal form a large area of close combination with the binder, which result in the physical “interlocking block” [
33]. Therefore, the raw RDX-based PBX with an irregular surface has better compressive strength properties than the H-RDX-based PBX.
In summary, the surface of H-RDX is smoother, and the compressive strength of H-RDX-based PBX is lower. However, due to the regular surface shape of H-RDX, the stress in each direction is uniform. Thus, the compressive strength of H-RDX-based PBX is better consistent.
3.3.2. Effect of Pressing Intensity on the Compressive Strength of Pressed H-RDX-Based PBX
The pressing intensity of the PBX will directly affect the density and porosity of the PBX, thereby affecting the mechanical properties of the pressed PBX. Therefore, the mechanical properties of H-RDX-based PBX prepared by 4 # molding powder under holding time of 8 s, pressing pressure of 42 kN (100 MPa), 52 kN (125 MPa), 62 kN (150 MPa), and 83 kN (200 MPa) were studied, as listed in
Table 6.
It can be observed from
Table 6 that the compressive strength of pressed H-RDX-based PBX increases with an increase in pressing intensity in the range of 100 MPa~200 MPa. According to the statistical theory of micro-crack brittle damage [
34], there are inevitably initial defects such as microcracks in the preparation process of PBX. When the pressing intensity becomes higher, the density of the PBX is higher, yet the porosity of the PBX is lower; thus, PBX has fewer and smaller initial microcracks or other defects. Under the stimulation of external pressure, the smaller initial microcracks expand steadily and slowly, thereby reducing the crack’s growth rate. Therefore, pressed PBX with fewer and smaller initial microcracks needs a greater external load to achieve the critical damage degree, which means that it can withstand greater compressive strength. In summary, the increase in pressing intensity can improve the compressive strength of PBX by reducing porosity, initial cracks, and other defects.
3.3.4. The Discussion of the Interfacial Reinforcement Effects between H-RDX and Binders
Compared with PVAc/H-RDX composites, the compressive strength of fluororubber/H-RDX composites was significantly improved, which was believed to originate from the interface reinforcement effect of fluororubber on H-RDX. It can be attributed to the following mechanisms.
According to the adsorption theory [
27,
28,
29,
30,
31,
32], the binder is adsorbed on the surface by wetting, and the movement of macromolecules or molecular chains forms a diffusion interface area. Furthermore, the molecules undergo physical adsorption or chemical reaction, forming a bond that crosses the secondary or main chemical valence of the interface. First, the -F group in fluororubber (FKM DS2603 or VITON A) molecule has high electronegativity and, thus, produces strong dipole–dipole interactions with the -NO
2 group on the surface of H-RDX crystal. Although the CH
3COO- group in PVAc can also produce dipole–dipole interactions with the -NO2 group on the surface of the H-RDX crystal, the volume of the CH
3COO- group is larger and electronegativity is weaker than that of the -F group; thus, the dipole–dipole interaction between CH
3COO- group and -NO
2 group is smaller. Additionally, for binders with the same weight, the number of −F groups of fluororubber is 156% more than that of CH
3COO- groups of PVAc, according to the molecular force summation formula of Fowkes [
27,
28,
29], and the total force between fluororubber and H-RDX crystal is also larger. At the same time, the fluorine content of FKM DS2603 is 2% higher than that of VITON A thus, the total dipole–dipole interaction between FKM DS2603 and H-RDX is larger, which results in the increase in intermolecular interaction and enhances the compressive strength of H-RDX-based PBX.
Diffusion theory [
27,
28,
29,
30,
31,
32] believes that the flexibility of the molecular chain increases, the side group reduces, and the crosslinking degree raises, and these are beneficial to molecular diffusion, resulting in bonding strength increases. The CH
3COO- group of PVAc is suspended outside the main chain, resulting in an increase in the spatial steric hindrance of the diffusion interface, which inhibits the spread of the PVAc molecular chain on the surface of the H-RDX crystal. Nevertheless, the space volume of the -CF
3 group on the fluororubber molecular chain is smaller than that of the CH
3COO- group; thus, its space steric hindrance is small, which is convenient for the diffusion of fluororubber molecular chain and molecular chain on the surface of H-RDX crystal to achieve greater bonding strength.
In addition, the H-RDX molecule contains the -NO
2 group, which is an electron donor and belongs to the Lewis base. However, the F atom in the fluororubber molecule has a strong ability to attract electrons, resulting in a positive charge around the C atom of the main chain, becoming a proton donor and belonging to Lewis acid. Moreover, the CH
3COO- group in PVAc can provide an electron pair, which belongs to the Lewis base. Consequently, according to the acid-base interaction theory [
28,
32], -NO
2 groups of H-RDX are easier to form coordination bonds with fluororubber molecules and increase the molecular interaction at the interface.
It is revealed that the interface reinforcement effect of fluororubber on H-RDX by the analysis of adsorption theory, diffusion theory and acid-base interaction theory. The essential reason is that the fluororubber molecular chain is easier to wet and diffuse on the surface of H-RDX crystal, forming coordination bonds and obtaining stronger dipole–dipole interaction. Hence, the compressive strength of the pressed H-RDX-based PBX can be improved by the use of fluororubber, which enhances molecular interaction on the interface.