Fahlman B.D. Materials Chemistry

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C.2.1. Procedure

CAS Registry Numbers for Chemicals:

Sodium aluminate: 1302-42-7

Copper (II) chloride dihydrate: 10125-13-0

1,4-phenylenediamine: 106-50-3

Ethanol, 200-proof: 64-17-5

Carbon dioxide (bone-dry grade): 124-38-9

Synthesis of aluminum oxide nanoparticles

1. Clean a silicon wafer by rinsing with distilled water, and dry with KimWip es.

Place the clean silicon substrate in a tall beaker, and place in the supercritical

ﬂuid reactor using long tweezers. With assistance from the instructor, fasten the

reactor to the supercritical ﬂuid syst em.

2. Using solid sodium aluminate powder, prepare a 4% (w/v) aqueous aluminate

solution in an 8-mL vial, and shake vigorously until dissolved. Filter this solu tion

into a clean 8-mL vial through a disposable pipette ﬁtted with a cotton plug.

3. In a separate 8-mL vial, p lace 0.2 g of the surfactant ( ask instructor which one to

use) in 6 mL of heptane (if AOT: sodium bis(2-ethylhexyl)sulfosuccinate) or

water (if ﬂuorinated surfactant: ammonium carboxylate perﬂuoropolyether –

[CF

O(CF

CF(CF

)O)

COO]



[NH

]

). Shake vigorously until the surfac-

tant is completely dissolved. Add two drops of the ﬁltered aluminate solution to

the surfactant solution, and shake vigorously until one phase is obtained (i.e., the

ﬁnal solution should not be cloudy).

4. With consultation with the instructor, prime the cosolvent pump and set the

appropriate reactor temperature and pressure (see Figure C.2).

5. Once the reactor pressure and temperature has stabilized, inject the microemul-

sion solution using the cosolvent pump.

6. After the microemulsion solution has been added to the reactor, allow the

pressure to remain at its initial setting. After this time, ﬂush the reactor for

5 min with a dynamic ﬂow of carbon d ioxide.

7. Vent the system and disconnect the reactor. Remove the silicon wafer using

tweezers and place in a vial until characterization studies are performed. Dip half

of the coated wafer in heptane (if AOT was used) or water (if ﬂuorinated

surfactant was used) and allow to air dry. Store the coated wafer until analysis

by placing it in a plastic weighing tray (polished side up), and place another

weighing tray on top. Completely tape the two-weighing trays together to prevent

dust from forming on the coated wafer.

Synthesis of copper nanoparticles

1. Prepare a 0.05 M copper solution using CuCl

·2H

O in absolute ethanol

(200 proof), and transfer this to a clean 8-mL vial. Also prepare a 0.04 M aqueous

solution of 1,4-phenylenediamine, and transfer to a second clean 8-mL vial.

698 Appendix C. Materials-Related Laboratory Experiments

Position the vials within the supercritical ﬂuid reactor, avoiding any contact

between the solutions. With consultation with your instructor, allow the system

to reach the desired pressure and temperature. Maintain these conditions for

45 min.

2. Vent the system and remove the vials from the reactor. Note color changes,

turbidity, and phases (i.e., is there one liquid present, or does there appear to be a

layer of two liquids?) of both solutions. Remove both vials and keep tightly

sealed until characterization studies are performed. Comment on what you

observe in the Results and Discus sion section of your formal report.

3. Repeat step 1 using ethanol for both copper and phenylenediamine solutions.

This time, when you vent the system after 45 min, place a carbon TEM grid at the

base of the collector vessel (the instructor will point this out). This technique,

known as RESS (rapid expansion of the supercritical solution), is a unique beneﬁt

of performing reactions in supercritical ﬂuids. When the system is vented, the

gas/liquid carbon dioxide expands, being rapidly converted from its original

Figure C.2. Photograph of the supercritical ﬂuid system used for nanoparticle synthesis. Shown is the

300-mL high-pressure reactor (A), with pressure/temperature controllers (B). The system is rated for

safe operation at temperatures and pressures below 200



C and 10,000 psi, respectively. The vessel may be

slowly vented, or exposed to a dynamic CO

ﬂow, using a multiturn restrictor valve (C), which provides

a sensitive control over system depressurization, allowing for the collection of CO

-solvated species in the

stainless steel collector (D). For deposition using the rapid expansion of the supercritical solution (RESS),

nanoparticles were blown onto a TEM grid that was placed under the stopcock below D. Also shown is the

cosolvent addition pump (E) used for the synthesis of aluminum oxide nanoparticles, capable of delivering

liquids into the chamber against a back-pressure of 5,000 psi.

C.2. Supercritical Fluid Facilitated Growth 699

high-pressure environment to a low-pressure gas. Place the gri ds in a vial for

characterization studies.

C.3. SYNTHESIS AND CHARACTERIZATION OF LIQUID CRYSTALS

(Van Hecke, G. R.; Karukstis, K. K.; Li, H.; Hendargo, H. C.;

Cosand, A. J.; Fox, M. M. J. Chem. Ed., 2005, 82, 1349)

This experiment will introduce you to some tec hniques of chemical synthesis based

on acid-base reactions, puriﬁcation by recrystallization, and brief characterization

by melting point. Also on the characterization side, you will investigate the absorp-

tion of polarized light by matter. A liquid crystal is a state of matter neither liquid

nor crystal but a state in-between. Liquid crystals are often called mesophases after

the Greek mesos for middle. Normally when a crystal melts it forms an ordinary

liquid phase. However, a substance which exhibits liquid crystalline behavior melts

at least twice, ﬁrst into the liquid crystalline or mesophase, and second, into the

ordinary liquid.

Molecules in a mesophase exhibit orientation with respect to each other, and, in

certain types of liquid crystals, exhibit some extent of ordered position with respect

to each other. Thus, mesophases are described by degrees of orientational and

positional order. Using ordering as a basis, liquid crystals fall into two types:

nematic and smectic. Nematic mesophases possess only orientation order while

smectic mesophases possess orientational and some positional order (Figure C.3).

Also shown in Figure C.3 is a special type of nematic phase, the chiral nematic or

Director

NEMATIC

SMECTIC

CHOLESTERIC (CHIRAL NEMATIC)

Pitch

Optical axis

Figure C.3. Schematic of three mesophases: the nematic and cholesteric (which have only orientation

order) and the smectic phase (which has orientational and positional order).

700 Appendix C. Materials-Related Laboratory Experiments

cholesteric phase (cholesteric is the older and still more common name but chiral

nematic is now the correct name). In this phase, not only do the molecules compris-

ing the phase point more or less in the same direction on a local scale, but also on a

larger scale that direction changes following a helix. The quantity called pitch is

deﬁned as the physical distance required for one complete revolution about the

optical axis. Cholesteric phases were the ﬁrst liquid crystals ever observed, and for

many years were thought to be a separate type of liquid crystal. Now it is known that

what made cholesteric liquid crystalline materials different is the fact that they are

composed of optically active or chiral molecules. The cholesteric phase derives its

name from the fact that the ﬁrst substances observed to exhibit what we today call

liquid crystallinity were derivatives of the naturally occurring substance cholesterol.

While many commercial liquid crystal devices employ the chlolesteric phase to

function, cholesterol and its derivatives are important objects of study in med icine

since cholesterol derivatives are components of the deposits that form on the wall of

arteries and lead to hardening of the arteries.

A nematic mesophase forms when rod-like molecules orient themselves on

average in a given direction. The director of the phase is a vector that points in a

direction determined by looking at the average of the directions in which all the

molecules point or are oriented. The director’s orientation is a function of tempera-

ture, pressure, and applied electric and magnetic ﬁelds. The many practical applica-

tions of liquid crystals depend critically on modifying the director by external

inﬂuences. This experiment will be partly concerned with what factors affect

the director of the cholesteric phase, which is the direction in which any local

collection of molecules points. What happens to the cholesteric director as a

function of temperature will be studied by determining the pitch of the phase as

a function of temperature.

Substances in their liquid crystalline phase behave like liquids in that they ﬂow

and ﬁll any shape container in which they are placed. However, even though they are

ﬂuids, they retain certain optical properties characteristic of a solid, especially those

optical properties which are inﬂuenced by polarized light. For this experiment how

the plane of polarization of plane polarized light changes on passage of such light

through a mesomorphic medium is particularly crucial. In the cholesteric meso-

phase, the director, which remember reﬂects the local organ ization of a collection of

molecules, follows a helica l path. The sense of this helix, left or right, determines the

angle of rotation of plane polarized light incident on a cholesteric sample. The pitch

of the helix also depends on external inﬂuences. In fact, the exact pitch is dependent

not only on temperature and pressure, but also in the case of mixtures of liquid

crystals, also on composition. You may choose to explore the effect of composition

during the second week of this experiment.

During the ﬁrst week of this experiment, you will synthesize cholesteryl non-

anoate, which is an ester derivative of cholesterol, and perform some simple

characterizations to test your successful synthesis. Cholesteryl nonanoate (ChNon)

is known to exhibit a chiral nematic, i.e., a cholesteric, liquid crystalline phase.

While you will synthesize and characterize cholesterol nonanoate, you will actually

C.3. Synthesis and Characteri zation of Liquid Crystals 701

study mixtures of two liquid crystalline materials each of which is a derivative of

cholesterol. The other derivative is cholesteryl chloride (ChCl) whose structure

along with that of cholesterol nonanoate is shown in Figure C.4. The reason to

study mixtures here is for convenience of handling. Though both pure materials

exhibit liquid crystalline phases (ChNon: at 74



C, solid:smectic; 80



C smectic:

cholesteric; 93



C cholesteric:isotropic, and ChCl: about 70



C, solid:cholesteric),

appropriate mixtures are liquid crystalline at much lower and more manageable

temperatures, for example, room temperature.

The driving force for the chemical reactions used in the synthetic scheme outlined

below is most readily understood in terms of Lewis acid-base chemistry. To begin,

cholesterol is dissolved in pyridine. According to the Lewis deﬁnition of acids and

bases, in which acids and bases are described in terms of their propensity to accept or

donate electron pairs, cholesterol is a weak acid (an electron pair acceptor) and pyridine

is a strong base (an electron pair donor). These two chemicals, then, undergo an acid-

base reaction, transferring a proton (an electron acceptor) to yield the pyridinium ion

and a negatively charged cholesterol species (which results as the proton accepts the

electrons from the pyridine leaving behind a negative charge on the cholesterol).

The next step involves the addition of nonanoyl chloride and is also understood

using the Lewis deﬁnition. The carbonyl (C═O) group on nonanoyl chloride is very

polar, yielding an electron-deﬁcient carbon, which is then a Lewis acid. The

negative cholesterol ion is an electron donor, or Lewis base, and reacts with the

positive carbon center to form a new bond and release a chloride ion. This chloride

ion is then neutralized by the pyridinium ion in another Lewis acid-base reaction to

form pyridine hydrochloride. Pyridine hydrochloride is soluble in water, while the

newly synthesized cholesteryl nonanoate is not. Addition of the reaction mixture

to aqueous sulfuric acid causes only the desired product, cholesteryl nonanoate, to

CHCl

Figure C.4. Molecular structures of (a) cholesterol nonanoate (ChNon) and (b) cholesteryl chloride

(ChCl). Pure cholesterol has the structure of cholesteryl chloride with the Cl replaced by a OH group.

702 Appendix C. Materials-Related Laboratory Experiments

precipitate. The resulting solid, collected by ﬁltration, contains impurities which you

will remove by recrystallization. While the reaction is straightforward, there are

certain hazards which must be avoided. Both pyridine and nonanoyl chloride react

readily with water in the air, forming the pyridinium ion and nonanoic acid. Even a

small amount of decomposition of these essential reactants will cause the intended

reaction to fail. For this reason, these reactants should be distilled prior to use, and

stored in such a way to minimize their contact with air.

C.3.1. Procedure

CAS Registry Numbers for Chemicals:

Cholesterol: 57-88-5

Dry nonanoyl chloride: 764-85-2

Cholesteryl chloride: 910-31-6

Reagent acetone: 67-64-1

1 M sulfuric acid: 7664-93-9

Dry pyridine: 110-86-1

Filter ﬂask (125 mL)

Buchner funnel

Two dram vial with screw cap

Glass stir rod

Graduated cylinder (50 mL)

Stir hot plate with magnetic stirrer

Rubber septum

Disposable syringes and needles

Microscope slides

Mylar ﬁlm and tape

Digital voltmeter

Polarizer sheet and l/4 wave plate

Melting point apparatus

Beckman DU650 spectrophotometers with temperature controllers and cell

holders

Abbe refractometers with temperature controllers

Thermocouple

1. Place about 1.5 g of cholesterol in a 125-mL Erlenmeyer ﬂask. The

cholesterol should be recrystallized from acetone prior to acquiring a

pure sample. Add 5–8 mL of dry pyridine (obtained by distillation over

potassium hydroxide) and a stir bar to ﬂask. Work quickly and carefully

when transferring the pyridine to the ﬂask, to minimize water absorption

from the ambient atmosphere. Once pyridine is transferred, immediately

cap ﬂask with a rubber septum and drying needle.

2. Stir solution in an ice/water bath for about 10 min. The cholesterol should

be dissolved. Use a plastic dish for the ice bath container.

C.3. Synthesis and Characteri zation of Liquid Crystals 703

3. Ensure that the nonanoyl chloride to be used is dried via distillation in

vacuo, and stored in a sealed stock bottle for maximum purity. Acid

chlorides, such as nonanoyl chloride, readily react with water to form the

corresponding carboxylic acid. Withdraw 1.2 mL of nonanoyl chloride

from the stock bottle using a fresh, clean/dry plastic syringe ﬁtted with a

syringe needle. Pass the syringe needle through the rubber septum on the

reaction ﬂask and add the nonanoyl chloride dropwise and slowly. Since

the amount of nonanoyl chloride is not the limiting reagent, you do not

need to be extremely concerned with the exact amount added provided the

amount is adequate. The amount added may be estimated by noting the

volume delivered by the syringe and the volume should be about 1.2 mL. A

precipitate should form on the addition of the acid chloride.

4. Stir the reaction mixture in an ice bath for 30 min using a magnetic stirrer.

Remove solution from ice bath and continue stirring at room temperature

for an additional 30 min on the magnetic stirrer.

5. Pour 50 mL of cold 1 M H

into the solution. Stir vigorously by hand

using a glass stir rod to break up oil globules. Collect the solid which is

your impure product using a typical suction ﬁltration appar atus. Draw air

through the sample for several minutes. Visual inspection should suggest

when the sample is relatively dry and ready for the next step.

6. To purify your product, recrystallize your collected solid from acetone. To

accomplish this, transfer the solid to a 125-mL ﬂask. Add a small amount

(20 mL to start) of acetone and a stir bar. Heat to fully dissolve the solid.

Add small amounts of acetone, order 1 mL at a time, as needed, to aid in

the dissolu tion. When solid is dissolved, remove from heat. Cool with the

aid of an ice bath. Crystals should form. If they do not, try scratching the

inside of the ﬂask with a glass rod. Or, boil off some solvent and recool.

Remove these crystals by suction ﬁltration just as you did to collect your

impure produc t. Wash these crystals with a cold 5 mL portion of acetone

and allow them to dry on the ﬁlter paper. Transfer to a preweighed vial.

Calculate yield of cholesteryl nonanoate from cholesterol and calculate the

conversion of cholesterol to cholesteryl nonanoate.

7. Using appropriate melting point apparatus, characterize the melting behav-

ior of the puriﬁed solid. Cholesteryl nonanoate exhibits a chiral nematic,

more commonly known as a cholesteric, liquid crystalline phase around



C and melts to the isotropic liquid around 93



C. The cholesteryl non-

anoate ﬁrst melts to form a smectic phase around 75



C and with further

heating transforms to the cholesteric phase around 85



8. In order to calculate the pitch of the liquid crystal, you will need the

average refractive index at several temperatures. Use an Abbe refractome-

ter to measure the refractive indices of your liquid crystal at a number of

different temperatures, about every 10



from room temperature to

60–70



704 Appendix C. Materials-Related Laboratory Experiments

9. As mentioned above you will be studying mixtures of cholesteryl

nonanoate and cholesteryl chloride rather than the pure materials. Mix-

tures are used for the convenience of working at temperatures closer to

room temperature. To prepare a mixture of a given composition, use the

mole fraction composition scale. A mole fraction of a component in a

mixture is deﬁned as the number of moles of that component in the mixture

divided by the total number of moles of all components in the mixture.

To actually prepare a mixture, add the desired amounts of each component

to a screw cap vial. Mix the components physically with a spatula to make a

reasonably uniform mixture of the solids. Place the vial in a sample oven

whose temperature has been set to about 100



C and allow the solids to melt

and mix. Mix the sample while hot, again with a spatula. At the oven

temperature the sample should appear clear since it should be in the isotropic

phase. As the sample cools note what happens.

10. Full details rega rding the determination of selective reﬂection and refrac-

tive indices may be found online (http://www.jce.divched.org/Journal)in

the Supplementary Documentation for the above article.

C.4. TEMPLATE SYNTHESIS AND MAGNETIC MANIPULA TION

OF NICKEL NANOWIRES

(Bentley, A. K.; Farhoud, M.; Ellis, A. B.; Lisensky, G. C.; Nickel, A. -M. L.;

Crone, W. C. J. Chem. Ed., 2005, 82, 765)

C.4.1. Procedure

Whatman Anodisc alumina membranes with polypropylene support rings (25-mm

membrane diameter) 0.02-mm pore diameter

Tweezers

Electrical tape

Cu sheet (12

 12

is enough to mak e approximately 15 substrates)

Nickel wire, 1 mm diameter  10 m long, 99.5%

AA batteries

Battery holders

Wires with alligator clips

Nickel electroplating solution

Compound optical microscope

Microscope slides and coverslips

Bar magnets

SEM specimen mounts

Note. The alumina membranes have 20-nm diameter pores on the upper face that

quickly widen within 5 mm of the surface to 200 nm throughout the membrane. Thus

one face has 20-nm pores and the other has 200-nm pores. The membranes are packed

C.4. Template Synthesis and Magne tic Manipulation 705

with the 20-nm pores facing upward, but the two faces cannot be easily distinguished

visually. However, the clear polypropylene support ring is wider on the 20-nm pore

side of the membrane, which is the side that will be coated with the conductive layer.

1. The Cu plates and battery holders should be prepared before the lab period

and can be reused indeﬁnitely. Cut rectangles of copper sheet approximately

1.25

 2

and then cut out corners of the rectangle to form the stem that is used

for electrical contact. We used a variety of copper sheets that ranged from 0.03

to 0.06

in thickness. To assemble the battery holder, ﬁrst cut a double-e nded

test lead in half using wire cutters. Then strip the cut ends and solder each lead

to the clip on one end of a battery holde r.

2. Remove an alumina membrane from the package by holding the polypropylene

support ring with tweezers (discard the paper circles separating the membranes

from each other). Always use tweezers to hold the membranes by the support

ring; the alumina will crack if handled directly. Cracked membranes cannot be

used for deposition, as the solution will leak through the membrane and deposit

on the copper plate. Dispose of cracked membranes in a glass disposal box.

There are two methods of applying a conductive backing to the membranes. If a

sputter coater is available (such as those used to coat samples with gold for

SEM), then a 250-nm thick layer of silver can be sputtered onto each membrane

before the lab period. An alternative method that can be used during the lab

period is to have students paint the upward-facing side of the membrane (the side

with 20-nm pores; see above) with GaIn eutectic using a cotton-tipped stick.

Students will not need to dip the cotton end into the GaIn more than once or

twice. The GaIn is applied by gently rubbing the GaIn-coated cotton tip over the

membrane surface. Students can check for gaps in the GaIn coating by looking at

the noncoated face of the membrane: any areas without GaIn will appear light

blue in color. Areas with GaIn will appear white or opaque. We have observed

similar success rates with either silver or GaIn as the conductive coating.

3. After the conductive layer is applied, mount the membrane on a copper plate

with the conductive, metal-coated side facing the copper by taping the mem-

brane’s support ring to the copper using insulating electrical tape, as shown in

Figure C.5 (top). Little if any electric tape should come in contact with the

alumina membrane, as it is hard to remove. It is essential to completely cover

both sides of the copper plate with the electrical tape to prevent any unwanted

electrodeposition on the copper. Leave the stem uncove red so electrical contact

can be made wi th the alligator clip, but this section of the copper should not

make contact with the electrolyte.

4. Set a AA battery inside the battery holder, making sure to align the positive and

negative ends of the battery with the labels on the holder. Clip the negative lead

from the battery to the exposed part of the copper and clip the positive lead to

the nickel wire. Place the two electrodes in a 50-mL beaker with the membrane

surface facing the nickel wire (Figure C.5 (bottom)).

5. After the electrodes are arranged in the beaker and connected to the battery,

pour in enough Ni-plating solution to just cover the top of the membrane

706 Appendix C. Materials-Related Laboratory Experiments

(approximately 40 mL). The electrodeposition of nickel will begin as soon as

the solution completes the circuit.

6. As the electrodeposition takes place, the membrane surf ace changes color from

a pale yellow/orange (for silver backing) or yellow/white (for GaIn backing)

to black. Allow the cell to sit for 50 min to make nanowires that are ~50 mm

long. To make shorter nanowires, stop the reaction sooner. The minimum time

required to produce nanowires that are visible using an optical microscope is

10 min.

7. To halt deposition, remove the battery from the cell and disconnect the wires

from the electrodes. Remove the Cu plate from the solution and rinse the

membrane surface with deionized water. The nickel-plating solution can be

returned to its original container and reused indeﬁnitely. We have used the same

500 mL of plating solution for approximately 50 deposit ions without any

noticeable change in quality.

Figure C.5. (top) Placement of the membrane on the copper electrode, fastened with electrical tape.

(bottom) The electrochemical cell used to synthesize Ni nanowires.

C.4. Template Synthesis and Magne tic Manipulation 707