Experimental

Materials

Bentonite (Sigma Aldrich), CuCl2

Urea (technical grade) and formalin (37 wt%) were purchased from Daejung Chemical, Korea.
Aqueous solution of formic acid (20 wt%) and NaOH (20 wt%) were used to adjust the pH of UF
resins during synthesis. NH4Cl (20 wt%) was used as a catalyst for curing reaction.

Methods
Preparation of modified-bentonite nanoclay
The bentonite nanoclay (BNT) was modified using transition metal ion (TMI) such as copper (II)
chloride as described in the previous method with some modification [ref]. First, BNT was
stirred in 1 M NaCl solution with weight the ratio of 1:20 for 48 h. Then, the mixture was
filtrated with the help of vacuum pump and the slurry was dried in oven at 80 °C for 12 h to get
the treated clay Na+ BNT. Furthermore, the Na+ BNT was mixed with 0.3 M CuCl 2 and stirred at
80 °C for 3 h for the ion exchange to occur. After that, the mixture was filtrated and the slurry
was dried in oven at 80 °C for 12 h to get the modified-bentonite nanoclay (TMI-BNT).
Preparation of modified UF resins
UF resins with the F/U molar ratio of 1.0 was prepared by using conventional alkaline-acid two
step reaction as described in previous method [ref]. In case for the TMI-BNT modified UF
resins, each 1%, 3%, and 5% of TMI-BNT nanocaly (based on non-volatile solids content of UF
resins) was first dispersed in formalin solution at 80 °C and the pH was adjusted to 8.
Subsequently, the mixture was mixed during methylolation step and the synthesized process was
carried out with the same condition as mentioned above. General properties of the liquid
modified UF resins used in this research are given in Table 1.
Table 1 General properties of modified UF resins
Level of TMI-BNT Non-volatile solids pH Specific Viscosity Gel time
(%) content (%) gravity (mPa.s) (s)a
0 58.1 8.2 1.21 240.2 204
1 58.3 8.2 1.21 250.2 194
3 58.9 8.2 1.21 252.2 192
5 59.3 8.2 1.21 300.0 154
a
Values measured at 3% NH4Cl level
ATR-FTIR analysis
ATR-FTIR measurements using a Bruker Alpha FTIR spectrometer were conducted to
investigated the functional group of liquid and cured modified UF resins adhesives. The liquid
and cured modified UF resins were scanned from 400-4000 cm -1 with a resolution of 4 cm-1 and
32 scans for each sample. The spectrum of each adhesive was then normalized.
DSC analysis
DSC analysis (Discovery 25, TA instruments, New Castle, United States) was used to
characterized the cure kinetics of the modified UF resins. Approximately, 5-6 mg of each
adhesive sample was mixed with 3% (based on non-volatile solids content of UF resins) of 20 wt
% NH4Cl solution. The mixture was sealed in in high-pressure capsule pan in order to suppress
the evaporation of water during DSC scanning. Each adhesive sample then heated from 30 to 200
°C at different heating rates of 2.5, 5, 10 and 20 °C/min under nitrogen flow of 50 mL/min. The
cure kinetics parameters were estimated using four different kinetics models: the Kissinger
method, the Model Free Kinetics isoconversional method, the nth-order Borchardt-Daniels
model (nth-BD) and autocatalytic Borchardt-Daniels (Auto-BD) model.
According to the Kissinger method, the cure kinetics parameters could be estimated using this
following equation: Tp2

activation energy (Ea) was calculating using two different methods