In [1]:
import warnings
warnings.simplefilter('ignore') # ignore warnings for nicer output
import numpy as np
from sympy import symbols, log, lambdify, solve
import scipy.constants
from ipywidgets import interact
from bokeh.io import push_notebook, show, output_notebook
from bokeh.plotting import figure
from bokeh.models import Span, layouts
output_notebook()
We define a function G that returns $G$ for a given phase. $G$ is given as a regular solution for a binary A, B system. The mixing enthalpy, $H_\textrm{mix}$, is a changable paramter (Hmix). The entropy, $S$, could concievably be modeled in several ways, but here a simple ideal mixing approximation is substituted.
In [2]:
# define the Gibbs free energy symbolically
ua, ub, S, Hmix, T, xb = symbols('ua ub S Hmix T xb')
xa = 1 - xb
G = ua*xa + ub*xb + Hmix*xa*xb - T*S
# define the ideal mixing entropy and substitute that in our Gibbs energy function
ideal_mixing_entropy = -scipy.constants.R*(xa*log(xa)+xb*log(xb))
G = G.subs(S, ideal_mixing_entropy)
Next we will create a plotting domain for $x_\textrm{B}$ and create a plot with widgets that allow the temperature, mixing enthalpy, and chemical potentials of the pure elements, $\mu_\textrm{A}$ and $\mu_\textrm{B}$, to be changed.
There are two plots below. The first is the free energy curve for the phase that is controlled by the temperature, mixing enthalpy and chemical potential sliders.
The bottom plot is the phase diagram for the phase. It plots the miscibility gap, if there is one. If there is no miscibility gap, the plot will be blank. The horizontal line indicates the temperature of the free energy curve.
Note: the root finding is currently broken for negative mixing enthalpies and the phase diagram will plot faulty lines
In [3]:
xb_plot = np.linspace(0, 1, 1000) # discritized plotting domain
p = figure(title="Free Energy, $G$", plot_height=300, plot_width=600, x_range=(0,1))
p.xaxis.axis_label = 'X_B'
p.yaxis.axis_label = 'G'
r = p.line(xb_plot, lambdify(xb, G.subs({T: 300, Hmix:0, ua: -2000, ub:-1000}), 'numpy')(xb_plot), line_width=3)
s1 = Span(location=None, dimension='height', line_color='red', line_dash='dashed', line_width=3)
s2 = Span(location=None, dimension='height', line_color='red', line_dash='dashed', line_width=3)
p.add_layout(s1)
p.add_layout(s2)
phase_diag = figure(title="Phase diagram", plot_height=300, plot_width=600, x_range=(0,1), y_range=(0,2000))
phase_diag.xaxis.axis_label = 'X_B'
phase_diag.yaxis.axis_label = 'T'
xt = phase_diag.line(np.linspace(0,0,2000), np.tile(np.linspace(0,2000,1000), 2), line_width=3)
ps1 = Span(location=None, dimension='height', line_color='red', line_dash='dashed', line_width=3)
ps2 = Span(location=None, dimension='height', line_color='red', line_dash='dashed', line_width=3)
hspan = Span(location=300, dimension='width', line_color='red', line_dash='dashed', line_width=3)
phase_diag.add_layout(ps1)
phase_diag.add_layout(ps2)
phase_diag.add_layout(hspan)
fig = layouts.Column(p, phase_diag)
show(fig, notebook_handle=True)
@interact(T=(0,2000, 10), Hmix=(-10000,20000, 200), ua=(-10000, 0, 100), ub=(-10000, 0, 100))
def update(T=300, Hmix=0, ua=-2000, ub=-1000):
# we have to do a little wrangling to keep the labels nice.
# first alias the args with prefix underscores
_T, _Hmix, _ua, _ub = T, Hmix, ua, ub
# redefine as symbols for the substitution and update the curve plot
ua, ub, Hmix, T = symbols('ua ub Hmix T')
r.data_source.data['y'] = lambdify(xb, G.subs({T: _T, Hmix: _Hmix, ua: _ua, ub:_ub}), 'numpy')(xb_plot)
# find the roots of the second derivative and plot those as spans
roots = solve(G.subs({T: _T, Hmix: _Hmix, ua: _ua, ub:_ub}).diff(xb).diff(xb), xb)
if roots:
# calculate the Spans
if all([root.is_real for root in roots]):
s1.location = float(roots[0])
s2.location = float(roots[1])
ps1.location = float(roots[0])
ps2.location = float(roots[1])
else:
s1.location = None
s2.location = None
ps1.location = None
ps2.location = None
else:
s1.location = None
s2.location = None
ps1.location = None
ps2.location = None
# calculate the miscibility gap, leaving T free.
hspan.location = _T
misc_roots = solve(G.subs({Hmix: _Hmix, ua: _ua, ub:_ub}).diff(xb).diff(xb), xb)
# calculate the miscibility gap
misc_xs = np.ravel(lambdify(T, misc_roots)(np.linspace(0,2000,1000)))
xt.data_source.data['x'] = misc_xs
push_notebook()
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