ChE 143

Sept 22, 2016

● After weighing HEC, immediately add NaOH/thiourea solution without lifting container from the
balance. (more accurate this way)

Sept 30, 2016

● REVISED METHODOLOGY:
➢ Collect samples from oven.
➢ Wipe containers clean of remaining solution then flip hydrogel such that bottom is facing
upwards.
➢ Put the hydrogel back in the oven and dry for 1 hour. (Or based from their notes at other dates,
they usually dry the hydrogel until it is completely dry.)

Oct 25, 2016

● Centrifuged sample at 4000 rpm for 3 mins. Centrifugation was repeated for 3 mins.
● Centrifugation time does not affect the amount of adhesive separated.
● Centrifuged sample: 30 g of TAPE
● Usable TAPE recovered: 19.9815 g of TAPE (66.605% yield)

Oct 26, 2016

● Tannic acid is stable and processable at T<200°C. (Xia, et al. 2014)

● Polyethylene glycol degrades significantly with air at T=80°C.
● TAPE was left to settle over sample C and while they were scraping off the TAPE, they found out
that it had formed a solid over the HEC layer that takes considerable force to separate.

Method of application Observation

B Oven-dried sample at 50°C for 30 Adhesive layer hardened and lost its tack
minutes

C Hand-pressed and over-dried at 50°C Upon peeling, a thin layer of adhesive stuck
for 30 minutes to the hydrogel layer; most of the adhesive
stuck to the glass slide

D Hand-pressed and air-dried sample Adhesive stuck to layer of HEC but removal
from glass is difficult, resulting to breakage
of adhesive

Oct 27, 2016

● Observations on TAPE layer:

➢ Adhesive forms a layer in itself but does not adhere to hydrogel.
➢ TAPE loses tack as it is exposed to air.
Nov 21, 2016

Sample Area (mm2) Slide + HEC (g) TAPE (g)

A 9.11 x 31.77 5.5943 0.0686
B 9.38 x3 1.49 5.7394 0.1994
C 9.41 x 30.66 5.6113 0.0469
● Allowed to settle for 10 minutes.
● The adhesive did not stick to the hydrogel upon removal.
● Sample D 0.0393 g of TAPE
● OBSERVATIONS: A white substance precipitates when we apply TAPE to the hydrogel.
● “I tried to observe the effect of NaOH/thiourea in the adhesive, whether it was the cause of the
whitening. No such whitening was observed upon mixing, and upon addition of HEC, gelation still
occurred. Will try to investigate blending again, seeing as layering seems far from effective.”

Nov 22, 2016

● Cause of whitening was explored. Since NaOH and thiourea seemed to be the cause of such whitening,
TAPE was tested with each separately.
➢ w/ thiourea: No observable change with the TAPE
➢ w/ NaOH: TAPE seemed to react with NaOH, causing the whitening to occur. A black
liquid was also found when the two were mixed.
● Washed hydrogel samples with distilled H2O 3 times to attempt removal of NaOH and thiourea on the
surface. Fourth wash is already relatively clear.
● Oven-dried hydrogels at T=60°C for drying curve. But they discontinued this and just dried samples
for 30 minutes due to lack of time since liquid water resurfaced again.

Nov 23, 2016

● Made 3 HEC samples (20mm by 20 mm) with 0.1 gram of TAPE, heated at T=30°C at different time
periods (t=10, 20, and 30 minutes).
➢ RESULT: Tested adhesion on filter paper (to simulate fibrous substrates) but all samples did
not adhere.
● Made 3 HEC samples (20mm by 20 mm) with 0.3 gram of TAPE, heated at T=30°C at different time
periods (t=10, 20, and 30 minutes).
➢ RESULT: Peeled off wax paper from samples and some of the adhesive stuck to the wax paper.
(THUS, HEC-TAPE BONDS MUST BE STRENGTHENED.)
➢ RESULT: Hydrogels successfully adhered to filter paper upon peeling of samples with t=10
and 20 mins, but some TAPE stuck to the paper surface. All TAPE from t=30 minutes was
stuck to the paper.
● Looking into dispersing TAPE and applying over HEC surface through brushing. Added Tween-80 to
some TAPE and allowed to emulsify for 1 hour.
Nov 24, 2016

● Prepared 3 samples.
➢ Sample A: 5.0022 g HEC + 35.0065 g crosslinking solution
➢ Sample B: 5.0066 g HEC + 34.9973 g crosslinking solution
➢ Sample C: 5.0069 g HEC + 35.0192 g crosslinking solution

Dec 1, 2016

● Placed samples A, B, and C in oven at T=60°C.

● Tried to increase chain length of PEG using H2O2 before reacting with TA.
➢ PEG (x=400): 2.0057 g
➢ H2O: 2 mL
➢ H2O2: 4.0113 g

Dec 2, 2016

● Removed samples from oven.

● Washed samples 3 times in distilled water and oven-dried at T=60°C for 30 minutes.
● Bottom was still not dry so flipped hydrogel and oven-dried again for 30 minutes.
● Prepared 2 specimens from sample A.
➢ Spec 1: HEC layered with TAPE with H2O2.
➢ Spec 2: HEC layered with TAPE (regular).
● Allowed to air-dry.

Dec 5, 2016

● Specimens 1 and 2 successfully adhered after application of mild pressure. Upon removal, no
adhesive was retained in the wax paper substrate
● To quantify the result above, experiments on adhesive mass and drying time are performed.

Trial Specimen (LxW, cm2) Adhesive mass (g) Drying time (days)

1 1.181 x 2.065 0.2120 1

2 1.263 x 2.141 0.1092 1

3 1.259 x 2.185 0.0498 1

4 1.349 x 2.092 0.1992 2

5 1.235 x 2.132 0.1086 2

6 1.168 x 2.337 0.0687 2

7 1.155 x 2.062 0.2098 3

8 1.136 x 2.116 0.1150 3

9 1.316 x 2.173 0.0761 3

● All samples were air-dried.
Dec 6, 2016

● Tested Samples 1, 2, and 3.

➢ Adhesive 1: Stuck to the filter paper but the adhesive layer fell apart from the hydrogel.
The adhesive was also still wet.
➢ Adhesive 2: Became relatively dry but adhered nicely to the filter paper.
➢ Adhesive 3: Became too dry. It did not adhere to the filter paper.

Dec 7, 2016

● Tested Samples 4, 5, and 6.

➢ Adhesives 4, 5, and 6 adhered to the filter paper upon application of mild pressure.
➢ Samples were positioned upright to test if they would fall by the force of gravity alone.
ChE 144
Feb 13, 2017

● Centrifuged samples of adhesive at 4,000 rpm for 10 minutes. Samples displayed lighter-colored
adhesives at the top layer which are removed manually.
● (D-1) Added 5-g sample of adhesive to hydrogel D-1
➢ Hydrogel + petri dish + cap = 23.8317 g
➢ Hydrogel + petri dish + cap + TAPE = 27.3301 g
➢ NOTES:
▪ 5-g TAPE was not enough to cover the entire area of the hydrogel.
▪ Lighter-colored adhesive appears immediately upon distribution of the adhesive
over the surface. Earlier tests indicated that this activity is due to the presence of
NaOH in the surface of the hydrogel.
▪ Blue to blue-green spots also starts to appear in the hydrogel within approximately
two minutes.
▪ Lighter-colored areas seem to be comprised of air bubbles.
▪ After approximately 10 minutes, the entire area of the adhesive has turned to a
lighter color of brown. Bubbles have also lessened considerably. However, the sizes
increased.
▪ The black/blue coloration seeped through the hydrogel and is now observable on
the areas of the adhesive area.
▪ After approximately an hour, dark-colored blotches increased in number, and the
dark coloration has also become very defined along the edges of the adhesive surface.
● (D-2) Due to results from D-1, we decided to wash off the remaining dried cross-linked solution on
the hydrogel surface by wiping it with moist sponge and re-drying at 30°C for 10 minutes.
(Oven-dried for 13 minutes but surface is still wet)
➢ Hydrogel + petri dish + cap = 23.8320 g
➢ Hydrogel + petri dish + cap + TAPE = 31.4097 g
➢ NOTES:
▪ 7.5-g TAPE was not enough to cover most of the hydrogel surface.
▪ No color lightening was observed.
▪ Dark blotches still appeared almost immediately.
▪ They hypothesized that the coloration is due to the unused tannic acid trapped in
the supernatant occluded in the solid phase.
▪ Blotches started appearing approximately 30 minutes after application.
● (D-3) Same as D-2. Wiped off the NaOH-thiourea from the surface using moist sponge. (Oven-dried
for 19 minutes but surface still glistens with moisture, but not enough for water to flow over the
surface)
➢ Hydrogel + petri dish + cap = 23.6016 g
➢ Hydrogel + petri dish + cap + TAPE = ???
➢ NOTES:
▪ 10-g TAPE almost covered the entire surface. However, the adhesive surprisingly
amounts to almost as much as the 7.5-g TAPE sample only.
▪ No color-lightening was observed. However, dark-colored blotches are still visible,
but in smaller numbers.
● Also tested the possibility of using an acid to remove the NaOH which causes the coloration of the
adhesive. Sample was submerged in 50:50 d H2O and 37% HCl solution.
➢ NOTES:
▪ Upon putting the acid solution to the dish, gas evolved around the hydrogel
specimens.
Feb 14, 2017

● Weighed specimens submerged in HCl solution.

➢ NOTES:
▪ There is a significant mass loss in hydrogel when washed with HCl.
▪ Texture of hydrogel became gum-like.
▪ Adheres strongly to the plastic spoon used.
● (D-1) Sample has been allowed to settle for approximately 20 hours.
➢ NOTES:
▪ Color of the adhesive is predominantly light brown, with large blackish-brown
blotches.
▪ Black coloration has seeped through the hydrogel and outlined the adhesive area
~1mm.
▪ No observable tannic acid smell. Odor is predominantly hydrogel odor.
▪ When they tried to remove the hydrogel from the dish, bending of the hydrogel
caused separation of the adhesive layer.
▪ Tannic acid odor re-appeared upon peeling off the adhesive layer.
▪ TAPE hardened into a separate layer and is no longer applicable to adhesion test.
● (D-2) Sample has been allowed to settle for approximately 20 hours.
➢ NOTES:
▪ There is a faint trace of the sour tannic acid odor.
▪ Sides are wet, which makes it easier to carve off the hydrogel.
▪ Adhesive layer peels off from the hydrogel.
▪ Only a portion of the adhesive was peeled off.
▪ Interphase interactions are not strong; adhesive easily peels off from the hydrogel.
▪ The TAPE did not harden, but it is not adhesive anymore.
● (D-3) Sample has been allowed to settle for approximately 21 hours.
➢ NOTES:
▪ Faint traces of tannic acid odor.
▪ Adhesive layer peels off from the hydrogel.
▪ Adhesive layer is no longer adhesive.
▪ Sample is very wet.
● “We decided to vary the ratio of TA to PEG because we deemed that theoretically, the aromatic groups
in TA increase the rigidity of the TAPE polymer. The hydroxyl groups also increase the intermolecular
attractive forces with cellulose. So, we decided to determine experimentally the best blend for this
application.”
● Due to the seemingly adhesive property of the samples drowned/washed with the acid, we desired to
formally test the adhesiveness of the said material.
➢ 2 samples were washed with 1M HCl for 5 mins and air-dried for 90 mins.
➢ 2 samples were washed with 2M HCl for 5 mins and air-dried for 90 mins.
➢ NOTES:
▪ Rotten egg smell suggests possible evolution of H2S gas upon washing with the acid.
▪ After air-drying, green to black spots were seen. This is possibly caused by
contamination with the TAPE adhesive (through the forceps used.) The conclusion
was reached from similar observations with the TAPE and HEC.
▪ The samples were still moist after drying, with those soaked in 2M HCl being
moister.
▪ The samples seem to be adhesive, but were not properly tested due to the
contamination.
 ▪ It should also be noted that the samples were not pat dry before air-drying.

April 5, 2017

● Prepared TAPE samples.

TRIAL TA mass (g) PEG mass (g)

A1 2.0600 20.3348

B1 3.7873 18.6630

C1 6.4012 16.0057

D1 9.9542 12.4354

E1 13.7735 8.6342

A2 2.0334 20.3584

B2 3.7391 18.6583

C2 6.3959 15.9915

D2 9.9423 12.4331

E2 13.7745 8.6153

April 6, 2017

● Centrifuged samples at IChem.

➢ RESULTS:
▪ A1, A2, B1, B2, C1, and C2 did not form precipitate. Therefore, it is concluded that it
couldn’t be used for analysis.
▪ D1 and D2 produced precipitate immediately. Centrifuged sample is still runny.
▪ E1 and E2 produced precipitate immediately. Centrifuged sample is more viscous
than (E).
● Centrifuge tubes broke. Apparently, generic centrifuge tubes can only withstand 9500 rpm. Advised
to buy Hi-Speed centrifuge tubes.