12 views

Uploaded by Marco Ravelo

- 159
- What is the Most Comment Solvent in Everyday Life
- A Thermodynamic Study of Selective Solvation in Solvent Mixtures
- Chapter 6 FFR
- tugas farfis 1
- Solubility of Organic Compounds
- EP2079723B1
- sensors-10-04887
- ni1995
- Pages From 590
- Solubility&Soln Notes
- Extraction of Caffeine from Tea Leaves of Twinings English Breakfast Tea Using the Single Extraction Method
- Pages From 600
- First Quarter
- Extraction.pdf
- test.txt
- Adei Reviewer - blank2.docx
- Joc NMR Solvent Peaks Very Important-1
- 1985 Book EnvironmentalGeochemistryAndHe
- Chap 13

You are on page 1of 7

https://www.researchgate.net/publication/233471526

Hansen Solubility Parameters of Polymers

DOI: 10.1080/00222340500522372

CITATIONS READS

4 136

2 authors, including:

Farhad Gharagheizi

170 PUBLICATIONS 3,549 CITATIONS

SEE PROFILE

All content following this page was uploaded by Farhad Gharagheizi on 14 April 2015.

Journal of Macromolecular Sciencew, Part B: Physics, 45:285–290, 2006

Copyright # Taylor & Francis Group, LLC

ISSN 0022-2348 print/1525-609X online

DOI: 10.1080/00222340500522372

Solubility Parameters of Polymers

Department of Chemical Engineering, Faculty of Engineering,

University of Tehran, Tehran, Iran

In this work a new improved method to estimate the Hansen solubility parameters, dd,

dp, and dh, as well as the radius of interaction sphere for a given polymer, is presented

starting from the idea that the solvents that dissolve a polymer have solubility par-

ameters near to that polymer. In this study, using intrinsic viscosities of the polymer

in these solvents and the molar volumes of the solvents, a correlation has been done.

Results fit data quite well.

Introduction

Solubility parameters have found their greatest use in the coatings industry to aid in the

selection of solvents. They are used in other industries, however, to predict compatibility

of polymers, chemical resistance, and permeation rates and even to characterize the

surfaces of pigments, fibers, and fillers. Liquids with similar solubility parameters will

be miscible, and polymers will dissolve in solvents whose solubility parameters are not

too different from their own.[1]

The solubility parameter has been used for many years to select solvents for coatings

materials. A lack of total success has stimulated research. The skill with which solvents

can be optimally selected with respect to cost, solvency, workplace environment,

external environment, evaporation rate, flash point, etc., has improved over the years as

a result of a series of improvements in the solubility parameter concept and widespread

use of computer techniques. Most, if not all, commercial suppliers of solvents have

computer programs to help with solvent selection.

The term solubility parameter was first used by Hildebrand and Scott.[2,3] The earlier

work of Scatchard and others contributed to this development.[4] The Hildebrand solubility

parameter is defined as the square root of the cohesive energy density:

rﬃﬃﬃﬃ

E

d¼ ð1Þ

V

Address correspondence to Farhad Gharagheizi, Department of Chemical Engineering, Faculty

of Engineering, University of Tehran, P.O. Box 1365-4563, Tehran, Iran. E-mail: fghara@engmail.

ut.ac.ir

285

286 F. Gharagheizi and M. T. Angaji

V is the molar volume of the pure solvent, and E is its (measurable) energy of vaporization.

The solubility parameter is an important quantity for predicting solubility relations, as can

be seen from the following brief introduction. Thermodynamics requires that the free

energy of mixing must be zero or negative for the solution process to occur spontaneously.

The free energy change for the solution process is given by the relation

where DGM is the free energy of mixing, DHM is the heat of mixing, T is the absolute temp-

erature, and DSM is the entropy change in the mixing process.

Equation (3) gives the heat of mixing as proposed by Hildebrand and Scott[2,3]:

DH M ¼ w1 w2 VM ðd1 d2 Þ2 ð3Þ

The ws are volume fractions of solvent and polymer, and VM is the volume of the mixture.

Equation 3 is not correct. This equation has often been cited as a shortcoming of this

theory in that only positive heats of mixing are allowed. It has been shown by Patterson,

Delmas, and coworkers that DGM noncomb is given by the right-hand side of Eq. (3) and not

DGM.[5 – 10] The correct relation is

2

DGM

noncomb ¼ w1 w2 VM ðd1 d2 Þ ð4Þ

The noncombinatorial free energy of solution DGM noncomb includes all free energy effects

other than the combinatorial entropy of solution occurring because of simply mixing

the components. Equation (4) is consistent with the Prigogine corresponding states

theory of polymer solutions and can be differentiated to give expressions predicting

both positive and negative heats of mixing.[3,5] Therefore, both positive and negative

heats of mixing can be expected from theoretical considerations and have been

measured accordingly. It has been shown clearly that solubility parameters can be used

to predict both positive and negative heats of mixing. Previous objections to the effect

that only positive values are allowed in this theory are not correct.

A more detailed description of the theory presented by Hildebrand and the succession

of research reports that have attempted to improve on it can be found in Barton’s extensive

handbooks.[11,12] The slightly older, excellent contribution of Gardon and Teas is also

a good source of related information, particularly for coatings and adhesion

phenomena.[13] The approach of Burrell, who divided solvents into hydrogen bonding

classes, has found numerous practical applications.[14] The approach of Blanks and

Prausnitz divided the solubility parameter into two components, nonpolar and polar.[15]

Both are worthy of mention.

A widely used solubility parameter approach to predicting polymer solubility is that

proposed by Hansen. The basis of these so-called Hansen solubility parameters (HSP) is

that the total energy of vaporization of a liquid consists of several individual parts.[16 – 19]

These arise from (atomic) dispersion forces, (molecular) permanent dipole – permanent

dipole forces, and (molecular) hydrogen bonding (electron exchange). The basic

equation that governs the assignment of Hansen parameters is that the total cohesion

energy, E, must be the sum of the individual energies which make it up.

E ¼ E D þ EP þ E H ð5Þ

Estimating Hansen Solubility Parameters 287

Dividing this by the molar volume gives the square of the total (or Hildebrand)

solubility parameter as the sum of the squares of the Hansen D, P, and H components.

E=V ¼ ED =V þ EP =V þ EH =V ð6Þ

d2 ¼ d2d þ d2p þ d2h ð7Þ

To sum up this section, it is emphasized that HSP quantitatively account for the cohesion

energy (density). An experimental latent heat of vaporization is considered much more

reliable as a method to arrive at a cohesion energy than using molecular orbital calcu-

lations or other calculations based on potential functions. Indeed, the goal of such

extensive calculations for polar and hydrogen bonding molecules should be to accurately

arrive at the energy of vaporization.

The object of our work is to describe a more rapid and accurate method to determine

the partial or Hansen solubility parameters as well as the radius of interaction sphere for a

given polymer using the tabulated Hansen solubility parameters of solvents. Intrinsic visc-

osities of a polymer in different solvents and molar volume of solvents were used as

weights of dissolving capacities of polymer. Equations corresponding to a system of

material points placed into a tridimensional space were used, and a computer program

was elaborated.

Common Methods

Determination of Hansen solubility parameters of a polymer by the classical method[1]

consist in testing of polymer solubility in different solvents with known partial solubility

parameters. Solvents which interact with the given polymer (dissolve or swell it) are rep-

resented as points in planes having as coordinates (0,dh,dp), (2dd,0,dp), (2dd,dh,0), and lie

within circles of radius, R, which represents the radius of interaction sphere (Fig. 1).

The coordinates of the center of the sphere represent the Hansen solubility parameters

of the polymer. Any of the three planes can be considered first for drawing of the circle,

which results in different values for R and for the Hansen solubility parameters.

288 F. Gharagheizi and M. T. Angaji

tacting the polymer of interest with 40 to 45 well-chosen liquids. One may then

observe or measure a number of different phenomena including full solution at a

given concentration, degree of swelling by visual observation or by measurement

of weight change, volume change, clarity, surface attack, etc. The object of the

studies is to determine differences in affinity of the polymer for the different

solvents. These differences are then traditionally used to divide the solvents into

two groups, one which is considered “good” and the other which is considered

“bad.” Such data can be entered into the SPERE program as discussed in

Hansen.[1] This program computes the three partial Hansen solubility parameters

and R, the radius of interaction sphere.

One of the more promising methods to evaluate polymer Hansen solubility parameters

for limited data is based on the intrinsic viscosity.[1,20,21] In this paper, a new, simple, and

easy method to estimate the Hansen solubility parameters of polymers is presented. In this

new method HSP is estimated from the intrinsic viscosity of polymer in a number of

solvents and the molar volumes of these solvents.

The authors of this paper consider that good and limiting solvents of a polymer can be

represented in the three-dimensional space of coordinate dd, dp, and dh as a system

of material points with different weights. The weights of the solvents are determined

by the liquid molar volumes of the solvents and intrinsic viscosities, normalized to

unity, of the polymer in the corresponding solvents, as it is well known that the

intrinsic viscosity of a polymer in a given solvent is a measure of polymer-solvent inter-

actions: the higher the interactions, the greater the values of intrinsic viscosity. The

Table 1

Properties of solvents and properties of solutions

Solvents [h]a dd dp dh Solubility V

Dimethyl formamide 0.947 17.4 13.7 11.3 1 77

Diethyl sulfoxide 0.182 18.4 16.4 10.2 1 71.3

gamma-Butyrolactone 0.689 19 16.6 7.4 1 76.8

Morpholine 1 18.8 4.9 9.2 1 87.1

Cyclohexane 0.718 17.8 6.3 5.1 1 104

Diacetone alcohol 15.8 8.2 10.8 0 124.2

Acetone 15.5 10.4 7 0 74

Diethylene glycol 16.2 7.8 12.6 0 118

momomethyl ether

Ethylene glycol 16.2 9.2 14.3 0 97.8

monoethyl ether

Ethylene glycol 15.9 4.7 10.6 0 136.1

monoethyl ether

acetate

a

Normalized intrinsic viscosity data from [h] ¼ [h]i/Max([h]i).[21]

Estimating Hansen Solubility Parameters 289

Table 2

The comparative results between this method and other reported results

Correlation dd dp dh

Ref.[1] 19 11 9

Ref.[1] 20 11 10

This Method 18.1 11.4 8.8

coordinates of the mass center of the system of material points represent the Hansen

solubility parameters of the polymer. It is obvious that the mass center is closer to

solvents with higher weights, the ones with smaller weights being poor solvents for

the polymer. The equations of the coordinates of the mass center, adapted to the

present situation, are:

dhp ¼ Sðdhi ½hvi i Þ=S½hvi i ð10Þ

where subscript index p designates the polymer and vi, [h]i are the molar volume of

solvents and intrinsic viscosity of polymer in the ith solvent normalized to unity. Nor-

malization to unity was done by dividing by the maximum obtained intrinsic viscosity.

Once the coordinates of the interaction sphere (dd, dp, and dh) are determined, the sep-

arating distances from its center to the points corresponding to good and limiting

solvents, Ri, are computed. The highest value of Ri is the well-known Hansen’s relation:

qﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃﬃ

Ri ¼ 4ðddi ddp Þ2 þ ðd pi d pp Þ2 þ ðdhi dhp Þ2 ð11Þ

Using this method to compute the Hansen solubility parameters of a polymer, all the good

and limiting solvents are included in the interior of the sphere or are at least on its surface.

The intrinsic viscosity of a sample of polyesterimide in 11 solvents was measured by

Segarceanu and Leca.[11] The normalized values of these data and the Hansen solubility

parameters of these solvents are shown in Table 1. Some of these solvents thus dissolve

the polymer and have an intrinsic viscosity, and some of them do not dissolve the

polymer and do not have any value of intrinsic viscosity.

The results of this improved method and the values reported by Hansen[1] and

Segarceanu and Leca[21] are compared in Table 2.

The results with this method fit the experimental data well.

Conclusion

1. This method is a very promising method of arriving at the polymer Hansen solubility

parameters with limited data.

2. The method is simple, uses literature data on solvents and polymers, and can be easily

implemented on a computer.

3. The equations used to determine the Hansen solubility parameters are simple and do

not imply special processing.

290 F. Gharagheizi and M. T. Angaji

References

1. Hansen, C.M. Hansen Solubility Parameters: A User’s Handbook; CRC Press: Boca Raton, FL,

2000.

2. Hildebrand, J.; Scott, R.L. The Solubility of Nonelectrolytes, 3rd Ed.; Reinhold: New York,

1950.

3. Hildebrand, J.; Scott, R.L. Regular Solutions, Prentice-Hall Inc.: Englewood Cliffs, NJ, 1962.

4. Scatchard, G. Equilibria in non-electrolyte solutions in relation to the vapor pressures and

densities of the components. Chem. Rev. 1931, 8 (2), 321– 333.

5. Patterson, D.; Delmas, G. New aspects of polymer solution thermodynamics. Off. Dig. Fed. Soc.

Paint Technol. 1962, 34 (450), 677– 692.

6. Delmas, D.; Patterson, D.; Somcynsky, T. Thermodynamics of polyisobutylene-n-alkane

systems. J. Polym. Sci. 1962, 57, 79 – 98.

7. Bhattacharyya, S.N.; Patterson, D.; Somcynsky, T. The principle of corresponding states and the

excess functions of n-alkane mixtures. Physica. 1964, 30, 1276– 1292.

8. Patterson, D. Role of free volume changes in polymer solution thermodynamics. J. Polym. Sci.

Part C. 1968, 16, 3379– 3389.

9. Patterson, D.D. Introduction to thermodynamics of polymer solubility. J. Paint Technol. 1969,

41 (536), 489– 493.

10. Biros, J.; Zeman, L.; Patterson, D. Prediction of the X Parameter by the solubility parameter and

corresponding states theories. Macromolecules 1971, 4 (1), 30 – 35.

11. Barton, A.F.M. Handbook of Solubility Parameters and Other Cohesion Parameters; CRC

Press: Boca Raton, FL, 1983.

12. Barton, A.F.M. Handbook of Polymer-Liquid Interaction Parameters and Solubility Par-

ameters; CRC Press: Boca Raton, FL, 1990.

13. Gardon, J.L.; Teas, J.P. Solubility Parameters. In Treatise on Coatings, Vol. 2, Characterization

of Coatings: Physical Techniques, Part II; Myers, R.R., Long, J.S., Eds.; Marcel Dekker:

New York, 1976, Chap. 8.

14. Burrell, H. Solubility parameters for film formers. Off. Dig. Fed. Soc. Paint Technol. 1972,

27 (369), 726– 758; Burrell, H. A solvent formulating chart. Off. Dig. Fed. Soc. Paint

Technol. 1957, 29 (394), 1159– 1173; Burrell, H. The use of the solubility parameter concept

in the united states. VI federation d’Associations de Techniciens des Industries des Peintures,

Vernis, Emaux et Encres d’Imprimerie de l’Europe Continentale, Congress Book 1962, 21 – 30.

15. Blanks, R.F.; Prausnitz, J.M. Thermodynamics of polymer solubility in polar and nonpolar

systems. Ind. Eng. Chem. Fundam. 1964, 3 (1), 1 – 8.

16. Hansen, C.M. The three dimensional solubility parameter-key to paint component affinities I.

J. Paint Technol. 1967, 39, 104–117.

17. Hansen, C.M. The three dimensional solubility parameter-key to paint component affinities II.

J. Paint Technol. 1967, 39, 505–510.

18. Hansen, C.M.; Skaarup, K. The three dimensional solubility parameter-key to paint component

affinities III. Independent Calculation of the Parameter Components. J. Paint Technol., 1967, 39,

511– 514.

19. Hansen, C.M.; Beerbower, A. Solubility Parameters. In Kirk-Othmer Encyclopedia of Chemical

Technology; Suppl. Vol., 2nd Ed.: Standen, A., Ed.; Interscience: New York, 1971; 889– 910.

20. Van Dyk, J.W.; Frisch, H.L.; Wu, D.T. Solubility, solvency, and solubility parameters. Ind. Eng.

Chem. Prod. Res. Dev. 1985, 24, 473– 478.

21. Segarceanu, O.; Leca, M. An improved method to calculate hansen solubility parameters of a

polymer. Prog. Org. Coat. 1997, 31, 307–310.

- 159Uploaded byMahanani Pramudyaningrum
- What is the Most Comment Solvent in Everyday LifeUploaded byDante Tong
- A Thermodynamic Study of Selective Solvation in Solvent MixturesUploaded byAli Due
- Chapter 6 FFRUploaded byAnto Baitanu
- tugas farfis 1Uploaded bywindyfebriandani
- Solubility of Organic CompoundsUploaded byJeremy Noceda
- EP2079723B1Uploaded bySample Son
- sensors-10-04887Uploaded byGanesh Babu
- ni1995Uploaded byBadruzamanIbad
- Pages From 590Uploaded bypalanaruva
- Solubility&Soln NotesUploaded bykallstea
- Extraction of Caffeine from Tea Leaves of Twinings English Breakfast Tea Using the Single Extraction MethodUploaded byKimberly Mae Mesina
- Pages From 600Uploaded bypalanaruva
- First QuarterUploaded byMaria Danica de Villa
- Extraction.pdfUploaded byDehom Enhad
- test.txtUploaded byalphagamaqq
- Adei Reviewer - blank2.docxUploaded byKimttrix Weizs
- Joc NMR Solvent Peaks Very Important-1Uploaded byjyotibamali
- 1985 Book EnvironmentalGeochemistryAndHeUploaded byDiego Xavier
- Chap 13Uploaded byMarko Quebral
- molecular diffusion in liquidsUploaded byperib
- Ozone Solubilities in Water and Aqueous Salt SolutionUploaded byAriPm
- methylene chloride.pdfUploaded byjayan perkasa
- Nota Tingkatan 2Uploaded byAsif Laa
- Oil-Field Biocides and Bio Based Solvents Market.Uploaded byChemicals IndustryARC
- Experiment 5 (Chemistry)Uploaded byS S Nanthavarman Subramaniam
- Experiments, Modelling and Scale-up for SCE From PlantsUploaded bymurdanetap957
- Exp - S4 - Mass Transfer With and Without Chemical Reaction.docUploaded byAnuj Srivastava
- Promo Carfosel 950Uploaded bySrdjan Jovanovic
- Bonding LabUploaded byThM4

- Gupta, J.P. Et Al. Calculation of Fire and Explosion Index Value for the Dow Guide Taking Credit Fot He Loss Control MeasuresUploaded byMarco Ravelo
- Wang, L-S-., et al. (2013). Ionic Liquids, Solubility Parameters and Selectivities for Organic Solutes. AIChem J. 59(8), 3034-3041.pdfUploaded byMarco Ravelo
- Wang, L-S-., et al. (2013). Ionic Liquids, Solubility Parameters and Selectivities for Organic Solutes. AIChem J. 59(8), 3034-3041.pdfUploaded byMarco Ravelo
- D 2064–91_Standard Test Method for Print Resistance of Architectural PaintsUploaded byMarco Ravelo
- Van Krevelen, D. an Hoftyzer, P. Practical Evaluation of the [η]-M Relationship II. Estimation of Kθ Values of Polymer Solutions. J. Appl. Pol. Sci. 11, 1409, (1967)Uploaded byMarco Ravelo
- Batista, M.L.S., Et Al. (2011). Chameleonic Behavior of Ionic Liquids and Its Impact on the Estimation of Solubility Parameters. Supporting InformationUploaded byMarco Ravelo
- Kemmere, M. et al (2002). Process design for the removal of residual monomer from latex products using supercritical CO2. Chem. Eng. Sci. 57, 3929–3937.pdfUploaded byMarco Ravelo
- Lazzaroni, M. Et Al (2005). Revision of MOSCED Parameters and Extension to Solid Solubility Calculations. Ind. Eng. Chem. Res. 44, 4075-4083Uploaded byMarco Ravelo
- Lazzaroni, M. Et Al (2005). Revision of MOSCED Parameters and Extension to Solid Solubility Calculations. Ind. Eng. Chem. Res. 44, 4075-4083Uploaded byMarco Ravelo
- Clausen, I. and Arlt, W. (2002). a Priori Calculation of Phase Equilibria for Thermal Separation Processes Using COSMO-RS. Chem. Eng. Technol. 25(1), 254-258Uploaded byMarco Ravelo
- Ivey, K.; Et Al. 2011. Computational Modeling of the Dehydrogenation of Methylamine. J. Mex. Chem. Soc. 55(1), 11-15Uploaded byMarco Ravelo
- Willey, R.; Fogler, H.S. & Cutlip, M.B. (2011). The Integration of Process Safety into a CRE Couse, Kintic Modeling of the T2 Incident. Proc. Saf. Prog. 30(1).pdfUploaded byMarco Ravelo
- Willey, R.; Fogler, H.S. & Cutlip, M.B. (2011). The Integration of Process Safety into a CRE Couse, Kintic Modeling of the T2 Incident. Proc. Saf. Prog. 30(1).pdfUploaded byMarco Ravelo
- Prasad, P.R. Et Al. 1990. Multiloop Control of a Polymerization Reactor. Pol Eng Sci. 30(6), 350-354Uploaded byMarco Ravelo
- Wang, Q. et al. (2017). Optimal design of a new aromatic extractive distillation process aided by a co-solvent mixture. Energy Procedia, 105, 4927-4934.pdfUploaded byMarco Ravelo
- Prediction of Acidity in Acetonitrile Solution With COSMO-RS. Journal of Computational Chemistry, Wiley (2008)Uploaded byMarco Ravelo
- The partial solubility parameters_An equation-of-state approach. Fluid Phase Equilibria, 240 (2006) 144-154.pdfUploaded byMarco Ravelo
- The partial solubility parameters_An equation-of-state approach. Fluid Phase Equilibria, 240 (2006) 144-154.pdfUploaded byMarco Ravelo
- Interpretacion de Resultados de PL en WinQSBUploaded byFide Garcia Torres
- Oishi, T. & Prusnitz, J. M. (1978). Solubilities of Some Volatile Polar Fluids in Copolymers. Ind. Eng. Chem. Fundam., 17(2), 109-113Uploaded byMarco Ravelo
- Matteoli, E. & Mansoori, G. (1995). a Simple Expression for Radial Distribution Functions of Pure Fluids and Mixtures. J. Chem. Phys. 103(11), 4672-4677Uploaded byMarco Ravelo
- Dhakal, P. Et al (2018). GC-MOSCED a Group Contribution Method for Predicting MOSCED Parameters. Fluid Phase Equilibria. 470, 232-240Uploaded byMarco Ravelo
- Dhakal, P. Et al (2018). GC-MOSCED a Group Contribution Method for Predicting MOSCED Parameters. Fluid Phase Equilibria. 470, 232-240Uploaded byMarco Ravelo
- Modelo de Solvatación COSMOTHERMUploaded byMarco Ravelo
- CE IndexUploaded byPablo Javier
- Cambio de Los Coeficientes de Transferencia en Reactores de Desintegración Catalítica. Maya Et Al. Rev. Mex. Ing. Quim. Vol. 2 (2003) 63-68Uploaded byMarco Ravelo
- Matteoli, E. & Mansoori, G. (1995). A simple expression for radial distribution functions of pure fluids and mixtures. J. Chem. Phys. 103(11), 4672-4677.pdfUploaded byMarco Ravelo
- Seki, S., et al. (2007). Effects of Alkyl Chain in Imidazolium-Type Room-Temperature Ionic Liquids as Lithium Secondary Battery Electrolytes. Electrochem. Solid-State Lett., 10(10) A237-A240.pdfUploaded byMarco Ravelo
- capcaity of chemical plant.pdfUploaded bykalyan555
- Cai, J. & Prausnitz, J. M. (2004). Thermodynamics for Fluid Mixtures Near to and Far From the Vapor–Liquid Critical Point. Fluid Phase Equilibria 219, 205–217Uploaded byMarco Ravelo

- Ndonesian Lake ManagementUploaded byKarlina Dewi
- PCM600_EjemploUploaded byCarlos Joan Camarena
- 9780387681870-c1Uploaded byTan Ching
- Introduction to the Special Issue Social Commerce. a Research Framework for Social Commerce. - LiangUploaded byfirebirdshockwave
- Collapsed StructuresUploaded byhello3232
- Modular Quality of Service Command-Line Interface OverviewUploaded byJilani Bouslama
- (Theoretical Perspectives in Architecture) Massimo Cacciari, Stephen Sartarelli (Transl.), Patrizia Lombardo (Introduction)-Architecture and Nihilism_ on the Philosophy of Modern Architecture-Yale UniUploaded byJadestin
- SQL Server 2005 Integration ServicesUploaded byLearnItFirst
- Microbiology in the 21st CenturyUploaded byThayumanavan
- Strategic ManagementUploaded byAdriana Popescu
- A Graphical Exploration of SPC.Uploaded bysofkk
- Calculating Forces in Pulley Mechanical Advantage Systems MaUploaded byAbdel Naser Al-sheikh Yousef
- cmocbUploaded byDean Arig
- Case Study PRISMS Goa Final P.pdfUploaded byCheGanJi
- math lesson planUploaded byapi-351996034
- MosheIdel-MessianicMystics.pdfUploaded bySoftbrain
- LEED v4 Ballot Version (BDC) - 13 11 13Uploaded byrasheedillikkal
- idmtUploaded byAdeel Raza
- honoring diversity checklistUploaded byapi-235065651
- When Onshore BPO Makes SenseUploaded byAlan Veeck
- Bourdon TubeUploaded bycocojam
- Research PaperUploaded byYusuf Sarıgöz
- Dagmar ModelUploaded byDheerendra Singh
- IRB460Uploaded byLucas Vinícius Costa
- Secrets of varga chartsUploaded byVenkatesh Bindu
- Exam P SampleUploaded bybezner_paul
- half harmonic oscillator.pdfUploaded byArkayan Laha
- BUploaded byANA MARIA CRISTIANA
- 94523.pdfUploaded by0917802400
- spu-lexicographyUploaded byBalazs Cs.