We are going to take a CALPHAD-based property model from the literature and use it to predict the viscosity of Al-Cu-Zr liquids.
For a binary alloy liquid under small undercooling, Gąsior suggested an entropy model of the form $$\eta = (\sum_i x_i \eta_i ) (1 - 2\frac{S_{ex}}{R})$$
where $\eta_i$ is the viscosity of the element $i$, $x_i$ is the mole fraction, $S_{ex}$ is the excess entropy, and $R$ is the gas constant.
For more details on this model, see
M.E. Trybula, T. Gancarz, W. Gąsior, Density, surface tension and viscosity of liquid binary Al-Zn and ternary Al-Li-Zn alloys, Fluid Phase Equilibria 421 (2016) 39-48, doi:10.1016/j.fluid.2016.03.013.
Władysław Gąsior, Viscosity modeling of binary alloys: Comparative studies, Calphad 44 (2014) 119-128, doi:10.1016/j.calphad.2013.10.007.
Chenyang Zhou, Cuiping Guo, Changrong Li, Zhenmin Du, Thermodynamic assessment of the phase equilibria and prediction of glass-forming ability of the Al–Cu–Zr system, Journal of Non-Crystalline Solids 461 (2017) 47-60, doi:10.1016/j.jnoncrysol.2016.09.031.
from pycalphad import Database
We can calculate the excess entropy of the liquid using the Al-Cu-Zr thermodynamic database from Zhou et al.
We add three new parameters to describe the viscosity (in Pa-s) of the pure elements Al, Cu, and Zr:
$ Viscosity test parameters
PARAMETER ETA(LIQUID,AL;0) 2.98150E+02 +0.000281*EXP(12300/(8.3145*T)); 6.00000E+03
N REF:0 !
PARAMETER ETA(LIQUID,CU;0) 2.98150E+02 +0.000657*EXP(21500/(8.3145*T)); 6.00000E+03
N REF:0 !
PARAMETER ETA(LIQUID,ZR;0) 2.98150E+02 +4.74E-3 - 4.97E-6*(T-2128) ; 6.00000E+03
N REF:0 !
Great! However, if we try to load the database now, we will get an error. This is because ETA
parameters are not supported by default in pycalphad, so we need to tell pycalphad's TDB parser that "ETA" should be on the list of supported parameter types.
dbf = Database('alcuzr-viscosity.tdb')
Failed while parsing: PARAMETER ETA(LIQUID,AL;0) 2.98150E+02 +0.000281*EXP(12300/(8.3145*T)); 6.00000E+03 N REF:0 Tokens: None
--------------------------------------------------------------------------- ParseException Traceback (most recent call last) <ipython-input-2-d711f4128286> in <module> ----> 1 dbf = Database('alcuzr-viscosity.tdb') ~/Projects/pycalphad/pycalphad/io/database.py in __new__(cls, *args) 127 elif fname.find('\n') == -1: 128 # Single-line string; it's probably a filename --> 129 return cls.from_file(fname, fmt=fmt) 130 else: 131 # Newlines found: probably a full database string ~/Projects/pycalphad/pycalphad/io/database.py in from_file(fname, fmt) 221 try: 222 dbf = Database() --> 223 format_registry[fmt.lower()].read(dbf, fd) 224 finally: 225 # Close file descriptors created in this routine ~/Projects/pycalphad/pycalphad/io/tdb.py in read_tdb(dbf, fd) 913 tokens = None 914 try: --> 915 tokens = grammar.parseString(command) 916 _TDB_PROCESSOR[tokens[0]](dbf, *tokens[1:]) 917 except ParseException: ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in parseString(self, instring, parseAll) 1826 else: 1827 # catch and re-raise exception from here, clears out pyparsing internal stack trace -> 1828 raise exc 1829 else: 1830 return tokens ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in parseString(self, instring, parseAll) 1816 instring = instring.expandtabs() 1817 try: -> 1818 loc, tokens = self._parse( instring, 0 ) 1819 if parseAll: 1820 loc = self.preParse( instring, loc ) ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in _parseCache(self, instring, loc, doActions, callPreParse) 1721 ParserElement.packrat_cache_stats[MISS] += 1 1722 try: -> 1723 value = self._parseNoCache(instring, loc, doActions, callPreParse) 1724 except ParseBaseException as pe: 1725 # cache a copy of the exception, without the traceback ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in _parseNoCache(self, instring, loc, doActions, callPreParse) 1560 if self.mayIndexError or preloc >= len(instring): 1561 try: -> 1562 loc,tokens = self.parseImpl( instring, preloc, doActions ) 1563 except IndexError: 1564 raise ParseException( instring, len(instring), self.errmsg, self ) ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in parseImpl(self, instring, loc, doActions) 3915 if maxException is not None: 3916 maxException.msg = self.errmsg -> 3917 raise maxException 3918 else: 3919 raise ParseException(instring, loc, "no defined alternatives to match", self) ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in parseImpl(self, instring, loc, doActions) 3900 for e in self.exprs: 3901 try: -> 3902 ret = e._parse( instring, loc, doActions ) 3903 return ret 3904 except ParseException as err: ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in _parseCache(self, instring, loc, doActions, callPreParse) 1721 ParserElement.packrat_cache_stats[MISS] += 1 1722 try: -> 1723 value = self._parseNoCache(instring, loc, doActions, callPreParse) 1724 except ParseBaseException as pe: 1725 # cache a copy of the exception, without the traceback ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in _parseNoCache(self, instring, loc, doActions, callPreParse) 1560 if self.mayIndexError or preloc >= len(instring): 1561 try: -> 1562 loc,tokens = self.parseImpl( instring, preloc, doActions ) 1563 except IndexError: 1564 raise ParseException( instring, len(instring), self.errmsg, self ) ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in parseImpl(self, instring, loc, doActions) 3750 raise ParseSyntaxException(instring, len(instring), self.errmsg, self) 3751 else: -> 3752 loc, exprtokens = e._parse( instring, loc, doActions ) 3753 if exprtokens or exprtokens.haskeys(): 3754 resultlist += exprtokens ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in _parseCache(self, instring, loc, doActions, callPreParse) 1721 ParserElement.packrat_cache_stats[MISS] += 1 1722 try: -> 1723 value = self._parseNoCache(instring, loc, doActions, callPreParse) 1724 except ParseBaseException as pe: 1725 # cache a copy of the exception, without the traceback ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in _parseNoCache(self, instring, loc, doActions, callPreParse) 1560 if self.mayIndexError or preloc >= len(instring): 1561 try: -> 1562 loc,tokens = self.parseImpl( instring, preloc, doActions ) 1563 except IndexError: 1564 raise ParseException( instring, len(instring), self.errmsg, self ) ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in parseImpl(self, instring, loc, doActions) 3915 if maxException is not None: 3916 maxException.msg = self.errmsg -> 3917 raise maxException 3918 else: 3919 raise ParseException(instring, loc, "no defined alternatives to match", self) ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in parseImpl(self, instring, loc, doActions) 3900 for e in self.exprs: 3901 try: -> 3902 ret = e._parse( instring, loc, doActions ) 3903 return ret 3904 except ParseException as err: ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in _parseCache(self, instring, loc, doActions, callPreParse) 1721 ParserElement.packrat_cache_stats[MISS] += 1 1722 try: -> 1723 value = self._parseNoCache(instring, loc, doActions, callPreParse) 1724 except ParseBaseException as pe: 1725 # cache a copy of the exception, without the traceback ~/anaconda3/envs/calphad-dev/lib/python3.6/site-packages/pyparsing.py in _parseNoCache(self, instring, loc, doActions, callPreParse) 1564 raise ParseException( instring, len(instring), self.errmsg, self ) 1565 else: -> 1566 loc,tokens = self.parseImpl( instring, preloc, doActions ) 1567 1568 tokens = self.postParse( instring, loc, tokens ) ~/Projects/pycalphad/pycalphad/io/tdb.py in parseImpl(self, instring, loc, doActions) 174 except ValueError: 175 pass --> 176 raise ParseException(instring, loc, self.errmsg, self) 177 178 def _tdb_grammar(): #pylint: disable=R0914 ParseException: Expected {{"ELEMENT" W:(ABCD...) [Suppress:(W:(ABCD...))] [Suppress:({Re:('[-+]?([0-9]+\\.(?!([0-9]|[eE])))|([0-9]*\\.?[0-9]+([eE][-+]?[0-9]+)?)')}...)] LineEnd} | {"SPECIES" W:(ABCD...) [Suppress:("%")] Group:({{W:(ABCD...) [Re:('[-+]?([0-9]+\\.(?!([0-9]|[eE])))|([0-9]*\\.?[0-9]+([eE][-+]?[0-9]+)?)')]}}...) [{Suppress:("/") W:(+-01...)}] LineEnd} | {"TYPE_DEFINITION" Suppress:(<SP><TAB><CR><LF>) !W:( !) SkipTo:(LineEnd)} | {"FUNCTION" W:(ABCD...) {{Re:('[-+]?([0-9]+\\.(?!([0-9]|[eE])))|([0-9]*\\.?[0-9]+([eE][-+]?[0-9]+)?)') | [","]...} {{SkipTo:(";") Suppress:(";") [Suppress:(",")]... [Re:('[-+]?([0-9]+\\.(?!([0-9]|[eE])))|([0-9]*\\.?[0-9]+([eE][-+]?[0-9]+)?)')] Suppress:({W:(YNyn) | <SP><TAB><CR><LF>})}}...}} | {"ASSESSED_SYSTEMS" SkipTo:(LineEnd)} | {"DEFINE_SYSTEM_DEFAULT" SkipTo:(LineEnd)} | {"DEFAULT_COMMAND" SkipTo:(LineEnd)} | {"DATABASE_INFO" SkipTo:(LineEnd)} | {"VERSION_DATE" SkipTo:(LineEnd)} | {"REFERENCE_FILE" SkipTo:(LineEnd)} | {"ADD_REFERENCES" SkipTo:(LineEnd)} | {"LIST_OF_REFERENCES" SkipTo:(LineEnd)} | {"TEMPERATURE_LIMITS" SkipTo:(LineEnd)} | {"PHASE" W:(ABCD...) Suppress:(<SP><TAB><CR><LF>) !W:( !) Suppress:(<SP><TAB><CR><LF>) Suppress:(W:(0123...)) Group:({Re:('[-+]?([0-9]+\\.(?!([0-9]|[eE])))|([0-9]*\\.?[0-9]+([eE][-+]?[0-9]+)?)')}...) LineEnd} | {"CONSTITUENT" W:(ABCD...) Suppress:(<SP><TAB><CR><LF>) Suppress:(":") Group:(Group:({{[Suppress:(",")] {W:(ABCD...) [Suppress:("%")]}}}...) [: Group:({{[Suppress:(",")] {W:(ABCD...) [Suppress:("%")]}}}...)]...) Suppress:(":") LineEnd} | {"PARAMETER" {"BMAGN" | "DF" | "DQ" | "G" | "GD" | "L" | "MF" | "MQ" | "NT" | "TC" | "THETA" | "V0" | "VS"} Suppress:("(") W:(ABCD...) [{Suppress:("&") W:(ABCD...)}] Suppress:(",") Group:(Group:({{[Suppress:(",")] {W:(ABCD...) [Suppress:("%")]}}}...) [: Group:({{[Suppress:(",")] {W:(ABCD...) [Suppress:("%")]}}}...)]...) [{Suppress:(";") W:(0123...)}] Suppress:(")") {{Re:('[-+]?([0-9]+\\.(?!([0-9]|[eE])))|([0-9]*\\.?[0-9]+([eE][-+]?[0-9]+)?)') | [","]...} {{SkipTo:(";") Suppress:(";") [Suppress:(",")]... [Re:('[-+]?([0-9]+\\.(?!([0-9]|[eE])))|([0-9]*\\.?[0-9]+([eE][-+]?[0-9]+)?)')] Suppress:({W:(YNyn) | <SP><TAB><CR><LF>})}}...}}} (at char 17), (line:1, col:18)
ETA
parameter to the TDB parser¶import pycalphad.io.tdb_keywords
pycalphad.io.tdb_keywords.TDB_PARAM_TYPES.append('ETA')
Now the database will load:
dbf = Database('alcuzr-viscosity.tdb')
Now that we have our ETA
parameters in the database, we need to write a Model
class to tell pycalphad how to compute viscosity. All custom models are subclasses of the pycalphad Model
class.
When the ViscosityModel
is constructed, the build_phase
method is run and we need to construct the viscosity model after doing all the other initialization using a new method build_viscosity
. The implementation of build_viscosity
needs to do four things:
ETA
parametersSince the build_phase
method sets the attribute viscosity
to the ViscosityModel
, we can access the property using viscosity
as the output in pycalphad caluclations.
from tinydb import where
import sympy
from pycalphad import Model, variables as v
class ViscosityModel(Model):
def build_phase(self, dbe):
super(ViscosityModel, self).build_phase(dbe)
self.viscosity = self.build_viscosity(dbe)
def build_viscosity(self, dbe):
if self.phase_name != 'LIQUID':
raise ValueError('Viscosity is only defined for LIQUID phase')
phase = dbe.phases[self.phase_name]
param_search = dbe.search
# STEP 1
eta_param_query = (
(where('phase_name') == phase.name) & \
(where('parameter_type') == 'ETA') & \
(where('constituent_array').test(self._array_validity))
)
# STEP 2
eta = self.redlich_kister_sum(phase, param_search, eta_param_query)
# STEP 3
excess_energy = self.GM - self.models['ref'] - self.models['idmix']
#liquid_mod = Model(dbe, self.components, self.phase_name)
## we only want the excess contributions to the entropy
#del liquid_mod.models['ref']
#del liquid_mod.models['idmix']
excess_entropy = -excess_energy.diff(v.T)
ks = 2
# STEP 4
result = eta * (1 - ks * excess_entropy / v.R)
self.eta = eta
return result
Now we can create an instance of ViscosityModel
for the liquid phase using the Database
object we created earlier. We can verify this model has a viscosity
attribute containing a symbolic expression for the viscosity.
mod = ViscosityModel(dbf, ['CU', 'ZR'], 'LIQUID')
print(mod.viscosity)
(1 + 0.240543628600637*(LIQUID0CU*LIQUID0ZR*(LIQUID0CU - LIQUID0ZR)**3*Piecewise((105.895 - 13.6488*log(T), (T >= 298.15) & (T < 6000.0)), (0, True)) + LIQUID0CU*LIQUID0ZR*(LIQUID0CU - LIQUID0ZR)**2*Piecewise((36.8512*log(T) - 270.5305, (T >= 298.15) & (T < 6000.0)), (0, True)) + LIQUID0CU*LIQUID0ZR*(LIQUID0CU - LIQUID0ZR)*Piecewise((75.3798 - 9.6125*log(T), (T >= 298.15) & (T < 6000.0)), (0, True)) + LIQUID0CU*LIQUID0ZR*Piecewise((392.8485 - 51.3121*log(T), (T >= 298.15) & (T < 6000.0)), (0, True)))/(1.0*LIQUID0CU + 1.0*LIQUID0ZR))*(LIQUID0CU*Piecewise((0.000657*exp(2585.84400745685/T), (T >= 298.15) & (T < 6000.0)), (0, True)) + LIQUID0ZR*Piecewise((0.01531616 - 4.97e-6*T, (T >= 298.15) & (T < 6000.0)), (0, True)))
Finally we calculate and plot the viscosity.
%matplotlib inline
import matplotlib.pyplot as plt
import numpy as np
from pycalphad import calculate
mod = ViscosityModel(dbf, ['CU', 'ZR'], 'LIQUID')
temp = 2100
# NOTICE: we need to tell pycalphad about our model for this phase
models = {'LIQUID': mod}
res = calculate(dbf, ['CU', 'ZR'], 'LIQUID', P=101325, T=temp, model=models, output='viscosity')
fig = plt.figure(figsize=(6,6))
ax = fig.gca()
ax.scatter(res.X.sel(component='ZR'), 1000 * res.viscosity.values)
ax.set_xlabel('X(ZR)')
ax.set_ylabel('Viscosity (mPa-s)')
ax.set_xlim((0,1))
ax.set_title('Viscosity at {}K'.format(temp));
We repeat the calculation for Al-Cu.
%matplotlib inline
import matplotlib.pyplot as plt
import numpy as np
from pycalphad import calculate
temp = 1300
models = {'LIQUID': ViscosityModel} # we can also use Model class
res = calculate(dbf, ['CU', 'AL'], 'LIQUID', P=101325, T=temp, model=models, output='viscosity')
fig = plt.figure(figsize=(6,6))
ax = fig.gca()
ax.scatter(res.X.sel(component='CU'), 1000 * res.viscosity.values)
ax.set_xlabel('X(CU)')
ax.set_ylabel('Viscosity (mPa-s)')
ax.set_xlim((0,1))
ax.set_title('Viscosity at {}K'.format(temp));